Process for preparing heat-treated supported aluminoxane in aliphatic solvent using solid aluminoxane

Abstract

The invention provides a method for preparing a supported single-site catalyst. The method includes forming a slurry comprising an inorganic oxide support, an organic solvent, and a solid aluminoxane activator; maintaining the temperature of the slurry at about 100 DEG C to about 200 DEG C for a period of time from about 0.5 hours to about 10 hours to form a supported aluminoxane slurry; and contacting the supported aluminoxane slurry with a single site catalyst component to form a supported single site catalyst. The organic solvent includes one or more branched aliphatic compounds having a boiling point of about 100 DEG C or more present in an amount of about 50% by weight or more relative to the total amount of the organic solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 320,993, filed on March 17, 2022, which is hereby incorporated by reference in its entirety for any and all purposes. Technical Field

[0003] The present technology generally relates to polyolefin catalyst systems. More specifically, the present technology relates to methods for preparing thermally treated supported aluminoxanes in aliphatic solvents. Background Art

[0004] Polyolefin is usually prepared by reacting olefin monomers in the presence of a catalyst, and the catalyst is composed of a carrier and a catalytic component deposited in the carrier pores and on the surface. For example, a type of polyolefin catalyst is a single-site catalyst (single-site catalyst), which usually includes a carrier, an activator and a single-site catalyst component, such as a metallocene component. Aluminoxane is usually used as an activator. Such catalysts are usually prepared by contacting methylaluminoxane (MAO) dissolved in toluene with a silica carrier in a toluene slurry to fix the aluminoxane activator on a silica carrier. For example, U.S. Patent number 5,856,255 describes such a method. Although solvent is usually removed from the resulting catalyst, it is difficult to remove all toluene, so the polymer produced by the resulting catalyst tends to contain some toluene.

[0005] Recently, there has been a push to produce polyolefins containing lower levels of aromatic compounds (e.g., toluene), especially in polyolefins intended for use in the food and beverage industry. Therefore, there is a need to produce supported single-site catalysts containing low amounts of toluene that can be used to produce polyolefins containing less residual toluene. The present disclosure meets this need by providing a method for preparing a thermally treated supported aluminoxane in an aliphatic solvent. Summary of the invention

[0006] In one aspect, a method for preparing a supported single-site catalyst is provided, the method comprising:

[0007] (a) forming a slurry comprising an inorganic oxide support, an organic solvent and a solid aluminoxane activator;

[0008] (b) maintaining the temperature of the slurry at about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry; and

[0009] (c) contacting the supported aluminoxane slurry with a single site catalyst component to form a supported single site catalyst;

[0010] The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is about 50 wt % or higher relative to the total amount of the organic solvent.

[0011] In some embodiments, the slurry in step (a) does not include any aromatic compounds. In some embodiments, the organic solvent comprising one or more branched aliphatic compounds comprises isoparaffins. In some embodiments, the organic solvent comprising one or more branched aliphatic compounds comprises one or more C7-C12 isoparaffins. In some embodiments, one or more C7-C12 isoparaffins are selected from one or more of C7-C10 isoparaffins and C9-C12 isoparaffins. In some embodiments, the organic solvent comprises mineral oil.

[0012] In some embodiments, the solid aluminoxane activator comprises methylaluminoxane. In some embodiments, the solid aluminoxane activator is obtained by solvent stripping, precipitation, heating and distillation to remove solvent and trimethylaluminum, or chemical treatment. In some embodiments, the total aluminum content of the solid aluminoxane activator is about 35 wt % to about 50 wt % based on the total weight of the solid aluminoxane activator.

[0013] In some embodiments, the method further comprises cooling the supported aluminoxane slurry to a temperature of about 50° C. or less before contacting the supported aluminoxane slurry with the single site catalyst component. In some embodiments, the method further comprises cooling the supported aluminoxane slurry to a temperature of about 25° C. before contacting the supported aluminoxane slurry with the single site catalyst component.

[0014] In some embodiments, the temperature of the slurry in step (b) is maintained at about 115° C. to about 155° C. In some embodiments, the temperature of the slurry in step (b) is maintained at about 120° C. or about 155° C.

[0015] In some embodiments, the organic solvent comprises one or more non-aromatic organic compounds having a boiling point higher than the maximum temperature reached by the slurry in an amount of about 50 wt % or more. In some embodiments, the organic solvent is present in an amount of about 60 wt % or more, about 70 wt % or more, about 75 wt % or more, about 80 wt % or more, about 90 wt % or more, or about 95 wt % or more.

[0016] In some embodiments, the method includes separating the supported aluminoxane from the organic solvent prior to contacting it with the single site catalyst component.

[0017] In some embodiments, the inorganic oxide support is heat treated (e.g., calcined). In some embodiments, the inorganic oxide support is dried. In some embodiments, the inorganic oxide support comprises silicon dioxide. In some embodiments, the inorganic oxide support comprises dried silicon dioxide. In some embodiments, the inorganic oxide support comprises silicon dioxide in an amount of about 50 wt % or more, about 60 wt % or more, about 80 wt % or more, about 90 wt % or more, or about 99 wt % or more.

[0018] In some embodiments, the single site catalyst component comprises a metallocene compound. In some embodiments, the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium or nickel. In some embodiments, the metallocene compound comprises titanium, zirconium or hafnium.

[0019] In some embodiments, the supported single site catalyst has a total residual solvent content of less than about 50 wt %. In some embodiments, the supported single site catalyst has a total residual solvent content of less than about 5 wt % or about 2 wt %. In some embodiments, the supported single site catalyst has a total residual aromatic solvent content of less than about 0.5 wt %.

[0020] In another aspect, there is provided a method for preparing a supported single-site catalyst, the method comprising:

[0021] (a) contacting an inorganic oxide support, an organic solvent, and a solid aluminoxane activator at a temperature of about 0° C. to about 50° C. to form a slurry;

[0022] (b) heating the slurry to a temperature of about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry;

[0023] (c) cooling the slurry to a temperature of about 0°C to about 50°C; and

[0024] (d) adding a single site catalyst component to a supported aluminoxane slurry to form a supported single site catalyst;

[0025] The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is about 50 wt % or higher relative to the total amount of the organic solvent.

[0026] In some embodiments, the inorganic oxide support is dried. In some embodiments, the inorganic oxide support is heat treated. In some embodiments, the supported single-site catalyst has a total residual solvent content of less than about 50% by weight. In some embodiments, the supported single-site catalyst has a total residual solvent content of less than about 5% by weight or about 2% by weight. In some embodiments, the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5% by weight. In some embodiments, the method further comprises contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin.

[0027] In another aspect, provided is a polyolefin produced by any of the methods described herein.

[0028] In another aspect, provided is a supported single site catalyst produced by any of the methods described herein.

[0029] In another aspect, a slurry is provided, comprising:

[0030] Inorganic oxide supports;

[0031] an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, present in an amount of about 50% by weight or higher relative to the total amount of the organic solvent; and

[0032] Solid aluminoxane activator.

[0033] In some embodiments, the slurry has a total residual solvent content of less than about 50 wt %. In some embodiments, the slurry has a total residual solvent content of less than about 5 wt % or about 2 wt %. In some embodiments, the slurry has a total residual aromatic solvent content of less than about 0.5 wt %.

[0034] Other features and aspects of the disclosure are discussed in more detail below. DETAILED DESCRIPTION

[0035] Various embodiments are described below. It should be noted that the specific embodiments are not intended to be exhaustive or limit the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be practiced with any other (one or more) embodiments.

[0036] As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If the usage of the term is unclear to one of ordinary skill in the art, "about" will mean up to plus or minus 10% of the particular term, taking into account the context in which it is used.

