Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene

Definitions

• This disclosure relates to catalyst compositions including support-activators for producing polyethylene and processes for preparing and using the same.
• aspects of this disclosure provide new support-activators and processes for their preparation, new catalyst compositions comprising the support-activators, methods for making the catalyst compositions, and processes for polymerizing olefins.
• the chemically- modified clay support-activators can readily activate metallocene compounds toward polymerization of olefins, and they are surprisingly easy and cost-effective to prepare and recover in high yield.
• the processes and the support-activators of this disclosure can largely avoid the previous difficulties in isolating chemically-modified clay support- activators, for example, from clay particle digestion 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 particles decrease in size.
• a colloidal smectite clay such as a dioctahedral smectite clay
• a liquid carrier also termed a “diluent”
• a heterocoagulation reagent comprising at least one cationic polymetallate
• a support-activator comprising an isolated smectite heteroadduct can be synthesized.
• the smectite heteroadduct also termed a heterocoagulated smectite, can be easily isolated from the resulting slurry by a conventional filtration process.
• the isolation process has often been difficult with previous chemically-modified clay support- activators, where filtration may require days, or multiple washing and centrifugation steps may be required.
• the smectite heteroadduct support-activator isolated in accordance with this disclosure can be used with few or no washing steps, further enhancing the usefulness, ease, and economy of preparation and use.
• the smectite heteroadducts prepared in this manner which can be used in combination with co-catalysts such as alkyl aluminum compound, afford very active support-activators for metallocene olefin polymerizations, particularly when compared to traditional MAO-SiCk or borane-derived support-activators.
• the heterocoagulation agents used in this process can be very inexpensive and can be used with co-catalysts such as alkyl aluminum compounds, which can also be very inexpensive as compared to aluminoxane and borane-based activators.
• the isolation of the smectite heteroadducts can be effected using a conventional filtration, without the need for centrifugation or high dilution of reaction mixtures, and without extensive washing of the solid thus obtained.
• This process provides the solid clay heteroadduct exhibiting better activity than the corresponding untreated clay, and comparable or better activity than the more difficult-to-prepare pillared clay supports, thereby fulfilling a need.
• the heterocoagulated clay materials of this disclosure are amorphous solids.
• the preparation of the heterocoagulated clay provides a three- dimensional structure, but one which is a non-pillared and non-crystalline and amorphous.
• this disclosure provides a support-activator comprising an isolated smectite heteroadduct, the smectite heteroadduct comprising the contact product in a liquid carrier of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (+25 millivolts) to about negative 25 mV (-25 millivolts).
• This disclosure also provides, in another aspect, a method of making a support-activator comprising a smectite heteroadduct, the method comprising: a) providing a colloidal smectite clay; b) contacting in a liquid carrier the colloidal smectite clay with a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV; and c) isolating the smectite heteroadduct from the slurry.
• this disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound; b) optionally, at least one co-catalyst; and c) at least one support-activator comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• This disclosure also provides, in another aspect, a method of making an olefin polymerization catalyst, the method comprising contacting in any order: 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, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• the optional co-catalyst can be an alkylating agent which may or may not be required for initiating efficient olefin polymerization depending upon the particular metallocene compound used to make the olefin polymerization catalyst.
• 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, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (+25 millivolts) to about negative 25 mV (-25 millivolts).
• compositions including the support-activator and the catalyst compositions, the methods of making the compositions, and the polymerization processes and associated methods are more fully described in the Detailed Description, the Figures, the Examples, and the claims which are provided herein.
• FIG. 1 provides a schematic representation of an aspect of this disclosure, illustrating a method to prepare, wash, and isolate the support-activator comprising a calcined smectite heteroadduct of this disclosure, and contrasts this process with the method to prepare, wash, and isolate a pillared clay.
• FIG. 2 provides a powder XRD (x-ray diffraction) pattern of a series of calcined products from combining aluminum chlorhydrate (ACH) and Volclay® HPM-20 montmorillonite. All of the samples were prepared according to the inventive methods according to the examples (see Examples 18, 20-21, and 23) except for the 6.4 mmol Al/g clay sample (top), representing typically prepared Aln-pillared clay (comparative Example 5), and the starting clay itself at the 0 mmol Al/g clay sample (comparative Example 3).
• FIG. 1 powder XRD (x-ray diffraction) pattern of a series of calcined products from combining aluminum chlorhydrate (ACH) and Volclay® HPM-20 montmorillonite. All of the samples were prepared according to the inventive methods according to the examples (see Examples 18, 20-21, and 23) except for the 6.4 mmol Al/g clay sample (top), representing typically prepared Aln-pillared clay (comparative Example 5), and the starting clay itself at the 0
• FIG. 3 illustrates a zeta potential titration for the volumetric addition of a 2.5 wt.% (weight percent) aqueous solution of aluminum chlorohydrate (ACH; measured density of 1.075 g/mL) into a 0.62 wt.% Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zeta potential versus the titrant volume (mL).
• the titration settings were 0.5 mL per titration point, followed by an equilibration delay of 30 seconds.
• the titrant volume indicates the cumulative volume of the aqueous aluminum chlorohydrate solution added. See also Table 4.
• FIG. 4 shows the conversion of the FIG. 3 plot into a zeta potential versus a mass ratio of aluminum to clay.
• FIG. 4 illustrates a zeta potential titration for the addition of a 2.5 wt.% aqueous solution of aluminum chlorohydrate (ACH; measured density of 1.075 g/mL) into a 0.62 wt.% Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zeta potential versus the A1 content (mmol Al/g clay).
• the titrant amount indicates the cumulative mmol of aluminum of the aqueous ACH solution added.
• FIG. 5 illustrates a zeta potential titration for the volumetric addition of a 4.58 wt.% aqueous solution of UltraPAC® 290 polyaluminum chloride (empirically Al2(OH)2.5Cl3.5) into a 1 wt.% Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zeta potential versus the titrant volume (mL).
• the titration settings were 1 mL per titration point, followed by an equilibration delay of 30 seconds.
• the titrant volume indicates the cumulative volume of the aqueous UltraPAC® 290 polyaluminum chloride solution added. See also Table 5.
• FIG. 6 provides a zeta potential titration (adjusted) for the volumetric addition of a 10 wt.% aqueous dispersion of NYACOL® AL27 colloidal alumina into a 0.75 wt.% Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zeta potential versus the titrant volume (mL).
• the titration settings were 1 mL per titration point from 0-27 mL and 3 mL per titration point afterwards, equilibration delay of 60 seconds.
• the titrant volume indicates the cumulative volume of the aqueous solution of NYACOL® AL27 colloidal alumina added. See Example 11 and Table 6.
• FIG. 7 illustrates a zeta potential titration for the volumetric addition of a 2.5 wt.% aqueous solution of aluminum chlorohydrate (ACH) into a 5 wt.% aqueous dispersion of AEROSIL® 200 fumed silica, plotting the measured zeta potential versus the titrant volume (mL).
• the titration settings were 1 mL per titration point, with an equilibration delay of 60 seconds.
• the titrant volume indicates the cumulative volume of the aqueous solution of ACH added. See Example 37.
• FIG. 8 shows the conversion of the FIG. 7 plot into a zeta potential versus a mass ratio of aluminum to clay.
• FIG. 8 provides a zeta potential titration for the addition of a 2.5 wt.% aqueous solution of aluminum chlorohydrate (ACH) into a 5 wt.% aqueous dispersion of AEROSIL® 200 fumed silica, plotting the measured zeta potential versus the A1 content (mmol Al/g clay).
• the titrant amount indicates the cumulative mmol of aluminum of the aqueous ACH solution added.
• FIG. 9 provides a zeta potential titration (adjusted) for the volumetric addition of an aluminum chlorohydrate (ACH) solution-treated AEROSIL® 200 fumed silica dispersion, containing 5 wt.% by silica, into a 1 wt.% Volclay® HPM-20 bentonite aqueous dispersion.
• the titration settings were 0.2 mL per titration point from 0-1.2 mL and 0.5 mL per titration point onwards, with an equilibration delay of 30 seconds.
• the titrant is a colloidal species, therefore, the zeta potential was adjusted using the described method of Example 11 to provide the plot in FIG. 9. See Example 38.
• FIG. 10 shows the results of a nitrogen adsorption/desorption BJH (Barrett, Joyner, and Halenda) pore volume analysis of the aluminum chlorhydrate (ACH) heterocoagulated clay of Example 18, providing a plot of pore diameter (Angstrom, A) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
• the recipe for the preparation of this heteroadduct slurry used 1.76 mmol Al/g clay.
• FIG. 11 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of a comparative sheared, then azeotroped, sample of Volclay® HPM-20 bentonite, but without further treatment, according to comparative Example 3 showing values for V3-ionm that are greater than 55% of the cumulative pore volume V3-30nm.
• FIG. 12 shows the results of a nitrogen adsorption/desorption BJH pore volume analysis of an untreated sample of Volclay® HPM-20 bentonite which was suspended in water, evaporated, and calcined, but without further treatment according to comparative Example 1, showing values for V3-ionm that are greater than 55% of the cumulative pore volume V3-30nm.
• FIG. 13 is a 3 ⁇ 4NMR spectrum of 7-phenyl-2-methyl-indene in CDCb, with contaminant CH2CI2 and water peaks identified, and showing the peak integration values.
• FIG. 14 is a 3 ⁇ 4 NMR spectrum of rac-dimethylsilylene bis(2-methyl-4-phenylindenyl)- zirconium di chloride in CDCb, with the peak integration values shown.
• polymetallate and similar terms such as “polyoxometallate”, are used interchangeably in this disclosure to refer to the water-soluble polyatomic cations that include two or more metal atoms (for example, aluminum, silicon, titanium, zirconium, or other metals) along with at least one bridging ligand between metals such as oxo, hydroxy and/or halide ligands.
• the specific ligands can depend upon the precursor and other factors, such as the process for generating the polymetallate, the solution pH, and the like.
• the polymetallates of this disclosure can be hydrous metal oxides, hydrous metal oxyhydroxides, and the like, including combinations thereof. Bridging ligands such as oxo ligands which bridge two or more metals can occur in these species, however, polymetallates can also include terminal oxo, hydroxyl, and/or halide ligands.
• polymetallate (polyoxometallate) species used according to this disclosure are cationic. These materials may be referred to as compounds, species, or compositions, but the person of ordinary skill in the art will understand that polymetallate compositions can contain multiple species in a suitable carrier such as in aqueous solution, depending upon, for example, the solution pH, the concentration, the starting precursor from which the polymetallate is generated in aqueous solution, and the like.
• polymetallates or “polyoxometallates”, regardless of whether the compositions include or consist primarily of cationic polyoxometallates, polyhydroxymetallates, polyoxohydroxymetallate, or species that include other ligands such as halides, or mixtures of compounds.
• polymetallates include but are not limted to polyaluminum oxyhydroxychlorides, aluminum chlorhydrate, polyaluminum chloride, or aluminum sesquichlorohydrate compositions, which can include linear, cyclic or cluster compounds.
• These compositions are referred to collectively as polymetallates, although the term “polymetallate” or “polyoxometallate” are also used to described a composition substantially comprising a single species.
• isopolymetallates which contain a single type of metal
• heteropolymetallates which contain more than one type of metal (or electropositive atoms such as phosphorus) are included in the general terms polymetallate or polyoxometallate.
• aluminum polymetallates such as provided by aluminum chlorhydrate (ACH) or polyaluminum chloride (PAC) are exemplary of a isopolymetallate.
• the polymetallates of this disclosure can be prepared from a first metal oxide which 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 a heteropolymetallate.
• the first metal oxide can comprise silica, alumina, zirconia and the like, including fumed silica, alumina, or zirconia
• the second metal oxide, the metal halide, or the metal oxyhalide can be obtained from an aqueous solution or suspension of the metal oxide, hydroxide, oxyhalide, or halide, such as ZrOCh, ZnO, NbOCb, B(OH)3, AlCb, or a combination thereof. Therefore, when different metals are employed in this preparation, the resulting species is considered a heteropolymetallate. Both isopolymetallates and heteropolymetallates may be referred to as simply “polymetallates”.
• the polymetallates according to this disclosure can be non-alkylating toward transition metal compounds such as metallocene compounds. That is, the subject polymetallates can be absent direct metal-carbon bonds as would be found in aluminoxanes or other organometallic species.
• polymetallates can be considered to encompass both oligomeric or polymeric species.
• polymetallates can be described herein according to the precursor materials or compositions from which the cationic polymetallates are generated to provide the heterocoagulation reagent.
• the polymetallate according to this disclosure can be at least one aluminum polymetallate.
• examples include, but are not limited to, aluminum chlorhydrate (ACH), also termed aluminum chlorohydrate, which encompasses multiple water soluble aluminum species, usually considered as having the general formula AlnCl3n-m(OH) m .
• ACH aluminum chlorhydrate
• PAC polyaluminum chloride
• PAC polyaluminum chloride
• aluminum polymetallates include, but are not limited to, compounds having the general formula [AlmOn(OH)xCly] # zH20 such as aluminum sequi chlorohydrate, and cluster-type species such as Keggin ions, for example, [A104Ali2(0H)24(H20)i2] 7+# 7[Cl] , sometimes referred to as “AI13- mer” polycation.
• Polyaluminum chloride (PAC) for example, can be produced by combining aqueous hydroxide with AlCh, and the resulting mixture of aluminum species has a range of basicities.
• Aluminum chlorhydrate (ACH) is generally considered the most basic, and polyaluminum chloride (PAC) being less basic.
• the clay heteroadduct or clay heterocoagulate according to this disclosure include the contact product of [1] a colloidal smectite clay, such as a dioctahedral smectite clay, and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier such as an aqueous carrier, in which the amount used is sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about +25 mV to about -25 mV.
• the smectite heteroadduct can be heated and dried and calcined to form the support- activator as described herein.
• polyoxometallate may be particularly useful to illuminate the calcined product. Regardless, the terms “polymetallate” and “polyoxometallate” are used interchangeably to describe the composition used to contact the colloidal smectite.
• polycations may also be termed “polycations” and can include both homopolycations and heteropolycations, depending upon whether the polycation includes a single type of metal or more than one type of metal.
• hydrotalcite is [Mg6Al2(0H)i6]C03 # 4H20 which is a heteropolycation according to this disclosure.
• polymetallates which are provided as exemplary only, include the e- Keggin cations [s-PMoi20 36 (OH)4 ⁇ Ln(H20)4 ⁇ 4] 5+ , wherein Ln can be La, Ce, Nd, or Sm. See, for example, Angew. Chem., Int. Ed. 2002, 41, 2398.
• Other examples include the lanthanide- containing cationic heteropolyoxovanadium clusters having the general formula [Ln2Vi20 32 (H20)8 ⁇ Cl ⁇ ]Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho, or Er. See , for example, RSC Adv. 2013, 3, 6299-6304.
• reference to “at least one” cationic polymetallate is used to refer to one or more sources of the cationic polymetallate being used in preparation of the heterocoagulation reagent. That is, even when a single source of the cationic polymetallate is used in preparing the heterocoagulation reagent in aqueous solution, and multiple species may result, these multiple species can be collectively referred to as a single or single type of cationic polymetallate. Therefore, reference to multiple or more than one cationic polymetallate is intended to refer to one or more precursor compositions or sources of the cationic polymetallate being used to prepare the heterocoagulation reagent.
• Heterocoagulation reagent used herein to describe a composition comprising any positively charged oligomeric or polymeric metal oxide containing species, existing in solution, or as a colloidal suspension which, when combined with a colloidal clay dispersion in an appropriate ratio, forms a readily filterable solid (as defined herein).
• Heterocoagulation reagent can be used interchangeably with the terms “polymetallate” or “polyoxometallate” to refer to any positively charged oligomeric or polymeric metal oxide containing species that function to form a clay heteroadduct.
• heterocoagulation reagent emphasizes that the composition comprising one or more cationic polymetallate species in a liquid carrier, when used in an amount sufficient to provide a slurry having a zeta potential in a range of from about +25 mV to about -25 mV when contacted with a colloidal smectite clay, forms a readily filterable solid.
• Heterocoagulation is a term in the art described by Lagaly in Ullmann’s Encyclopedia of Chemistry 2012. Within the context of this disclosure, “heterocoagulation” is defined as the process by which negatively charged colloidal clay particles are combined with positively charged species of a heterocoagulation reagent to form a readily filterable solid, unless otherwise specified. Heterocoagulation is also sometimes referred to in the art and herein as heteroaggregation, such as described by Cerbelaud et al. Advances in Physics: X , 2017, vol. 2, 35-53.
• Heteroadduct or heterocoagulate refers to the contact product obtained from combining the heterocoagulation reagent and the colloidal clay. That is, the agglomerate formed by the attraction of negatively charged colloidal clay particles with positively charged species in the heterocoagulation reagent is referred to as a “heteroadduct”.
• a heterocoagulation reagent or smectite heteroadduct
• the agglomerate formed by the attraction of negatively charged colloidal clay particles with positively charged species in the heterocoagulation reagent is referred to as a “heteroadduct”.
• Wu Cheng et al. in U.S. Patent No. 8,642,499, which is incorporated herein by reference.
• these terms refer to the “readily filterable” contact product of a heterocoagulation reagent and a colloidal clay, as defined herein.
• the ratio of the pillaring reagent such as an aluminoxychloride (also termed a heterocoagulation reagent) to clay is expressed as mm (also mmol or millimoles) Al/g clay, indicating the number of millimoles of Al in the pillaring or heterocoagulation agent versus the grams of clay.
• mm also mmol or millimoles
• the millimoles Al are calculated based on the Al weight percent or wt.% AhCh content provided by the manufacturer.
• the millimoles of A1 are determined by the weight used in the recipe and the empirical formula provided by the manufacturer.
• Readily Filterable The terms “readily filterable”, “readily filtered”, “easily filterable”, “easily filtered or separated” and the like are used herein to describe a composition according to this disclosure in which the solids in a mixture containing a liquid phase can be separated by filtration from the liquid phase without resorting to centrifugation, ultra-centrifugation, or dilute solutions of less than about 2 wt.% solids, long settling times followed by decanting the liquid away from solids, and other such techniques.
• a readily filterable clay heteroadduct can be isolated or separated in good yield in a matter of minutes or less, or time periods of less than about one hour, from the soluble salts and byproducts of the synthesis, by passing a slurry comprising the heteroadduct through conventional filtering materials, such as sintered glass, metal or ceramic frits, paper, natural or synthetic matte-fiber and the like, under gravity or vacuum filtration conditions.
• This disclosure provides some specific experimental and quantitative methods by which filterability can be assessed. For example, specific methods of quantifying filterability of the heteroadduct slurry are provided which demonstrate that the slurry can be considered readily filterable or readily filtered when prepared according to the methods of this disclosure. Colloids or suspensions as described by Lagaly in Ulmmann ’s Encyclopedia of Chemistry 2012, that require long sedimentation times or ultrafiltration are not considered to be “filterable” in the context of this disclosure.
• the readily filterable suspensions or slurries of this disclosure can afford clear filtrates upon filtration, while “non-readily-filterable” suspensions which take substantially longer to filter can contain particulate matter that is observable as a cloudy or non- clear filtrate to the naked eye, indicative of colloidal clay dispersions.
• the support- activator according to this disclosure is prepared to provide a slurry of the smectite heteroadduct having a zeta potential near the upper (positive) boundary of about +25 mV (millivolts) or near the lower (negative) boundary of about -25 mV, upon filtration of the heteroadduct, some cloudiness can be observed in the filtrate, which dimishes as the smectite heteroadduct is prepared using ratios of colloidal smectite clay and heterocoagulation reagent that provide a slurry having a zeta potential closer to or approaching 0 mV.
• Colloid The term “colloid”, “colloidal clay”, “colloidal solution”, “colloidal suspension” and similar terms are used as defined by Gerhard Lagaly in Ullmannn ’s Encyclopedia of Industrial Chemistry , in the chapter entitled “Colloids”, which published 15 January 2007. These terms are used interchangeably.
• Catalyst composition and catalyst system are used to represent the combination of recited components which ultimately form, or are used to form, the active catalyst according to this disclosure.
• the use of these terms does not depend upon any specific contacting steps, order of contacting, whether any reaction may occur between or among the components, or any product which may form from any contact of any or all of the recited components.
• the use of these terms also does not depend upon the nature of the active catalytic site, or the fate of any co catalyst, the metallocene compound(s), or support-activator, after contacting or combining any of these components in any order.
• Catalyst activity refers to the polymerization activity of a catalyst composition comprising a dried or calcined clay heteroadduct as disclosed herein, which is typically expressed as weight of polymer polymerized per weight of catalyst clay support- activator only, absent any transition metal catalyst components such as a metallocene compound, any co-catalyst such as an organoaluminum compound, or any co-activators such as an aluminoxane, per hour of polymerization. In other words, the weight of polymer produced divided by the weight of calcined clay heteroadduct per hour, in units of g/g/hr (grams per gram per hour).
• Activity of a reference or comparative catalyst composition refers to the polymerization activity of a catalyst composition comprising a comparative catalyst composition and is based upon the weight of a comparative ion-exchanged or pillared clay or weight of the clay component by itself that is used to prepare clay heteroadducts.
• Terms such as “increased activity” or “improved activity” describe the activity of a catalyst composition according to this disclosure which is greater than the activity of a comparative catalyst composition that uses the same catalyst components such as metallocene compound and co-catalyst, except that the comparative catalyst composition utilizes a different support-activator or activator generally, such as a pillared clay, or the clay component used in the catalytic reaction is not a heterocoagulated clay.
• the increased or improved activity according to this disclosure includes an activity based upon the calcined clay heteroadduct greater than or equal to about 300 grams of polyethylene polymer per gram of calcined heterocoagulated clay per hour (g/g/hr), using a standard set of ethylene homopolymerization conditions.
• the standard set of ethylene homopolymerization conditions include the following.
• a 2 L stainless steel reactor equipped with a marine type impeller is set at about 500 rpm, and the slurry polymerization conditions include 1 L of purified isobutane diluent, 90°C polymerization temperature, 450 total psi ethylene pressure, typically 30 or 60 minute run length, metallocene catalyst composition comprising (l-Bu-3-MeCp)2ZrCl2 with triethylaluminum (TEAL) co catalyst, optionally using the metallocene as a stock solution which contained the TEAL, which is charged in an amount to provide a metallocene-to-clay ratio of about 7x KG 5 mmol metallocene/mg calcined clay.
• TEAL triethylaluminum
• TEAL triethylaluminum
• one alkyl aluminum cocatalyst was used in the polymerization runs and usually was selected from TEAL or triisobutylaluminum (TIBAL).
• contact product is used herein to describe compositions wherein the components are combined together or “contacted” in any order, unless a specific order is stated or required or implied by the context of the disclosure, in any manner, and for any length of time.
• contact product can include reaction products, it is not required for the respective components to react with one another, and this term is used regardless of any reaction which may or may not occur upon contacting the recited components.
• the recited components can be contacted by blending or mixing or the components can be contacted by adding the components in any order or simultaneously into a liquid carrier.
• any components can occur in the presence or absence of any other component of the compositions described herein, unless otherwise stated or required or implied by the context in which the term is used. Combining or contacting the recited components or any additional materials can be carried out by any suitable method. Therefore, 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 which may be blended, mixed, slurried, dissolved, reacted, treated, or otherwise contacted in some manner.
• Pore diameter Pore diameter (pore size). Nitrogen adsorption/desorption measurements were used to determine pore size and pore volume distributions using the BJH method. Based upon the International Union of Pure and Applied Chemistry (IUPAC) system for classifying porous materials (see Pure & Appl. Chem., 1994, 66, 1739-1758), and Klobes etal. , National Institute of Standards and Technology Special Publication 960-17, pore sizes are defined as follows. “Micropore” and “microporous” as used herein refers to pores present in catalysts or catalyst supports produced according to processes of the disclosure having a diameter of less than 20 A.
• IUPAC International Union of Pure and Applied Chemistry
• Poresopore and “mesoporous” as used herein refers to pores present in catalysts or catalyst supports produced according to processes of the present disclosure having a diameter in a range of from 20 A to less than 500 A (that is from 2 nm to ⁇ 50 nm).
• Mesopore and “macroporous” as used herein refers to pores present in catalysts or catalyst supports produced according to processes of the present disclosure having a diameter equal to or greater than 500 A (50 nm).
• micropore, mesopore and macropore are considered distinct and non-overlapping, such that pores are not counted twice when summing up percentages or values in a distribution of pore sizes (pore diameter distribution) for any given sample.
• d50 means the median pore diameter as measured by porosimetry.
• d50 corresponds to the median pore diameter calculated based on pore size distribution and is the pore diameter above which half of the pores have a larger diameter.
• the d50 values reported herein are based on nitrogen desorption using the well-known calculation method described by E. P. Barrett, L. G. Joyner and P. P. Halenda (“BJH”), “The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms,” J Am. Chem. Soc., 1951, 73 (1), pp 373-380.
• the “median pore diameter” can be calculated based upon, for example, volume, surface area or based on pore size distribution data.
• Median pore diameter calculated by volume means the pore diameter above which half of the total pore volume exists.
• Median pore diameter calculated by surface area means that pore diameter above which half of the total pore surface area exists.
• median pore diameter calculated based on pore size distribution means the pore diameter above which half of the pores have a larger diameter according to the pore size distribution determined as described elsewhere herein, for example, through derivation from nitrogen adsorption-desorption isotherms.
• Transition metal catalyst refers to a transition metal compound or composition which can function as, or be transformed into, an active olefin polymerization catalyst when contacted with the support-activator of this disclosure, either in its current form or when contacted with a co-catalyst which is capable of transferring or imparting a polymerization-activatable ligand to the transition metal catalyst.
• the use of the term “catalyst” is not intended to reflect any specific mechanism or that the “transition metal catalyst” itself represents an active site for catalytic polymerization when it is activated or when it has been imparted with a polymerization-activatable ligand.
• the transition metal catalyst is described according to the transition metal compound or compounds used in the process for preparing a polymerization catalyst, and can include metallocene compounds and defined herein, and related compounds.
• Co-catalyst is used herein to refer to a chemical reagent, compound, or composition which is capable of imparting a ligand to the metallocene which can initiate polymerization when the metallocene is otherwise activated with the support-activator.
• the “co-catalyst” is used herein to refer to a chemical reagent, compound, or composition which is capable of providing a polymerization-activatable ligand to a metallocene compound.
• Polymerization-activatable ligands include, but are not limited to, hydrocarbyl groups such as alkyls such as methyl or ethyl, aryls and substituted aryls such as phenyl or tolyl, substituted alkyls such as benzyl or trimethyl silylmethyl (-CEhSiMs), hydride, silyl and substituted groups such as trimethylsilyl, and the like. Therefore, in an aspect, a co-catalyst can be an alkylating agent, a hydriding agent, a silylating agent, and the like.
• the co-catalyst provides a polymerization-activatable ligand to the metallocene compound.
