Process for producing single-site catalysts

Abstract

A process for producing a supported single-site catalyst is provided. The process includes forming a slurry including a dry inorganic oxide support, an organic solvent, and an aluminoxane activator, maintaining the temperature of the slurry at about 100° C. to about 200° C. for about 0.5 to about 10 hours to form a supported aluminoxane slurry, and contacting the supported aluminoxane slurry with a single-site catalyst component to form the supported single-site catalyst. The organic solvent includes one or more non-aromatic organic compounds having a boiling point of about 100° C. or greater in an amount of about 50% by weight or greater based on the total amount of organic solvent.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 257,830, filed October 20, 2021, which is hereby incorporated by reference in its entirety for all purposes.

[0002] FIELD OF THEINVENTION The present technology relates generally to polyolefin catalyst systems. More specifically, the present technology relates to a method for preparing supported aluminoxanes in an aliphatic solvent. [Background technology]

[0003] Polyolefins are generally prepared by reacting olefin monomers in the presence of a catalyst consisting of a support and a catalytic component deposited in the pores and on the surface of the support. For example, one type of polyolefin catalyst is a single-site catalyst, which typically includes a support, an activator, and a single-site catalytic component such as a metallocene component. Aluminoxane is commonly used as an activator. Such catalysts are prepared in a conventional manner by contacting methylaluminoxane (MAO) dissolved in toluene with a silica support in a toluene slurry to immobilize the aluminoxane activator on the silica support. For example, U.S. Patent No. 5,856,255 describes such a process. The solvent is typically removed from the resulting catalyst, but it is difficult to remove all of the toluene, and therefore the polymers produced from the resulting catalyst tend to contain some toluene.

[0004] Recently, there has been a demand to produce polyolefins with lower levels of aromatic compounds, such as 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 with lower residual toluene. Summary of the Invention

[0005] A process for producing a supported single-site catalyst is provided. In one embodiment, the process includes forming a slurry including a dry inorganic oxide support, an organic solvent, and an aluminoxane activator, maintaining the temperature of the slurry at about 100° C. to about 200° C. for about 0.5 to about 10 hours to form a supported aluminoxane slurry, and contacting the supported aluminoxane slurry with a single-site catalyst component to form the supported single-site catalyst. The organic solvent includes one or more non-aromatic organic compounds having a boiling point of about 100° C. or greater in an amount of about 50% by weight or greater based on the total amount of organic solvent.

[0006] In one embodiment, the process includes contacting a dry inorganic oxide support, an organic solvent, and an aluminoxane activator at a temperature of about 0° C. to about 50° C. to form a slurry, heating the slurry to a temperature of about 100° C. to about 200° C. for about 0.5 to about 10 hours to form a supported aluminoxane slurry, cooling the slurry to a temperature of about 0° C. to about 50° C., and adding a single-site catalyst component to the supported aluminoxane slurry to form the supported single-site catalyst. The organic solvent comprises one or more non-aromatic organic compounds having a boiling point of about 100° C. or greater in an amount of about 50% by weight or greater based on the total amount of organic solvent.

[0007] A slurry composition is also provided. The slurry includes a dry inorganic oxide support, an organic solvent, and an aluminoxane activator. The organic solvent includes one or more non-aromatic organic compounds having a boiling point of about 100° C. or greater in an amount of about 50% by weight or greater, based on the total amount of organic solvent.

[0008] Other features and aspects of the disclosure are discussed in more detail below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Before describing some exemplary embodiments, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description as the invention is capable of other embodiments and of being practiced or carried out in various ways.

[0010] In general, the present disclosure relates to a process for producing a supported single-site catalyst using a mostly non-aromatic solvent. It has been found that an aluminoxane activator can be sufficiently immobilized on an inorganic oxide support when the temperature is raised above 100° C. for a sufficient time using a slurry containing the activator, the support, and an organic solvent with a mostly non-aromatic component having a boiling point of about 100° C. or higher. The single-site catalyst components can then be added to the supported aluminoxane to form the supported single-site catalyst.

[0011] The single-site catalyst can 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 in a slurry or isolated form to a second vessel where the single-site catalyst component is added. In another embodiment, a "one-pot" process is used in which 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.

[0012] The support can be any suitable dehydrated inorganic oxide. Such inorganic oxide support materials include Group IIA, IIIA, IVA, or 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 magnesia, chromia, titania, zirconia, and the like. For example, inorganic oxides useful 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, SiO2-iO2, SiO2-TiO2-MgO. In one embodiment, the support comprises silica in an amount of about 60% by weight or more, such as about 80% by weight or more, such as about 90% by weight or more, such as about 99% by weight or more.