[0037] In the context of describing elements (especially in the context of the following claims), the use of the terms "a", "an", "the", and similar references should be interpreted as covering both the singular and the plural, unless otherwise specified herein or the context is clearly contradictory. Unless otherwise specified herein, the enumeration of numerical ranges herein is intended only as a shorthand method for individually citing each individual value within the range, and each individual value is incorporated into the specification as if it were individually listed herein. Unless otherwise specified herein or the context is clearly contradictory, all methods described herein can be performed in any suitable order. Unless otherwise specified, the use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the embodiments without limiting the scope of the claims. Any language in the specification should not be interpreted as indicating that any unclaimed element is required.

[0038] In general, alkyl, alkenyl, aryl or ether groups (e.g., alkyl groups) as defined below may be substituted, wherein one or more bonds to hydrogen atoms contained in the group are replaced by bonds to non-hydrogen atoms or non-carbon atoms. Substituted groups also include groups in which one or more bonds to carbon or hydrogen atoms are replaced by one or more bonds to heteroatoms (including double bonds or triple bonds). Therefore, unless otherwise indicated, substituted groups are substituted by one or more substituents. In some embodiments, substituted groups are substituted by 1, 2, 3, 4, 5 or 6 substituents. Examples of substituents include: halogen (i.e., F, Cl, Br, and I); hydroxy; alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy, heterocyclooxy, and heterocycloalkoxy; carbonyl (oxo); carboxyl; ester; carbamate; oxime; hydroxylamine; alkoxyamine; aralkyloxyamine; thiol; sulfide; sulfoxide; sulfone; sulfonyl; sulfonamide; amine; N-oxide; hydrazine; hydrazide; hydrazone; azide; amide; urea; amidine; guanidine; enamine; imide; isocyanate; isothiocyanate; cyanate; thiocyanate; imine; nitro; nitrile (i.e., CN); and the like.

[0039] As used herein, "alkyl" groups include straight and branched alkyl groups having 1 to about 20 carbon atoms, typically 1 to 12 carbons, or in some embodiments 1 to 8 carbon atoms. As used herein, "alkyl groups" include cycloalkyl groups as defined below. Alkyl groups can be substituted or unsubstituted. Alkyl groups can be substituted once or more times. Alkyl groups can be substituted twice or more times. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups. Examples of branched alkyl groups include but are not limited to isopropyl, sec-butyl, tert-butyl, neopentyl, isopentyl and 1-cyclopentyl-4-methylpentyl. Representative substituted alkyl groups can be substituted once or more by, for example, amino, sulfhydryl, hydroxyl, cyano, alkoxy and / or halogen groups (e.g., F, Cl, Br and I groups). As used herein, the term haloalkyl is an alkyl group with one or more halogen groups. In some embodiments, haloalkyl refers to perhaloalkyl.

[0040] Alkenyl groups are straight chain, branched or cyclic alkyl groups having 2 to about 20 carbon atoms and also including at least one double bond. In some embodiments, alkenyl groups have 1 to 12 carbons, or typically have 1 to 8 carbon atoms. Alkenyl groups can be substituted or unsubstituted. Alkenyl groups especially include, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl and hexadienyl groups. Alkenyl groups can be substituted similarly to alkyl groups. Divalent alkenyl groups (i.e., alkenyl groups having two points of attachment) include, but are not limited to, CH-CH=CH2, C=CH2, or C=CHCH3.

[0041] As used herein, an "aryl" or "aromatic" group is a cyclic aromatic hydrocarbon that does not contain heteroatoms. Aryl groups include monocyclic, bicyclic, and polycyclic ring systems. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptadenyl, biphenylene, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group. The term "aryl group" refers to a substituted or unsubstituted aryl group.

[0042] The term "alkylaryl" refers to an aryl group having an alkyl substituent. The term "arylalkyl" refers to an alkyl group having an aryl substituent.

[0043] In general, the present disclosure relates to a method for preparing a supported single site catalyst using a non-aromatic solvent (e.g., one or more branched aliphatic compounds having a boiling point of about 100° C. or higher). It was found that the aluminoxane activator can be sufficiently fixed on the inorganic oxide support using a slurry comprising a solid aluminoxane activator, an inorganic oxide support, and an organic solvent (comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or higher). The single site catalyst component can then be added to the supported aluminoxane to form a supported single site catalyst.

[0044] In one aspect, a method for preparing a supported single site catalyst comprises:

[0045] (a) forming a slurry comprising an inorganic oxide support, an organic solvent and a solid aluminoxane activator;

[0046] (b) maintaining the temperature of the slurry at about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry; and

[0047] (c) contacting the supported aluminoxane slurry with a single site catalyst component to form a supported single site catalyst;

[0048] The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is about 50 wt % or higher relative to the total amount of the organic solvent.

[0049] In another aspect, a method for preparing a supported single site catalyst comprises:

[0050] (a) contacting an inorganic oxide support, an organic solvent, and a solid aluminoxane activator at a temperature of about 0° C. to about 50° C. to form a slurry;

[0051] (b) heating the slurry to a temperature of about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry;

[0052] (c) cooling the slurry to a temperature of about 0°C to about 50°C; and

[0053] (d) adding a single site catalyst component to a supported aluminoxane slurry to form a supported single site catalyst;

[0054] The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is about 50 wt % or higher relative to the total amount of the organic solvent.

[0055] In another aspect, the slurry comprises:

[0056] Inorganic oxide supports;

[0057] an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, present in an amount of about 50% by weight or higher relative to the total amount of the organic solvent; and

[0058] Solid aluminoxane activator.

[0059] The single site catalyst may be formed in a single vessel or in a series of vessels. For example, in one embodiment, the supported aluminoxane is produced in one vessel and then transferred, either as a slurry or in separate form, to a second vessel where the single site catalyst component is added. In another embodiment, a "one pot process" is used where a supported aluminoxane slurry is formed and the single site catalyst component is added to the slurry in the same vessel used to form the slurry.

[0060] The carrier can be any suitable dried inorganic oxide. Such inorganic oxide carrier materials include Group IIA, Group IIIA, Group IVA or Group IVB metal oxides, such as silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica, alumina or silica-alumina are magnesium oxide, chromium oxide, titanium dioxide, zirconium oxide, etc. For example, inorganic oxides that can be used in the present invention include but are not limited to SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2 and double oxides thereof, such as SiO2-Al2O3, SiO2-MgO, SiO2iO2, SiO2-TiO2-MgO. In some embodiments, the inorganic oxide carrier is dried. In some embodiments, the inorganic oxide carrier includes silica (e.g., dried silica). In one embodiment, the support comprises silica in an amount of about 50 wt % or more, about 60 wt % or more, such as about 80 wt % or more, such as about 90 wt % or more, such as about 99 wt % or more.

[0061] The support can be any suitable inorganic oxide, which can be heat treated (e.g., calcined to remove any residual moisture). General conditions for calcination include calcining at a sufficient temperature and time to reduce the total volatiles to the desired amount, wherein the total volatiles are determined by measuring the weight loss (e.g., about 0.1 wt % and 8 wt %) when the sample is destructively calcined at 1000°C. In some embodiments, calcination can be performed by heating the support to a temperature of about 150°C to about 850°C, preferably about 200°C to about 700°C, for a period of time generally of about 1 minute to about 600 minutes (e.g., 50 minutes to 600 minutes), preferably about 50 minutes to about 300 minutes. The calcining atmosphere can be air or an inert gas. Calcination should be carried out under appropriate conditions to avoid sintering. Calcination can be carried out in a calcining furnace, which is selected from a rotary calcining furnace, a fixed bed furnace, and a multi-hearth furnace.

[0062] The specific particle size, surface area, pore size, pore volume, etc. of the support material can be selected as known in the art. For example, the particle size range can be from about 0.1 micron to 600 microns, and the surface area range can be about 50 m 2 / g to 1000m 2 / g, the pore size range can be about 50 angstroms to 500 angstroms, and the pore volume range can be about 0.3 cc / g to 5.0 cc / g.