• the co-catalyst can engage in a metathesis reactions to exchange an exchangeable ligand such as a halide or alkoxide on the metallocene compound with a polymerization-activatable/initiating ligand such as methyl or hydride.
• the co-catalyst is an optional component of the catalyst composition, for example, when the metallocene compounds already includes a polymerization-activatable/initiating ligand such as methyl or hydride.
• a co-catalyst can be used for other purposes, such as to scavenge moisture from the polymerization reactor or process.
• the term “co catalyst” may refer to an “activator” or may be used interchangeably with “co-catalyst” as explained herein.
• activator refers generally to a substance that is capable of converting a metallocene component into an active catalyst system which can polymerize olefins, and is intended to be independent of the mechanism by which such activation occurs.
• an “activator” can convert the contact product of a metallocene component and a component that provides an activatable ligand (such as an alkyl or a hydride) to the metallocene, for example, when the metallocene compound does not already comprise such a ligand, into a catalyst system which can polymerize olefins. This term is used regardless of the actual activating mechanism.
• activators can include, but are not limited to a support- activator, aluminoxanes, organoboron or organoborate compounds, ionizing compounds such as ionizing ionic compounds, and the like.
• Aluminoxanes, organoboron or organoborate compounds, and ionizing compounds may be referred to as “activators” or “co-activators” when used in a catalyst composition in which a support-activator is present, but the catalyst composition is supplemented by one or more aluminoxane, organoboron, organoborate, ionizing compounds, or other co-activators.
• Support-activator refers to an activator in a solid form, such as ion-exchanged-clays, protic-acid-treated clays, or pillared clays, and similar insoluble supports which also function as activators.
• a metallocene with an activatable ligand or optionally with a metallocene and a co-catalyst which can provide an activatable ligand provides a catalyst system which can polymerize olefins.
• Ion-exchanged clay is understood by the person skilled in the art as a clay (also referred to as a “monoionic” or “monocationic” clay) in which the exchangeable ions of a naturally-occurring or synthetic clay have been replaced by or exchanged with another selected ion or ions.
• Ion exchange can occur by treatment of the naturally-occurring or synthetic clay with a source of the selected cation, usually from concentrated ionic solutions such as 2 N aqueous solutions of the cation, including through multiple exchange steps, for example, three exchange steps.
• the exchanged clay can be subsequently washed several times with deionized water to remove excess ions produced by the treatment process, for example as described in Sanchez, etal. , Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 423, 1-10, and Kawamura etal. , Clay and Clay Minerals , 2009, 57(2), 150-160. Generally, centrifugation is used to isolate the clay from solution between ion treatments and washings.
• metallocene compound describes a transition metal or lanthanide metal compound comprising at least one substituted or unsubstituted cycloalkadienyl-type ligand or alkadienyl-type ligand, including heteroatom analogs thereof, regardless of the specific bonding mode, for example, regardless of whether the cycloalkadienyl-type ligand or alkadienyl-type ligand are bonded to the metal in an h 5 -, h 3 -, or ⁇ -bonding mode, and regardless of whether more than one of these bonding modes is accessible by such ligands.
• the term “metallocene” is also used to refer to a compound comprising at least one pi-bonded allyl-type ligand in which the r
• metalocene includes compounds with substituted or unsubstituted h 3 to h 5 -cy cl oal kadi eny 1 -type and h 3 to h 5 - alkadienyl-type ligands, q 3 -al lyl -type ligands, including heteroatom analogs thereof, and including but not limited to cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, q 3 -allyl ligands, pentadienyl ligands, boratabenzenyl ligands, 1,2-azaborolyl ligands, l,2-diaza-3,5- diborolyl ligands, substituted analogs thereof, and partially saturated analogs thereof.
• Partially saturated analogs include compounds comprising partially saturated h 5 -cy cl oal kadi eny 1 -type ligands, examples of which include but are not limited to tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted analogs thereof, and the like.
• the metallocene is referred to simply as the “catalyst,” in much the same way the term “co-catalyst” is used herein to refer to, for example, an organoaluminum compound.
• a metallocene ligand can be considered in this disclosure to include at least one substituted or at one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or l,2-diaza-3,5-diborolyl ligand, including substituted analogs thereof.
• any substituent can be selected independently from a halide, a C1-C2 0 hydrocarbyl, a C1-C2 0 heterohydrocarbyl, a C1-C2 0 organoheteryl, a fused C4-C12 carbocyclic moiety, or a fused C4-C11 heterocyclic moiety having at least one heteroatom selected independently from nitrogen, oxygen, sulfur, or phosphorus.
• Organoaluminum compounds and organoboron compounds Organoaluminum compounds and organoboron compounds.
• organoaluminum compound and an organoboron compounds as used herein include neutral compounds such as AllVfe and BEt3 and also include anionic complexes such as LiAlMe4, LiAlEE, NaBEE, and LiBEt4, and the like.
• hydride compounds of aluminum and boron are include in the definitions of organoaluminum and organoboron compounds, respectively, whether the compound is neutral or anionic.
• Pillared clay is defined as a clay species in which ordered layers with basal spacing are substantially greater than 9 A to 13 A.
• a powder clay sample is analyzed using an X-ray diffraction apparatus capable of scanning 2Q angles of 2° or greater, species containing such pillared ordering are typically observed to possess a substantial peak at 2Q values between 2° to 9°.
• a pillaring agent for example, an oxygen-containing inorganic cation such as an oxygen- containing cation of lanthanum, aluminum, or iron.
• Aluminum pillared clays are often prepared by contacting the pillaring agent with the clay in an amount ranging from about 5 mmol Al/g clay or 6 mmol Al/g clay, up to about 30 mmol Al/g clay.
• Typical pillared clay preparations may contrast with preparations of the support-activator according to this disclosure, in which the support-activator disclosed herein can be prepared using less than or equal to about 2.0 mmol Al/g clay, less than or equal to about 1.7 mmol Al/g clay, less than or equal to about 1.5 mmol Al/g clay, less than or equal to about 1.3 mmol Al/g clay, or less than or equal to about 1.2 mmol Al/g clay, but greater than about 0.75 mmol Al/g clay, or greater than about 1.0 mmol Al/g clay.
• the pillaring agent used to form a pillared clay can be selected from the same heterocoagulation reagents used to form the heterocoagulated clay of this disclosure. As explained herein, even during the preparation of the smectite heteroadducts as disclosed herein, some pillared clay species may be formed.
• Basal spacing refers to the distance, usually expressed in angstroms or nanometers, between similar faces of adjacent layers in the clay structure.
• the basal distance is the distance from the top of a tetrahedral sheet to the top of the next tetrahedral sheet of an adjacent 2: 1 layer and including the intervening octahedral sheet, with or without modification or pillaring.
• Basal spacing values are measured using X-ray diffraction analysis (XRD) of the dOOl plane.
• Natural montmorillonite as found for example in bentonite, has a basal spacing range of from about 12 A to about 15 A.
• the XRD test method for determining basal spacing is described in: Pillared Clays and Pillared Layered Solids, R. A. Schoonheydt et al. , Pure Appl. Chem ., 71(12), 2367-2371, (1999); and U.S. Patent No.
• Zeta potential refers to the difference in electrical potential between the juncture of the Stern layer (a layer of firmly-attached counterions which forms to neutralize the surface charge of a colloidal particle) and diffuse layer (a cloud of loosely attached ions residing farther from the particle surface than the Stem layer), and the bulk solution or slurry. This property is expressed in units of voltage, for example millivolts (mV). Zeta potential can be derived by quantifying the “Electrokinetic Sonic Amplitude Effect” (ESA), which is the generation of ultrasound waves as a result of applying an electric potential across a colloidal suspension, as described in U.S. Patent No. 5,616,872, which is incorporated herein by reference.
• ESA Electrokinetic Sonic Amplitude Effect
• Hydrocarbyl group As used herein, the term “hydrocarbyl” group is used according to the art-recognized IUPAC definition, as a univalent, linear, branched, or cyclic group formed by removing a single hydrogen atom from a parent hydrocarbon compound. Unless otherwise specified, a hydrocarbyl group can be aliphatic or aromatic; saturated or unsaturated; and can include linear, cyclic, branched, and/or fused ring structures; unless any of these are otherwise specifically excluded. See IUPAC Compendium of Chemical Terminology , 2 nd Ed (1997) at 190.
• hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups and the like.
• Heterohydrocarbyl group is used in this disclosure to encompass a univalent, linear, branched, or cyclic group, formed by removing a single hydrogen atom from a carbon atom of a parent “heterohydrocarbon” molecule in which at least one carbon atom is replaced by a heteroatom.
• the parent heterohydrocarbon can be aliphatic or aromatic.
• heterohydrocarbyl groups include halide-substituted, nitrogen-substituted, phosphorus-substituted, silicon-substituted, oxygen- substituted, and sulfur- substituted hydrocarbyl groups in which a hydrogen has been removed form a carbon atom to generate a free valence.
• heterohydrocarbyl groups include, but are not limited to, -CH2OCH3, -CEbSPh, -CH2NHCH3, -CH 2 CH 3 NMe2, -CH 2 SiMe 3 , -CMe 2 SiMe 3 , -CH 2 (C 6 H4-4- OMe), -CH 2 (C 6 H4-4-NHMe), -CH 2 (C 6 H4-4-PPh 2 ), -CH 2 CH 3 PEt 2 , -CH2CI, -CH 2 (2,6-C 6 H 3 Cl2), and the like.
• Heterohydrocarbyl encompasses both heteroaliphatic groups (including saturated and unsaturated groups) and heteroaromatic groups. Therefore, heteroatom- substituted vinylic groups, heteroatom-substituted alkenyl groups, heteroatom- substituted dienyl groups, and the like are all encompassed by heterohydrocarbyl groups.
• Organoheteryl group The term “organoheteryl” group is also used in accordance with its art-recognized IUPAC definition, as univalent group containing carbon, which is thus organic, but which has its free valence at an atom other than carbon. See IUPAC Compendium of Chemical Terminology , 2 nd Ed (1997) at 284.
• An organoheteryl group can be linear, branched, or cyclic, and includes such common groups as alkoxy, aryloxy, organothio (or organylthio), organogermanium (or organylgermanium), acetamido, acetonylacetanato, alkylamido, dialkylamido, arylamide, diarylamido, trimethyl silyl, and the like.
• Groups such as -OMe, -OPh, -S(tolyl), -NHMe, -NMe 2 , -N(aryl) 2 , -SiMes, -PPh 2 , -03S(C 6 H )Me, -OCF 2 CF 3 , -0 2 C(alkyl), -0 2 C(aryl), -N(alkyl)CO(alkyl), -N(aryl)CO(aryl), -N(alkyl)C(0)N(alkyl) 2 , hexafluoroacetonylacetanato, and the like.
• An organyl group can be linear, branched, or cyclic, and the term “organyl” may be used in conjunction with other terms, as in organylthio- (for example, MeS-) and organyloxy.
• Heterocyclyl group The IUPAC Compendium compares organyl groups to other groups such as heterocyclyl groups and organoheteryl groups. These terms are set out in the IUPAC Compendium of Chemical Terminology , 2 nd Ed (1997) as follows, which demonstrates the convention to associate the “-yl” suffix on the portion of the molecule or group that bears the valence from the missing hydrogen. Thus, heterocyclyl groups are defined as univalent groups formed by removing a hydrogen atom from any ring atom of a heterocyclic compound.
• piperidin-l-yl piperidin-2-yl the piperidin-l-yl group is also considered an organoheteryl group, whereas the piperidin-2-yl group is also considered a heterohydrocarbyl group.
• the valence of a “heterocyclyl” can occur on any appropriate cyclic atom, whereas the valence of a “organoheteryl” occurs on a heteroatom and the valence of a heterohydrocarbyl occurs on a carbon atom.
• Hydrocarbylene group and hydrocarbylidene group are also defined according to its ordinary and customary meaning, as set out in the IUPAC Compendium of Chemical Terminology , 2 nd Ed (1997), as a divalent group formed by removing two hydrogen atoms from a hydrocarbon, the free valencies of which are not engaged in a double bond.
• a hydrocarbylene group in which the free valencies are not engaged in a double bond is distinguished from a hydrocarbylidene group such as an alkylidene group.
• a “hydrocarbylidene” group is a divalent group formed from a hydrocarbon by removing two hydrogen atoms from the same carbon atom, the free valencies of which are part of a double bond.
• heterohydrocarbylene group and heterohydrocarbylidene group.
• heterohydrocarbylene by analogy to hydrocarbylene group, is used to refer to a divalent group formed by removing two hydrogen atoms from a parent heterohydrocarbon molecule, the free valencies of which are not engaged in a double bond.
• the hydrogen atoms can be removed from two carbon atoms, two heteroatoms, or one carbon and one heteroatom, such that the free valencies are not engaged in a double bond.
• heterohydrocarbylidene groups include but are not limited to -CH2OCH2-, -CH2NPI1CH2-, -SiMe2(l,2-C 6 H4)SiMe2-, -CMe 2 SiMe2-, -CH 2 NCMe3-, -CH 2 CH 2 PMe-, -CH2[l,2-C 6 H3(4-OMe)]CH2-, -and the like.
• a “heterohydrocarbylidene” group is a divalent group formed from a heterohydrocarbon by removing two hydrogen atoms from the same carbon atom, the free valencies of which are part of a double bond.
• Halide and halogen are used herein to refer to the ions or atoms of fluorine, chlorine, bromine, or iodine, individually or in any combination, as the context and chemistry allows or dictates. These terms may be used interchangeably regardless of charge or the bonding mode of these atoms.
• polymer is used herein generically to include olefin homopolymers, copolymers, terpolymers, and so forth.
• a copolymer is derived from an olefin monomer and one olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers.
• polymer encompasses copolymers, terpolymers, and the like, derived from any olefin monomer and comonomer(s) disclosed herein.
• an ethylene polymer would include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and so forth.
• an olefin copolymer such as an ethylene copolymer
• an olefin copolymer can be derived from ethylene and a comonomer, such as propylene, 1 -butene, 1 -hexene, or 1-octene. If the monomer and comonomer were ethylene and 1 -hexene, respectively, the resulting polymer would be categorized an as ethylene/1 -hexene copolymer.
• the term “polymerization” includes homopolymerization, copolymerization, terpolymerization, and so forth.
• a copolymerization process includes contacting one olefin monomer such as ethylene and one olefin comonomer such as 1 -hexene to produce a copolymer.
• one olefin monomer such as ethylene
• one olefin comonomer such as 1 -hexene
• polyolefin types such as “HDPE” for high density polyethylene, may be used herein.
• polymer is used herein to refer to inorganic compositions used in the preparation and formation of pillars in modified clays.
• pillars are known to be formed in smectite clays based on the use of a polymeric cationic hydroxy metal complexes of metals such as aluminum, zirconium, and/or titanium, such as aluminum chlorohydroxide complexes (also known as “chlorhydrate” or “chlorhydrol”).
• 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.
• the term polymer is not limited by molecular weight and therefore encompasses both lower molecular weight polymers, sometimes referred to as oligomers, as well as higher molecular weight polymers.
• Procatalyst 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 B runs ted acid, or when activated by a support-activator as disclosed herein.
• formulas for the polymetallates used as heterocoagulation agents disclosed herein are empirical formulas. Therefore, formulas such as (Al,Mg)2Si40io(OH)2(H20)8 are empirical polymetallate formulas which can be considered to encompass oligomeric or polymeric species, and formulas such as FeOx(OH) y (H20)z] n+ also can be considered to encompass oligomers or polymers in which the variable subscripts are not required to be integers.
• the Applicant when the Applicant discloses or claims a chemical moiety that has a certain number of carbon atoms, such as a Cl to C12 (or Ci to C12) alkyl group, or in alternative language having from 1 to 12 carbon atoms, the Applicant’s intent is to refer to a moiety that can be selected independently from an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, as well as any range between these two numbers (for example, a Cl to C6 alkyl group), and also including any combination of ranges between these two numbers (for example, a C2 to C4 and C6 to C8 alkyl group).
• a Cl to C12 or Ci to C12 alkyl group
• the Applicant’s intent is to refer to a moiety that can be selected independently from an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, as well as any range between these two numbers (for example, a Cl to C6 alkyl group
• any range of numbers recited in the specification or claims such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
• any number R falling within the range is specifically disclosed.
• the following numbers R within the range are specifically disclosed:
• R RL+k(RU-RL), wherein k is a variable ranging from 1% to 100% with a 1% increment, e.g., k is 1%, 2%, 3%, 4%, 5%. . . . 50%, 51%, 52%. . . . 95%, 96%, 97%, 98%, 99%, or 100%. Moreover, any numerical range represented by any two values of R, as calculated above is also specifically disclosed.
• any general or specific structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents, unless stated otherwise.
• the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan.
• values or ranges may be expressed in this disclosure using the term “about”, for example, “about” a stated value, greater than or less than “about” a stated value, or in a range of from “about” one value to “about” another value.
• other embodiments disclosed include the specific recited value, a range between specific recited values, and other values close to the specific recited value.
• 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.
• a support-activator an organoaluminum compound
• a metallocene compound is meant to encompass one, or mixtures or combinations of more than one, catalyst support-activator, organoaluminum compound, or metallocene compound, respectively.
• describing a compound or composition as “consisting essentially of’ should not be construed as “comprising,” as this phrase is intended to describe the recited component that includes materials which do not significantly alter composition or method to which the term is applied.
• a precursor or catalyst component can consist essentially of a material which can include impurities commonly present in a commercially produced sample of the material when prepared by a certain procedure.
• a claim includes different features and/or feature classes (for example, a method step, feedstock features, and/or product features, among other possibilities), the transitional terms comprising, consisting essentially of, and consisting of apply only to feature class to which is utilized and it is possible to have different transitional terms or phrases utilized with different features within a claim.
• a method can comprise several recited steps (and other non-recited steps) but utilize a catalyst system preparation consisting of specific or alternatively consisting essentially of specific steps but utilize a catalyst system comprising recited components and other non-recited components.
• compositions and processes are described in terms of “comprising” various components or steps, the compositions and processes can also “consist essentially of’ or “consist of’ the various components or process steps.
• the terms “substantial” and “substantially” as applied to any criteria such as a property, characteristic or variable means to meet the stated criteria in sufficient measure that one skilled in the art would understand that the benefit to be achieved, or the condition or property value desired is met.
• the term “substantially” may be used when describing a metallocene catalyst or catalyst system which is substantially free of or substantially absent an aluminoxane, a borate activator, a protic-acid-treated clay, or a pillared clay.
• substantially free can be used to describe a composition in which none of the recited component the composition is substantially free of was added to the composition, and only impurity amounts such as amounts derived from the purity limits of the other components or generated as a byproduct are present.
• the composition when a composition is said to be “substantially free” of a particular component, the composition may have less than 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.
• references to the Periodic Table or groups of elements within the Periodic Table refer to the Periodic Table of the Elements, published by the International Union of Pure and Applied Chemistry (IUPAC), published on-line at http://old.iupac.org/reports/periodic_table/; version dated 19 Feb. 2010. Reference to a “group” or “groups” of the Periodic Table as reflected in the Periodic Table of Elements using the IUPAC system for numbering groups of elements as Groups 1-18.
• IUPAC International Union of Pure and Applied Chemistry
• any Group is identified by a Roman numeral according, for example, to the Periodic Table of the Elements as published in “Hawley's Condensed Chemical Dictionary” (2001) (the “CAS” system) it will further identify one or more element of that Group so as to avoid confusion and provide a cross-reference to the numerical IUPAC identifier.
• references which may provide some background information related to this disclosure include, for example, U.S. Patent Nos. 3,962,135; 4,367,163; 5,202,295; 5,360,775; 5,753,577; 5,973,084; 6,107,230; 6,531,552; 6,559,090; 6,632,894; 6,943,224; 7,041,753; 7,220,695; 9,751,961; and U.S. Patent Application Publication Nos. 2018/0142047 and 2018/0142048; each of which is incorporated by reference herein in its entirety. Additional publications which may provide some background information related to this disclosure include:
• the support-activator of this disclosure can be formed by starting with a slurry of an expanding-type clay in a liquid carrier, such as smectite or dioctahedral smectite clay, and contacting the clay in the slurry with a heterocoagulation reagent, which comprises at least one cationic polymetallate made under the conditions specified herein.
• a heterocoagulated clay forms which can be isolated very conveniently by a filtration and subsequently dried and calcined, to provide a support-activator that is useful to support and activate metallocene catalyst toward olefin polymerization.
• the clay heteroadduct in good yield can be effected by controlling the ratio or amount of heterocoagulation reagent used relative to the clay, which is measured by a zeta potential measurement of the slurry in which the clay heteroadduct is formed.
• the clay heteroadduct comprises the contact product in a liquid carrier of [1] a smectite clay such as a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of the resulting clay heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• a smectite clay When a smectite clay is contacted with a heterocoagulation reagent in a liquid carrier using a greater number of moles of cationic polymetallate per gram of clay than specified immediately above, such that the resulting slurry has a zeta potential greater than about +25 mV, which with a cationic polymetallate such as aluminum chlorhydrate (ACH) and colloidal smectite clay can occur when using a recipe of greater than about 2.3 mmol Al/g clay, greater than about 2.5 mmol Al/g clay, greater than about 2.7 mmol Al/g clay, or greater than about 3.0 mmol Al/g clay (millimoles of A1 per gram of clay), large amounts of the corresponding pillared clay can form.
• a cationic polymetallate such as aluminum chlorhydrate (ACH) and colloidal smectite clay
• a slurry of the desired smectite heteroadduct can include some corresponding pillared clay as observed by powder X-ray diffraction (XRD), and formation of some pillared clay is secondary or incidental to the support-activator formation
• XRD powder X-ray diffraction
• a support- activator having too high a concentration of pillared clay as compared to the clay heteroadduct results in a loss of the ready filterability of the slurry, such that the ease of isolation of the support-activator is compromised.
• a smectite clay When a smectite clay is contacted with a heterocoagulation reagent in a liquid carrier using a smaller number of moles of cationic polymetallate per gram of clay, such that the resulting slurry has a zeta potential less than about -25 mV, which when using a cationic polymetallate aluminum chlorhydrate (ACH) and colloidal smectite clay can occur at less than about 0.5 mmol Al/g clay, less than about 0.6 mmol Al/g clay, or less than about 0.8 mmol Al/g clay, or in some cases, less than about 1.0 mmol Al/g clay (millimoles of A1 per gram of clay), a small amount of the clay heteroadduct is formed and a substantial amount of the colloidal smectite clay remains.
• ACH cationic polymetallate aluminum chlorhydrate
• the clay heteroadduct support-activator of this disclosure can be used with few or no subsequent washing steps following isolation by filtration. That is, the isolated heteroadduct support- activator can be used directly in catalyst formation with a metallocene, and co-catalysts such as aluminum alkyls if desired, without extensive or time-consuming purification, washing, or other such purification stages commonly used in other clay-based supports. This advantage can provide a substantial economic advantage and enhanced ease of use when preparing olefin polymerization catalysts.
• this disclosure provides a support-activator comprising an isolated smectite heteroadduct, the smectite heteroadduct comprising the contact product in a liquid carrier of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• This disclosure also provides, in another aspect, a method of making a support-activator comprising a smectite heteroadduct, the method comprising: a) providing a colloidal smectite clay; b) contacting in a liquid carrier the colloidal smectite clay with a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• This method can further comprise the step of c) isolating the smectite heteroadduct from the slurry.
• this disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one transition metal catalyst, such as a metallocene compound; b) optionally, at least one co-catalyst; and c) at least one support-activator comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• transition metal catalyst such as a metallocene compound
• co-catalyst such as a metallocene compound
• at least one support-activator comprising
• a method of making an olefin polymerization catalyst 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 smectite heteroadduct as described according to this disclosure.
• Still another aspect of this 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 smectite heteroadduct, as described herein.
• An expanding-type clay such as smectite or the 2:1 dioctahedral smectite clay, or a combination of expanding-type clays, can be used in the preparation of the support-activator described herein.
• These expanding-type clays may be described as phyllosilicates or phyllosilicate clays, because certain members of the clay minerals group of the phyllosilicates can be used.
• Suitable starting clays can include the layered, naturally occurring or synthetic smectites. Starting clays can also include the dioctahedral smectite clays.
• suitable starting clays may also include clays such as montmorillonites, sauconites, nontronites, hectorites, beidellites, saponites, bentonites, or any combination thereof.
• Smectites are 2:1 layered clay minerals that carry a lattice charge and can expand when solvated with water and alcohols. Therefore, suitable starting clays can include, for example, the monocation exchanged, dioctahedral smectites, such as the lithium-exchanged clays, sodium-exchanged clays, or potassium-exchanged clays, or a combination thereof.
• Water can also be coordinated to the layered clay structural units, either associated with the clay structure itself or coordinated to the cations as a hydration shell.
• the 2: 1 layered clays When dehydrated, have a repeat distance or dOOl basal spacing of from about 9 A (Angstrom) to about 12 A (Angstrom) in the powder X-Ray Diffraction (XRD); or alternatively, in a range of from about 10 A (Angstrom) to about 12 A (Angstrom) in the powder X-Ray Diffraction (XRD).
• the layered smectite clays are termed 2:1 clays, because their structures are “sandwich” structures which include two outer sheets of tetrahedral silicate and an inner sheet of octahedral alumina which is sandwiched between the silica sheets. Therefore, these structures are also referred to as “TOT” (tetrahedral-octahedral-tetrahedral) structures. These sandwich structures are stacked one upon the other to yield a clay particle.
• This arrangement can provide a repeated structure about every nine and one-half angstroms (A), as compared with the pillared or intercalated clays produced by the insertion of “pillars” of inorganic oxide material between these layers to provide a larger space between the natural clay layers.
• the clay used to prepare the support-activator can be a colloidal smectite clay.
• the smectite clay can have an average particle size of less than about 10 pm (microns), less than about 5 pm, less than about 3 pm, less than 2 pm, or less than 1 pm, wherein the average particle size is greater than about 15 nm, greater than about 25 nm, greater than about 50 nm, or greater than about 75 nm. That is, any ranges of clay particle sizes between these recited numbers are disclosed. While clays that are unable to give colloidal suspensions can be used, these are less preferred than the colloidal clays.
• the clay used to prepare the support-activator can be absent a bivalent or trivalent ion exchanged smectite, for example, Mg-exchanged or Al-ion exchanged montmorillonite which are described in U.S. Patent No. 6,531,552.
• the clay used to prepare the support-activator can be absent mica or synthetic hectorite, as described in U.S. Patent Nos. 6,531,552 and 5,973,084.
• the clay used to prepare the support-activator can be absent a trioctahedral smectite or can be absent vermiculite.
• the smectite clay can also comprise structural units characterized by the following formula:
• polymetallate and similar terms such as “polyoxometallate” refer to the polyatomic cations that include two or more metals (for example, aluminum, silicon, titanium, zirconium, or other metals) along with at least one bridging ligand between metals such as oxo, hydroxy and/or halide ligands.