[0063] Before forming a slurry with an organic solvent and an aluminoxane activator, the inorganic oxide support is dehydrated. For example, the support can be chemically dehydrated, or dehydrated by heating or calcining the support at a temperature and time sufficient to remove water. For example, drying or calcining the support is generally performed by heating the support to a temperature of about 100°C to about 1000°C, such as about 150°C to about 600°C, such as about 200°C to about 300°C, for a period of about 1 minute to about 100 hours, such as about 50 minutes to about 5 hours. The atmosphere during drying can be air or an inert gas. Other methods known in the art, such as azeotropic distillation, can also be used to effectively dehydrate the inorganic oxide support.

[0064] Aluminoxane activators may exist in the form of linear, cyclic, cage or polymeric structures, of which the simplest monomeric compounds are tetraalkylaluminoxanes, such as tetramethylaluminoxane (CH3)2AlOAl(CH3)2 or tetraethylaluminoxane (C2H5)2AlOAl(C2H5)2. Preferred compounds for olefin polymerization catalysts are oligomeric materials, sometimes referred to as polyalkylaluminoxanes, which typically contain from about 4 to 20 repeating units:

[0065]

[0066] Where R is C1-C 10 Although linear and cyclic aluminoxanes are generally considered to have the structure

[0067]

[0068] Where m and n are integers of 4 or greater, the exact configuration of the aluminoxane remains unknown.

[0069] Methylaluminoxane may contain some higher alkyl groups to improve its solubility. In addition to MAO, non-limiting examples of hydrocarbyl aluminoxanes for use in the present invention include ethyl aluminoxane (EAO), isobutyl aluminoxane (IBAO), n-propyl aluminoxane, n-octyl aluminoxane, etc. The hydrocarbyl aluminoxane may also contain up to about 20 mole percent (based on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, mercaptans, alkyl disiloxanes, etc. to improve activity, solubility and / or stability.

[0070] Solid aluminoxanes can be prepared in any manner known in the art. For example, one suitable method is by partial hydrolysis of a trialkylaluminum compound. The trialkylaluminum compound can be hydrolyzed by adding free water or a hydrous solid, which can be a hydrate or a porous material that has absorbed water. Since it is difficult to control the reaction by adding water itself even if the mixture is vigorously stirred, free water is usually added in the form of a solution or dispersion in an organic solvent. Suitable hydrates include salt hydrates such as CuSO4.5H2O, Al2(SO4)3.18H2O, FeSO4.7H2O, AlCl3.6H2O, Al(NO3)3.9H2O, MgSO4.7H2O, MgCl2.6H2O, ZnSO4.7H2O, Na2SO4.10H2O, Na3PO4.12H2O, LiBr.2H2O, LiCl.1H2O, LiI.2H2O, LiI.3H2O, KF.2H2O, NaBr.2H2O, etc., and alkali metal or alkaline earth metal hydroxide hydrates such as NaOH.H2O, NaOH.2H2O, Ba(OH)2.8H2O, KOH.2H2O, CsOH.1H2O, LiOH.1H2O, etc. A mixture of any of the above hydrates may be used. The molar ratio of free water or water in a hydrate or porous material (eg, alumina or silica) to the total alkylaluminum compound in the mixture can vary widely, for example, from about 2:1 to about 1:4, such as from about 4:3 to about 1:3.5.

[0071] About hydrolysis process, the method for preparing solid aluminoxane by alkylaluminum compound can include precipitation, heating and distillation to remove solvent and trimethylaluminum, and chemical treatment.These methods are described in U.S. Patent Nos. 6,255,419 and 6,518,445 and US2015 / 0376306, wherein the disclosure of solid aluminoxane is incorporated herein by reference.For example, a toluene solution of methylaluminoxane can be introduced into a glass reactor equipped with a stirring blade under a nitrogen atmosphere, and then an appropriate amount of nitrogen-substituted hexane is added dropwise at room temperature under stirring.Solid methylaluminoxane can then be filtered, washed with hexane and dried under reduced pressure.In other embodiments, solid aluminoxane can be prepared by reacting a solution comprising alkylaluminoxane, trialkylaluminum and hydrocarbon solvent with at least one organic compound containing elements of Groups 15-17 in the periodic table under heating conditions.

[0072] Solid aluminoxanes can also be prepared by non-hydrolytic methods, for example, by reacting an alkylaluminum compound with an organic compound having one or more oxygen-containing functional groups (e.g., carbonyl, carboxyl, and / or hydroxyl); examples of such compounds include PhCOMe, PhCOOH, PhCOOMe, Ph3COH, etc. Alternatively, the trialkylaluminum can be treated with carbon dioxide.

[0073] Such solid aluminoxanes can be prepared by precipitation methods as described in U.S. Pat. Nos. US 8,404,880, Chem. Mater. 2016, 28, 7444-7450, and Macromol. Chem. Phys. 2004, 205, 1394–1401, wherein the disclosure of solid aluminoxanes is incorporated herein by reference. In some embodiments, solid aluminoxanes are obtained by heating an aromatic hydrocarbon solution containing polyalkylaluminoxanes and trimethylaluminum to cause precipitation of a solid polyalkylaluminoxane composition. In some embodiments, solid aluminoxanes are obtained by controlled hydrolysis of trimethylaluminum (TMA) with benzoic acid, followed by pyrolysis.

[0074] In some embodiments, the solid aluminoxane activator comprises methylaluminoxane.In some embodiments, the solid aluminoxane activator is obtained by solvent stripping, precipitation, heating and distillation to remove solvent and trimethylaluminum, or chemical treatment as described above.

[0075] In some embodiments, the solid aluminoxane activator has a total aluminum content in the range of about 35 wt % to about 50 wt % or about 39 wt % to about 47 wt %, including about 35 wt %, about 36 wt %, about 37 wt %, about 38 wt %, about 39 wt %, about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt %, about 45 wt %, about 46 wt %, about 47 wt %, about 48 wt %, about 49 wt %, and about 50 wt %, based on the total weight of the solid aluminoxane activator.

[0076] In some embodiments, the solid aluminoxane activator is either free of trimethylaluminum or has a trimethylaluminum content of no more than about 30 mol%, including about 25 mol%, about 20 mol%, about 15 mol%, about 10 mol%, about 5 mol%, and about 1 mol%. In some embodiments, the solid aluminoxane activator has a trimethylaluminum content of no more than about 20 mol% of the total aluminum present in the solid aluminoxane activator.

[0077] The organic solvent used to form the slurry containing the support material and the aluminoxane activator (e.g., the slurry in step (a)) comprises one or more branched aliphatic hydrocarbon compounds having a boiling point of about 100°C or higher. Such hydrocarbon compounds may be saturated or unsaturated hydrocarbons having from about 7 to about 12 carbon atoms (e.g., isoparaffins). Suitable isoparaffins include, for example, C7-C12 isoparaffins, C7-C10 isoparaffins, C9-C12 isoparaffins, C10-C12 isoparaffins, and the isoparaffins sold under the trade name ISOPAR®. TM Those sold and manufactured by Exxon Mobil. ISOPAR TM Illustrative examples include ISOPARTM E (mixture of C7-C10 isoparaffins) and ISOPAR TM G (mixture of C9-C12 isoparaffins). Suitable branched hydrocarbons are isohexadecane, isododecane, 2,5-dimethyldecane, isotetradecane and combinations thereof. The organic solvent may also contain mineral oil. The slurry in step (a) is substantially free of any aromatic content or aromatic compounds.

[0078] The organic solvent generally contains one or more non-aromatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is greater than 50% by weight relative to the total amount of the organic solvent contained in the slurry formed by mixing the organic oxide support, the aluminoxane activator and the organic solvent. In some embodiments, the non-aromatic compound accounts for about 60% by weight or more of the organic solvent, such as about 70% by weight or more, such as about 80% by weight or more, such as about 90% by weight or more, relative to the total amount of the organic solvent contained in the slurry. In some embodiments, the non-aromatic compound accounts for about 60% by weight to about 100% by weight of the organic solvent, including about 70% by weight to about 100% by weight, about 80% by weight to about 100% by weight, about 90% by weight to about 100% by weight, relative to the total amount of the organic solvent contained in the slurry. In some embodiments, the slurry does not contain aromatic compounds.

[0079] The solvent typically contains very small amounts of contaminants, such as water and non-inert compounds. For example, in some embodiments, the solvent contains about 100 ppm or less, such as about 50 ppm or less, such as about 10 ppm or less of impurities, such as water, polar compounds, non-hydrocarbon compounds and other non-inert substances. In this regard, in some embodiments, the solvent is purged of air and purified prior to use in preparing a slurry as described herein.

[0080] The single site catalyst component may comprise any transition metal or metallocene single site catalyst known in the art. For example, the single site catalyst may include "half sandwich" and "full sandwich" compounds having one or more Cp ligands (cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl) bonded to at least one Group 3 to Group 12 metal atom and one or more leaving groups bonded to at least one metal atom.

[0081] The Cp ligand is one or more rings or (one or more) ring systems, at least a portion of which includes a π-bonded system, such as cyclodienyl ligands and heterocyclic analogs. The (one or more) rings or (one or more) ring systems typically contain atoms selected from Groups 13 to 16 atoms, and in some embodiments, the atoms constituting the Cp ligand are selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, wherein carbon constitutes at least 50% of the ring members. For example, the (one or more) Cp ligands can be selected from substituted and unsubstituted cyclopentadienyl ligands and ligands isomorphous to cyclopentadienyl. Non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthryl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthroindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthracenyl, thienoindenyl, thienofluorenyl, hydrogenated forms thereof (e.g., 4,5,6,7-tetrahydroindenyl or "H4Ind"), substituted forms thereof (as discussed and described in more detail below), and heterocyclic forms thereof.

[0082] The metal atom "M" of the single-center compound can be selected from atoms of Groups 3 to 12 and lanthanide atoms; or can be selected from atoms of Groups 3 to 10; or can be selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir and Ni; or can be selected from atoms of Groups 4, 5, and 6; or can be Ti, Zr, or Hf atoms; or can be Hf; or can be Zr. The oxidation state of the metal atom "M" can be 0 to +7; or can be +1, +2, +3, +4 or +5; or can be +2, +3 or +4. The group bonded to the metal atom "M" makes the compounds and structures described in the structures below electrically neutral unless otherwise stated. (One or more) Cp ligands form at least one chemical bond with the metal atom M to form a "metallocene catalyst component". The difference between the Cp ligand and the leaving group bonded to the metal atom M is that they are very resistant to substitution / abstraction reactions.

[0083] In some embodiments, the single site catalyst component comprises a metallocene compound. In some embodiments, the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium or nickel. In some embodiments, the metallocene compound comprises titanium, zirconium or hafnium.

[0084] In one embodiment, the single site catalyst may be represented by the formula:

[0085] (C5R x ) y R′ z (C5Rm )MQ n-y-1

[0086] in:

[0087] M is a metal from Group IIIB to Group VIII of the Periodic Table; (C5R x ) and (C5R m ) are the same or different cyclopentadienyl or substituted cyclopentadienyl groups bonded to M;

[0088] R are the same or different and are hydrogen or a hydrocarbyl group, such as an alkyl, alkenyl, aryl, alkaryl or aralkyl group, containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a C4-C6 ring;

[0089] R' is a C1-C4 substituted or unsubstituted alkylene group, a dialkyl or diaryl germanium or silicon, or a bridged group of two (C5R x ) and (C5R m ) an alkylphosphine or arylphosphine or alkylamine or arylamine group of the ring;

[0090] Q is a hydrocarbon radical having 1 to 20 carbon atoms, such as an aryl, alkyl, alkenyl, alkaryl or aralkyl radical, a hydrocarboxy radical having 1 to 20 carbon atoms or a halogen, and may be the same as or different from each other;

[0091] z is 0 or 1;

[0092] y is 0, 1, or 2;

[0093] When y is 0, z is 0;

[0094] n is 0, 1, 2, 3 or 4, depending on the valence of M, and

[0095] ny≥1.

[0096] Illustrative but non-limiting examples of the metallocenes represented by the above formula are dialkyl metallocenes such as bis(cyclopentadienyl)dimethyltitanium, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dimethylhafnium and bis(cyclopentadienyl)diphenylhafnium, bis(cyclopentadienyl)dineopentyltitanium, bis(cyclopentadienyl)dineopentylzirconium, bis(cyclopentadienyl)dibenzyltitanium, bis(cyclopentadienyl)dibenzylzirconium, bis(cyclopentadienyl)dimethylvanadium; monoalkyl metallocenes such as bis(cyclopentadienyl)methyltitanium chloride, bis(cyclopentadienyl)ethyltitanium chloride, bis(cyclopentadienyl)phenyltitanium chloride, bis(cyclopentadienyl)diphenyl cyclopentadienyl) methyl zirconium chloride, bis(cyclopentadienyl) ethyl zirconium chloride, bis(cyclopentadienyl) phenyl zirconium chloride, bis(cyclopentadienyl) methyl titanium bromide; trialkyl metallocenes, such as cyclopentadienyl trimethyl titanium, cyclopentadienyl triphenyl zirconium, cyclopentadienyl trineopentyl zirconium, cyclopentadienyl trimethyl zirconium, cyclopentadienyl triphenyl hafnium, cyclopentadienyl trineopentyl hafnium, cyclopentadienyl trimethyl hafnium; monocyclopentadienyl titanocenes, such as pentamethyl cyclopentadienyl titanium trichloride, pentaethyl cyclopentadienyl titanium trichloride; bis(pentamethyl cyclopentadienyl) diphenyl titanium, carbene represented by the formula bis(cyclopentadienyl) titanium=CH2 and derivatives of such reagents; substituted bis(cyclopentadienyl) titanium ( IV) compounds, for example: bis(indenyl)diphenyltitanium or bis(indenyl)titanium dichloride, bis(methylcyclopentadienyl)diphenyltitanium or bis(methylcyclopentadienyl)titanium dihalide; dialkyl, trialkyl, tetraalkyl and pentaalkylcyclopentadienyltitanium compounds, for example bis(1,2-dimethylcyclopentadienyl)diphenyltitanium or bis(1,2-dimethylcyclopentadienyl)titanium dichloride, bis(1,2-diethylcyclopentadienyl)diphenyltitanium or bis(1,2-diethylcyclopentadienyl)titanium dichloride; silicon-, phosphine-, amine- or carbon-bridged cyclopentadiene complexes, for example dimethylsilyldicyclopentadienyltitanium or dimethylsilyldicyclopentadienyltitanium dichloride, methylphosphinedicyclopentadienyltitanium diphenyltitanium or methylphosphine dicyclopentadienyltitanium dichloride, methylene dicyclopentadienyl diphenyltitanium or methylene dicyclopentadienyltitanium dichloride and other dihalide complexes, and bridged metallocene compounds, such as isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di-tert-butylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, di-tert-butylmethylene(cyclopentadienyl)(fluorenyl) )Hafnium dichloride, cyclohexylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diisopropylmethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, diisopropylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, diisobutyl Methylene (cyclopentadienyl) (fluorenyl) titanium dichloride, di-tert-butyl methylene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexyl (cyclopentadienyl) (fluorenyl) titanium dichloride, diisopropyl methylene (2,5-dimethylcyclopentadienylfluorenyl) titanium dichloride, racemic-ethylene bis (1-indenyl) zirconium (IV) dichloride, racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) zirconium (IV) dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanyl (silanylene) bis (1-indenyl) 1-Indenyltetramethylcyclopentadienyl)zirconium (IV) dichloride, 1,1,2,2-tetramethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, 1-Indenyltetramethylcyclopentadienyl)zirconium (IV) dichloride, 1-Dimethylsilylbis(2-methyl-4-tert-butyl-1-cyclopentadienyl)zirconium (IV) dichloride, 1,1,2,2-tetramethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, 1,1,2,2-tetramethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, 1-Dimethylsilylbis(2-methyl-4-tert-butyl-1-cyclopentadienyl)zirconium (IV) dichloride, 1,1,2,2-tetramethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, 1,1,2,2-tetramethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, 1,1,2,2-tetramethylsilylbis( 1,1,2,2-tetramethylsilylenebis(1-indenyl)hafnium(IV)dichloride, 1,1,2,2-tetramethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, ethylene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride, ethylenebis(1-indenyl)titanium(IV)dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, 1,1,2,2-tetramethylsilylenebis(1-indenyl)titanium(IV)dichloride, 1,1,2,2-tetramethylsilylenebis(4,5,6,7-tetrahydro- ...2-Tetramethylsilylenebis(1-indenyl)titanium(IV) dichloride, racemic-1,1,2,2-tetramethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride and ethylene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV) dichloride.