• the polymetallates can be hydrous metal oxides, hydrous metal oxyhydroxides, and the like, and can include bridging ligands such as oxo ligands which bridge two or more metals can occur in these species, and can also include terminal oxo, hydroxyl, and/or halide ligands. While many polymetallate species are anionic, and the suffix “-ate” is often used to reflect an anionic species, the polymetallate (polyoxometallate) compounds used according to this disclosure are cationic.
• the heterocoagulation reagents of this disclosure can be positively-charged species that when combined in the appropriate ratio with a colloidal suspension of clay form a coagulate which is readily filtered and easily washed.
• the positively charged species include soluble polyoxometallate, polyhydroxylmetallate and polyoxohydroxymetallate cations, and related cations partially halide substituted, such as polyaluminum oxyhydroxychlorides or aluminum chlorhydrate or polyaluminum chloride species that are linear, cyclic or cluster compounds. These compounds are referred to collectively as polymetallates.
• the latter aluminum compounds can contain from about 2 to about 30 aluminum atoms.
• Useful heterocoagulation reagents also include any colloidal species that are characterized by a positive zeta potential when dispersed in an aqueous solvent or in a mixed aqueous and organic (for example, alcohol) solvent.
• useful dispersions of the heterocoagulation reagents can exhibit greater than (>) +20 mV (positive 20 mV) zeta potential, greater than +25 mV zeta potential, or greater than +30 mV zeta potential.
• the starting colloidal clay may include monovalent ions or species such as protons, lithium ions, sodium ions, or potassium ions, at least a portion, some, most, substantially all, or all of these ions are replaced by the heterocoagulation reagents during formation of the readily filterable clay heteroadduct.
• protons, lithium ions, sodium ions, or potassium ions and the like do not afford the filterability provided by the cationic polymetallates of this disclosure. This feature can be observed by the long filtration times that result when preparing and attempting to isolate the hydrochloric acid-treated support-activators, such as in Examples 40 and 41.
• the formation of the clay heteroadduct does not leach A1 ions from the clay.
• aluminum-containing heterocoagulation reagents such as ACH or PAC
• the aluminum content of the support-activator is actually increased over that of the starting clay, albeit in amounts far less than the aluminum content of the corresponding pillared clay.
• the heterocoagulation reagent can comprise a colloidal suspension of boehmite (an aluminum oxide hydroxide) or a metal oxide such as a fumed metal oxide which affords a positive zeta potential (for example, fumed alumina).
• the heterocoagulation reagent can comprise a chemically-modified or chemically-treated metal oxide, for example an aluminum chlorhydrate-treated fumed silica, such that when in suspension, the chemically-treated metal oxide affords a positive zeta potential, as described below.
• the heterocoagulation reagent may be generated by treating a metal oxide or metal oxide hydroxide and the like in a fluidized bed with reagents which will afford a positive zeta potential when the agent is dispersed in a suspension.
• the heterocoagulation agent can exhibit a positive value greater than +20 mV prior to combination with the phyllosilicate clay component.
• the cationic polymetallate can include a first metal oxide which is chemically-treated with a second metal oxide, a metal halide, a metal oxyhalide, or a combination thereof in an amount sufficient to provide a colloidal suspension of the chemically- treated first metal oxide having a positive zeta potential, for example, a zeta potential of greater than positive 20 mV (millivolts). That is, the chemically-treated first metal oxide is the contact product of the first metal oxide with [1] a second metal oxide, that is, another different metal oxide, [2] a metal halide, [3] a metal oxyhalide, or [4] a combination thereof.
• the first metal oxide which is chemically-treated can comprise fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, and the like, or any combination thereof.
• the second metal oxide, the metal halide, or the metal oxyhalide can be obtained from an aqueous solution or suspension of a metal oxide, hydroxide, oxyhalide, or halide, such as ZrOCh, ZnO, NbOCb, B(OH)3, AlCb, or a combination thereof.
• treatment may consist of dispersing the fumed oxide in a solution of aluminum chlorhydrate. In the case of fumed silica, which in suspension may exhibit a negative zeta potential, after treatment with aluminum chlorhydrate the suspension of the chemically-treated fumed silica exhibits a positive zeta potential of greater than about +20 mV.
• the cationic polymetallate composition can comprise or be selected from [1] fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, which is chemically- treated with [2] polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxy chloride, or any combination thereof.
• the cationic polymetallate composition can comprise or be selected from aluminum chlorhydrate-treated fumed silica, aluminum chlorhydrate-treated fumed alumina, aluminum chlorhydrate-treated fumed silica-alumina, or any combination thereof.
• the treated metal oxide may form a coreshell structure of a positively charged shell and negative core, or a continuous structure of intermixed negative and positive 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 before chemical treatment. Nevertheless, fumed metal oxides which possess no zeta potential, or a positive zeta potential less than about +20 mV, may also be chemically treated with species, such as aluminum chlorohydrate and the like, after which treatment, a colloidal suspension having a zeta potential greater than about +20 mV can be obtained.
• the heterocoagulation reagent can include a mixture of metal oxides formed in the fuming process, or subsequent to the fuming process, that because of their composition, exhibits a positive zeta potential.
• a mixture of metal oxides formed in the fuming process, or subsequent to the fuming process, that because of their composition, exhibits a positive zeta potential is fumed silica-alumina.
• the heterocoagulation reagent may include any colloidal inorganic oxide particles such as described by Lewis, et al. in U.S. Patent No. 4,637,992, which is incorporated herein by reference, such as colloidal ceria or colloidal zirconia or any positively charged colloidal metal oxide disclosed therein.
• the heterocoagulation reagent may comprise magnetite or ferrihydrite.
• the cationic polymetallate can comprise or be selected from boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.
• the heterocoagulation reagents can include a cationic oligomeric or polymeric aluminum species in solution, such as aluminum chlorohydrate, also known as aluminum chlorhydrate (ACH), polyaluminum chloride (PAC), aluminum sesquichlorohydrate, or any combination or mixture thereof.
• a cationic polymetallate heterocoagulation reagent can include or be selected from an aluminum species or any combinations of species having the empirical formula:
• the cationic polymetallate can comprises or can be selected from aluminum species having the formula [A104(Ali2(OH)24(H20)2o] 7+ , which is the so-called “Ali3-mer” polycation and which is thought to be the precursor to AI13 pillared clays.
• aluminum chlorhydrate When aluminum chlorhydrate is used as the heterocoagulation reagent or chemical treatment reagent for treating other metal oxides, aluminum chlorhydrate (ACH) solution or solid powder from commercial sources can be utilized.
• Aluminum chlorhydrate solutions may be referred to as polymeric cationic hydroxy aluminum complexes or aluminum chlorhydroxides, which refers to the polymers formed from a monomeric precursor having the general empirical formula 0.5[Al2(OH)5Cl(H2O)2].
• Preparation of aluminum chlorhydrate solution is described in U.S. Patent Nos. 2,196,016 and 4,176,090, which are incorporated herein by reference, and can involve treating aluminum metal with hydrochloric acid in amounts which produce a composition having the formula indicated above.
• the aluminum chlorhydrate solutions may be obtained using various sources of aluminum such as alumina (AI2O3), aluminum nitrate, aluminum chloride or other aluminum salts and treatment with acid or base.
• alumina AI2O3
• aluminum nitrate aluminum chloride or other aluminum salts and treatment with acid or base.
• the numerous species that can be present in such solutions, including the tridecameric [A104(Ali2(OH)24(H20)2o] 7+ (Ali3-mer) polycation, are described in Perry and Shafran, Journal of Inorganic Biochemistry , 2001, 87, 115-124, which is incorporated herein by reference.
• the species disclosed in this study, either individually or in combination, which are present in such solutions can be used as cationic polymetallates for heterocoagulation of the smectite clay.
• aqueous aluminum chlorhydrate solutions used according to this disclosure can have an aluminum content, calculated or expressed as the weight percent of AI2O3, in a range of from about 15 wt.% to about 55 wt.%, although more dilute concentrations can be used.
• Alternative aluminum concentrations in aqueous aluminum polymetallate solutions such as aqueous aluminum chlorhydrate solutions can include: from about 0.1 wt.% to about 55 wt.% AI2O3; from about 0.5 wt.% to about 50 wt.% AI2O3; from about 1 wt.% to about 45 wt.% AI2O3; from about 2 wt.% to about 40 wt.% AI2O3; from about 3 wt.% to about 37 wt.% AI2O3; from about 4 wt.% to about 35 wt.% AI2O3; from about 5 wt.% to about 30 wt.% AI2O3; or from about 8 wt.% to about 25 wt.% AI2O3; each range including every individual concentration expressed in tenths (0.1) of a weight percentage encompassed therein, and including any subranges therein.
• the recitation of from about 0.1 wt.% to about 30 wt.% AI2O3 includes the recitation of from 10.1 wt.% to about 26.5 wt.% AI2O3.
• solid polymetallate aush as solid aluminum chlorhydrate can be used and added to the slurry of the colloidal clay when preparing the heterocoagulate. Therefore, the concentrations disclosed above are not limiting but rather exemplary.
• the cationic polymetallate can comprise or can be selected from an oligomer prepared by copolymerizing (co-oligomerizing) soluble rare earth salts with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or a combination thereof, according to U.S. Patent No. 5,059,568, which is incorporated herein by reference, for example, where the at least one rare earth metal can be cerium, lanthanum, or a combination thereof.
• the heterocoagulation reagent can comprise an aqueous solution of lanthanides and AI13 Keggin ions, such as described by McCauley in U.S. Patent No. 5,059,568.
• the calcined clay-heteroadducts of the present disclosure prepared using the McCauley type polymetallates do not afford a uniform intercalated structure with basal spacings of greater than 13 A (Angstroms).
• 13 A Angstroms
• Ce-Al heterocoagulation reagent-to-colloidal clay ratio used according to this disclosure. This smaller amount arises by the conditions of contacting the smectite clay and the heterocoagulation reagent in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about +25 mV (millivolts) to about -25 mV.
• exemplary polymetallates of this disclosure can include: [1] the e- Keggin cations [s-PMoi2036(OH)4 ⁇ Ln(H20)4 ⁇ 4] 5+ , wherein Ln can be La, Ce, Nd, or Sm; and [2] the lanthanide-containing cationic heteropolyoxovanadium clusters having the general formula [Ln2Vi2032(H20)8 ⁇ Cl ⁇ ]Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho, or Er.
• the heterocoagulation agent may be a layered double hydroxide, such as a magnesium aluminum hydroxide nitrate as described by Abend el al ., Colloid Polym. Sci. 1998, 276, 730-731, or synthetic hematite, hydrotalcite, or other positively charged layered double hydroxides, including but not limited to those described in U.S. Patent No. 9,616,412, which are incorporated herein by reference.
• the cationic polymetallate used as a heterocoagulation reagent can be a layered double hydroxide or a mixed metal layered hydroxide.
• the mixed metal layered hydroxide can be selected from a Ni-Al, Mg- Al, or Zn-Cr-Al type having a positive layer charge.
• the layered double hydroxide or mixed metal layered hydroxide can comprise or can be selected from magnesium aluminum hydroxide nitrate, magnesium aluminum hydroxide sulfate, magnesium aluminum hydroxide chloride, Mg x (Mg,Fe)3(Si,Al)40io(OH)2(H20)4 (x is a number from 0 to 1, for example, about 0.33 for ferrosaponite), (Al,Mg)2Si40io(OH)2(H20)8, synthetic hematite, hydrozincite (basic zinc carbonate) Zn5(0H)r,(C03)2, hydrotalcite [Mg6Al2(0H)i6]C03 # 4H20, tacovite [Nir,Al2(0H)r,]C03*4H
• the heterocoagulation reagent can include aqueous solutions of Fe polycations, as described by Oades, Clay and Clay Minerals, 1984, 32(1), 49-57, or described by Cornell and Schwertmann in “The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses”, 2003, Second Edition, Wiley VCH.
• the cationic polymetallate can comprise or can be selected from an iron polycation having an empirical formula FeOx(OH) y (H20)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.
• Example 40 and Example 41 do not afford clay heteroadducts as provided by the cationic polymetallates of this disclosure, for example, these acid-treated clays generally are not readily filterable.
• monovalent ions such as protons from HC1 or H2SO4 in aqueous solutions, such as described by Nakano et al. in U.S. Patent No. 6,531,552 and references therein, which are incorporated herein by reference, cannot form stable, readily filterable heterocoagulated clay adducts whether using dilute or concentrated acid.
• Colloidal dispersions of smectite such as bentonites or montmorillonites, have a permanent negative charge, and thus exhibit a permanent negative zeta potential even at low pH.
• colloidal dispersions of smectites become less negative, and may even approach a zeta potential of about negative 30 mV (-30 mV).
• the monovalent cation-clay product is difficult to filter and may require isolation by centrifugation, or high dilution and settling tanks. Without washing and removal of monovalent ion salts, the flocculated clay does not lead to metallocene-support-activator catalysts with sufficient practical activity. Furthermore, to the extent that simple ion intercalation, such as in sodium-exchanged montmorillonite or aluminum- exchanged montmorillonite, may be evident in the powder XRD of the calcined clay heteroadduct, these materials are thought to be arise as undesirable byproducts or result from incomplete reaction of the colloidal clay with the polymetallate.
• the colloidal smectite clay can comprise or be selected from colloidal montmorillonite, such as Volclay® HPM-20 bentonite.
• the heterocoagulation reagent can comprise or be selected from aluminum chlorhydrate, polyaluminum chloride, or aluminum se squi chi orohy drate .
• the cationic polymetallate can comprises or be selected from a complex of Formula I or Formula II or any combination of complexes of Formula I or Formula II, according to the following formulas:
• M(II) is at least one divalent metal ion
• M(III) is at least one trivalent metal ion
• A is at least one inorganic anion
• L is an organic solvent or water
• n is the valence of the inorganic anion A or, in the case of a plurality of anions A, is their mean valence
• x is a number from 0.1 to 1
• m is a number from 0 to 10.
• M(II) can be, for example, zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium; independently, M(III) can be, for example, iron, chromium, manganese, bismuth, cerium, or aluminum; A can be, for example, hydrogencarbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide, or carbonate; n can be, for example, a number from 1 to 3; and L can be, for example, methanol, ethanol or isopropanol, or water. Further to this aspect, the cationic polymetallate can be selected from a complex of Formula I, wherein M(II) is magnesium, M(III) is aluminum, and A can be carbonate.
• the cationic polymetallate can comprises polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride, or a combination thereof.
• the cationic polymetallate can include linear, cyclic or cluster aluminum compounds containing, for example, from 2-30 aluminum atoms.
• the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clay in recipe for preparing the smectite heteroadduct can be in a range of, for example, from about 0.75 mmol Al/g clay to about 2.0 mmol Al/g clay, from about 0.8 mmol Al/g clay to about 1.9 mmol Al/g clay, from about 1.0 mmol Al/g clay to about 1.8 mmol Al/g clay, from about 1.1 mmol Al/g clay to about 1.8 mmol Al/g clay, or from about 1.1 mmol Al/g clay to about 1.7 mmol Al/g clay.
• the millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride per grams (g) of colloidal smectite clay in recipe for preparing the smectite heteroadduct can be, for example, about 0.75 mmol Al/g clay, about 0.8 mmol Al/g clay, about 0.9 mmol Al/g clay, about 1.0 mmol Al/g clay, about 1.1 mmol Al/g clay, about 1.2 mmol Al/g clay, about 1.3 mmol Al/g clay, about 1.4 mmol Al/g clay, about 1.5 mmol Al/g clay, about 1.6 mmol Al/g clay, about 1.7 mmol Al/g clay, about 1.8 mmol Al/g clay, about 1.9 mmol Al/g clay, or about 2.0 mmol Al/g clay, including any ranges between any of these ratios or
• the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal clay in the recipe to prepare the isolated or calcined smectite heteroadduct can be about 90% or less, about 80% or less, about 70% or less, about 60% or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less of a comparative ratio of millimoles of aluminum to grams of colloidal clay used for the preparation of a pillared clay using the same colloidal smectite clay and heterocoagulation reagent.
• the ratio of aluminum regent to clay in a pillaring recipe is expressed in mmol Al/g clay, indicating the number of millimoles of Al in the aluminum chlorhydrate reagent versus the grams of clay in the recipe. Specifically, this ratio reflects the ratio employed in the synthesis recipe, not the ratio in the final pillared clay product.
• the amount of Al used in the pillared clay preparation is far in excess of the amount of Al that eventually is intercalated between the layers in the final pillared clay solid.
• the heterocoagulated clay of this disclosure are amorphous solids. Therefore, the preparation of the heterocoagulated clay provides a three-dimensional structure, but one which is a non-pillared and non-crystalline and amorphous. While not intending to be bound by theory, it is believed that the regular crystalline structure of the starting smectite is not simply expanded upon contact with the cationic polymetallates as described, but rather disrupted upon preparation of the clay heteroadducts to provide a non-crystalline, non regular, non-layered amorphous material.
• Factors which can affect formation of an amorphous three-dimensional structure include reaction time, reaction temperature, purity of the starting clay and clay particle size, method of drying, and the like, which are readily determinable as described herein for each heterocoagulation reagent and clay system.
• the heterocoagulation agent may be added to a slurry of the colloidal clay, the colloidal clay may be added to a slurry or solution of the heterocoagulation agent, or the heterocoagulation agent and colloidal clay may be added to a liquid carrier at the same time or during an overlapping time period.
• the heterocoagulation agent and colloidal clay may be added simultaneously to a heel of heteroadduct product, such as adding the heterocoagulation agent and clay as either a solid or a suspension, to a vessel or reactor containing water or a water-containing heel.
• the liquid carrier in which the clay heteroadduct is prepared can be water or water-based, in which additional components can be added, such as an alcohol and/or at least one surfactant.
• Suitable surfactants can include anionic surfactants, cationic surfactants, or non-ionic surfactants. Specific examples of liquid carriers or “diluents” and specific examples of surfactants are provided in the Aspects of the Disclosure section.
• the ratio of heterocoagulation reagent to clay to be used in the recipe is defined as a ratio that affords a coagulated product mixture such as a slurry having a zeta potential in a range of from about positive (+)25 mV (millivolts) to about negative (-)25 mV. Therefore, the amount of heterocoagulation reagent added to a known sample of clay, that is, the ratio of cationic polymetallate (heterocoagulation reagent) to clay, is determined by titrating the clay with the heterocoagulation reagent.
• the ratio of heterocoagulation reagent to clay can be reported in millimoles (mmol) of aluminum (Al) in the cationic aluminum polymetallate to grams (g) of clay.
• the actual amount of cationic polymetallate used in the formation of the clay heteroadduct, that is, the ratio of heterocoagulation reagent to clay may depend upon factors such as the degree of positive charge of the cationic polymetallate, the zeta potential of the clay, and the like.
• the heterocoagulation reagent and the clay are combined in a ratio such that the resulting slurry (dispersion) of the heterocoagulated clay which forms exhibits a zeta potential in a range of from about +25 mV to about -25 mV.
• the heterocoagulation reagent and the clay are combined in a ratio such that the resulting dispersion of the heterocoagulated clay which forms exhibits a zeta potential in a range of from about +22 mV to about -22 mV, from about +20 mV to about -20 mV, from about +18 mV to about -18 mV, from about +15 mV to about -15 mV, from about +10 mV to about -10 mV, from about +5 mV to about -5 mV, or about 0 mV.
• a Colloidal Dynamic Zetaprobe AnalyzerTM was used for zeta potential measurements, including to dynamically track the evolving zeta potential during titrations of colloidal clay dispersions with cationic polymetallate titrants. Exemplary results from a zeta potential titration are illustrated in the Figures and described in the Examples, and data are presented for example in Table 4 through Table 6. For example, FIG.
• FIG. 3 plots the zeta potentials of a series of dispersions formed during the titration of Volclay® HPM-20 montmorillonite with aluminum chlorhydrate (ACH), plotting the cumulative titrant volume of the aqueous ACH solution added (x) versus zeta potential (mV, (>')) of the dispersion.
• FIG. 4 plots the cumulative mmol Al/g clay versus zeta potential (mV) of the dispersion for the same titration. Samples of some of the solid products formed during this zeta potential titration of HPM-20 clay with ACH were collected, and FIG.
• the aluminum weight percent can be derived from multiplying the aluminum oxide weight percent by the weight proportion of aluminum in the empirical formula. From this aluminum weight percent, the molar amount of aluminum heterocoagulation reagent can be determined, and the molar aluminum/clay mass ratio can be obtained.
• FIG. 4 illustrates that one ratio of aluminum chlorohydrate (ACH) to Volclay® HPM-20 expressed in mmol Al/g of clay that falls within the desired zeta potential range is 1.76 mmol Al/g clay.
• the actual ratio may vary slightly depending on the lot, method of preparation, contamination or age of the aluminum chlorhydrate, and or the particular batch of Volclay® HPM-20.
• FIG. 2 presents the zeta potential titration of Volclay® HPM-20 from American Colloid Company with 22 wt.% aluminum chlorhydrate from GEO Specialty Chemicals.
• the mmol Al/g clay can thus be determined as the point at which the zeta potential of colloidal species in the mixture falls below +25 mV and above -25mV, for example, between about +10mV and -10m V, providing a heterocoagulated solid that is readily isolated by conventional methods of filtration such as using filter paper, as described in detail hereinbelow.
• ready filtration of the resulting clay heteroadduct can be carried out with or without vacuum assistance, a belt filter, and the like.
• the colloidal smectite such as the dioctahedral smectites described herein
• This zero zeta potential point may be considered a nominal target ratio of cationic polymetallate to colloidal clay.
• Aspects of electrophoretic mobility are described in, for example, Gu, etal. , Clay and clay minerals, 1990, 38(5), 493-500.
• the experimentally derived ratio of heterocoagulation reagent (cationic polymetallate) to 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. A solution of the selected heterocoagulation agent is prepared and added to the dispersion in portions, with the zeta potential of the dispersion being measured after each addition.
• the ratio of cationic polymetallate to colloidal clay used to prepare the easily filterable clay heteroadduct is calculated by determining the ratio of heterocoagulation reagent needed to achieve zero or essentially zero zeta potential from the resultant zeta potential titration curve.
• extrapolation of the points closest to zero zeta potential may be used to estimate the crossover point at which the zeta potential curve crosses from a negative zeta potential to a positive zeta potential, thus describing the nominal target ratio.
• zeta potential titration curve when the zeta potential titration curve is discontinuous near zero, and remains discontinuous at or near the bounds of zeta potential (for example, ⁇ 20 mV or ⁇ 25 mV), linear extrapolation between the points on the titration curve directly before and after the discontinuity may be used to estimate the heterocoagulation reagent to clay ratio useful to achieve the desired zeta potential.
• zeta probe (zeta potential) titrations and determinations of the nominal target ratios of heterocoagulation reagent to clay are provide in the figures and Examples section of the disclosure. For example, see FIG. 2 through FIG. 8, Example 8 through Example 12, and Example 38.
• the ratio of mmol of aluminum (mmol Al) of aluminum chlorohydrate to grams of Volclay® HPM-20 colloidal montmorillonite used to prepare the clay heteroadducts can be significantly less, sometimes over an order of magnitude less, than the ratio of mmol Al/g clay used to prepare pillared HPM-20 clay with aluminum chlorohydrate. That is, using the same cationic polymetallate and colloidal clay, but using a mmol Al/g clay ratio which exceeds the range dictated by the zeta potential from about +25 mV to about -25 mV for the clay heteroadduct dispersion, pillared clays will form.
• the ratio of cationic polymetallate to colloidal clay to form the clay heteroadducts of the present disclosure differs from that used in, for example, U.S. Patent Appl. Publication No. 2018/0142047 and 2018/0142048 to W.R. Grace, which employ lanthanide containing-Al-pillared clays as support-activators.
• Products such as these may be referred to herein as a “heteroadduct” for convenience even though outside the zeta potential range for ready filterability.
• a “heteroadduct” for convenience even though outside the zeta potential range for ready filterability.
• Example 26 where using a recipe for 0.30 mmol Al/g clay using powdered ALOXICOLL® 5 IP aluminum chlorhydrate (Parchem Fine and Specialty Chemicals) provided a contact product heteroadduct which was difficult to process and isolate, and centrifugation was required to isolate product.
• the starting clay particles such as montmorillonite carry a permanent negative charge due to isomorphous substitution of ions into one of the “TOT” layers, for example, substitution of Mg 2+ for Al 3+ in the octahedral alumina layer which imparts a negative charge. Therefore, the starting clay forms a dispersion or suspension in water as the negatively-charged clay particles repel each other and are stabilized in the polar aqueous environment.
• the contact of cations such as the cationic polymetallates disclosed herein with the negatively-charged colloidal clays is thought to initially promote coagulation of the colloidal clay, through coulombic attraction of opposite charges and neutralization of the clay surfaces.
• This neutralization results in precipitation of the clay heteroadduct from the polar aqueous carrier as large agglomerated or coagulated particles which are readily filterable.
• additional cationic polymetallate is added in excess to the coagulate composition, such as when preparing ion- exchanged, protic acid treated or pillared clays, some or all of the agglomerated surface may be “re-charged” as positively-charged species, and thereby become re-suspended in a polar carrier such as water. This re-suspension provides a dispersion of highly-charged species which are difficult-to-impossible to filter off and which plug the filter media.
• the clay heteroadducts of this disclosure are formed below these high ratios and thereby thought to avoid the re-charging and re-suspension of the clay heteroadduct.
• the near zero zeta potential surface of the clay heteroadducts provides a readily filterable product and coincidentally substantially avoids pillaring of the clays, and further avoids the uniformly intercalated clay structures of the pillared clay and of the starting clay.
• these structures form thermally stabile, robust structures which can serve as very active support-activators for metallocenes.
• FIG. 1 provides a schematic summary of the practical and desirable aspects of preparing neutral or weakly charged dispersions with a low magnitude, near zero, or zero zeta potential. Filtration of clay heteroadducts with these properties proceeds rapidly, and typically few sequential filtrations are required in order to generate a support with desirable surface area, porosity, and polymerization activity. In contrast, highly charged dispersions, like the type obtained from the preparation of pillared clays, are not readily filterable and must be processed using relatively more expensive and cumbersome methods to obtain a useful support-activator.
• the clay heteroadduct of the present disclosure after filtration and calcination at 300°C or higher, can exhibit no, or substantially no dOOl peak of 2 theta (2Q) less than 10 degrees in the powder XRD scan. This feature is illustrated in the examples of FIG.
• Example 12 through Example 30 provide the preparative methods for the formation of ACH-clay heteroadducts from 0 mmol Al/g clay to 6.4 mmol Al/g clay examined in this figure, including some comparative Examples.