[0097] Single site catalyst components are described, for example, in U.S. Pat. Nos. 2,864,843; 2,983,740; 4,665,046; 4,874,880; 4,892,851; 4,931,417; 4,952,713; 5,017,714; 5,026,798; 5,036,034; 5,064,802; 5,081,231; 5,145,81 9; 5,162,278; 5,245,019; 5,268,495; 5,276,208; 5,304,523; 5,324,800; 5,329,031: 5,329,033; 5,330,948; 5,347,025; 5,347,026; and 5,347,752, the teachings of which are incorporated herein by reference.

[0098] In order to form a single site catalyst, a slurry comprising a carrier, aluminoxane and an organic solvent is formed. For example, in one embodiment, a dried inorganic oxide carrier is mixed with a portion of an organic solvent to form a slurry. Any suitable mixing means can be used to form a slurry in any suitable container. For example, in one embodiment, the container can be equipped with a condenser and an agitator or impeller. The container can be an open or closed reactor. Aluminoxane can then be added to the slurry. For example, in one embodiment, aluminoxane is added in the form of a solution in an organic solvent to form a slurry comprising a carrier, aluminoxane and an organic solvent. In such an embodiment, the total organic solvent comprises an organic solvent for slurrying the carrier and an organic solvent added with the aluminoxane.

[0099] In one embodiment, the weight ratio of the aluminoxane added to the support is from about 0.5: 1 to about 5: 1, such as from about 1: 1 to about 3: 1, such as from about 2: 1 to about 2.5: 1. It is worth noting that if the aluminoxane is dissolved in an aromatic solvent, the amount added should not be such that the resulting organic solvent contains more than 50 weight percent aromatic compounds after addition.

[0100] It has been found that in order to adequately fix the aluminoxane activator on the support, the temperature of the slurry in step (b) must be maintained at about 100°C or higher for a sufficient period of time. Thus, in one embodiment, the temperature of the slurry is raised to a temperature of about 100°C or higher, such as about 110°C or higher, such as about 120°C or higher, such as about 130°C or higher, such as about 140°C, such as about 150°C or higher. Typically, the temperature is maintained below about 200°C. In some embodiments, the temperature of the slurry in step (b) is maintained at about 100° C. to about 200° C. or about 115° C. to about 155° C., including about 100° C., about 105° C., about 110° C., 115° C., about 120° C., about 125° C., about 130° C., about 135° C., about 140° C., about 145° C., about 150° C., about 155° C., about 160° C., about 165° C., about 170° C., about 175° C., about 180° C., about 190° C., about 195° C., or about 200° C. In some embodiments, the temperature of the slurry in step (b) is maintained at about 120° C. or about 155° C. In some embodiments, the temperature of the slurry in step (b) is maintained at about 100°C to about 200°C, including about 110°C to about 200°C, about 120°C to about 200°C, about 130°C to about 200°C, about 140°C to about 200°C, about 150°C to about 200°C. However, depending on the pressure of the solvent and the reactor, the temperature may be greater than about 200°C. The temperature can be maintained for a period of about 0.5 hours to about 10 hours, such as about 2 hours to about 6 hours, to form a supported aluminoxane slurry. In some embodiments, the period is about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, about 6 hours, about 6.5 hours, about 7 hours, about 7.5 hours, about 8 hours, about 8.5 hours, about 9 hours, about 9.5 hours, or about 10 hours. In one embodiment, the temperature of the slurry remains below the boiling point of the organic solvent. In one embodiment, in the whole process, the pressure remains on about 130kPa or lower, for example, about 90kPa to about 130kPa or about 90kPa to about 110kPa. In one embodiment, in the whole process, the pressure remains on about 90kPa, about 95kPa, about 100kPa, about 105kPa, about 110kPa, about 115kPa, about 120kPa, about 125kPa or about 130kPa. However, in some embodiments, when using a closed reactor system, the pressure can be increased to higher than 130kPa, and reach a temperature higher than the boiling point of the solvent under atmospheric pressure.

[0101] After forming the supported aluminoxane slurry, the slurry can be cooled to a temperature of about 50° C. or less, such as about 15° C. to about 50° C. or about 15° C. to about 30° C. In some embodiments, the slurry is cooled to a temperature of about 50° C., about 45° C., about 40° C., about 35° C., about 30° C., about 25° C., about 20° C., about 15° C., about 10° C., or about 5° C. to about 30° C. For example, in one embodiment, the slurry is allowed to gradually cool back to room temperature.

[0102] After the supported aluminoxane slurry is formed, it is contacted with a single site catalyst component to form a supported single site catalyst. The single site catalyst component may be supported on the supported aluminoxane in any manner known in the art.

[0103] In one embodiment, for example, the slurry may be separated from the organic solvent, optionally stored, and then combined with the single site catalyst component. In another embodiment, the slurry may be combined with the single site catalyst component in a separate container. Alternatively, in another embodiment, a "one pot process" may be used, wherein, after cooling the slurry, the single site catalyst component is added to the supported aluminoxane slurry in the same container in which the slurry is formed.

[0104] In any such embodiment, the single site catalyst component can be added to the supported aluminoxane as a solution in a solvent (e.g., toluene). The mixture of the single site catalyst component and the supported aluminoxane can then be mixed, for example, by stirring for a period of time sufficient to load the catalyst component onto the support. For example, the single site catalyst component can be added to the supported aluminoxane in the form of a slurry and stirred at a temperature of about 0° C. to about 50° C., for example, about 15° C. to about 30° C., for a period of time of about 5 minutes to about 5 hours, for example, about 1 hour to about 3 hours.

[0105] In addition, in some embodiments, the single-site catalyst component can be treated prior to combination with the supported aluminoxane. For example, pretreatment can include treating the single-site catalyst component with Al-alkyls, Mg-alkyls, Zn-alkyls, other main group alkyls (e.g., TEA, TIBA, MgBu2, ZnEt2), borates, olefins, Lewis bases, or any combination thereof as known in the art.

[0106] In one embodiment, the weight ratio of the catalyst components added to the supported aluminoxane is from about 1:25 to about 1:200, such as from about 1:50 to about 1:100, such as from about 1:60 to about 1:90.

[0107] The resulting solid single site catalyst may then be separated from the solvent by any suitable means, such as by filtration and washing in a non-aromatic organic liquid, and then dried, such as by vacuum drying.

[0108] In some embodiments, the total residual solvent content of the solid single-site catalyst is less than about 50% by weight, including less than about 40% by weight, less than about 30% by weight, less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight. In some embodiments, the total residual solvent content of the solid single-site catalyst is less than about 5% by weight or less than about 2% by weight. In some embodiments, the total residual solvent content of the solid single-site catalyst is from about 0% by weight to about 50% by weight, from about 0% by weight to about 5% by weight, from about 0% by weight to about 2% by weight, from about 0% by weight to about 1% by weight. In some embodiments, the total residual solvent content of the solid single-site catalyst is from about 0.1% by weight to about 50% by weight, from about 0.1% by weight to about 5% by weight, from about 0.1% by weight to about 2% by weight, from about 0.1% by weight to about 1% by weight, from about 0.1% by weight to about 0.5% by weight. In some embodiments, the total residual solvent content of the solid single site catalyst is from about 0.01 wt % to about 50 wt %, from about 0.01 wt % to about 5 wt %, from about 0.01 wt % to about 2 wt %, from about 0.01 wt % to about 1 wt %, from about 0.01 wt % to about 0.5 wt %, from about 0.01 wt % to about 0.1 wt %.

[0109] In some embodiments, the total residual solvent content includes residual isohexane content. In some embodiments, the total residual solvent content includes total residual aromatic solvent content (e.g., residual toluene content). In some embodiments, the total residual solvent content includes residual isohexane content. In some embodiments, the total residual solvent content includes total residual aromatic solvent content (e.g., residual toluene content).

[0110] In some embodiments, the total residual aromatic solvent content (e.g., toluene solvent content) of the solid single-site catalyst is less than about 50% by weight, including less than about 40% by weight, less than about 30% by weight, less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.01% by weight. In some embodiments, the total residual aromatic solvent content (e.g., toluene solvent content) of the solid single-site catalyst is less than about 0.5% by weight. In some embodiments, the total residual aromatic solvent content of the solid single-site catalyst is from about 0% by weight to about 50% by weight, from about 0% by weight to about 5% by weight, from about 0% by weight to about 2% by weight, from about 0% by weight to about 1% by weight. In some embodiments, the total residual aromatic solvent content of the solid single site catalyst is from about 0.1 wt % to about 50 wt %, from about 0.1 wt % to about 5 wt %, from about 0.1 wt % to about 2 wt %, from about 0.1 wt % to about 1 wt %, from about 0.1 wt % to about 0.5 wt %. In some embodiments, the total residual aromatic solvent content of the solid single site catalyst is from about 0.01 wt % to about 50 wt %, from about 0.01 wt % to about 5 wt %, from about 0.01 wt % to about 2 wt %, from about 0.01 wt % to about 1 wt %, from about 0.01 wt % to about 0.5 wt %, from about 0.01 wt % to about 0.1 wt %.

[0111] In some embodiments, the solid single site catalyst has a residual isohexane content of less than about 50% by weight, including less than about 40% by weight, less than about 30% by weight, less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.01% by weight. In some embodiments, the solid single site catalyst has a residual isohexane content of less than about 0.5% by weight. In some embodiments, the solid single site catalyst has a residual isohexane content of about 0% by weight to about 50% by weight, about 0% by weight to about 5% by weight, about 0% by weight to about 2% by weight, about 0% by weight to about 1% by weight. In some embodiments, the solid single site catalyst has a residual isohexane content of about 0.1 wt % to about 50 wt %, about 0.1 wt % to about 5 wt %, about 0.1 wt % to about 2 wt %, about 0.1 wt % to about 1 wt %, about 0.1 wt % to about 0.5 wt %. In some embodiments, the solid single site catalyst has a residual isohexane content of about 0.01 wt % to about 50 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 2 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, about 0.01 wt % to about 0.1 wt %.

[0112] In another aspect, a polyolefin prepared by any of the methods described herein is provided. Specifically, the obtained supported solid single-site catalyst can also be contacted with an olefin monomer to prepare the polyolefin. Suitable monomers include, but are not limited to, substituted or unsubstituted C2 to C 40 α-olefins, including C2 to C 20 α-olefins and C2 to C 12 α-olefins, and may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In some embodiments, the monomers include optional (one or more) comonomers, the comonomers including ethylene or C4 to C 40 Olefins, C4 to C 20 Olefins, C6 to C 12 The comonomer may be (i) linear, branched or cyclic and / or (ii) strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0113] The invention thus summarized will be more readily understood by reference to the following examples which are provided for illustration only and are not intended to be limiting of the invention.

[0114] Example

[0115] The catalyst described below is prepared by fixing methylaluminoxane and metallocene catalyst components (e.g., bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride and racemic-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride) on dehydrated silica having a nominal size, surface area, and pore volume of 33 μm, 280 μm, and 10 μm, respectively. 2 After forming each catalyst, the relative productivity was obtained using the same polymerization test conditions for each catalyst.

[0116] A typical ethylene polymerization process is as follows: a 4-L elevated autoclave is charged with isobutane (900 g), 1-hexene (28 g), TIBA (0.5 mL of a 20% solution in isohexane), a catalyst (0.025 g), and ethylene (125 psi). The contents are stirred at 800 RPM using a marine impeller. The polymerization temperature is 85° C. The polymerization time is 1 hour. After 1 hour of run time, the reactor is vented and cooled, and the resin is then collected. The resin is obtained after vacuum drying at 65° C. The catalyst activity (g polymer / g catalyst / hour) is determined by dividing the amount of polymer produced by the amount of catalyst added.

[0117] A typical propylene polymerization process is as follows: a 4-L elevated autoclave is charged with propylene (1030 g), hydrogen (50 mg), TIBA (0.5 mL 20% isohexane solution) and catalyst (0.005 g). The contents are stirred at 800 RPM using a marine impeller. The polymerization temperature is 70° C. The polymerization time is 1 hour. After 1 hour of run time, the reactor is vented and cooled, and then the resin is collected. The resin is obtained after vacuum drying at 65° C. The catalyst activity (g polymer / g catalyst / hour) is determined by dividing the amount of the prepared polymer by the amount of the added catalyst.

[0118] Comparative Example A (One Pot Method)

[0119] Formation of supported aluminoxane slurry and catalyst

[0120] In a 250mL three-necked flask equipped with an overhead stirring arm and a condenser, dehydrated silica (6.6g) was slurried in toluene (57.6g). Solid MAO (5.3g) was loaded and stirred at room temperature for 30 minutes. The internal temperature was raised to 120°C and the reaction was maintained for 4 hours. The "sMAO slurry" was cooled back to ambient temperature. Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.23g) was added and stirred for 2 hours. The solid was collected on a coarse sintered disc filter and washed with 1×20mL toluene and 3×20mL isohexane. The solid was dried under vacuum until the mass was constant.

[0121] Polymerization was carried out according to the above method. The average polymer productivity was 6,023 g / g catalyst / hour.

[0122] Example 1

[0123] Formation of supported aluminoxane slurry

[0124] In a 250 mL three-necked flask equipped with an overhead stirring arm and a condenser, dehydrated silica (6.6 g) was stirred in an ISOPAR TM G (42.5 g) was slurried. Solid MAO (4.5 g) was charged and the reaction mixture was stirred at room temperature for 30 minutes. The internal temperature was raised to 120°C and the reaction was maintained for 4 hours. The "sMAO slurry" was cooled back to ambient temperature.

[0125] Formation of Catalyst 1

[0126] Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.05 g) was added to an aliquot of the sMAO slurry (14.7 g, 15.8 wt% solids) and stirred for 2 hours. The solids were collected on a coarse sintered disc filter and washed with 1×20 mL Isopar G and 3×20 mL isohexane. The solids were dried under vacuum until the mass was constant (0.03 wt% residual toluene, 1.66 wt% residual isohexane).

[0127] Polymerization was carried out according to the above method. The average polymer productivity was 5,769 g / g catalyst / hour.