• XRD patterns below about 10 degrees 2Q shown in FIG. 2 illustrate, there are two main peak changes as the proportion of cationic polymetallate is increased in the preparative recipe. Firstly, an XRD peak at about 9 degrees 2 theta (2Q) corresponding to the starting clay disappears, and a peak from about 9 degrees (2Q) to about 10 degrees (2Q) gradually grows in as the proportion of cationic polymetallate is increased.
• the disappearance of the 9 degrees (2Q) peak appears to indicate the course of the reaction to form the heterocoagulated clay which is largely amorphous, and the subsequent 9-10 degrees (2Q) peak likely represents simple ion intercalation, such as Al 3+ ion intercalation, characterized by a smaller basal spacing than the initial ion exchanged clay.
• a peak grows in from about 4 degrees (2Q) to about 6 degrees (2Q), and tis peak represents the major product at 6.4 mmol Al/g clay.
• This 4-6 degrees (2Q) peak likely corresponds to the Keggin ion-intercalated pillared structure which forms as the concentration of added polymetallate increases.
• the 6.4 mmol Al/g clay product could not easily be isolated with simple filtration and instead had to be isolated and washed using multiple centrifugation and decanting steps.
• the starting clay colloidal clay as a comparative sample also could not be readily filtered.
• the zeta potential data and XRD data indicated that the range of zeta potential of ⁇ 25 mV corresponds to a range of approximately 1 mmol Al/g clay to 1.8 mmol Al/g clay. Similarly, the range of zeta potential of ⁇ 15 mV in which the clay heteroadduct is less charged corresponds to a range of approximately 1.3 mmol Al/g clay to 1.7 mmol Al/g clay.
• FIG. 2 demonstrates that, at 1.52 mmol Al/g clay, the powder XRD indicates little or virtually no pillaring (XRD pattern between 4.8 degrees (2Q) to 5.2 degrees (2Q)) and little or virtually no simple ion exchanged clay (XRD pattern between 9 degrees (2Q) and 10 degrees (2Q)) relative to the mineral impurities that exist in the starting colloidal clay in the range of 2 theta between 20-30 degrees 2Q.
• the near zero charge of the heteroadduct provided by the 1.5 mmol Al/g clay recipe corresponds to less than about half of the amount (ratio) of aluminum that may be actually incorporated into an Aln-pillared smectite, and a much smaller fraction of the aluminum that is used in pillaring recipes.
• ratio ratio of aluminum that may be actually incorporated into an Aln-pillared smectite
• the amount of heterocoagulation reagent that provides the zeta potential of 0 (zero) mV heteroadduct is an order of magnitude less than the amount used for optimized pillaring recipes of 15 mmol Al/g clay. It was surprisingly discovered that the clay heteroadduct of this disclosure is characterized by the absence or substantial absence of a regularly intercalated, pillared structure, and yet the clay heteroadduct provides comparable and often greater activity as a metallocene support-activator than the pillared clays.
• the clay heteroadduct of this disclosure is not the regularly intercalated, pillared structure such as described by Jensen et al. in U.S. Patent Appl. Publication Nos. 2018/0142047 and 2018/0142048.
• the clay heteroadducts of this disclosure are not or are substantially not regularly complex-ion intercalated (“not regularly intercalated”), microporous catalytic components comprising layered, colloidal clay having a multiplicity of pillars interposed between the expanded molecular layers of the clay.
• the clay heteroadducts of this disclosure are not regularly ordered, and there is no evidence of the consistent regularity imparted by consistent pillars and/or consistent intercalated layers of aluminum oxides or hydroxides, such as derived from an AI13 Keggin ion or a lanthanide-centered poly- Al 13 pillar as in U.S. Patent Appl. Publication Nos. 2018/0142047 and 2018/0142048.
• powder XRD peaks indicative of some pillaring can be detected.
• the XRD pattern of the 1.76 mmol Al/g clay sample corresponds approximately to a +23 mV zeta potential, but the intensity of the peak is substantially less than that of pillaring-type recipes, for example, using 6.4 mmol Al/g clay and greater.
• the calcined clay heteroadduct of this disclosure is absent the ordered domains as evidenced by the lack of XRD peaks between 0-12 degrees 2Q.
• the isolated clay heteroadducts are collected, for example by filtration, and they are not washed.
• the isolated clay heteroadducts are minimally washed, for example one time or two times with an appropriate washing liquid such as water, for example, just sufficient to provide some purification benefit.
• an appropriate washing liquid such as water, for example, just sufficient to provide some purification benefit.
• the difference in the preparation of the ACH-clay heteroadduct between Example 22 and Example 23 is whether the preparation of the product employed one filtration versus two filtrations, the later including a single wash between each filtration.
• the filtrate obtained from filtering the slurry was characterized by a conductivity of 1988 pS/cm
• the Example 23 preparation of a clay heteroadduct employing two filtrations with a wash between provided a filtrate which was characterized by a conductivity of 87 pS/cm, a difference of almost 23 -fold.
• the polymerization activities of catalysts prepared using these support-activators varied by only 10%, which the skilled person would recognize as within the range of variability bench-scale polymerization tests.
• Example 24 versus Example 25 support- activators further point to the economically-beneficial aspects of the support-activators, where a single filtration of the clay heteroadduct versus two filtrations again affords essentially the same polymerization activity.
• the catalyst formed from the single filtration support- activator exhibited an activity of 3581 g/g/h versus 3547 g/g/h observed for the catalyst formed from the double filtration support-activator.
• Example 29 single filtration heteroadduct slurry of Example 29 having a conductivity of 1750 pS/cm actually provided a higher activity than the Example 28 sample which was washed and filtered twice after the initial filtration and having a slurry conductivity of 169 pS/cm.
• Example 29 the single filtration heteroadduct slurry of Example 29 having a conductivity of 1750 pS/cm actually provided a higher activity than the Example 28 sample which was washed and filtered twice after the initial filtration and having a slurry conductivity of 169 pS/cm.
• the clay heteroadduct slurry of this disclosure can be immediately filtered and then dried or calcined, thus providing a far more efficient synthesis of the support-activator.
• Formation of the heterocoagulation agent has not been found to be very temperature sensitive, in that the clay forms a heteroadduct with the heterocoagulation agent over a wide range of temperatures.
• formation of the clay heteroadduct proceeds in a range of from about 20 °C to about 30°C, although temperatures ranging from almost 0°C to the boiling point of the slurry containing the clay heteroadduct can be used.
• the pH of the solution containing the heterocoagulation agent can be adjusted to provide for minimum zeta potential of the heterocoagulated product, which can be readily determined through experimentation as described by Goldberg, etal. , Clay and Clay Minerals, 1987, 35, 220-270.
• the resulting heteroadducts isolated by this method also can be used with metallocenes for olefin polymerization. Further, this method to adjust the zeta potential may be used in such cases where the ratio of heterocoagulation agent to clay does not itself afford a zeta potential between and including the ⁇ 25 mV (or alternatively, ⁇ 22 mV, ⁇ 20 mV, and the like) range disclosed herein.
• this pH adjustment method requires an additional step in the synthesis and isolation of the clay heteroadduct, and it has been observed that this method does not guarantee ready filterability or optimum final polymerization activity.
• pH adjustment in such cases can lead to protonated or hydroxylated clays, heterocoagulation reagents, and/or clay heteroadducts, which can affect the properties and ultimate catalytic activity of the clay heteroadduct.
• this disclosure provides for the removal of salts and minor amounts of non-coagulated, colloidal materials formed in the preparation of the heterocoagulated product.
• soluble by-products such as sodium chloride and the like
• this disclosure provides for the removal of salts and minor amounts of non-coagulated, colloidal materials formed in the preparation of the heterocoagulated product.
• soluble by-products such as sodium chloride and the like
• washing can be accomplished by re-suspension of the isolated heterocoagulated product into water, by mechanical stirring or shaking to form a slurry, which can then be re-filtered.
• This method contrasts the pillaring processes that generally requires multiple washing and isolations steps using high speed centrifugation, decantation, changing pH of the pillaring agent-clay solution, or large dilution and settling tanks for isolation of the pillared clay product.
• Such additional steps add time and cost to the separating and washing a pillared or chemically-treated clay mineral adduct from impurities such as its starting components, nano- or micro-sized quartz, and other inorganic metal oxides.
• filtration of the clay heteroadduct may be conducted batchwise through sintered glass frit, metal frit, common filter paper, felt or other filtration media, or continuously filtered using a moving belt filter.
• Filtration is practical because it is fast, for example, filtration can be completed in 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 conductance meter.
• concentration of the slurry when the concentration of the slurry is in a range of 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 in a range of from about 100 pS/cm (0.1 mS/cm) to about 50,000 pS/cm (50 mS/cm), from about 250 pS/cm to about 25,000 pS/cm, or from about 500 pS/cm to about 15,000 pS/cm, or alternatively from about 1,000 pS/cm (1 mS/cm) to about 10,000 pS/cm (10 mS/cm).
• the heterocoagulated solid may be dried via azeotropic methods if desired, as carried out in some of the Examples.
• Azeotropic drying is believed to preserve pore volume and surface area during drying as compared to simply heating the heterocoagulated solid.
• the filtered smectite heteroadduct may be re-suspended in a slurry with a solvent that will reduce the boiling point of water present in the heterocoagulated product.
• This water lost during drying may be characterized as free water or chemically-bound water. That is, water lost during drying can derive from free water which is located in the heteroadduct pores or on the external surface and chemically-bound water which is generated from dehydrating surface hydroxyls during the drying and calcining process.
• Various alcohols are useful as azeotroping agents including, but not limited to, 1 -butanol, 1-hexanol, isopentanol, ethanol and the like, including any combinations thereof.
• Freeze-drying, flash-drying, fluidized bed drying, or any combination thereof also can be used to remove water from the clay heteroadduct. These methods whether used alone or in combination during the removal of water may help to preserve pore volume and surface area during the drying process.
• spray drying of a suspension of the clay heteroadduct can be employed to control support-activator and supported catalyst particle morphology.
• suspensions of the clay heteroadduct in aqueous solvent or organic solvents or in combinations of aqueous and organic solvents can be spray dried. Dry or wet milling and sieving may be employed to refine the heterocoagulated clay morphology, size and size distribution.
• Spray drying and/or sieving of the clay heteroadduct can be used, as can other methods known to those in the art for removing fines or larger particles that can be problematic in conveying or using the heteroadduct as a support-activator.
• the heterocoagulated solid can be calcined or heated in a fluidized bed, for example, temperatures in a range of from about 100°C to about 900°C.
• the heterocoagulated smectite clay can be calcined or heated in a fluidized bed at temperatures ranging from about 100 °C to about 900 °C, from about 200 °C to about 800°C, from about 250°C to about 600°C, or from about 300°C to about 500 °C.
• Calcining can be conducted in the ambient atmosphere (air), for example, calcining can be carried out in dry air at temperature in a range of at least 110°C, for example, the temperature can be in a range of from about 200°C to about 800°C, and for a time in the range of about 1 minute to about 100 hours.
• air ambient atmosphere
• calcining can be carried out in dry air at temperature in a range of at least 110°C, for example, the temperature can be in a range of from about 200°C to about 800°C, and for a time in the range of about 1 minute to about 100 hours.
• the smectite heteroadduct can be calcined using any one of the following conditions: a) a temperature ranging from about 110°C to about 600°C and for a time period ranging from about 1 hour to about 10 hours; b) a temperature ranging from about 150°C to about 500°C and for a time period ranging from about 1.5 hours to about 8 hours; or c) a temperature ranging from about 200°C to about 450°C and for a time period ranging from about 2 hours to about 7 hours.
• the clay heteroadduct may also be calcined at temperatures from about 225°C to about 700°C for a period of time in a range of about 1 hour to about 10 hours, most preferably, temperatures from about 250°C to about 500°C and a time in a range of about 1 hour to about 10 hours.
• calcining in air can be carried out at temperatures in a range of from 200°C to 750°C, from 225°C to 700°C, from 250°C to 650°C, from 225°C to 600°C, from 250°C to 500°C, from 225°C to 450°C, or from 200°C to 400°C.
• a calcining temperature selected from any single temperature or range of two temperatures, for example, temperatures separated by at least 10°C (that is 10 Centigrade degrees) in the range of 110°C to 800°C can be used for developing final catalytic activity.
• Thermal treatment such as calcining can be conducted in ambient atmosphere or under other such conditions which facilitate the removal of water, for example, calcining may be carried out in a carbon monoxide atmosphere. Use of such atmospheres may remove surface hydroxyls more efficiently at lower temperatures as compared to the temperatures used in an ambient air calcining process, thus preserving greater pore volume and surface area during dehydration of the surface.
• the heterocoagulated product may be described as a continuous, non-crystalline combination of clay and inorganic oxide particles, which we refer to herein as an activator-support or support-activator.
• the determination of the total porosities, pore volume distributions, and surface areas of the activator supports of this disclosure can be achieved through any method known in the art, for example, an analysis using nitrogen gas adsorption-desorption measurements.
• the adsorption isotherm or desorption isotherm plots the volume of gas (in this case, nitrogen) that either adsorbs onto, or desorbs from, the surface of an analyte (clay heteroadduct) as pressure is either increased or decreased, respectively, at a constant temperature.
• Isotherm data can be analyzed using the BJH method to determine total pore volume and generate a pore size distribution as described below, and isotherm data can be analyzed using the BET method to determine surface area.
• Heterocoagulation of the smectite clay can provide activator supports that have substantial porosity and exhibit catalyst activation properties when combined with metallocenes or other organotransition metal compounds capable of polymerizing olefins.
• the calcined clay heteroadduct can exhibit a BJH porosity in a range of from about 0.2 cc/g to about 3.0 cc/g, from about 0.3 cc/g to about 2.5 cc/g, or from about 0.5 cc/g to about 1.8 cc/g.
• the calcined clay heteroadduct can also exhibit a BJH porosity of greater than or equal to 0.5 cc/g.
• Calcined clay heteroadducts having a porosity as low as about 0.2 cc/g can be used, for example, heteroadducts exhibiting a BJH porosity in a range of from about 0.2 cc/g to about 0.5 cc/g, but clay heteroadducts having a porosity of less than about 0.2 cc/g can exhibit lower polymerization activity, for example, ⁇ 200 g PE/g support-activator/hr, when combined with metallocenes such as bis(l-butyl-3-methylcyclopentadienyl)zirconium dichloride) to make the catalyst system.
• the term “g support-activator” refers to the grams of the calcined clay heteroadduct used to make the catalyst. A comparison of the BJH porosities of clays and clay heteroadduct is presented in FIG.
• FIG. 11 The BJH pore volume analysis of the starting montmorillonite which was calcined but otherwise non-azeotroped and untreated with a heterocoagulation agent is presented in FIG. 11 (Example 1).
• the pore volume analysis of the starting montmorillonite which was sheared, then azeotroped and calcined, but otherwise untreated with a heterocoagulation agent is presented in FIG. 12 (Example 3).
• the pore volume analysis of the aluminum chlorhydrate (ACH) heterocoagulated clay of Example 18 (1.76 mmol Al/g clay) is presented in FIG. 10.
• ACH aluminum chlorhydrate
• Cumulative pore volume between specific pore diameter bounds can be determined using the BJH method derived pore volume distribution.
• the cumulative pore volume between pore diameters of X nm (nanometers) and Y nm (Vx-Ymn), in which X nm is the lower bound of pore diameter, and Y is the upper bound of the pore diameter, is determined by subtracting from the total cumulative pore volume from pore diameters 0 nm to Y nm by the total cumulative pore volume from pore diameters 0 nm to X nm. In situations where the total cumulative pore volume for either the upper bound or lower bound of pore diameter is not available, this pore volume is estimated by linear interpolation between the two closest pore diameter points for which cumulative pore volume data is available.
• the combined or cumulative pore volume of pores between 3-10 nm diameter can comprise less than 55% of the cumulative pore volume of pores between 3-30 nm (V3-30nm).
• V3-ionm can comprise less than 50% of the cumulative pore volume V3-30nm, or alternatively, V3-ionm can comprise less than 40% of the cumulative pore volume V3-30nm. This feature is illustrated by the data of FIG. 10, which sets out the BJH pore volume analysis of Example 18 smectite heteroadduct, in which the value of V3-ionm is about 0.33 (V3-30nm).
• the smaller mesopores from 2 nm to 10 nm make up the majority of the total mesopore volume (2 nm to 50 nm), where the total mesopore volume can be calculated, for example, by V2-ionm+Vio-30nm+V3o-50nm.
• the clay heteroadducts of this disclosure are characterized by the volume of the smaller mesopores V3-ionm that is exceeded by Vio-30nm alone. While not wishing to be bound by theory, it is thought that the increased proportion of larger mesopores as a share of the total porosity in this disclosure facilitates diffusion and accessibility of the metallocene compound to the ionizing site on clay heteroadduct surface.
• pore size distributions determined by the BJH method may be depicted by plotting dV(log D) vs. pore diameter.
• the diameter showing the highest value of this function can be represented by the term DM and is considered the most frequently appearing pore diameter. That is, DM is the diameter corresponding to the point with the highest value of DV(log D) in the region between 30 A and 500 A pore diameter.
• the ordinate value of DM, which is the maximum value, is represented by the term DVM.
• this logarithmic differential pore volume distribution typically possesses a local maximum between about 30 A and about 40 A (Angstroms).
• This local maximum intensity also may be the global maximum DVM.
• the intensity at DVM can be at most about 200% of the intensity of the maximum value of dV(log D) between 200 A and 500 A.
• the intensity at DVM can be at most about 120% of the intensity of the maximum value of dV(log D) between 200 A and 500 A.
• the intensity at DVM can be at most about 100% of the intensity of the maximum value of dV(log D) between 200 A and 500 A.
• the maximum value of dV(log D) between 200 A and 500 A exceeds all values of dV(log D) between 30 A and 200 A. This contrasts to, for example, the acid treated clays of Uchino et al. in U.S. Patent No. 6,677,411, which is incorporated by reference herein, in which the maximum DVM values observed in the logarithmic differential pore size distributions of the desirable embodiments possess associated diameters DM between 60 A and 200 A.
• 7,220,695 define a preferred embodiment in which the diameter DM showing maximum D VM value resides between 60 A and 200 A (Angstroms).
• the most frequently appearing pore diameter DM of the clay heteroadducts of this disclosure resides either in the range of from 30 A to 40 A or in the range from 200 A to 500 A.
• 6,677,411 demonstrate substantially lower intensities in the 200 A and 500 A range compared to the 60 A to 200 A range.
• the maximum value of dV(log D) in the 200 A and 500 A range is typically less than 10% that of the maximum value of dV(log D) in the 60 A and 200 A range.
• the clay heteroadducts of this disclosure can provide a maximum value of dV(log D) in the 200 A and 500 A range, which is typically greater than 100% that of the maximum value of dV(log D) in the 60 A and 200 A range.
• the presence of a larger share of the bigger mesopores in the clay heteroadducts of this disclosure is thought to be desirable due to greater ease of metallocene diffusion to ionizing sites of the support-activator.
• the clay heteroadducts prepared in slurry form within the zeta potential range according to this disclosure unexpectedly exhibited an improved ease of isolation as compared to the analogous pillared clays prepared using the same smectite clay and heterocoagulation reagent.
• the clay heteroadducts could be readily isolated by filtration, unlike the pillared clays. This enhanced filterability was observed and quantified by, for example, comparing the settling rate of slurries of a clay heteroadduct versus the settling rate of an analogous pillared clay prepared using the same clay and a slurry containing identical amounts of the clay.
• a slurry settling rate comparison between a pillared clay and a heterocoagulated clay, each prepared with a 5 wt.% aqueous dispersion of HPM-20 clay, is set out in Table 1.
• Each slurry was prepared as described in the referenced Examples and added to a graduated cylinder, and the settling rate was measured over time by the observed volume of the substantially clear layer which is absent the cloudiness of visible colloidal particles at the top of the slurry.
• the settling rate of the heterocoagulated clay was significantly faster, for example, 5-fold faster on a volume basis.
• one method by which the filterability of the heterocoagulated clay slurries may be assessed as being “readily filterable” is by examining the settling rate of the slurry as compared with the settling rate of pillared clay slurries.
• a composition such as the clay heteroadduct is readily or easily filterable if the settling rate (as explained herein) of a 2.5 wt.% of the aqueous heteroadduct slurry 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 or more, than the settling rate of a 2.5 wt.% of the aqueous pillared clay slurry prepared using the same colloidal smectite clay, the same heterocoagulation reagent, and the same liquid carrier, wherein the settling rates are compared at about 12 hours, about 18 hours, about 24 hours, about 30 hours, about 36 hours, about 48 hours, about 72 hours, about 95 hours, about 96 hours, or about 100 hours, or more from the start of the settling test.
• this disclosure provides other methods of quantifying filterability of the heteroadduct slurry demonstrates that the slurry can be considered readily filterable and readily filtered.
• a composition such as the clay heteroadduct is readily or easily filterable if the slurry is characterized by the following filtration behavior:
• the proportion of a filtrate obtained at a filtration time of 10 minutes using either vacuum filtration or gravity filtration, based upon the weight of the liquid carrier in the slurry of the smectite heteroadduct is in a range of (1) from about 50% to about 100% by weight of the liquid carrier in the slurry before filtration, that is, of the initial slurry water weight (2) from about 60% to about 100% by weight of the liquid carrier in the slurry, (3) from about 70% to about 100% by weight of the liquid carrier in the slurry, or (4) from about 80% to about 100% by weight of the liquid carrier in the slurry before filtration; and
• the feature of performing the filtration with 0 to 2 hours after the initial formation is specified because some non-heteroadduct slurries including some pillared clay slurry compositions can be filtered more easily after the slurry is allowed an initial settling period of several days.
• the heteroadduct slurry and the pillared clay slurry were filtered using a 20 micron filter within several minutes after the contacting step between the colloidal clay and the polymetallate. Essentially all of the water from the heteroadduct slurry had been filtered off at the 10 minute mark after initiating the vacuum filtration, while essentially none of the water from the pillared clay slurry had been filtered off at 10 minutes after initiating vacuum filtration.
• a filter having a specified opening size can be easily identified by the person of ordinary skill, for example the 20 pm filter used in the examples, which allows the clay heteroadduct to meet both of these criteria, but no filter size will allow the pillared clay to meet both of these criteria.
• either gravity or vacuum filtration can be used in the “readily filterable” test because at the point in time at which the measurements of the filtrates is specified (10 minutes after initiating the filtration), a proper filter size can be easily identified by the person of ordinary skill which will allow the clay heteroadduct to meet both criteria [a] and [b], whereas the pillared clay will fail at least one of criteria [a] and [b].
• a composition such as the clay heteroadduct can be considered readily filterable or readily filtered if the slurry is characterized by the following filtration behavior:
• 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 obtained from filtration of a 2.0 wt.% slurry of a pillared clay prepared using the colloidal smectite clay, the heterocoagulation reagent, and the liquid carrier, and wherein the weight of the first filtrate and the weight of the second filtrate are measured after identical filtration times of 5 minutes, 10 minutes or 15 minutes; and
• this test compares the filtrates collected from slurries of the heteroadduct versus the pillared clay, whereas the prior test compares the filtrate collected from a slurry of the heteroadduct versus the aqueous carrier in the initial slurry.
• the calcined clay heteroadduct can be used as a substrate or catalyst support-activator for one or more suitable polymerization catalyst precursors such as metallocenes, other organometallic compounds, and/or organoaluminum compounds and the like, or other catalyst components in order to prepare an olefin polymerization catalyst composition. Therefore, in one aspect, when a clay heteroadduct is prepared as disclosed herein and combined with an organo- main group metal, such as alkylaluminum compounds and group 4 organotransition metal compound such as a metallocene, an active olefin polymerization catalyst or catalyst system is provided.
• organo- main group metal such as alkylaluminum compounds and group 4 organotransition metal compound such as a metallocene
• the support-activator of this disclosure can be used with metallocene compounds (also referred to herein as metallocene catalysts) and co-catalysts such as organoaluminum compounds, the resulting composition exhibits catalytic polymerization activity in the absence or substantial absence of an ion-exchanged, protic-acid-treated, or pillared clay, or aluminoxane or borate activators.
• metallocene compounds also referred to herein as metallocene catalysts
• co-catalysts such as organoaluminum compounds
• heteroadduct support- activator metallocene, and co-catalyst such as aluminum alkyl compound if desired to impart an activatable alkyl ligand to the metallocene provides an active catalyst with the need for other activators such as aluminoxane or borate activators.
• Metallocene compounds are well-understood in the art, and the skilled person will recognize that any metallocene can be used with the support-activator described in this disclosure, including for example, both non-bridged (non-ansa) metallocene compounds or bridged (ansa) metallocene compounds, or combinations thereof. Therefore, one, two, or more metallocene compounds can be used with the clay heteroadduct support-activators of this disclosure.
• the metallocene can be a metallocene comprising a group 3 to group 6 transition metal or a metallocene comprising a lanthanide metal or a combination of more than one metallocene.
• the metallocene can comprise a group 4 transition metal (titanium, zirconium, or hafnium).
• the metallocene compound can comprises, consists of, consists essentially of, or is selected from a compound or a combination of compounds, each independently having the formula:
• X 1 is selected from titanium, zirconium, or hafnium
• a linker substituent selected from: a) >EX 5 2, -EX 5 2 EX 5 2-, -EX
• linker substituents which can bridge X 1 and X 2 include C1-C2 0 hydrocarbylene group, a C1-C2 0 hydrocarbylidene group, a C1-C2 0 heterohydrocarbyl group, a C1-C2 0 heterohydrocarbylidene group, a C1-C2 0 heterohydrocarbylene group, or a C1-C2 0 heterohydrocarbylidene group.
• X 1 and X 2 can be bridged by at least one substituent having the formula >EX 5 2, -EX 5 2EX 5 2-, or -BX 5 -, wherein E is independently C or Si, X 5 in each occurrence is selected independently from a halide, a C1-C2 0 aliphatic group, a C 6 -C2 0 aromatic group, a C1-C2 0 heteroaliphatic group, a C4-C2 0 heteroaromatic group, or a C1-C2 0 organoheteryl group.
• Metallocene compounds are understood by the person skilled in the art, who will recognize and appreciate the methods of making and using the metallocene in olefin polymerization catalyst systems. Many metallocenes and processes to make metallocenes and organotransition metal compounds are known in the art, such as disclosed in U.S. Patent Nos.
• this disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound; b) optionally, at least one co-catalyst; and c) at least one support-activator as described herein.
• the co-catalyst includes compounds such as a trialkyl aluminum which are thought to impart a ligand to the metallocene which can initiate polymerization when the metallocene is otherwise activated with the support-activator.
• the co-catalyst may be considered optional, for example, in scenarios in which the metallocene may already include a polymerization-activatable/initiating ligand such as methyl or hydride.
• a co-catalyst can be used for other purposes, such as to scavenge moisture from the polymerization reactor or process.
• the co-catalyst can comprise or be selected from, for example, an alkylating agent, a hydriding agent, or a silylating agent.
• the metallocene compound, the support-activator, and the co-catalyst can be contacted in any order.
• the co-catalyst can comprises or can be selected from an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organoaluminum compound which can independently have the formula Al(X A ) n (X B )m, M X [A1X A 4], Al(X c ) n (X D )3-n, M X [A1X C 4], that is, can be neutral molecular compounds or ionic compounds/salts of aluminum, wherein each of the variables of these formulas is defined in the Aspects section of this disclosure.
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexyl aluminum, trioctylaluminum, ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl-(3- alkylcyclopentadiyl)aluminum, and the like, including any combination thereof.
• TAA triethylaluminum
• TSA triethylaluminum
• tributylaluminum trihexyl aluminum
• trioctylaluminum ethyl-(3-alkylcyclopentad
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organoboron compound which can independently have the formula B(X E ) q (X F )3-q or M- V [BX E 4], that is, can be neutral molecular compounds or ionic compounds/salts of boron, wherein each of the variables of these formulas is defined in the Aspects section of this disclosure.
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylboron ethoxide, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinanylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, and the like, including a Lewis base adduct thereof, or any combination or mixture thereof.
• the co-catalyst can comprise or can be a halogenated organoboron compound, for example a fluorinated organoboron compound, examples of which include tris(pentafluorophenyl)boron, tris[3,5- bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis- (pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis [3,5-bis(trifluoro- methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and any combination or mixture thereof.
• a fluorinated organoboron compound examples of which include tri
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organozinc or organomagnesium compound which can independently have the formula M c (X G ) r (X H )2-r, wherein each of the variables of this formula is defined in the Aspects section of this disclosure.
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, butylethylmagnesium, dibutylmagnesium, n- butyl-sec-butylmagnesium, dicyclopentadienylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like, including any combination thereof.
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organolithium compound which can independently have the formula Li(X J ), wherein each of the variables of the formula(s) are defined in the Aspects section of this disclosure.
• the co-catalyst can comprise, consists of, consist essentially of, or be selected from methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and t-butyllithium), hexyllithium, iso-butyllithium, and the like, or any combination thereof.
• co-activators in addition to the calcined smectite heteroadduct activator support can be used in the catalyst compositions of this disclosure if desired.
• co-activators include but are not limited to an ion- exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate activator, an aluminate activator, an ionizing ionic compound, a solid oxide treated with an electron withdrawing anion, or any combination thereof.
• Aluminoxanes also referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes
• Aluminoxanes can be used to contact the other catalyst components, for example, in any solvent which is substantially inert to the reactants, intermediates, and products of the activation step such as a saturated hydrocarbon solvent or a solvent such as toluene.
• the catalyst composition formed in this manner may be isolated if desired or the catalyst composition may be introduced into the polymerization reactor without being isolated.
• aluminoxanes are oligomeric, wherein the aluminoxane compound can comprise linear structures, cyclic, or cage structures, or mixtures thereof.
• cyclic aluminoxane compounds having the formula (R-Al-O)n, wherein R can be a linear or branched alkyl having from 1 to about 12 carbon atoms, and n can be an integer from 3 to about 12.
• the (AlRO)n moiety also constitutes the repeating unit in a linear aluminoxane, for example, having the formula: R(R-Al-0)nAlR2, wherein R can be a linear or branched alkyl having from 1 to about 12 carbon atoms, and n can be an integer from 1 to about 75.
• R group can be a linear or branched Ci-Cs alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, and wherein n can represent an integer from 1 to about 50.
• n may be variable within a single sample of aluminoxane, and such a combination or population of organoaluminoxane species is usually present in any sample.
• Organoaluminoxanes can be prepared by various procedures known in the art, for example, organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, each of which is incorporated by reference herein, in its entirety.
• an aluminoxane may be prepared by reacting water which is present in an inert organic solvent with an aluminum alkyl compound such as AIR3 to form the desired organoaluminoxane compound.
• organoaluminoxanes may be prepared by reacting an aluminum alkyl compound such as AIR3 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
• the aluminoxane compound can be methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propyl-aluminoxane, n-butyl aluminoxane, t- butyl aluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2- pentylaluminoxane, 3-pentyl-aluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.
• methyl aluminoxane (MAO), ethyl aluminoxane (EAO), or isobutyl aluminoxane (IBAO) can be used as optional co-catalysts, and these aluminoxanes can be prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively.
• These compounds can be complex compositions, and are sometimes referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively.
• aluminoxanes can be used in combination with a trialkylaluminium, such as disclosed in U.S. Patent No. 4,794,096, which is herein incorporated by reference in its entirety.
• the molar ratio of the aluminum present in the aluminoxane to the metallocene compound(s) in the composition can be lower than the typical molar ratio that would be used in the absence of the support- activator of the present disclosure.
• aluminoxane amounts can be, for example, from about 1:10 moles Al/moles metallocene (mol Al/mol metallocene) to about 100,000:1 mol Al/mol metallocene or from about 5:1 mol Al/mol metallocene to about 15,000:1 mol Al/mol metallocene.
• the relative amounts of aluminoxane can be reduced.
• the amount of optional aluminoxane added to a polymerization zone can be less than the previous typical amount within a range of about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.
• aluminoxane can be used in an amount typically used in the prior art, but with the additional use of a support- activator of the present disclosure in order to obtain further advantages for such a combination.
• Organoboron compounds can also comprise an optional organoboron co-activator if desired, in addition to the recited components (support-activator, metallocene, and optional co-catalyst).
• the organoboron compound can comprise or be selected form neutral boron compounds, borate salts, or combinations thereof.
• the organoboron compounds can comprise or be selected from a fluoroorgano boron compound, a fluoroorgano borate compound, or a combination thereof, and any such fluorinated compounds known in the art can be utilized.
• fluoroorgano boron compound is used herein to refer to the neutral compounds of the form BY3
• fluoroorgano borate compound is used herein to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation] + [BY4] , where Y represents a fluorinated organic group.
• fluoroorgano boron and fluoroorgano borate compounds are typically referred to collectively by organoboron compounds, or by either name as the context requires.
• fluoroorgano boron compounds that can be used as co activators include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5- bis(trifluoromethyl)phenyl]boron, and the like, including mixtures thereof.
• fluorinated aryl borates such as, N,N-dimethylanilinium tetrakis- (pentafluorophenyl)borate, triphenylcarbenium t
• fluoroorgano borate and fluoroorgano boron compounds are thought to form weakly-coordinating anions when combined with metallocene compounds, as disclosed in U.S. Patent No. 5,919,983, which is incorporated herein by reference in its entirety.
• any amount of organoboron compound can be utilized as an optional co activator.
• the molar ratio of the organoboron compound to the metallocene compound in the composition can be from about 0.1:1 mole of organoboron or organoborate compound per mole of metallocene (mol/mol) to about 10:1 mol/mol, or from about 0.5 mol/mol to about 10 mol/mol (mole of organoboron or organoborate compound per mole of metallocene), or alternatively in a range of from about 0.8 mol/mol to about 5 mol/mol (mole of organoboron or organoborate compound per mole of metallocene).
• the amount can be reduced or adjusted downward in the presence of a clay- heteroadduct support-activator.
• the optional co-activators which can be used in addition to the recited components of the catalyst compositions of this disclosure can comprise or can be selected from ionizing compounds.
• ionizing compound examples are disclosed in U.S. Patent Nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference, in its entirety.
• ionizing compound is term of art and refers to a compound, particularly an ionic compound, which can function to enhance activity of the catalyst composition.
• the fluoroorgano borate compounds described herein as optional organoboron co-activators can also be considered and function as ionizing compound co-activators.
• the scope of the ionizing compounds is broader than the fluoroorgano borate compounds, as compounds such as fluoroorgano aluminate are encompassed by ionizing compounds.
• the ionizing compounds may be capable of interacting or reacting with the metallocene compound and converting the metallocene into a cationic or an incipient cationic metallocene compound, which activates the metallocene to polymerization activity.
• the ionizing compound may function by completely or partially extracting an anionic ligand from the metallocene, particularly a non-cycloalkadienyl ligand or non-alkadienyl ligand such as (X 3 ) or (X 4 ) of the metallocene formula (X 1 )(X 2 )(X 3 )(X 4 )M disclosed herein, to form a cationic or incipient cationic metallocene.
• the ionizing compound can function as an activator (co-activator) regardless of any mechanism by which it functions.
• the ionizing compound may ionize the metallocene, abstract an X 3 or X 4 ligand in a fashion as to form an ion pair, weakens the metal-X 3 or metal-X 4 bond, or simply coordinate to an X 3 or X 4 ligand, or any other mechanisms by which activation may occur. Further, it is not necessary that the ionizing compound activate (co-activate) the metallocene only, as the activation function of the ionizing compound is evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition containing catalyst composition that does not comprise any ionizing compound.
• ionizing compounds include, but are not limited to, the list of compounds presented in the Aspects section of this disclosure.
• the optional co-activators which can be used in addition to the recited components of the catalyst compositions of this disclosure can comprise or can be selected from other support-activators, sometimes termed activator-supports, which when used in the catalyst compositions described herein are termed co-activator-supports.
• activator-supports which when used in the catalyst compositions described herein are termed co-activator-supports.
• Examples of optional co-activator-supports are disclosed in U.S. Patent Nos. 6,107,230; 6,653,416; 6,992,032; 6,984,603; 6,833,338; and 9,670,296 each of which is incorporated herein by reference, in its entirety.
• the optional co-activator-support may comprise or be selected from silica, alumina, silica-alumina, or silica-coated alumina which is treated with at least one electron- withdrawing anion.
• the silica-coated alumina can have a weight ratio of alumina- to-silica in a range of from about 1 : 1 to about 100: 1, or from about 2: 1 to about 20: 1, in this aspect.
• the at least one electron-withdrawing anion can comprise or be selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like, or combinations thereof.
• the optional co-activator-supports can be selected from, for example, fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica- alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, and the like, any of which or any combinations of which can be employed in catalyst compositions disclosed herein.
• the co-activator-support can comprise or be selected from solid oxides treated with an electron withdrawing anion such as fluorided silica-alumina, or sulfated alumina and the like.
• co-activator-supports can include, but are not limited to, those listed in the Aspects section of this disclosure.
• the relative concentration or ratio of metallocene such as a group 4 metallocene of the formula (X 1 )(X 2 )(X 3 )(X 4 )M to the calcined clay heteroadduct can be expressed as moles of M (metal) per grams of calcined clay heteroadduct (mol M/g heteroadduct).
• M metal
• mol M/g heteroadduct moles of M (metal) per grams of calcined clay heteroadduct
• the ratio of moles of M per grams of calcined clay heteroadduct can be in a range of from about 0.025 mol M/g heteroadduct to about 0.000000005 mol M/g heteroadduct.
• the moles of M per grams of calcined clay heteroadduct can be used in a range of from about 0.0005 mol M/g heteroadduct to about 0.00000005 mol M/g heteroadduct, or alternatively, from about 0.0001 mol M/g heteroadduct to 0.000001 mol M/g heteroadduct.
• these recited ranges include the end points as well as intermediate values and subranges within the recited range.
• These ratios reflect the catalyst recipe, that is, these ratios are based on the amount of the components combined to give the catalyst composition, regardless of what the ratio may be in the final catalyst.
• the relative concentration or ratio of co-catalyst to the calcined clay heteroadduct can be expressed as moles of co-catalyst (for example, organoaluminum compound) per grams of calcined clay heteroadduct (mol co-catalyst/g heteroadduct).
• co-catalyst for example, organoaluminum compound
• mol co-catalyst/g heteroadduct mol co-catalyst/g heteroadduct
• the ratio of moles of co-catalyst per grams of calcined clay heteroadduct that can be used is in a range of from about 0.1 mol co-catalyst/g heteroadduct to about 0.00001 mol co-catalyst/g heteroadduct, or alternatively, from about 0.01 mol co-catalyst/g heteroadduct to about 0.0001 mol co-catalyst/g heteroadduct.
• Catalyst compositions can be produced by contacting the transition metal compound such as a metallocene, the calcined clay heteroadduct, and the co-catalyst such as an organoaluminum compound under suitable conditions.
• Contacting can occur in any number of ways, for example by blending, by contact in a carrier liquid, by feeding each component into a reactor separately or in any order or combination.
• various combinations of the components or compounds can be contacted with one another before being further contacted in a reactor with the remaining compound(s) or component(s).
• all three components or compounds can be contacted together before being introduced into a reactor.
• additional optional components which can be used in the catalyst system disclosed herein, such as co activators, ionizing ionic compounds, and the like, contacting steps using these optional components can occur in any way and in any order.
• the catalyst composition can be prepared by first contacting a transition metal compound such as a metallocene, with a co-catalyst such as an organoaluminum compound, for a time period of from about 1 minute to about 24 hours, or alternatively from about 1 minute to about 1 hour, at a contact temperature that can range from about 10°C to about 200°C, alternatively from about 12°C to about 100°C, alternatively from about 15°C to about 80°C, or alternatively from about 20°C to about 80°C, to form a first mixture, and this first mixture can then be contacted with a calcined clay heteroadduct to form the catalyst composition.
• a transition metal compound such as a metallocene
• a co-catalyst such as an organoaluminum compound
• the metallocene, the co-catalyst such as an organoaluminum compound, and the calcined clay heteroadduct can be pre-contacted before being introduced into a reactor.
• the pre-contacting step may occur over a time period of from about 1 minute to about 6 months.
• the pre-contacting step may occur over a time period of from about 1 minute to about 1 week at a temperature from about 10°C to about 200°C or from about 20°C to about 80°C, to provide the active catalyst composition.
• any subset of the final catalyst components also can be pre-contacted in one or more pre contacting steps, each with its own pre-contacting time period.
• a catalyst composition can comprise post-contacted components.
• a catalyst composition can comprise a post-contacted metallocene, a post-contacted co-catalyst such as an organoaluminum compound, and a post-contacted calcined clay heterodduct component.
• a post-contacted metallocene a post-contacted metallocene
• a post-contacted co-catalyst such as an organoaluminum compound
• a post-contacted calcined clay heterodduct component It is not uncommon in the field of catalyst technology that the specific and detailed nature of the active catalytic site and the specific nature and fate of each component used to make the active catalyst are not precisely known. While not intending to be bound by theory, the majority of the weight of the catalyst composition based upon the relative weights of the individual components can be thought of as comprising the post-contacted calcined clay heteroadduct. Because the nature of the active site and post-contacted components are not precisely known, the catalyst composition may simply be described according to its components or referred to
• the polymerization activity of the catalyst composition can be expressed as the weight of polymer polymerized per weight of support-activator comprising the calcined smectite heteroadduct, per unit of time, for example, gram polymer/gram (calcined) support- activator/hour (g/g/hr). That is, activity can be calculated on the basis of the support-activator alone, absent any metallocene or co-catalyst components. This measurement allows comparisons of the various activator supports, including with other activators, where the metallocene, co-catalyst, and other conditions are the same or substantially the same.
• the activity values disclosed in the Examples were measured under slurry polymerization conditions, using isobutane as the diluent, unless otherwise specified, and with a polymerization temperature of from about 50°C to about 150°C, (for example at a temperature of 90°C), and using a combined ethylene and isobutane pressure in a range of from about 300 psi to about 800 psi, for example 450 psi for the total combined ethylene and isobutane.
• Activity data are reported as the weight of polymer produced divided by the weight of calcined clay heteroadduct per hour.
• Catalyst activity can be a function of the metallocene and the calcined clay heteroadduct, as well as other components and conditions. Under the conditions explained above, the activity based on the weight of the calcined clay heteroadduct can be greater than about 1,000 grams of polyethylene polymer per gram of calcined clay heteroadduct per hour (g PE/g heteroadduct/hr, or simply, g/g/hr).
• the activity based on the weight of the calcined clay heteroadduct can be greater than about 2000 g/g/hr, greater than about 4,000 g/g/hr, greater than about 6,000 g/g/hr, greater than about 8,000 g/g/hr, greater than about 10,000 g/g/hr, greater than about 15,000 g/g/hr, greater than about 25,000 g/g/hr, or greater than about 50,000 g/g/hr.
• the upper limit for each of these activities can be about 70,000 g/g/hr, such that the activities can range from greater than these disclosed values, and less than about 75,000 g/g/hr.
• the activator supports can have a polymerization activity of about 500 g/g/hr, about 750 g/g/hr, about 1,000 g/g/hr, about 1,250 g/g/hr, about 1,500 g/g/hr, 1,750 g/g/hr, about 2,000 g/g/hr, about 2,500 g/g/hr, about 3,500 g/g/hr, about 5,000 g/g/hr, about 7,500 g/g/hr, about 10,000 g/g/hr, about 12,500 g/g/hr, about 15,000 g/g/hr, about 17,500 g/g/hr, about 20,000 g/g/hr, about 25,000 g/g/hr, about 30,000 g/g/hr, about 35,000 g/g/hr, about 40,000 g/g/hr, about 50,000 g/g/hr, about
• activity levels can be achieved that are in a range between two of the recited values recited, for example, activity levels can be obtained in the range of 500- 75,000 g/g/hr, in the range as well as intermediate values and ranges such as 1,000-50,000 g/g/hr, 2,000-40,000 g/g/hr, or 2,500-20,000 g/g/hr.
• aluminoxane such as methyl aluminoxane was needed to activate the metallocene and form the catalyst composition.
• Methyl aluminoxane (MAO) is an expensive activator compound which can greatly increase the polymer production costs.
• no organoboron compound or ionizing compound, such as borate compounds were required to in order to activate the metallocene and form the catalyst composition.
• ion- exchanged, protic-acid-treated or pillared clays which require similarly multi-step preparations which increase costs, were also not required to activate the metallocene and form the catalyst composition.
• an active heterogeneous catalyst composition can be easily and inexpensively produced and used for polymerizing olefin monomers including comonomers if desired in the absence of any aluminoxane compounds, boron compounds or borate compounds, ion-exchanged-, protic-acid-treated- or pillared-clays.
• MAO or other aluminoxanes, boron or borate compounds, ion-exchanged-clays, protic-acid-treated-clays, or pillared-clays are not required in the disclosed catalyst systems, these compounds can be used in reduced amounts or typical amounts according to other aspects of the disclosure.
• this disclosure describes a process of contacting at least one olefin monomer and the disclosed catalyst composition to produce at least one polymer (polyolefin).
• polymer is used herein to include homopolymers, copolymers of two olefin monomers, and polymers of more than two olefin monomers such as terpolymers.
• polymers of two or more than two olefin monomers are referred to as simply copolymers.
• the catalyst composition can be used to polymerize at least one monomer to produce a homopolymer or a copolymer.
• homopolymers are comprised of monomer residues which have from 2 to about 20 carbon atoms per molecule, preferably 2 to about 10 carbon atoms per molecule.
• the olefin monomer can comprise or be selected from ethylene, propylene, 1-butene, 3-methyl-l- butene, 1-pentene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 1 -hexene, 3 -ethyl- 1 -hexene, 1- heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof.
• homopolymers of ethylene homopolymers of propylene, and homopolymers of other olefins are encompassed by this disclosure.
• copolymers of ethylene and at least one comonomer and less commonly, copolymers of two non-ethylene copolymers are encompassed by this disclosure.
• each monomer may have from about 2 to about 20 carbon atoms per molecule.
• Comonomers of ethylene can include, but are not limited to, aliphatic 1- olefins having from 3 to 20 carbon atoms per molecule, such as, for example, propylene, 1- butene, 1-pentene, 4-methyl- 1-pentene, 1 -hexene, 1-octene, styrene, vinylcyclohexane and other olefins, and conjugated or non-conjugated diolefins such as 1,3 -butadiene, isoprene, piperylene, 2, 3-dimethyl-l, 3-butadiene, 1,4-pentadiene, 1,7-hexadiene, and other such diolefms and mixtures thereof.
• ethylene can be copolymerized with at least one comonomer comprising or selected from 1-butene, 4-methyl- 1-pentene, 1-hexene, 1-octene, or 1- decene.
• An amount of comonomer can be introduced into a reactor zone which is sufficient to produce a copolymer that can incorporate from about 0.01 wt.% to about 10 wt.% comonomer or even beyond this range, based upon the total weight of the monomer and comonomer in the copolymer; alternatively, from about 0.01 wt.% to about 5 wt.% comonomer; alternatively still, from about 0. 1 wt.% to about 4 wt.% comonomer; or alternatively still, any amount of comonomer can be introduced into a reactor zone that provides a desired copolymer.
• the catalyst composition can be used to homopolymerize ethylene, or propylene, or copolymerize ethylene with a comonomer, or copolymerize ethylene and propylene.
• several comonomers may be polymerized with monomer in the same or different reactor zones to achieve the desired polymer properties.
• Non-conjugated dienes useful as comonomers can be straight chain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes having from 6 to 15 carbon atoms.
• Suitable non-conjugated dienes can include, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene and 1,6-octadiene; (b) branched chain acyclic dienes, such as 5-methyl- 1,4-hexadiene; 3,7-dimethyl-l,6-octadiene; and 3,7-dimethyl-l,7-octadiene; (c) single ring alicyclic dienes, such as 1,4-cyclohexadiene; 1,5-cyclo-octadiene and 1,7- cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2.2.
• straight chain acyclic dienes such as 1,4-hexadiene and
• alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbomenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbomene, and 5-vinyl-2-norbomene (VNB); and (e) cycloalkenyl-substituted alkenes, such as vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene, and vinyl cyclododecene.
• MNB 5-methylene-2-norbornene
• NNB 5-propenyl-2-norbornene
• non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, 5- methylene-2-norbornene, 5-ethylidene-2-norbornene, and tetracyclo-(A-l l,12)-5,8-dodecene.
• Particularly useful di olefins include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB). Note that throughout this description the terms “non-conjugated diene” and “diene” are used interchangeably.
• the catalyst compositions can be used for polymerizing olefins to make oligomeric and polymeric materials having a wide range of densities, for example, in a range of from about 0.66 g/mL (also, g/cc) to about 0.96 g/mL, which are used in numerous applications.
• the catalyst compositions disclosed herein are particularly useful for the production of copolymers.
• copolymer resins may have a density of 0.960 g/cc or less, preferably 0.952 g/cc or less, or more preferably 0.940 g/cc or less.
• Copolymer resins can contain at least about 65 wt.% (percent by weight) of ethylene units, that is, the weight percent of ethylene monomers actually incorporated into the copolymer resin.
• the copolymer resins of this disclosure can contain at least about 0.5 wt.%, for example, from 0.5 wt.% to 35 wt.% of an alpha-olefin (a-olefm), referring to the weight percent of alpha-olefin comonomers actually incorporated into the copolymer resin.
• a-olefm alpha-olefin
• the catalyst compositions prepared according to the present disclosure are also useful for preparing: (a) ethylene/propylene copolymers, including “random copolymer” in which the commoner is distributed randomly along the polymer back-bone or chain; (b) “propylene random copolymer”, in which a random copolymer of propylene and ethylene comprising about 60 wt.% of the polymer derived from propylene units; and (c) “impact copolymer” meaning two or more polymers in which one polymer is dispersed in the other polymer, typically one polymer comprising a matrix phase and the other polymer comprising an elastomer phase.
• the catalyst compositions described herein may further be used to prepare polyalphaolefins with monomers containing more than three carbons. Such oligomers and polymers are particularly useful, for example, as lubricants.
• any number of polymerization methods or processes can be used with the catalyst compositions of this disclosure.
• slurry polymerization, gas phase polymerization, and solution polymerization and the like can be used.
• Multi-reactor combinations can be configured in a serial or parallel configuration, or a combination thereof, depending upon the desired polymerization sequence.
• reactor systems and combinations can include, for example, dual slurry loops in series, multiple slurry tanks in series, or slurry loop combined with gas phase, or multiple combinations of these processes, in which polymerization of ethylene, propylene and alpha-olefins separately or together can be carried out.
• gas phase reactors can comprise fluidized bed reactors or tubular reactors
• slurry reactors can comprise vertical loops or horizontal loops or stirred tanks
• solution reactors can comprise stirred tank or autoclave reactors.
• any polymerization zone known in the art which can produce polyolefins such as ethylene and alpha- olefin-containing polymers including polyethylene, polypropylene, ethylene alpha-olefin copolymers, as well as more generally to substituted olefins such as vinylcyclohexane, can be utilized.
• a stirred reactor can be utilized for a batch process, and then the reaction can be carried out continuously in a loop reactor or in a continuous stirred reactor or in a gas phase reactor.
• the catalyst compositions comprising the recited components can polymerize olefins in the presence of a diluent or liquid carrier, and these two terms are used interchangeably herein, even if a catalyst component is not soluble in the diluent or liquid carrier.
• Suitable diluents used in slurry and solution polymerization are known in the art and include hydrocarbons which are liquid under reaction conditions.
• term “diluent” as used in this disclosure does not necessarily mean that the material is inert, as it is possible that a diluent can contribute to polymerization such as in bulk polymerizations with propylene.
• Suitable hydrocarbon diluents can include, but are not limited to cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, and n-hexane, and higher boiling solvents such as ISOPARTM and the like.
• Isobutane works well as the diluent in a slurry polymerization. Examples of such slurry polymerization technologies can be found in U.S. Patent Nos.
• the propylene or alpha-olefin itself can comprise the solvent, which are known in the art as bulk polymerizations.
• polymerization reactors suitable for use with the catalyst system can comprise at least one raw material feed system, at least one feed system for catalyst or catalyst components, at least one reactor system, at least one polymer recovery system or any suitable combination thereof.
• Suitable reactors can further comprise any, or combination of, a catalyst storage system, an extrusion system, a cooling system, a diluent recycling system, a monomer recycling system, and comonomer recycling system or a control system.
• Such reactors can comprise continuous take-off and direct recycling of the catalyst, diluent, monomer, comonomer, inert gases, and polymer as desired.
• continuous processes can comprise the continuous introduction of a monomer, a comonomer, a catalyst, a co-catalyst if desired, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent.
• the polymerization methods can be carried out over a wide temperature range, for example, the polymerization temperatures may be in a range of from about 50°C to about 280°C, and in another aspect, polymerization reaction temperatures may be in a range of from about 70°C to about 110°C.
• the polymerization reaction pressure can be any pressure that does not terminate the polymerization reaction. In one aspect, polymerization pressures may be from about atmospheric pressure to about 30000 psig. In another aspect, polymerization pressures may be from about 50 psig to about 800 psig.
• the polymerization reaction can be carried out in an inert atmosphere, that is, in an atmosphere substantially free of molecular oxygen and under substantially anhydrous conditions; thus, in the absence of water as the reaction begins. Therefore a dry, inert atmosphere, for example, dry nitrogen or dry argon, is typically employed in the polymerization reactor.
• hydrogen can be used in a polymerization process to control polymer molecular weight.