[0128] Formation of Catalyst 2

[0129] rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride (0.04 g) was added to an aliquot of the sMAO slurry (16.3 g, 15.8 wt% solids) and stirred for 2 hours. The solids were collected on a coarse sintered disk filter and filtered with 1×20 mL ISOPAR TM G and 3 x 20 mL isohexane. The solid was dried under vacuum until the mass was constant.

[0130] The polymerization was carried out according to the above-mentioned method for polymerizing propylene. The average polymer productivity was 20,044 g / g catalyst / hour.

[0131] Example 2

[0132] Formation of supported aluminoxane slurry and catalyst 3

[0133] In a 250 mL three-necked flask equipped with an overhead stirring arm and a condenser, dehydrated silica (5.0 g) was stirred in an ISOPAR TMG (37.7 g). Charge solid MAO (4.0 g) and stir at room temperature for 30 minutes. Raise the internal temperature to 150°C and maintain the reaction for 4 hours. Cool the "sMAO slurry" back to ambient temperature. Add bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.18 g) and stir for 2 hours. Collect the solid on a coarse sintered disk filter and filter with 1×20 mL ISOPAR TM G and 3 x 20 mL isohexane washes. The solid was dried under vacuum until the mass was constant (0.13 wt% residual toluene, 1.62 wt% residual isohexane).

[0134] The polymerization was carried out according to the above method. The average polymer productivity was 4,839 g / g catalyst / hour.

[0135] Example 3

[0136] Formation of supported aluminoxane slurry and catalyst 4

[0137] In a 250mL three-necked flask equipped with an overhead stirring arm and a condenser, dehydrated silica (4.1g) was slurried in methylcyclohexane (40.4g). Solid MAO (3.3g) was loaded and stirred at room temperature for 30 minutes. The internal temperature was raised to 100°C and the reaction was maintained for 4 hours. The "sMAO slurry" was cooled back to ambient temperature. Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.15g) was added and stirred for 2 hours. The solid was collected on a coarse sintered disc filter and washed with 1×20mL methylcyclohexane and 3×20mL isohexane. The solid was dried under vacuum until the mass was constant (0.28 wt% residual toluene, 1.85 wt% residual isohexane).

[0138] Polymerization was carried out according to the above method. The average polymer productivity was 6,057 g / g catalyst / hour.

[0139] Paragraph 1. A method for preparing a supported single-site catalyst, the method comprising:

[0140] (a) forming a slurry comprising an inorganic oxide support, an organic solvent and a solid aluminoxane activator;

[0141] (b) maintaining the temperature of the slurry at about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry; and

[0142] (c) contacting the supported aluminoxane slurry with a single site catalyst component to form a supported single site catalyst;

[0143] The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is about 50 wt % or higher relative to the total amount of the organic solvent.

[0144] Paragraph 2. The process according to paragraph 1, wherein the slurry in step (a) does not contain any aromatic compounds.

[0145] Paragraph 3. The method according to any one of paragraphs 1 to 2, wherein the organic solvent comprising one or more branched aliphatic compounds comprises an isoparaffin.

[0146] Paragraph 4. The method according to any one of paragraphs 1 to 3, wherein the organic solvent comprising one or more branched aliphatic compounds comprises one or more C7-C12 isoparaffins.

[0147] Paragraph 5. The method according to paragraph 4, wherein the one or more C7-C12 isoparaffins are selected from one or more of C7-C10 isoparaffins and C9-C12 isoparaffins.

[0148] Paragraph 6. The method according to any one of paragraphs 1 to 5, wherein the organic solvent comprises mineral oil.

[0149] Paragraph 7. The method according to any of the preceding paragraphs, wherein the solid aluminoxane activator comprises methylaluminoxane.

[0150] Paragraph 8. The method according to Paragraph 7, wherein the solid aluminoxane activator is obtained by solvent stripping, precipitation, heating and distillation to remove solvent and trimethylaluminum, or chemical treatment.

[0151] Paragraph 9. The method according to any of paragraphs 7 to 8, wherein the total aluminum content of the solid aluminoxane activator is from about 35 wt % to about 50 wt % based on the total weight of the solid aluminoxane activator.

[0152] Paragraph 10. The method according to any of the preceding paragraphs, further comprising cooling the supported aluminoxane slurry to a temperature of about 50°C or less before contacting the supported aluminoxane slurry with the single site catalyst component.

[0153] Paragraph 11. The method according to any of the preceding paragraphs, further comprising cooling the supported aluminoxane slurry to a temperature of about 25°C prior to contacting the supported aluminoxane slurry with the single site catalyst component.

[0154] Paragraph 12. The method according to any of the preceding paragraphs, wherein the temperature of the slurry in step (b) is maintained at about 115°C to about 155°C.

[0155] Paragraph 13. The method according to paragraph 12, wherein the temperature of the slurry in step (b) is maintained at about 120°C or about 155°C.

[0156] Paragraph 14. The method according to any of the preceding paragraphs, wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point higher than the maximum temperature reached by the slurry in an amount of about 50 wt % or greater.

[0157] Paragraph 15. A method according to any of the preceding paragraphs, wherein the organic solvent is present in an amount of about 60 weight % or greater, about 70 weight % or greater, about 75 weight % or greater, about 80 weight % or greater, about 90 weight % or greater, or about 95 weight % or greater.

[0158] Paragraph 16. The process according to any of the preceding paragraphs, wherein the process comprises separating the supported aluminoxane from the organic solvent prior to contacting the supported aluminoxane with the single site catalyst component.

[0159] Paragraph 17. The method according to any of the preceding paragraphs, wherein the inorganic oxide support comprises silica.

[0160] Paragraph 18. The method according to paragraph 17, wherein the inorganic oxide support comprises dried silica.

[0161] Paragraph 19. A method according to any of the preceding paragraphs 17 to 18, wherein the inorganic oxide support comprises silica in an amount of about 50 wt % or more, about 60 wt % or more, about 80 wt % or more, about 90 wt % or more, or about 99 wt % or more.

[0162] Paragraph 20. The method according to any of the preceding paragraphs, wherein the single site catalyst component comprises a metallocene compound.

[0163] Paragraph 21. The method of paragraph 20, wherein the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel.

[0164] Paragraph 22. The method according to paragraph 21, wherein the metallocene compound comprises titanium, zirconium, or hafnium.

[0165] Paragraph 23. The process according to any of the preceding paragraphs, wherein the supported single site catalyst has a total residual solvent content of less than about 50 wt%.

[0166] Paragraph 24. The process according to paragraph 23, wherein the supported single site catalyst has a total residual solvent content of less than about 5 wt % or about 2 wt %.

[0167] Paragraph 25. The process according to any of the preceding paragraphs, wherein the supported single site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%.

[0168] Paragraph 26. A method for preparing a supported single-site catalyst, the method comprising:

[0169] (a) contacting an inorganic oxide support, an organic solvent, and a solid aluminoxane activator at a temperature of about 0° C. to about 50° C. to form a slurry;

[0170] (b) heating the slurry to a temperature of about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry;

[0171] (c) cooling the slurry to a temperature of about 0°C to about 50°C; and

[0172] (d) adding a single site catalyst component to a supported aluminoxane slurry to form a supported single site catalyst;

[0173] The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount thereof is about 50 wt % or higher relative to the total amount of the organic solvent.

[0174] Paragraph 27. The method according to paragraph 26, wherein the inorganic oxide support is heat treated.

[0175] Paragraph 28. The process according to any of paragraphs 26 to 27, wherein the supported single site catalyst has a total residual solvent content of less than about 50 wt%.

[0176] Paragraph 29. The process according to paragraph 28, wherein the supported single site catalyst has a total residual solvent content of less than about 5 wt % or about 2 wt %.

[0177] Paragraph 30. The process according to any of paragraphs 26 to 29, wherein the supported single site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%.

[0178] Paragraph 31. The process of any of paragraphs 26 to 30, further comprising contacting the supported single site catalyst with an olefin monomer to produce a polyolefin.