• a method of deactivating a catalyst by adding carbon monoxide to the polymerization zone as described in U.S. Patent No. 9,447,204, which is incorporated by reference herein, may be used to mitigate or stop an uncontrolled, or runaway polymerization.
• the polymerizations disclosed herein are commonly carried out using a slurry polymerization process in a loop reaction zone or a batch process, or a gas phase zone utilizing a fluidized bed or a stirrer bed.
• a typical polymerization method is a slurry polymerization process (also known as the “particle form process”), which is disclosed, for example in U.S. Patent No. 3,248, 179, which is incorporated herein by reference.
• Other polymerization methods for slurry processes can employ a loop reactor of the type disclosed in U.S. Patent No. 3,248,179, and those utilized in a plurality of stirred reactors either in series, parallel, or combinations thereof.
• the polymerization reactor system can comprise at least one loop slurry reactor, and can include vertical or horizontal loops or a combination, which can independently be selected from a single loop or a series of loops. Multiple loop reactors can comprise both vertical and horizontal loops.
• the slurry polymerization can be performed in an organic solvent as the carrier or diluent. Examples of suitable solvents include propane, hexane, cyclohexane, octane, isobutane, or combinations thereof. Olefin monomer, carrier, catalyst system components, and any comonomer can be continuously fed to a loop reactor where polymerization occurs. Reactor effluent can be flash evaporated to separate the solid polymer particles.
• a method for producing polyolefin polymers according to the disclosure is a gas phase polymerization process, using for example a fluidized bed reactor.
• This type reactor, and means for operating the reactor are described in, for example, U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541,270; EP-A- 0 802202, Belgian Patent No. 839,380, each of which is incorporated herein by reference.
• Gas phase polymerization systems can employ a continuous recycle stream containing one or more monomers continuously cycled through the fluidized bed in the presence of the catalyst under polymerization conditions.
• the recycle stream can be withdrawn from the fluidized bed and recycled back into the reactor.
• polymer product can be withdrawn from the reactor and fresh monomer can be added to replace the polymerized monomer.
• Such gas phase reactors can comprise a process for multi-step gas-phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone.
• gas phase processes contemplated by the disclosed polymerization process include series or multistage polymerization processes.
• gas phase processes that can be used in accordance with the disclosure include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-0794200, EP-Bl-0649 992, EP-A-0 802202, and EP-B-634421 all of which are incorporated herein by reference.
• the ethylene partial pressure may vary in a range suitable for providing practical polymerization conditions, for example, in a range of from 10 psi to 250 psi, for example, from 65 psi to 150 psi, from 75 psi to 140 psi, or from 90 psi to 120 psi.
• a molar ratio of comonomer to ethylene in the gas phase also may vary in a range suitable for providing practical polymerization conditions, for example, in a range of from 0.0 to 0.70, from 0.0001 to 0.25, more preferably from 0.005 to 0.025, or from 0.025 to 0.05.
• the reactor pressure can be maintained in a range suitable for providing practical polymerization conditions, for example, in a range of from 100 psi to 500 psi, from 200 psi to 500 psi, or from 250 psi to 350 psi, and the like.
• a gaseous stream containing one or more monomers in a fluidized gas bed process used for producing polymers, can be continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions.
• the gaseous stream can be withdrawn from the fluidized bed and recycled back into the reactor, and simultaneously, polymer product can be withdrawn from the fluidized bed and withdrawn from the reactor, while fresh monomer can be added to replace the polymerized monomer. See, for example, U.S. Patent Nos.
• antistatic compounds can be fed simultaneous with the finished catalyst into a polymerization zone.
• antistatic compounds such as those described in US Patent Nos. 7,919,569; 6,271,325; 6,281,306; 6,140,432 and 6,117,955, each of which is incorporated herein by reference in its entirety, can be used.
• the clay heteroadduct can be contacted with or impregnated with one or more antistatic compounds.
• Antistatic compounds may be added at any point, for example, they can be added any time after calcination such as up to and including the final post-contacted catalyst preparation.
• so-called “self-limiting” compositions may be added to the clay heteroadduct to inhibit chunking, fouling, or uncontrolled or runaway reaction in the polymerization zone.
• U.S. Patent Nos. 6,632,769; 6,346,584; and 6,713,573, each of which is incorporated herein by reference disclose additives that can release a catalyst poison above a threshold temperature.
• such compositions can be added at any time after calcination, in order to limit or stop polymerization activity above a desired temperature.
• the polymerization reactor also can comprise a solution polymerization reactor, in which the monomer is contacted with the catalyst composition by suitable stirring or other means.
• Solution polymerizations can be effected in a batch manner, or in a continuous manner.
• a carrier comprising an inert organic diluent or excess monomer can be employed, and the polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in the reaction medium. Agitation can be employed during polymerization to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone, and adequate means are utilized for dissipating the exothermic heat of polymerization.
• the reactor also can comprise a series of at least one separator that employs high pressure and low pressure to separate the desired polymer.
• the polymerization reactor can comprise a tubular reactor, which can make polymers by free radical initiation or alternatively by employing the disclosed catalysts.
• Tubular reactors can have several zones where fresh monomer, initiators, or catalysts and cocatalysts are added.
• monomer can be entrained in an inert gaseous stream and introduced at one zone of the reactor, and initiators, the catalysts composition and/or catalyst components can be entrained in a gaseous stream and introduced at another zone of the reactor.
• These gas streams can then be intermixed for polymerization, in which heat and pressure can be appropriately adjusted to obtain optimal polymerization reaction conditions.
• the catalysts and processes of this disclosure are not limited by possible reactor types or combinations of reactor types.
• the disclosed catalysts and processes can be used in multiple reactor systems which can comprise reactors combined or connected to perform polymerizations, or multiple reactors that are not connected.
• the polymer can be polymerized in one reactor under one set of conditions, and then the polymer can be transferred to a second reactor for polymerization under a different set of conditions.
• the polymerization reactor system can comprise the combination of two or more reactors.
• Production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors interconnected by a transfer device to transfer the polymers resulting from the first polymerization reactor into the second reactor, in which polymerization conditions are different in the individual reactors.
• polymerization in multiple reactors can include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization.
• Such reactors can include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, a combination of autoclave reactors or solution reactors with gas or loop reactors, multiple solution reactors, or multiple autoclave reactors, and the like.
• the catalyst compositions used in this process can produce high quality polymer particles without substantially fouling the reactor.
• the particle size of the calcined heterocoagulated product can be in a range of from about 10 microns (pm) to about 1000 microns, from about 25 microns to about 500 microns, from about 50 microns to about 200 microns, or from about 30 microns to about 100 microns to provide good control of the polymer particle production during polymerization.
• the particle size of the calcined heterocoagulated product can be in a range of from about 1 micron to about 1000 microns, from about 5 to about 500 microns, or from about 10 microns to about 200 microns, or from about 15 microns to about 60 microns, to provide good control of the polymer particle and polymerization reaction.
• the suitable particle size in other polymerization reactor systems can be a function of the total productivity of the catalyst and the optimal particle size and particle size distribution of the final polymer-catalyst composite particle.
• the optimal size and size distribution can be determined by the polymerization reactor system, such as whether the particles are easily fluidizable in a gas phase system but sufficiently large that they are not entrained in the fluidizing gas, which can result in plugging downstream filters.
• the optimal size and size distribution in the polymerization system may be balanced against the ease with which they are conveyed or handled in storage silos or extrusion facilities when the catalyst-polymer composite particles are melted and extruded into pellets.
• Polymers produced using the catalyst composition of this disclosure can be formed into various articles, such as, for example, household containers and utensils, film products, car bumper components, drums, fuel tanks, pipes, geomembranes, and liners.
• additives and modifiers can be added to the polymer in order to provide desired effects, such as a desired combination of physical, structural and flow properties. It is believed that by using the methods and materials described herein, articles can be produced at a lower cost, while maintaining desired polymer properties obtained for polymers produced using transition metal or metallocene catalyst compositions as disclosed herein.
• the major peak among them is not less than 4 degrees 2 theta, or a peak greater in intensity than that which would be exhibited by the clay mineral itself after calcination at 300°C, such as from 8 degrees 2 theta to 12 degrees 2 theta; (3) combining the calcined heterocoagulated clay-adduct composition and a metallocene, for example, bis(l-butyl-3-methylcyclopentadienyl) zirconium dichloride, at a temperature in the range of from 15°C to 100°C to produce a mixture; and
• a metallocene for example, bis(l-butyl-3-methylcyclopentadienyl) zirconium dichloride
• Fumed Silica AEROSIL® 200
• fumed aluminum oxide aqueous dispersion AERODISP® W400
• An aqueous dispersion of colloidal alumina NYACOL® AL27 was obtained from Nano Technologies, Inc.
• the clay dispersions, clay heteroadducts, pillared clays, and other compositions could be prepared using a dual-speed ConairTM WaringTM Commerical Lab Blender model 7010G, equipped with timer. Blender speeds may be referred to as “low” speed versus “high” speed blending as follows.
• the Model 7010G blender was connected to a Staco Energy Variable Transformer (Model number 3PN1010B), and the blender speed was adjusted by changing the setting on the Transformer.
• “low speed” blending was achieved by setting the Transformer between 0 to 50
• “high speed” blending was achieved by setting the Transformer between 50 to 100.
• Milli-Q® water Deionized water referred to herein as Milli-Q® water was obtained by initially pretreating water using a Prepak 1 Pretreatment Pack, and then further purifying the water using a Millipore Milli-Q® Advantage A10 Water Purification System. This water was typically used within 2 hours of collection.
• Hexane, heptane, toluene and dichloromethane were dried over activated molecular sieves and degassed with nitrogen prior to use.
• Instrument grade isobutane, used as solvent for the ethylene homopolymerizations was purchased from Airgas and purified by passage through columns of activated charcoal, alumina, 13X molecular sieves, and finally an OxyClearTM gas purifier Model No. RGP-Rl-500, from Diamond Tool and Die, Inc.
• Ultra-high purity grade ethylene and hydrogen were obtained from Airgas.
• the UHP (ultra-high purity) ethylene was further purified by passage through columns of activated charcoal, alumina, 13X molecular sieves, and an OxyClearTM gas purifier Model No.
• RGP-Rl-500 The UHP hydrogen was purified by passage through an OxyClearTM gas purifier Model No. RGP-Rl-500. Purified propylene was obtained as a slip stream from a commercial polypropylene plant. All preparations involving the handling of organometallic compounds were carried out under a nitrogen (N2) atmosphere using Schlenk techniques or in a glove box.
• N2 nitrogen
• Zeta potentials of the colloidal suspensions disclosed herein were derived from measuring the electroacoustic effect upon application of electric field across the suspension.
• the apparatus used to perform these measurements was a Colloidal Dynamics Zetaprobe AnalyzerTM.
• zeta potential measurements were used to determine the dispersed clay concentration in a 0.5 wt.% to 1 wt.% Volclay® HPM-20/water dispersion as follows.
• a 250 g to 300 g sample of the dispersion to be measured was transferred to the measurement vessel containing an axial bottom stirrer.
• the stirring speed was set fast enough to prevent settling or substantial settling of the dispersion but slow enough to allow the electroacoustic probe to be fully immersed in the mixture when fully lowered.
• the stirring speed was set between 250 rpm and 350 rpm, most often 300 rpm.
• the Colloidal Dynamic Zetaprobe AnalyzerTM measurement parameters used were the following: 5 readings at 1 reading/minute; particle density of 2.6 g/cc; dielectric constant of 4.5.
• An initial estimated colloidal weight percentage of 0.7 wt.% to 1.0 wt.% (concestimate) was typically entered into the Zetaprobe AnalyzerTM software.
• Measuring a 5 wt.% Volclay® HPM- 20/water dispersion provided a zeta potential of -46 mV. If the final dispersed clay concentration is referred to as “cone” in the equation below, then the final dispersed clay concentration can be calculated from the initial estimated concentration according to the following formula.
• cone concestimate * (measured zeta potential/(-46))
• the Zetaprobe AnalyzerTM was also used to dynamically track evolving zeta potential during titrations of clay dispersions with either colloidal dispersions or non-colloidal solutions.
• the cationic polymetallate titrant (or other cationic titrant) was added to a 0.5 wt.% to 5.0 wt.% Volclay® HPM-20/water dispersion at 0.25 mL to 2.0 mL per titration point, with an equilibration delay of from 30 seconds to 120 seconds.
• the Zetaprobe software calculates zeta potential using a colloidal particle weight percentage which does not factor in the colloidal titrant.
• the measured zeta potential was adjusted to reflect the extra colloidal content of the measured solution through the following method. Initially, both the weight of the titrand clay and the titrant cationic species were determined by the following equations (where * indicates multiplication, W is weight, V is volume).
• Wtitrant Vtitrant * densitytitrant * SOlids%titrant
• the density for 5% Volclay® HPM-20 aqueous dispersion (titrand) was determined to be approximately 1.03 g/mL.
• the titrant weight was scaled according to its particle density relative to the particle density of the titrand Volclay® HPM-20 (montmorillonite), to provide an effective titrant weight (Wefftitrant), which in this example was calculated as follows.
• Wefftitrant Wtitrant * particle densitytitrant / particle densitytitrand
• the effective colloidal particle weight percentage (wt.% eff ) was then calculated, to provide an estimate of the relative increase in colloidal content compared to an equivalent titration using a non-colloidal titrant.
• the inverse of this value was then multiplied by the measured zeta potential to determine an adjusted zeta potential as follows.
• zeta potential titrations of clay dispersions with a cationic polymetallate such as the titration of Volclay® HPM-20 montmorillonite with aluminum chlorhydrate (ACH)
• the zeta potential was measured before and during the titration as a function of the titrant volume and the mmol Al/g clay.
• Samples of the solid material formed at various points during the titration were collected (for example, at 0 mmol Al/g clay, 1.17 mmol Al/g clay, 1.52 mmol Al/g clay, and so forth), and each sample was dried, calcined, and analyzed by powder XRD (x-ray diffraction).
• FIG. 3 plots the zeta potentials of the series of dispersions provided by the titration of Volclay® HPM-20 montmorillonite with aluminum chlorhydrate (ACH), plotting titrant volume versus zeta potential (mV) of the dispersion, and FIG. 4 plots the mmol Al/g clay versus zeta potential (mV) of the dispersion for the same titration.
• FIG. 2 provides a powder XRD pattern of a series of calcined products collected from during this zeta potential titration of HPM-20 clay with ACH.
• Powder X-ray patterns of clays and clay heteroadducts were obtained using standard X- ray powder diffraction techniques on a Bruker D8 daVinci instrument, with a Bragg Brentano geometry with a “theta-theta” scan type, using a Back-loading holder with zero background Silicon chip.
• the detector used was a Linear Silicon Strip (LynxEYE) PSD detector.
• the test sample was placed in the sample holder of a two circle goniometer, enclosed in a radiation safety enclosure.
• the X-ray source was a 2.0 kW Cu X-ray tube, maintained at an operating current of 40 kV and 25 mA.
• the X-ray optics were the standard Bragg-Brentano para-focusing mode with the X-ray diverging from a DS slit (0.6 mm) at the tube to strike the sample and then converging at a position sensitive X-ray Detector (Lynx-Eye, Bruker-AXS).
• the two-circle 250 mm diameter goniometer was computer controlled with independent stepper motors and optical encoders.
• Flat compressed powder samples were scanned at 0.8° (20) per minute (2-30° 20 over 35 minutes).
• the software suite for data collection and evaluation was Windows based. Data collection was automated using the COMMANDER program by employing a BSML file, and data was analyzed by the program DIFFRAC.EVA.
• Pore volumes of the clay heteroadducts are reported as the cumulative volume in cc/g (cm 3 /g, cubic centimeters per gram) of all pores discemable by nitrogen desorption methods.
• the pore diameter distribution and pore volumes were calculated with reference to nitrogen desorption isotherm (assuming cylindrical pores) by the B.E.T. (or BET) technique as described by S. Brunauer, P. Emmett, and E. Teller in the J. Am. Chem. Soc ., 1939, 60, 309; see also ASTM D 3037, which identifies the procedure for determining the surface area using the nitrogen BET method.
• the pore volume distribution can be useful in understanding catalyst performance, and the pore volume (total pore volume), various attributes of pore volume distribution such as the percentage of pores in various size ranges, as well as “pore mode”, which describes the pore diameters corresponding to local maxima in the dV(log D) vs. pore diameter distribution, were derived from nitrogen adsorption-desorption isotherms based on the method described by E. P. Barrett, L. G. Joyner and P. P. Halenda (“BJH”), in “The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms,” J. Am. Chem. Soc., 1951, 73 (1), pp 373-380.
• Table 3 A reports properties and polymerization data for comparative supports and inventive heterocoagulated clay supports, using (l-n-butyl-3- methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) as metallocene and co-catalyst.
• the selected pressure and temperature in the reactor for calculating activities reported in Table 3 A were 450 total psi and 90°C, which were maintained electronically by an ethylene mass flow controller, or alternatively, manually using a jacketed temperature controller.
• Table 3B reports surface area and porosity properties of comparative supports and inventive heterocoagulated clay supports.
• the metallocene catalyst for the polymerization runs of Table 3A was (l-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and using triethylaluminum (AlEt3 or TEA) as a co-catalyst or alkylating agent, with 1.8 mmol of AlEt3 (3 mL of 0.6 M solution of TEA in hexanes) typically being used for the polymerization runs in this table.
• the post- contacted catalyst components that is the composition containing all the listed catalyst system components that were previously contacted to form the composition, were prepared in an inert atmosphere glove box and transferred to a catalyst charge tube or vessel.
• the catalyst charge vessel contents were then charged to the reactor by flushing them in with 1 L of isobutane.
• the reactor temperature control system was then turned on and is allowed to reach a few degrees lower than the temperature set-point, which typically took about 7 minutes.
• the reactor was brought to run pressure by opening a manual feed valve for the ethylene, and polymerization runs were continued for the times reported in Table 3 A, for example, for 30 minutes or 60 minutes.
• Table 3A Properties and polymerization data for comparative supports and inventive heterocoagulated clay supports.
• the polymerizations were performed at 450 psi reactor pressure and 90°C, using (l-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) as metallocene and co-catalyst.
• AlEt3 triethylaluminum
• MCN metallocene
• PE polyethylene
• Table 3B Surface area and porosity properties of comparative supports and inventive heterocoagulated clay supports.
• NA not available
• DVlogDmax30-40max/DvlogD200-500max also abbreviated DVM(30-40) / DVM(2OO-5OO>
• DVM(30-40) / DVM(2OO-5OO> is the ratio of the maximum value of dV(log D) between 30 A and 40 A and the maximum value of dV(log D) between 200 A and 500 A
• DVlogDmax200-500max/DvlogD60-200max also abbreviated DVM(2OO-5OO> / DVM(6O- 2 00)
• DVM(2OO-5OO> is the ratio of the maximum value of dV(log D) between 200 A and 500 A and the maximum value of dV(log D) between 60 A and 200 A.
• the contents of the catalyst charge tube can be pushed into the reaction vessel with ethylene at several degrees below the set point temperature of the run, for example, about 10 degrees centigrade below the set point temperature.
• two charge tubes were used.
• the reactor pressure was controlled by the mass flow controller.
• the consumption of ethylene and the temperature were monitored electronically.
• the reactor temperature was maintained at the set point temperature ⁇ 2°C.
• the polymerization was stopped by shutting off the ethylene inlet valve and venting the isobutane. The reactor was returned to ambient temperature.
• polymer melt indices specifically, melt index (MI) and high load melt index (HLMI)
• MI melt index
• HLMI high load melt index
• Polymer density was measured according to ASTM D 1505-03.
• the 3 ⁇ 4 NMR spectra of metallocene compounds were collected at room temperature by placing 20 mg of the metallocene sample into a 10 mm NMR tube, to which 3.0 mL of CDCb were added. 3 ⁇ 4 NMR spectra were acquired on a Bruker AVANCETM 400 NMR (400.13 MHz). Chemical shifts are reported in ppm (d) relative to TMS, or referenced to the chemical shifts of residual solvent proton resonances. Coupling constants are reported in Hertz (Hz).
• the NMR determination of isotactic pentads content in the polypropylene was obtained by place 400 mg of polymer sample into a 10 mm NMR tube, into which 1.7 g of tetracholoroethane-d2 and 1.7 g of o-dichlorobenzene were added.
• the 13 C NMR spectra were acquired on a Bruker AVANCETM 400 NMR (100.61 MHz, 90° pulse, 12 s delay between pulse). About 5000 transients were stored for each spectrum, and the mmmm pentad peak (21.09 ppm) was used as reference.
• the microstructure analysis was carried out as described by Busico, et al. , Macromolecules, 1994, 27, 4521-4524.
• the polypropylene Melt Flow Rate (MFR) was determined at 230°C under the load of 2.16 kg according to ASTM D-1238 procedure.
• Polypropylene melting temperature Tm was obtained according to ASTM D-3417 procedure using DSC and TA Instrument, Inc. Model: DSC Q1000.
• a 5.16 g sample of Volclay® HPM-20 clay powder was placed in a round-bottom flask and combined with 40 mL to 60 mL of n-butyl alcohol. This mixture was agitated vigorously and was then rotary evaporated at 45°C to dry. This drying step was stopped shortly after the alcohol was visibly evaporated. The odor of n-butyl alcohol was typically noticeable from the sample after this process.
• a 5.39 g sample of wet clay was obtained, and 4.46 g of this material was then calcined for 6 hours at 300°C to afford 3.3 g of a black powder.
• a Waring® blender was charged with 100 g of the colloidal clay dispersion prepared according to Example 4, followed by, with stirring, 6.9 g of 50 % GEO aluminum chlorhydrate solution with reported basicity of 83.47%. After addition of the aluminum chlorhydrate, the mixture was stirred at high a high rate (rpm) for an additional 3 minutes. The pH of the mixture was measured as pH 4.23. Attempts to filter the resulting mixture through FisherbrandTM P8 filter paper were unsuccessful. Therefore, two aliquots of the mixture were transferred to 50 milliliter plastic centrifuge tubes, and the samples were centrifuged for a total of 140 minutes at 3600 rpm on a Beckmann Coulter Allegra 6 centrifuge.
• the resulting clear supernatant was decanted off each tube and replaced with deionized water.
• the samples were shaken to re suspend the solids and centrifuged again. This process was repeated multiple times (typically 4 to 8 times) until the supernatant of one centrifuged sample afforded a conductivity of 67 pS/cm and a pH of 6.0.
• the supernatant was then decanted and a minimum of deionized water was used to transfer the solids to an Erlenmeyer flask along with approximately 70 mL of n-butanol.
• Rotary evaporation afforded 2.11 g of off-white powder. A 437 mg sample of this powder was charged to porcelain bowl and placed in an 300°C oven for 6 hours to afford 0.301 grams of a dark grey powder.
• a 150 g portion of this 5 wt.% aqueous dispersion of HPM-20 was transferred into a Waring® blender, and 9.35 g of GEO aluminum chlorohydrate 50 wt.% aqueous solution was pipetted into a vial and was added all at once to the dispersion.
• the mixture was blended at high speed for 5 minutes, then portioned into four 50 mL centrifuge tubes and centrifuged at 3000 rpm to 3500 rpm for 30 to 60 minutes.
• the supernatant pH and conductivity were measured (Eutech PCSTestr 35). The supernatant was decanted and the remaining wet solid was re suspended in deionized Milli-Q® water.
• centrifugation process centrifuge, supernatant pH/conductivity measurement, supernatant removal, and re-suspension in deionized Milli-Q® water was repeated until the conductivity of the supernatant reached 100 to 300 pS/cm. In total, six centrifugations were performed, at which point the supernatant was discarded for a final time.
• To the remaining wet solid was added 200 mL of 1 -butanol, which after rotary evaporation at 45°C yielded 9.75 g of wet solid. This wet solid was then ground with a pestle and mortar, 4.28 g of this solid were transferred to a porcelain crucible and were calcined for 6 hours at 300°C to afford 1.65 g of a grey -black powder.
• EXAMPLE 7 Comparative example of the preparation of aluminum chlorhydrate (AI13 Keggin- ion)-pillared clay using powdered aluminum chlorhydrate (6.4 mg Al/g clay)
• the centrifugation process (centrifuge, supernatant pH/conductivity measurement, supernatant removal, and re suspension in deionized Milli-Q® water) was repeated until the conductivity of the supernatant reached 100 to 300 pS/cm (in total, six centrifugations were performed, with final supernatant pH of 4.25 and conductivity of 225 pS/cm), at which point the supernatant was discarded for a final time.
• the remaining wet solid was combined with 100 to 200 mL of 1 -butanol in a round- bottom flask and rotary evaporated at 45°C to afford 5.54 g of wet solid, which was then ground with a pestle and mortar. A 1.8 g portion of this solid was transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford 1.2 g of a grey -black powder.
• a 60 g sample of a 5 wt.% HPM-20 clay dispersion in water was combined with 240 g of Milli-Q® deionized water to give 300 g of a 1 wt.% HPM-20 aqueous dispersion.
• Upon standing for a time period of from 30 minutes to an hour a significant amount of settled clay was observed in this diluted dispersion.
• the colloidal portion was decanted off, and the settled portion was collected, dried and weighed. This process provided 900 mg of HPM-20 clay which was collected, corresponding to a 0.7% colloidal content for the diluted dispersion.
• a zeta potential measurement was performed on this diluted HPM-20 aqueous dispersion using an initial colloidal content estimate of 0.7 wt.% to determine the actual colloidal content of the clay dispersion.
• Measuring a 5 wt.% HPM-20 aqueous dispersion results in a zeta potential measurement of -46 mV (negative 46 millivolts).
• the initial colloidal content estimate was adjusted to match this zeta potential.
• the HPM-20 colloidal content of the dispersion was determined to be 0.62%.
• Colloidal Dynamic Zetaprobe measurement parameters were as follows: 5 readings, 1 reading/minute; particle density of 2.6 g/cc; dielectric constant of 4.5.
• a 2.5 wt.% aqueous solution of aluminum chlorohydrate (ACH) was obtained through dilution of a 50 wt.% aluminum chlorohydrate solution (GEO).
• GEO aluminum chlorohydrate solution
• a volumetric titration of this 2.5 wt.% ACH solution into the 0.7 wt.% HPM-20 aqueous dispersion was then performed.
• Titration settings were 0.5 mL per titration point, with an equilibration delay of 30 seconds, that is, following the addition of 0.5 mL of the aqueous ACH solution, a 30 second delay to allow for equilibration was taken prior to the zeta potential measurement.
• FIG. 3 and Table 4 report the results of this zeta potential titration for the volumetric addition of the 2.5 wt.% aqueous solution of aluminum chlorohydrate (ACH) into the 0.7 wt.% HPM-20 aqueous dispersion, plotting the measured zeta potential versus the titrant volume (mL).
• the titrant volume indicates the cumulative volume of the aqueous aluminum chlorohydrate solution added.