[0179] Paragraph 32. A polyolefin produced by the method according to Paragraph 31.

[0180] Paragraph 33. A supported single site catalyst produced by the process according to any one of Paragraphs 1 to 31.

[0181] Paragraph 34. A slurry comprising:

[0182] Inorganic oxide supports;

[0183] an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, present in an amount of about 50% by weight or higher relative to the total amount of the organic solvent; and

[0184] Solid aluminoxane activator.

[0185] Paragraph 35. The method of paragraph 34, wherein the slurry has a total residual solvent content of less than about 50 wt%.

[0186] Paragraph 36. The method of paragraph 35, wherein the slurry has a total residual solvent content of less than about 5 wt % or about 2 wt %.

[0187] Paragraph 37. The method of any of paragraphs 34 to 36, wherein the slurry has a total residual aromatic solvent content of less than about 0.5 wt%.

[0188] While certain embodiments have been illustrated and described, it will be appreciated that changes and modifications may be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined by the following claims.

[0189] The embodiments exemplarily described herein may be appropriately implemented in the absence of any one or more elements, one or more limitations not specifically disclosed herein. Therefore, for example, the terms "comprise", "include", "contain", etc. should be widely understood and unrestricted. In addition, the terms and expressions used herein have been used as descriptive terms rather than limiting terms, and the use of such terms and expressions is not intended to exclude any equivalents of the features shown and described or parts thereof, but it should be recognized that various modifications can be made within the scope of the claimed technology. In addition, the phrase "essentially consisting of..." should be understood to include those elements specifically enumerated and those additional elements that will not have a substantial impact on the basic features and novel features of the claimed technology. The phrase "consisting of..." excludes any unspecified elements.

[0190] The present disclosure is not limited to the specific embodiments described in this application. It will be appreciated by those skilled in the art that many modifications and variations may be made without departing from its spirit and scope. In addition to those listed herein, those skilled in the art will appreciate from the foregoing description that functionally equivalent methods and compositions within the scope of the present disclosure. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is limited only by the terms of the appended claims and the full range of equivalents enjoyed by such claims. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds, compositions or biological systems, which may of course vary. It should also be understood that the terms used herein are only used to describe specific embodiments and are not intended to be limiting.

[0191] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0192] Those skilled in the art will appreciate that, for any and all purposes, particularly in providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily understood to fully describe and be able to decompose the same range into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be easily decomposed into a lower third, a middle third, and an upper third, etc. Those skilled in the art will also appreciate that all language, such as "at most," "at least," "greater than," "less than," etc., includes the numbers listed and refers to a range that can be subsequently decomposed into subranges as discussed above. Finally, those skilled in the art will appreciate that a range includes each individual member.

[0193] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference, as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

[0194] Other embodiments are set forth in the following claims.

Claims

1. A method for preparing a supported single-site catalyst, the method comprising: (a) forming a slurry comprising an inorganic oxide support, an organic solvent and a solid aluminoxane activator; (b) maintaining the temperature of the slurry at about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry; and (c) contacting the supported aluminoxane slurry with a single site catalyst component to form a supported single site catalyst; The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount of the branched aliphatic compounds is about 50 wt % or higher relative to the total amount of the organic solvent.

2. The process according to claim 1, wherein the slurry in step (a) does not contain any aromatic compounds.

3. The method according to any one of claims 1 to 2, wherein the organic solvent comprising one or more branched aliphatic compounds comprises an isoparaffin.

4. The method according to any one of claims 1 to 3, wherein the organic solvent comprising one or more branched aliphatic compounds comprises one or more C7-C12 isoparaffins.

5. The method according to claim 4, wherein the one or more C7-C12 isoparaffins are selected from one or more of C7-C10 isoparaffins and C9-C12 isoparaffins.

6. The method according to any one of claims 1 to 5, wherein the organic solvent comprises mineral oil.

7. The process of any one of claims 1 to 6, wherein the solid aluminoxane activator comprises methylaluminoxane.

8. The method according to claim 7, wherein the solid aluminoxane activator is obtained by solvent stripping, precipitation, heating and distillation to remove solvent and trimethylaluminum, or chemical treatment.

9. The method of any one of claims 7 to 8, wherein the total aluminum content of the solid aluminoxane activator is from about 35 wt% to about 50 wt%, based on the total weight of the solid aluminoxane activator.

10. The method of any one of claims 1 to 9, further comprising cooling the supported aluminoxane slurry to a temperature of about 50°C or less before contacting the supported aluminoxane slurry with the single site catalyst component.

11. The process of any one of claims 1 to 10, further comprising cooling the supported aluminoxane slurry to a temperature of about 25°C prior to contacting the supported aluminoxane slurry with the single site catalyst component.

12. The method of any one of claims 1 to 11, wherein the temperature of the slurry in step (b) is maintained at about 115°C to about 155°C.

13. The method of claim 12, wherein the temperature of the slurry in step (b) is maintained at about 120°C or about 155°C.

14. The method of any one of claims 1 to 13, wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point higher than the maximum temperature reached by the slurry in an amount of about 50 wt% or more.

15. The method of any one of claims 1 to 14, wherein the organic solvent is present in an amount of about 60 wt % or more, about 70 wt % or more, about 75 wt % or more, about 80 wt % or more, about 90 wt % or more, or about 95 wt % or more.

16. The process according to any one of claims 1 to 15, wherein the process comprises separating the supported aluminoxane from the organic solvent prior to contacting it with the single site catalyst component.

17. The method of any one of claims 1 to 16, wherein the inorganic oxide support comprises silica.

18. The method of claim 17, wherein the inorganic oxide support comprises dried silica.

19. The method of any one of claims 17 to 18, wherein the inorganic oxide support comprises silica in an amount of about 50 wt % or more, about 60 wt % or more, about 80 wt % or more, about 90 wt % or more, or about 99 wt % or more.

20. The process of any one of claims 1 to 19, wherein the single site catalyst component comprises a metallocene compound.

21. The method of claim 20, wherein the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel.

22. The method of claim 21, wherein the metallocene compound comprises titanium, zirconium, or hafnium.

23. The process of any one of claims 1 to 22, wherein the total residual solvent content of the supported single site catalyst is less than about 50 wt%, and / or wherein the total residual aromatic solvent content of the supported single site catalyst is less than about 0.5 wt%.

24. A method for preparing a supported single-site catalyst, the method comprising: (a) contacting an inorganic oxide support, an organic solvent, and a solid aluminoxane activator at a temperature of about 0° C. to about 50° C. to form a slurry; (b) heating the slurry to a temperature of about 100° C. to about 200° C. for a period of about 0.5 hour to about 10 hours to form a supported aluminoxane slurry; (c) cooling the slurry to a temperature of about 0°C to about 50°C; and (d) adding a single site catalyst component to the supported aluminoxane slurry to form a supported single site catalyst; The organic solvent contains one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, and the amount of the branched aliphatic compounds is about 50 wt % or higher relative to the total amount of the organic solvent.

25. The method of claim 24, wherein the inorganic oxide support is heat treated.

26. The process of any one of claims 24 to 25, wherein the supported single site catalyst has a total residual solvent content of less than about 50 wt. %, and / or wherein the supported single site catalyst has a total residual aromatic solvent content of less than about 0.5 wt. %.

27. The process of any one of claims 24 to 26, further comprising contacting the supported single site catalyst with an olefin monomer to produce a polyolefin.

28. A polyolefin produced by the process according to claim 27.

29. A supported single site catalyst produced by a process according to any one of claims 1 to 27.

30. A slurry, comprising: Inorganic oxide supports; an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or higher, present in an amount of about 50% by weight or higher relative to the total amount of the organic solvent; and Solid aluminoxane activator.

31. The process of claim 30, wherein the slurry has a total residual solvent content of less than about 50 wt%, and / or wherein the supported single site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%.

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