• Milli-Q® deionized water to give a 1 wt.% HPM-20 aqueous dispersion.
• Approximately 280 g of this 1 wt.% colloidal dispersion was transferred to the measurement vessel of a Colloidal Dynamics Zetaprobe AnalyzerTM, containing an axial bottom stirrer. The stirring speed was set as described above.
• a zeta potential measurement was performed on this diluted HPM-20 aqueous dispersion using an initial colloidal content estimate of 1 wt.% to determine the actual colloidal content of the clay dispersion. Measuring a 5 wt.% HPM-20 aqueous dispersion results in a zeta potential of -46 mV.
• the initial colloidal content estimate is adjusted to match this zeta potential.
• the HPM-20 clay colloidal content of the dispersion was estimated to be 0.67%.
• Colloidal Dynamic Zetaprobe Measurement parameters were the following: 5 readings, 1 reading/minute; particle density of 2.6 g/cc; dielectric constant of 4.5.
• a 4.58 g sample of polyaluminum chloride (abbreviated “PAC”) UltraPAC® 290 (17.1% AI2O3 content) was diluted into a 100 mL volumetric flask using Milli-Q® deionized water. A volumetric titration of this 4.58 wt.% UltraPAC® 290 solution into the aforementioned 1 wt.% HPM-20 clay dispersion was then performed. Titration settings were 1 mL per titration point, with an equilibration delay of 30 seconds.
• PAC polyaluminum chloride
• FIG. 5 and Table 5 report the results from these zeta potential measurements, where titrant volume indicates the cumulative volume of the 4.58 wt.% aqueous UltraPAC® 290 solution added, plotting the measured zeta potential versus the titrant volume (mL).
• the amount of UltraPAC® 290 dispersion used to achieve -20 mV, neutral, and +20 mV zeta potential is summarized in Table 5.
• a 1 wt.% HPM-20 clay dispersion was prepared by addition of approximately 60 g of 5 wt.% HPM-20 aqueous dispersion into 240 g of Milli-Q® water. A 285 g to 300 g portion of the 1 wt.% dispersion was transferred to the measurement container of the Zetaprobe and an initial zeta potential measurement was taken to estimate the true particle wt.% of the solution.
• a zeta potential measurement was performed on this diluted HPM-20 aqueous dispersion to determine the actual colloidal content of the clay dispersion. Measuring a 5 wt.% HPM-20 aqueous dispersion results in a zeta potential of -44.2 mV. The initial colloidal content estimate is adjusted to match this zeta potential. In this instance, the HPM-20 clay colloidal content of the dispersion was determined to be 0.92%.
• Colloidal Dynamic Zetaprobe Measurement parameters were the following: 5 readings, 1 reading/minute; particle density of 2.6 g/cc; dielectric constant of 4.5.
• Titration settings were as follows: 1 mL per titration point from 0 mL to 27 mL, and 3 mL per titration point afterwards, with an equilibration delay of 60 seconds.
• FIG. 6 and Table 6 report the results from these measurements, where titrant volume indicates the cumulative volume of the NYACOL® AL27 alumina dispersion added.
• the titrant is also a colloidal species.
• the zeta potential is adjusted using the previously described method to provide the date in FIG. 6.
• the amount of NYACOL® AL27 dispersion used to achieve -20 mV, neutral, and +20 mV zeta potential is summarized in Table 6.
• a Waring® Blender was charged with 475.22 grams of deionized water. With stirring, 25.09 grams of HPM-20 clay from American Colloid was added slowly. After the clay addition was completed, the mixture was stirred for 5 minutes on high to afford a homogeneous suspension with no lumps, after which 9.53 grams of aluminum chlorhydrate 50 wt.% aqueous solution (GEO) was added with stirring, and stirred continued for 9 minutes. The mixture was poured into a high density polyethylene bottle. The Waring® flask was rinsed with 42.5 grams of deionized Milli-Q® water, and the rinse water was transferred to the bottle. The bottle was shaken to thoroughly mix the contents, and the conductivity of the slurry was measured as 4.03 mS/cm, and the pH was 5.89.
• GEO aluminum chlorhydrate 50 wt.% aqueous solution
• a second batch of the aluminum chlorhydrate clay heteroadduct was prepared in the same fashion using 380.26 grams of deionized Milli-Q® water, 20.03 grams of HPM-20 clay, and 7.70 grams of aluminum chlorhydrate 50 wt.% aqueous solution (GEO).
• the conductivity of this batch was measured to be 3.64 mS/cm and the pH was 5.58.
• the contents of the second batch were transferred, along with 30 grams of deionized water to transfer residual slurry, to the bottle containing the first batch. The bottle was shaken to afford a grey slurry with no visible lumps.
• the final conductivity of the combined batches was 3.84 mS/cm and the final pH was 5.87.
• EXAMPLE 13 Comparative example of the preparation of an aluminum sesquichlorohydrate clay heteroadduct using powdered aluminum sesquichlorohydrate (ASCH, 6.4 mmol Al/g clay)
• the supernatant was decanted and the remaining wet solid was re-suspended in deionized Milli-Q® water.
• the centrifugation process (centrifuge, supernatant pH/conductivity measurement, supernatant removal, and re-suspension in deionized Milli-Q® water) was repeated until the conductivity of the supernatant reached 100 to 300 pS/cm. Achieving this conductivity required, in total, six centrifugations to be performed, with the final supernatant pH measured to be 4.3 and the conductivity measured to be 286 pS/cm.
• EXAMPLE 14 Spray drying, screening, and calcining unwashed aluminum chlorhydrate clay heteroadduct retained on a 325 mesh screen (1.76 mmol Al/g clay)
• a portion of the aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/g clay) mixture (slurry) prepared according to Example 12 was spray dried using a Buchi B290 laboratory spray drier. Some of the spray-dried clay heteroadduct was screened through a 325 mesh screen. Two grams of the material retained on the 325 mesh screen were charged to a 300°C oven and heated for 6 hours in air. While still hot, the material was transferred to a vacuum chamber and left to cool to room temperature under vacuum. EXAMPLE 15. Spray drying, screening, and calcining unwashed aluminum chlorhydrate clay heteroadduct passing through a 325 mesh screen (1.76 mmol Al/g clay)
• a portion of the aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/g clay) mixture (slurry) prepared according to Example 12 was spray dried using a Buchi B290 laboratory spray drier. Some of the spray-dried clay heteroadduct was screened through a 325 mesh screen. Two grams of through-screen material were charged to a 300°C oven and heated for 6 hours in air. While still hot, the material was transferred to a vacuum chamber and left to cool to room temperature under vacuum.
• EXAMPLE 16 Spray drying and calcining washed aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/g clay)
• a portion of the aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/g clay) slurry prepared according to Example 12 was filtered through FisherbrandTM P8 filter paper using a Buchner funnel and vacuum. The 158 gram filter cake was then transferred to a HDPE bottle and re-suspended in about 1.2 liter of deionized water by shaking. The conductivity of the thus- obtained slurry was 114 pS/cm and the pH was 6.25. This slurry was filtered again through FisherbrandTM P8 filter paper and left on filter under vacuum overnight to afford 109.03 grams of a grey solid.
• a 97.07 gram sample of this solid was charged to a HDPE bottle along with 452 g of deionized water and shaken until no lumps were visible in the slurry.
• the conductivity of this slurry was 112 pS/cm and the pH was 6.33.
• a portion of this aluminum chlorhydrate clay heteroadduct slurry was spray dried using a Buchi B290 laboratory spray drier.
• a 1.77 gram sample of the spray dried material was charged to a 300°C oven for 6 hours in air to calcine. While still hot, the material was then transferred to a vacuum chamber and left to cool to room temperature under vacuum.
• EXAMPLE 17 Single filtration, azeotroping, and calcining an aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/g clay)
• the off-white powder containing some flakes and chunks was very gently ground to a uniform powder and 1.04 grams were charged to a porcelain crucible that was calcined in air for 6 hours at 300°C. The calcined material was cooled down under vacuum and 0.867 grams were transferred to an inert atmosphere glove box.
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35), to provide a pH of 6.1 and a conductivity of 1516 pS/cm.
• the filtrate was discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.
• a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender.
• a 0.325 g sample of GEO ACH aqueous dispersion (50 wt.%) was pipetted into a vial and combined with 20 mL of deionized Milli-Q® water, which was then poured all at once into the clay dispersion.
• the resulting mixture was then blended at high speed for 5 minutes, then vacuum filtered through Fisher P8 Qualitative-Grade Filter Paper (coarse porosity). Filtration was slow ( ⁇ 1 drop/second).
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35), which provided a pH of 7.3 and a conductivity of 487 pS/cm.
• the filtrate was discarded, and the remaining wet solid was re-suspended in 50 mL of deionized Milli-Q® water and centrifuged once at 3000 rpm to 3500 rpm for 30 to 60 minutes. After removing the supernatant (having a measured conductivity of 180 pS/cm), the remaining wet solid was re-suspended in 50 to 100 mL of 1-butanol and rotary evaporated at 45°C.
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35), which provided a pH of 6.25 and a conductivity of 1166 pS/cm.
• the filtrate was discarded and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.
• the filtration process (suspension of wet solid in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the re suspended slurry reached 100 to 300 pS/cm. In this case, one additional filtration was performed to obtain a slurry with a pH of 6.2 and a conductivity of 188 pS/cm. The remaining wet solid was re-suspended in 150 to 200 mL of 1 -butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to obtain 2.97 g of a light grey powder.
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 6.2 and a conductivity of 1518 pS/cm.
• the filtrate was discarded and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.
• This filtration process (suspension of wet solid in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the re suspended slurry reached 100 to 300 pS/cm. In this case, one additional filtration was performed to obtain a slurry with a pH of 6.1 and a conductivity 199 pS/cm. The remaining wet solid was re-suspended in 150 to 200 mL of 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar to obtain 3.19 g of a light grey powder. A 1.65 g sample of this solid was transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford 0.9 g of a grey-black powder. The powder XRD pattern of this sample appears in FIG. 2.
• EXAMPLE 22 Comparative example of the preparation and single filtration of aluminum chlorhydrate (ACH)-clay heteroadduct (2.5 mmol Al/g clay)
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 4.72 and a conductivity of 1988 pS/cm.
• a portion of the wet solid filter cake was re suspended in 50 to 100 mL of 1 -butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to obtain 0.66 g of a light grey powder. A 0.64 g portion of this solid was transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford 0.5 g of a grey -black powder.
• EXAMPLE 23 Comparative example of the preparation and additional washing/filtration of aluminum chlorhydrate (ACH)-clay heteroadduct, as compared to Example 22 (2.5 mmol Al/g clay)
• a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender.
• a 2.71 g sample of GEO aluminum chlorohydrate 50 wt.% aqueous solution was pipetted into a vial and was added all at once to the dispersion. The mixture became viscous quickly, and 100 mL of deionized Milli-Q® water was added in order to facilitate stirring.
• the mixture was then blended at high speed for 5 minutes, then vacuum filtered through Fisher P8 Qualitative-Grade Filter Paper (coarse porosity). After allowing 15 to 30 minutes for the filtration, the filtrate pH and conductivity were measured (Eutech PCSTestr 35). The filtrate was discarded and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.
• the filtration process (suspension of wet solid in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the re- suspended slurry reached 100 to 300 pS/cm. In this case, one additional filtration was performed to obtain a slurry with a pH of 4.67 and a conductivity of 87 pS/cm.
• the remaining wet solid was re-suspended in 50 to 100 mL of 1 -butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to obtain 3.73 g of a light grey powder. A 1.37 g portion of this solid was transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford 0.6 g a grey-black powder.
• the powder XRD pattern of this sample appears in FIG. 2.
• EXAMPLE 24 Comparative example of the preparation and single filtration of Aluminum chlorhydrate (ACH)-clay heteroadduct (3.5 mmol Al/g clay)
• the filtration process (suspension of the wet solid in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the re suspended slurry reached 100 to 300 pS/cm. In this case, one additional filtration was performed to obtain a slurry with pH of 4.5, and conductivity of 180 pS/cm. The remaining slurry was re suspended in 50 to 100 mL of 1 -butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to obtain 4.33 g of a light grey powder. A 1.36 g portion of this solid was transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford 0.6 g a grey-black powder. The powder XRD pattern of this sample appears in FIG. 2.
• EXAMPLE 26 Comparative example of the preparation of aluminum chlorhydrate (ACH)-clay heteroadduct using powdered ACH reagent (0.3 mmol Al/g clay)
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH 6.5 and a conductivity of 780 pS/cm.
• the filtrate was discarded and the remaining wet solid was re-suspended in 50 mL of deionized Milli- Q® water and centrifuged once at 3000 rpm to 3500 rpm for 30 to 60 minutes. After removing the supernatant (having a conductivity of 180 pS/cm), the remaining wet solid was re-suspended in 50 to 100 mL of 1 -butanol and rotary evaporated. The resulting solid was then ground with a pestle and mortar then transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford a grey -black powder.
• EXAMPLE 27 Comparative example of the preparation of aluminum chlorhydrate (ACH)-clay heteroadduct using powdered ACH reagent (0.6 mmol Al/g clay)
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 7.2 and a conductivity of 180 pS/cm.
• the filtrate was discarded and the remaining wet solid was re suspended in 50 mL of deionized Milli-Q® water and centrifuged once at 3000 rpm to 3500 rpm for 30 to 60 minutes.
• the remaining wet solid was re-suspended in 50 to 100 mL of 1 -butanol and rotary evaporated at 45°C.
• the resulting solid was then ground with a pestle and mortar to afford 2 g of a grey powder, then transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford a grey -black powder.
• EXAMPLE 28 Preparation and additional washing of Aluminum chlorhydrate (ACH)-clay heteroadduct using powdered ACH reagent as compared to Example 29 (1.52 mmol Al/g clay)
• the filtration process (suspension of wet solid in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the supernatant reached 100 to 300 pS/cm. In this case, two filtrations were performed to yield a filtrate with pH of 6.3 and a conductivity of 169 pS/cm.
• the remaining wet solid was re suspended in 150 to 200 mL of 1 -butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to obtain 3.44 g of a light grey powder. A 1.5 g portion of this solid was transferred to a clay crucible and calcined for 6 hours at 300°C to afford 1.0 g of a grey -black powder.
• EXAMPLE 29 Preparation and single filtration of aluminum chlorhydrate (ACH)-clay heteroadduct using powdered ACH reagent as compared to Example 28 (1.52 mmol Al/g clay) With stirring, 30 g of HPM-20 clay was added slowly over the course of 1 to 2 minutes into a Waring® blender containing 570 g of deionized Milli-Q® water while stirring at low speed to afford a grey colloidal dispersion containing no, or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
• ACH aluminum chlorhydrate
• the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 5.8 and a conductivity of 1750 pS/cm.
• a portion of the remaining wet solid was re-suspended in 50 to 100 mL of 1 -butanol and rotary evaporated at 45°C.
• the solid was then ground with a pestle and mortar to afford 1 g of a grey powder, which was then transferred to a porcelain crucible and calcined for 6 hours at 300°C to afford 0.6 g of a grey-black powder.
• EXAMPLE 30 Preparation of aluminum chlorhydrate (ACH)-clay heteroadduct using powdered ACH reagent (1.76 mmol Al/g clay)
• the mixture was then blended at high speed for 5 minutes, then vacuum filtered through FisherbrandTM P8 Qualitative-Grade Filter Paper and washed with 100 mL of deionized Milli- Q® water. After allowing 15 to 30 minutes for the filtration, the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 6.1 and a conductivity of 1799 pS/cm.
• a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender.
• a 1.30 g sample of ALOXICOLL® 31L solution was weighed into a vial and added to the dispersion, along with enough deionized Milli-Q® water to facilitate stirring.
• the mixture was then blended at high speed for 5 minutes, and the conductivity was measured (Eutech PCSTestr 35) to provide a conductivity of 2600 pS/cm.
• the mixture was then vacuum filtered through FisherbrandTM P8 Qualitative-Grade Filter Paper and washed briefly with 100 mL of deionized Milli-Q® water.
• EXAMPLE 32 Comparative example of the preparation of aluminum sesquichlorohydrate-clay heteroadduct (2.5 mmol Al/g clay)
• a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender.
• a 2.79 g sample of ALOXICOLL® 31L solution was weighed into a vial and added to the dispersion, along with enough deionized Milli-Q® water to facilitate stirring.
• the mixture was then blended at high speed for 5 minutes, and the conductivity was measured (Eutech PCSTestr 35) to provide a conductivity of 2800 pS/cm.
• the mixture was then vacuum filtered through FisherbrandTM P8 Qualitative-Grade Filter Paper and washed briefly with 100 mL of deionized Milli-Q® water.
• a 177.28 gram sample of a 5.0 wt.% Volclay® HPM-20 suspension prepared according to the procedure in Example 4 was charged to a Waring® Blender. With stirring, 1.32 g of UltraPAC® 290 solution (GEO) was added to the HPM-20 clay slurry, after which it was stirred on high for 9 minutes. The grey heteroadduct viscous mass was then transferred into a HDPE poly bottle along with 210 grams deionized water in 2 portions.
• UltraPAC® 290 solution GEO
• the grey heteroadduct slurry was then shaken by hand for approximately 1 minute, affording a pH of 4.31 and a conductivity of 1672 pS/cm Filtration of the slurry through FisherbrandTM P8 coarse filter paper afforded 28.03 g of wet cake, which was transferred to a HDPE bottle, to which 308 g of deionized water was also charged.
• the bottle was shaken to afford no lumps in the slurry and a pH of 4.76 and conductivity of 200 pS/cm
• the slurry was filtered through FisherbrandTM P8 filter paper to give 22.30 g of wet cake, which was transferred to a stir-bar-equipped Erlenmeyer along with 200 mL of n-butanol and stirred until no clumps were visible.
• the stir bar was removed and the mixture rotary evaporated from a 45°C bath to afford 9.49 g of an off-white powder which was lightly ground to a fine powder using a mortar and pestle. 1.10 grams of off-white powder was charged to porcelain crucible and then a 300°C oven and calcined for 6 hours to yield 0.8960 grams of dark grey powder. This powder was cooled to ambient temperature under vacuum before being transferred to an inert atmosphere glove box.
• a 201.23 gram sample of a 5.0 wt.% HPM-20 clay suspension prepared as in Example 4 was charged to a Waring® Blender. With stirring, 3.036 g of UltraPAC® 290 solution (GEO) was added to the HPM-20 slurry. The resultant thick mass could not be stirred by the Waring® Blender and was transferred to a HDPE bottle with two triturations of deionized water totaling 185 g. The bottle was shaken by hand until no clumps or lumps were visible. The resultant slurry pH was 3.8 and the conductivity was 26 mS/cm. The slurry was filtered through FisherbrandTM Coarse filter paper no.
• the remaining filter cake was re-suspended in a new HDPE bottle in 281 g of deionized water, with shaking, to provide a slurry having a pH of 4.11 and conductivity of 150 pS/cm. After sitting overnight, the slurry was filtered through FisherbrandTM P8 paper and 18.25 g of filter cake transferred to an Erlenmeyer flask along with 100 mL of n-butanol. The flask was shaken to break up chunks and then rotary evaporated from a 40°C bath, to afford 9.08 g of an off-white powder.
• a 2.384 g sample of the off-white powder was charged to a porcelain crucible and placed in a 300°C oven for 6 hours, affording 1.72 g of grey powder which was placed under vacuum to cool down to ambient temperature and then placed in an inert atmosphere glove box.
• a 199.31 g sample of a 5.0 wt.% HPM-20 clay suspension prepared according to Example 4 was charged to a Waring® Blender. With stirring, 4.36 g of UltraPAC® 290 solution from GEO Specialty Chemicals was added to the HPM-20 clay slurry. The flask was removed from the blender and swirled until the viscous grey mass could be stirred using the blender, after which it was stirred on high for 9 minutes.
• the viscous mass was then poured into a HDPE polymer bottle along with 2 portions of deionized water totaling 85 grams giving a total of 275 g of grey heteroadduct slurry, which was then shaken by hand for approximately 1 minute, affording a slurry pH of 3.73 and a conductivity of 6.79 mS/cm. Filtration of the slurry through FisherbrandTM P8 coarse filter paper, followed by re-suspension of the filter cake in approximately 200 mL of deionized water afforded a slurry conductivity of 1 mS/cm.
• a 80 g sample of 5 wt.% colloidal suspension of HPM-20 clay was added to a graduated addition funnel.
• a 9.7 g portion of NYACOL® AL-27 dispersion (20% AI2O3) was added to a separate addition funnel, and this suspension was diluted to the 80 mL volume level.
• the solutions were simultaneously added into a Waring® blender containing 137 g of Milli-Q® water at low blend speed. The resulting mixture was then blended at high speed for approximately 5 minutes, and subsequently vacuum filtered through Fisher P8 Qualitative-Grade Filter Paper. After allowing 15 to 30 minutes for the filtration, the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 9.1 and a conductivity of 451 pS/cm).
• a 15 g sample of AEROSIL® 200 fumed silica is combined with 277 g of deionized Milli-Q® water in a beaker.
• the mixture is dispersed using an ULTRA- TURRAX® dispersing tool at 5400 rpm for 10 minutes and further dispersed at 7000 rpm for an additional 5 minutes to create a 5 wt.% (by silica) dispersion.
• a 270 g portion of this dispersion is transferred to the measurement vessel of a Colloidal Dynamics Zetaprobe AnalyzerTM, containing an axial bottom stirrer.
• the stirring speed is set fast enough to prevent substantial settling of the dispersion but slow enough to allow the electroacoustic probe to be fully immersed in the mixture when fully lowered.
• Typical stirring speeds are set between 250 and 350 rpm, most often 300 rpm.
• a 2.5 wt.% solution of aluminum chlorhydrate is prepared by diluting 6.16 g of aqueous ACH (50 wt.% aluminum chlorhydrate; GEO Specialty Chemicals) into 117 g of water. A volumetric zeta potential titration of this 2.5 wt.% ACH solution into the aforementioned 5 wt.% AEROSIL® 200 dispersion is then performed. Titration settings are 1 mL per titration point, with an equilibration delay of 60 seconds. The resultant data is depicted in FIG. 7 for ACH- AEROSIL® 200.
• the zeta potential versus titrant volume data from FIG. 7 are converted into a zeta potential versus AEROSIL® 200 fumed silica mass ratio data, which is plotted in FIG. 8.
• an arbitrary point was selected at a ratio above 0.04 g ACH/g AEROSIL® 200, corresponding to a zeta potential of approximately +30 mV, and below the ratio of an approximate monolayer to prepare the heterocoagulation reagent.
• the ratio of heterocoagulation reagent to clay was then determined in the usual fashion as set out in Example 8 through Example 11, specifically, by zeta potential titration of the clay with this ACH-fumed silica heterocoagulation reagent.
• EXAMPLE 38 Zeta potential titration of clay with ACH-fumed silica, and determination of ACH-SiCh/clay ratio
• a 15 g sample of AEROSIL® 200 fumed silica was combined with 277 g of deionized Milli-Q® water in a beaker. This mixture was dispersed using an ULTRA- TURRAX® dispersing tool at 6000 rpm to 7000 rpm for 10 minutes, after which 7.86 g of GEO aluminum chlorohydrate (ACH) solution was added. This mixture was then dispersed at 7000 rpm for an additional 5 minutes to create a 5 wt.% (by silica) ACH-AEROSIL® 200 fumed silica dispersion.
• ACH aluminum chlorohydrate
• a volumetric titration of the ACH-AEROSIL® 200 fumed silica dispersion into the clay dispersion was then performed. Titration settings were 0.2 mL per titration point from 0 to 1.2 mL and 0.5 mL per titration point onwards, with an equilibration delay of 30 seconds, thus providing the data illustrated in FIG. 9.
• the titrant is also a colloidal species.
• the zeta potential was adjusted using the previously described method in Example 11 to provide the plot in FIG. 9.
• the amount of AEROSIL® 200 fumed silica in the ACH- AEROSIL® 200 fumed silica dispersions used to achieve -20 mV, neutral, and +20 mV zeta potential is summarized in Table 7.
• a 15 g sample of AEROSIL® 200 fumed silica was combined with 277 g of deionized Milli-Q® water in a beaker, and the mixture was dispersed using an ULTRA- TURRAX® dispersing tool at 6000-7000 rpm for 10 minutes.
• a 7.86 g sample of GEO aluminum chlorohydrate solution was then added, followed by dispersion at 7000 rpm for an additional 5 minutes.
• the filtration process (suspension of wet solid in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the filtrate reached 100 to 300 pS/cm. In this case, two additional filtrations were performed.
• the remaining wet solid was re-suspended in 150 to 200 mL of 1 -butanol and rotary evaporated at 45°C.
• the solid was then ground with a pestle and mortar to obtain 6.60 g of a light grey powder. A 3.1 g portion of this solid was transferred to a porcelain crucible and calcined at 6 hours at 300°C to afford 1.45 g of a grey -black powder.
• This suspension was vacuum filtered again for 2 to 3 hours. Once again the filtrate was discarded and the remaining wet solid was re-suspended in 80 mL of deionized Milli-Q® water. The resulting suspension’s pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 3.09 and a conductivity of 217 pS/cm). The remaining wet solid was re-suspended in 150 to 200 mL of 1 -butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to obtain 0.58 g of light grey flakes. This solid was transferred to a clay crucible and calcined for 6 hours at 300°C to afford 0.45 g of a grey powder.
• the suspension was vacuum filtered again for 2 to 3 hours. Once again the filtrate was discarded and the remaining wet solid was re-suspended in 80 mL of deionized Milli-Q® water.
• the resulting suspension ’s pH and conductivity were measured (Eutech PCSTestr 35) to provide a pH of 3.25 and a conductivity of 213 pS/cm.
• the remaining wet solid was re-suspended in 150 to 200 mL of 1 -butanol and rotary evaporated at 45°C.
• the resulting solid was then ground with a pestle and mortar to obtain 1.73 g of light grey flakes. This solid was transferred to a clay crucible and calcined at 6 hours at 300°C to afford 1.2 g of a grey powder.
• a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender. Then, 1.66 g of GEO aluminum chlorohydrate 50 wt.% aqueous solution was pipetted into a vial and was added all at once to the dispersion. An additional 28 mL of deionized Milli-Q® water was added to the mixture in order to facilitate stirring. The mixture was blended at high speed for 5 minutes, and subsequently transferred to a bottle. The blender was washed with an additional 70 g of deionized Milli-Q® water, and 184 g of a slurry was obtained.
• the slurry was added to a 250 mL KIMAX® graduated cylinder until it reached the 183 mL mark, and the slurry was left standing undisturbed. Over time, the slurry settled and formed a layer that was substantially clear of visible colloidal particles. The volume of this clear layer was recorded periodically, and after 95 h (hours) of settling time, the volume of the clear layer, referred to as the settling volume, was 15 mL.
• EXAMPLE 43 Comparative example of a slurry settling test for an ACH-pillared clay (5.7 mmol Al/g clay)
• a 5 wt.% aqueous dispersion of HPM-20 clay is prepared by slowly adding 40 g of HPM-20 clay over the course of 1 to 2 minutes into a Waring® blender containing 760 g of deionized Milli-Q® water while stirring at low speed to afford a grey colloidal dispersion containing no, or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to obtain the slightly viscous 5 wt.% aqueous dispersion of HPM-20 clay.
• a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender.
• a 6.18 g sample of GEO aluminum chlorohydrate 50 wt.% aqueous solution was pipetted into a vial and was added all at once to the dispersion.
• An additional 13.8 mL of deionized Milli-Q® water was added to the mixture, which was then blended at high speed for 5 minutes, and subsequently transferred to a bottle.
• the blender was washed with an additional 30 g of deionized Milli-Q® water.
• a 50 g portion of Milli-Q® deionized water was then added to the mixture to obtain 194 g of a slurry.
• the slurry was added to a 250 mL KIMAX® graduated cylinder until it reached the 183 mL mark, and the slurry was left standing undisturbed. Over time, the slurry settled and formed a layer that was substantially clear of visible colloidal particles. The volume of this clear layer was recorded periodically, and after 95 h (hours) of settling time, the volume of the clear layer, referred to as the settling volume, was 3 mL.
• a 5 wt.% aqueous dispersion of HPM-20 clay was prepared as described in Example 42.
• the resulting mixture was then vacuum filtered through an 11 cm Fisher P8 Qualitative- Grade Filter Paper inside a 550 mL Buchner funnel, using a Welch 2034 DryFastTM diaphragm pump. After 10 minutes of filtration, 222 g of filtrate was obtained, with 24 g of wet cake remaining. The resulting filtrate was rotary evaporated at 55°C to obtain 0.23 g in solid remains.
• EXAMPLE 45 Comparative example of a filtrate quantification test for an ACH-pillared clay (5.7 mmol Al/g clay)
• a 5 wt.% aqueous dispersion of HPM-20 clay was prepared as described in Example 43. A 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender. A 6.18 g sample of GEO aluminum chlorohydrate 50 wt.% aqueous solution was pipetted into a vial and was added all at once to the dispersion. An additional 44 g of deionized Milli-Q® water was added to the mixture, which was then blended at high speed for 5 minutes, subsequently transferred to a bottle, and 100 g of Milli-Q® deionized water was then added to the mixture to obtain a slurry with a total mass of 250 g.
• the resulting mixture was then vacuum filtered through an 11 cm Fisher P8 Qualitative- Grade Filter Paper inside a 550 mL Buchner funnel, using a Welch 2034 DryFastTM diaphragm pump. After 20 minutes of filtration, 39 g of filtrate was obtained. The unfiltered mixture was allowed to settle for 96 hours, after which time vacuum filtered using the same filter paper grade and pump was applied, which yielded an additional 172 g of filtrate with 40 g of wet cake remaining. The resulting filtrate was rotary evaporated at 55°C to obtain 1.4 g in solid remains.
• n-BuLi (8.56 mL, 2.5 M in hexane, 21.4 mmol) was added to 60 mL of dry toluene, which was then added to a solution of 7-phenyl-2-methyl-lH-indene (4.41 g, 21.4 mmol) at room temperature with stirring. After stirring at room temperature for period of 6 h, the reaction mixture was cooled to -35°C and a solution of dichlorodimethylsilane (1.29 mL, 10.7 mmol) in THF (5 mL) was added. This mixture was stirred and heated to 80°C for approximately 18 hours.
• the resulting mixture was cooled to ambient temperature and the solution was passed through silica gel, washed with dichloromethane, and the volatiles were removed from the filtrate via rotary evaporation.
• the resulting crude product was purified by column chromatography (hexane to Et20 ratio of 200: 1 v:v), providing a yellow solid (2.65 g, 53% yield).
• the cold ligand solution was then added to a slurry of ZrCl4(THF)2 (333 mg, 0.875 mmol) in hexane (10 mL), which was cooled to -35°C in advance.
• the resulting orange slurry was allowed to warm to room temperature and stirred overnight, after which the volatile components were removed under vacuum, and the residual solid was extracted with dichloromethane (DCM). After passing the dichloromethane extract through a syringe filter, the solution was concentrated until orange crystals formed. Hexane was added to allow more product to precipitate. The crystalline solid was collected by filtration and dried under high vacuum (280 mg, 51% yield).
• EXAMPLE 49 Propylene polymerization catalyzed by rac-dimethylsilylene bis(2-methyl-4- phenylindenyl)zirconium di chloride, calcined clay heteroadduct of Example 17, and trialkylaluminum
• Propylene polymerization was conducted in a bench scale 2-liter reactor per the following procedure.
• the reactor was first preheated to at least 100°C with a nitrogen purge to remove residual moisture and oxygen, and was thereafter cooled to 50°C. Under nitrogen, 1 liter (L) of dry heptane was introduced into the reactor.
• L dry heptane was introduced into the reactor.
• reactor temperature was about 50°C
• 2.0 mL of tri-n-octylaluminum (0.92 M, in hexanes) 2.0 mL of tri-n-octylaluminum (0.92 M, in hexanes)
• catalyst slurry prepared as above were added to the reactor.
• the pressure of the reactor was raised to 28.5 psig at 50°C by introducing nitrogen.
• the reactor temperature was then raised to 70 °C, and the total reactor pressure was raised to and controlled at 90 psig by continually 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 0 psig and the reactor temperature was cooled to 50°C. The reactor was opened, and 500 mL of methanol was added to the reactor contents, and the resulting mixture was stirred for 5 minutes and then filtered to obtain the polymer product. The obtained polymer was vacuum dried at 80°C for 6 hours. The polymer was evaluated for melt flow rate (MFR) and isotacticity, and the activity of catalyst was also determined. Table 8 below summarizes the propylene polymerization results of this example.
• MFR melt flow rate
• EXAMPLE 50 Propylene polymerization catalyzed by rac-dimethylsilylene bis(2-methyl-4- phenylindenyl)zirconium di chloride, calcined clay heteroadduct of Example 16, and trialkylaluminum
• Example 49 The procedure in Example 49 was repeated using the spray dried and calcined washed clay heteroadduct of Example 16, and carrying out the polymerization at a temperature 80°C rather than 70°C as in Example 49.
• Table 8 summarizes the propylene polymerization results of this example.
• EXAMPLE 51 Ethylene homopolymerization catalysis inventive and comparative supports and metallocene catalysts
• Table 9 illustrates some actual and constructive examples of components that can be selected and used to prepare the heterocoagulated clay activator support, and additional components that can be selected and used in combination with the activator support to generate the olefin polymerization catalyst.
• Any one or more than one of the compounds or compositions set out in each component listing can be selected independently of any other compound or composition set our in any other component listing.
• this table discloses that any one or more than one of Component 1, any one or more than one of Component 2, optionally any one or more than one of Component A, and optionally any one or more than one of Component B, can be selected independently of each other and combined or contacted in any order to provide the heterocoagulated clay activator support, as disclosed herein.
• Any one or more than one of Component 3 (metallocene), optionally any one or more than one of Component C, and optionally any one or more than one of Component D, can be selected independently of each other and combined or contacted in any order with each other and the heterocoagulated clay activator support to provide an olefin polymerization catalyst, as disclosed herein.
• Table 9 Actual and constructive examples of components that can be selected independently and used to prepare a heterocoagulated clay activator support and an olefin polymerization catalyst.
• TEA triethylaluminum
• TnOA tri-n-octylaluminum
• TiBA triisobutylaluminum
• MAO methylaluminoxane
• EAO ethylaluminoxane
• groups such as “hydrocarbyl” or “Si-containing hydrocarbyl” groups may be considered to have from 1 to about 12 carbons, such as for example, methyl, n-propyl, phenyl, trimethylsilylmethyl, neopentyl, and the like.
• each group or substituent is selected indepdendently of any other group of substituent. Therefore, each “R” substituent is selected independently of any other R substituent, each “Q” group is selected independently of any other Q group, and the like.
• the co-catalyst component is referred to as optional (Optional Component C), and includes alkylating agents, hydriding agents and the like.
• a co catalyst component such as those listed is typically used in the formation of the polymerization catalyst because the metallocene is commonly halide-substituted and the co-catalyst can provide a polymerization-activatable/initiating ligand such as methyl or hydride.
• a catalyst composition for olefin polymerization 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, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• 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, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• the catalyst composition comprises: a) at least one metallocene compound; b
• a method of making an olefin polymerization catalyst comprising contacting in any order: 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, the smectite heteroadduct comprising the contact product of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate in a liquid carrier and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• a support-activator comprising an isolated smectite heteroadduct, the smectite heteroadduct comprising the contact product in a liquid carrier of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV.
• a method of making a support-activator comprising: a) providing a colloidal smectite clay; b) contacting in a liquid carrier the colloidal smectite clay with a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in a range of from about positive 25 mV (millivolts) to about negative 25 mV; and c) isolating the smectite heteroadduct from the slurry.
• Aspect 6 Aspect 6.
• Aspect 7 A support-activator or a method of making a support-activator according to any one of Aspects 4-5, wherein the isolated smectite heteroadduct is [1] washed with water,
• the smectite clay is [1] natural or synthetic, and/or [2] a dioctahedral smectite clay.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-12, wherein: a) the smectite clay is colloidal; and/or b) the smectite clay has an average particle size of less than about 10 pm (microns), less than about 5 pm, less than about 3 pm, less than 2 pm, or less than 1 pm, wherein the average particle size is greater than about 15 nm, greater than about 25 nm, greater than about 50 nm, or greater than about 75 nm.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of the previous aspects such as Aspects 1-13, wherein the smectite clay comprises structural units characterized by the following formula:
• the cations intercalated between structural units are selected from monocations.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-17, wherein the smectite clay is monocation exchanged with at least one of lithium, sodium, or potassium.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from a cationic oligomeric or cationic polymeric aluminum species.
• Aspect 20 wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from a cationic oligomeric or cationic polymeric aluminum species.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein the cationic polymetallate comprises linear, cyclic or cluster aluminum compounds containing from 2-30 aluminum atoms.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein: a) the colloidal smectite clay comprises colloidal montmorillonite, such as HPM-20 Volclay; and b) the heterocoagulation reagent comprises aluminum chlorhydrate, polyaluminum chloride, or aluminum sesquichlorohydrate.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from an aluminum species or any combinations of species having the empirical formula:
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from aluminum species having the empirical formula 0.5[Al2(OH)5Cl(H2O)2] or [A104(Ali2(OH)24(H20)2o] 7+ (“Ali3-mer”) polycation.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to Aspect 33, wherein the at least one rare earth metal is selected from cerium, lanthanum, or a combination thereof.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from a complex of Formula I or Formula II or any combination of complexes of Formula I or Formula II, according to the following formulas:
• M(II) is at least one divalent metal ion
• M(III) is at least one trivalent metal ion
• A is at least one inorganic anion
• L is an organic solvent or water
• n is the valence of the inorganic anion A or, in the case of a plurality of anions A, is their mean valence
• x is a number from 0.1 to 1
• m is a number from 0 to 10.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to Aspect 35, wherein:
• M(II) comprises, consists of, consists essentially of, or is selected from zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium;
• M(III) comprises, consists of, consists essentially of, or is selected from iron, chromium, manganese, bismuth, cerium, or aluminum;
• A comprises, consists of, consists essentially of, or is selected from hydrogencarbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide, or carbonate.
• n is a number from 1 to 3;
• L comprises, consists of, consists essentially of, or is selected from methanol, ethanol or isopropanol, or water.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-18, wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from a layered double hydroxide or a mixed metal layered hydroxide.
• the cationic polymetallate comprises, consists of, consists essentially of, or is selected from an iron polycation having an empirical formula FeOx(OH) y (H20) 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.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-45, wherein the smectite heteroadduct is calcined in an atmosphere comprising air or carbon monoxide or in an inert atmosphere such as nitrogen.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-45, wherein the smectite heteroadduct is calcined in air or carbon monoxide in a fluidized bed.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-43, wherein the calcined smectite heteroadduct is calcined at a temperature of 250°C or higher.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-43, wherein the calcined smectite heteroadduct is calcined at a temperature of 300°C or higher.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-43, wherein the calcined smectite heteroadduct is calcined at a temperature of 350°C or higher.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-51, wherein the calcined smectite heteroadduct is absent or substantially absent ordered domains characterized by a powder X-ray diffraction (XRD) peak in a range of from 0 degrees 2Q (2 theta) to 13 degrees 2Q.
• XRD powder X-ray diffraction
• V3-ionm 3-10 nm diameter
• dV log D
• pore diameter a logarithmic differential pore volume distribution
• dV log D
• DM lowest value
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-65, wherein the smectite heteroadduct is amorphous.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-66, wherein the catalyst composition or the support- activator further comprises an ion-exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate co-activator, or any combination thereof.
• a catalyst composition a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support- activator according to any one of Aspects 1-66, wherein the catalyst composition or the support- activator is substantially absent an ion-exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate co-activator, or any combination thereof.
• Aspect 69 A method of making a support-activator according to any one of Aspects 5-
• Aspect 70 A method of making a support-activator according to any one of Aspects 5-
• smectite heteroadduct is subsequently dried by heating, azeotropic drying, freeze drying, flash drying, fluidized bed drying, spray drying, or any combination thereof.
• Aspect 71 A method of making a support-activator according to any one of Aspects 5-
• Aspect 72 A method of making a support-activator according to any one of Aspects 5- 71, wherein the isolated smectite heteroadduct is dried to a constant weight to obtain a dry smectite heteroadduct.
• Aspect 73 A method of making a support-activator according to any one of Aspects 5- 71, wherein the smectite heteroadduct is calcined at a temperature in a range of from about 110°C to about 900°C, for a time period in a range of from about 1 hour to about 12 hours.
• Aspect 74 A method of making a support-activator according to any one of Aspects 5- 71, wherein the smectite heteroadduct is calcined for a time and temperature sufficient to achieve a catalyst productivity of at least about 1,500 g polymer/g support-activator, or a catalyst productivity in a range of from about 1,500 g polymer/g support-activator to about 30,000 g polymer/g support-activator.
• an inert atmosphere such as nitrogen or argon
• Aspect 76 A method of making a support-activator according to any one of Aspects 5- 75, wherein the concentration of the smectite heteroadduct solids in the slurry is at least about 5 wt.%.
• Aspect 77 A method of making a support-activator according to any one of Aspects 5- 76, wherein the concentration of the smectite heteroadduct solids 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 solids in the slurry is in a range of from about 2 wt.% to about 30 wt.%, from about 3 wt.% to about 20 wt.%, or from about 5 wt.% to about 15 wt.%.
• Aspect 78 A method of making a support-activator according to any one of Aspects 5-
• the contacting step is conducted in the substantial absence of an ion-exchanged clay, a protic-acid-treated clay, an aluminoxane, a borate co-activator, or any combination thereof.
• Aspect 79 A method of making a support-activator according to any one of Aspects 5-
• the proportion of a filtrate obtained at a filtration time of 10 minutes using either vacuum filtration or gravity filtration, based upon the weight of the liquid carrier in the slurry of the smectite heteroadduct is in a range of (1) from about 50% to about 100% by weight of the liquid carrier in the slurry before filtration, (2) from about 60% to about 100% by weight of the liquid carrier in the slurry before filtration, (3) from about 70% to about 100% by weight of the liquid carrier in the slurry before filtration, or (4) from about 80% to about 100% by weight of the liquid carrier in the slurry before filtration; and
• 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 obtained from filtration of a 2.0 wt.% slurry of a pillared clay prepared using the colloidal smectite clay, the heterocoagulation reagent, and the liquid carrier, and wherein the weight of the first filtrate and the weight of the second filtrate are measured after identical filtration times of 5 minutes, 10 minutes or 15 minutes; and
• X 1 is selected from titanium, zirconium, or hafnium
• X 1 is selected from a substituted or an unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or l,2-diaza-3,5-diborolyl, wherein any substituent is selected independently from a halide, a C1-C20 hydrocarbyl, a C1-C20 heterohydrocarbyl, a C1-C20 organoheteryl, a fused C4-C12 carbocyclic moiety, or a fused C4-C11 heterocyclic moiety having at least one heteroatom selected independently from nitrogen, oxygen, sulfur, or phosphorus; c) X 2 is selected from: [1] a substituted or an cyclopentadienyl, indenyl, fluorenyl, pentadien
• a catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst, according to Aspect 85, wherein X 1 and X 2 are bridged by a linker substituent selected from: a) >EX 5 2, -EX 5 2 EX 5 2-, -EX 5 2EX3 ⁇ 4X 5 2-, or >C CX 5 2, wherein E in each occurrence is independently selected from C or Si; b) -BX 5 -, -NX 5 -, or -PX 5 -; or c) [-SiX 5 2(l,2-C 6 H )SiX 5 2-], [-CX 5 2(1,2-C 6 H 4 )CX 5 2-], [-SiX 5 2(l,2-C 6 H 4 )CX 5 2-], [-SiX 5 2(l,2-C2H 2 )SiX 5 2-], [-CX 5 2(1,2-C 6
• a linker substituent selected from a C1-C20 hydrocarbylene group, a C1-C20 hydrocarbylidene group, a C1-C20 heterohydrocarbyl group, a C1-C20 heterohydrocarbylidene group, a C1-C20 heterohydrocarbylene group, or a C1-C20 heterohydrocarbyliden
• a catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 86-88, wherein X 5 in each occurrence is selected independently from a halide, a Ci-Cis or C1-C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C6-C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C18 or C1-C12 heterohydrocarbyl group, a C1-C21 or C1-C15 organosilyl group, a Ci- Ci8 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18 or C1-C12 organonitrogen group.
• X 5 in each occurrence is selected independently
• a catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 85-90, wherein X 1 is selected from a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group.
• a catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 85-90, wherein X 1 is selected from a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from a halide, a C1-C18 or C1-C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C 6 -C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C21 or C1-C15 organosilyl group, a C1-C18 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18
• a catalyst composition a process for polymerizing olefins, or a method of making an olefin polymerization catalyst, according to any one of Aspects 85-90, wherein X 1 ,
• X 2 or both X 1 and X 2 are selected independently from a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from: a) a silicon group having the formula -SiH 3 , -S1H2R, -S1HR2, -S1R3, -SiR2(OR), - SiR(OR) 2 , or -Si(OR) 3 ; b) a phosphorus group having the formula -PHR, -PR2,-P(0)R2, -P(OR)2, -P(0)(OR)2, -P(NR 2 )2, or -P(0)(NR 2 ) 2 ; c) a boron group having the formula -BH2, -BHR, -BR2, -BR(OR), or -B(OR)2; d) a germanium group having the formula -GeH 3 , -G
• Aspect 94 A catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst, according to any one of Aspects 85-90, wherein X 1 ,
• X 2 , or X 1 and X 2 are substituted with a fused carbocyclic or heterocyclic moiety selected from pyrrole, furan, thiophene, phosphole, imidazole, imidazoline, pyrazole, pyrazoline, oxazole, oxazoline, isoxazole, isoxazoline, thiazole, thiazoline, isothiozoline, or a partially saturated analogs thereof.
• a catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 85-97, wherein: [1] X 3 and X 4 are selected independently from a halide, a hydride, a C1-C2 0 aliphatic group, a C 6 -C2 0 aromatic group, a C1-C2 0 heteroaliphatic group, a C4-C2 0 heteroaromatic group, or a C1-C2 0 organoheteryl group; [2] X 3 and X 4 together are a substituted or an unsubstituted 1,3-butadiene having from 4 to 20 carbon atoms; or [3] X 3 and X 4 together with M form a substituted or an unsubstituted, saturated or unsaturated C4-C5 metallacycle moiety, wherein any substituent on the metallacycle mo
• a catalyst composition, a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 85-97, wherein: [1]
• X 3 and X 4 are selected independently from a halide, a hydride, a C1-C18 or C1-C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C 6 -C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C21 or C1-C15 organosilyl group, a C1-C18 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18 or C1-C12 organonitrogen group; or [2] X 3 and X 4 together are a substituted or an unsubstituted 1,3- butadiene having from 4 to 18 carbon atoms; or [3] X 3 and X 4 together with M form a substituted or an unsubstituted, saturated or uns
• Aspect 102 A catalyst composition or a process for polymerizing olefins according to any one of Aspects 1-3, 6-68, or 83-101, wherein the catalyst composition further comprises a co-catalyst.
• Aspect 103 A method of making an olefin polymerization catalyst according to any one of Aspects 1-3, 6-68, or 83-102, wherein the contacting step further comprises contacting, in any order, the metallocene compound and the support-activator with a co-catalyst.
• X A is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, or a C4-C20 heteroaromatic group; or [3] two X A together comprise a C4-C5 hydrocarbylene group and the remaining X A is/are selected independently from a hydride, a Ci- C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; c) X B is selected independently from: [1] a halide or a C1-C20 organohetery
• n is a number from 1 to 3, inclusive; b) X c is selected independently from a hydride or a C1-C20 hydrocarbyl; c) X D is a formal anionic species selected independently from: fluoride; chloride; bromide; iodide; bromate; chlorate; perchlorate; hydrocarbyl sulfate; hydrocarbyl sulfite; sulfamate; hydrocarbylsulfide, hydrocarbylcarbonate; hydrogen-carbonate (bicarbonate); carbamate; nitrite; nitrate; hydrocarbyloxalate; dihydrocarbylphosphate; hydrocarbylselenite; sulfate; sulfite; carbonate; oxalate; phosphate; phosphite; selenite; selenide; sulfide
• X E is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, or a C4-C20 heteroaromatic group; [3] a fluorinated C1-C20 hydrocarbyl, or a fluorinated C1-C20 heterohydrocarbyl; or [4] a fluorinated C1-C20 aliphatic group, a fluorinated C6-C20 aromatic group, a fluorinated C1-C20 heteroaliphatic group, or a fluorinated C4-
• M c (X G )r(X H )2-r wherein a) M c is zinc or magnesium; a) r is a number from 1 to 2, inclusive; b) X G is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; or [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, or a C4-C20 heteroaromatic group; and c) X H is selected independently from: [1] a halide or a C1-C20 organoheteryl; or [2] a halide, a C1-C12 alkoxide group, or a C6-C10 aryloxide group.
• a co-activator selected from an ion- exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate co-activator, an aluminate co-activator, an ionizing ionic compound, a solid oxide treated with an electron withdrawing anion, or any combination thereof.
• a catalyst composition a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 1-3, 6-68, or 83-104, wherein the catalyst composition further comprises an ionic ionizing compound.
• a catalyst composition a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 1-3, 6-68, or 83-104, wherein catalyst composition further comprises a co-activator comprising a solid oxide treated with an electron withdrawing anion.
• a catalyst composition a process for polymerizing olefins, or a method of making an olefin polymerization catalyst according to any one of Aspects 1-3, 6-68, or 83-120, wherein the catalyst composition further comprises a carrier or diluent, or the contacting in any order occurs in a carrier or diluent.
• Aspect 127 A process for polymerizing olefins according to any one of Aspects 1-3, 6- 68, or 83-126, wherein the process comprises at least one slurry polymerization, at least one gas phase polymerization, at least one solution polymerization, or any multi-reactor combinations thereof.
• Aspect 128 A process for polymerizing olefins according to any one of Aspects 1-3, 6- 68, or 83-127, wherein the process comprises polymerization in a gas phase reactor, a slurry loop, dual slurry loops in series, multiple slurry tanks in series, a slurry loop combined with a gas phase reactor, a continuous stirred reactor in a batch process, or combinations thereof.
• Aspect 129 A process for polymerizing olefins according to any one of Aspects 1-3, 6- 68, or 83-128, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer or an olefin copolymer.
• Aspect 130 A process for polymerizing olefins according to any one of Aspects 1-3, 6- 68, or 83-129, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer, the homopolymer comprising olefin monomer residues having from 2 to about 20 carbon atoms per monomer molecule.
• Aspect 131 A process for polymerizing olefins according to Aspect 130, wherein the olefin monomer is selected from ethylene, propylene, 1-butene, 3 -methyl- 1 -butene, 1-pentene, 3- methyl-l-pentene, 4-methyl- 1-pentene, 1 -hexene, 3 -ethyl- 1 -hexene, 1-heptene, 1-octene, 1- nonene, or 1-decene.
• the olefin monomer is selected from ethylene, propylene, 1-butene, 3 -methyl- 1 -butene, 1-pentene, 3- methyl-l-pentene, 4-methyl- 1-pentene, 1 -hexene, 3 -ethyl- 1 -hexene, 1-heptene, 1-octene, 1- nonene, or 1-decene.
• Aspect 132 A process for polymerizing olefins according to any one of Aspects 2, 6-68, or 83-129, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an ethylene-olefin comonomer copolymer, the copolymer comprising a-olefm comonomer residues having from 3 to about 20 carbon atoms per monomer molecule.
• Aspect 133 A process for polymerizing olefins according to Aspect 132, wherein the olefin comonomer is selected from an aliphatic C3 to C20 olefin, a conjugated or nonconjugated C3 to C20 diolefm, or any mixture thereof.
• Aspect 134 A process for polymerizing olefins according to Aspect 132, wherein the olefin comonomer is selected from propylene, 1-butene, 2-butene, 3 -methyl- 1 -butene, 1-pentene, 2-pentene, 3 -methyl- 1-pentene, 4-methyl- 1-pentene, 1 -hexene, 3 -ethyl- 1 -hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, 1,3 -butadiene, isoprene, piperylene, 2, 3-dimethyl-l, 3-butadiene, 1,4-pentadiene, 1,7-hexadiene, vinylcyclohexane, or any combination thereof.
• the olefin comonomer is selected from propylene, 1-butene, 2-butene, 3 -methyl- 1 -butene, 1-pentene, 2-
• Aspect 135. A method of making an olefin polymerization catalyst according to any one of Aspects 3, 6-68, or 83-126, wherein: a) the metallocene compound and the co-catalyst are contacted [1] for a time period from about 1 minute to about 24 hours or from about 1 minute to about 1 hour and [2] at a temperature from about 10°C to about 200°C or from about 15°C to about 80°C, to form a first mixture; followed by b) contacting the first mixture with the support-activator comprising a calcined smectite heteroadduct to form the catalyst composition.
• Aspect 136 A method of making an olefin polymerization catalyst according to any one of Aspects 3, 6-68, or 83-126, wherein the metallocene compound, the co-catalyst, and the support-activator comprising a calcined smectite heteroadduct are contacted [1] for a time period from about 1 minute to about 6 months or from about 1 minute to about 1 week and [2] at a temperature from about 10°C to about 200°C or from about 15°C to about 80°C, to form the olefin polymerization catalyst.
• 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 is prepared according to Aspect 137.

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• 2020
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