[0013] The particular particle size, surface area, pore diameter, pore volume, etc. of the support material can be selected as known in the art. For example, the particle size can range from about 0.1 to 600 micrometers and the surface area can range from about 50 to 1000 m. 2 / g, the pore diameter can be in the range of about 50-500 angstroms, and the pore volume can be in the range of about 0.3-5.0 cc / g.

[0014] The inorganic oxide support is dehydrated prior to forming a slurry with the organic solvent and the aluminoxane activator. For example, the support can be dehydrated either chemically or by heating or calcining the support at a temperature and time sufficient to remove the water. For example, drying or calcining the support is typically performed by heating the support to a temperature of about 100° C. to about 1000° C., e.g., about 150° C. to about 600° C., e.g., about 200° C. to about 300° C., for about 1 minute to about 100 hours, e.g., about 50 minutes to about 5 hours. The atmosphere during drying can be air or an inert gas.

[0015] Aluminoxane activators can exist in the form of linear, cyclic, cage, or polymeric structures, the simplest monomeric compounds being the tetraalkylaluminoxanes, such as tetramethylaluminoxane, (CH3)2AlOAl(CH3)2, or tetraethylaluminoxane, (C2H5)2AlOAl(C2H5)2. Preferred compounds for use in olefin polymerization catalysts are oligomeric materials, sometimes called polyalkylaluminoxanes, which usually contain from about 4 to 20 repeating units:

[0016] [ka] wherein R is C1-C 10 Linear and cyclic aluminoxanes are often of the structure

[0017] [ka] where m and n are integers equal to or greater than 4, and the exact configuration of the aluminoxane remains unknown.

[0018] Methylaluminoxanes can contain some higher alkyl groups to improve their solubility. In addition to MAO, non-limiting examples of hydrocarbyl aluminoxanes for use in the present invention include ethylaluminoxane (EAO), isobutylaluminoxane (IBAO), n-propylaluminoxane, n-octylaluminoxane, etc. Hydrocarbyl aluminoxanes can also contain up to about 20 mole percent (based on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric acids, and carboxylic acids, thiols, alkyldisiloxanes, etc. to improve activity, solubility, and / or stability.

[0019] Aluminoxanes can be prepared by any method known in the art. For example, one suitable method is by partial hydrolysis of trialkylaluminum compounds. Trialkylaluminum compounds can be hydrolyzed by adding either free water or water-containing solids, and can be either hydrates or porous materials that absorb water. Free water is usually added in the form of a solution or dispersion in an organic solvent, since it is difficult to control the reaction by adding water itself, even with vigorous stirring of the mixture. 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, and alkali or alkaline earth metal hydroxide hydrates such as NaOH·H2O, NaOH·2H2O, Ba(OH)2·8H2O, KOH·2H2O, CsOH·1H2O, LiOH·1H2O, etc. Mixtures of any of the above hydrates may be used. The molar ratio of free water or water in a hydrate or porous material such as alumina or silica to the total alkylaluminum compounds in the mixture can vary over a wide range, such as from about 2:1 to about 1:4, such as from about 4:3 to about 1:3.5.

[0020] Such hydrocarbyl aluminoxanes and processes for preparing hydrocarbyl aluminoxanes are described, for example, in U.S. Patent Nos. 4,908,463, 4,924,018, 5,003,095, 5,041,583, 5,066,631, 5,099,050, 5,157,008, 5,157,137, 5,235,081, 5,248,801, and 5,371,260, the teachings of which are incorporated herein by reference. Methylaluminoxanes can contain various amounts of aluminum, such as about 5 to about 35 mole percent as unreacted trimethylaluminum. In some embodiments, the aluminum content as trimethylaluminum is less than about 23 mole percent of the total aluminum value, and in some embodiments, less than about 20 mole percent.

[0021] Aluminoxanes can also be prepared by non-hydrolytic processes, for example, by reaction of alkylaluminum compounds with organic compounds having one or more oxygen-containing functional groups, such as carbonyl, carboxyl, and / or hydroxyl groups, examples of such compounds include PhCOMe, PhCOOH, PhCOOMe, Ph3COH, etc. Alternatively, trialkylaluminums can be treated with carbon dioxide.

[0022] The organic solvent used to form the slurry containing the support material and the aluminoxane activator generally contains one or more aliphatic hydrocarbon compounds having a boiling point of about 100° C. or higher. Such hydrocarbon compounds can be straight or branched chain, saturated or unsaturated hydrocarbons having from about 7 to about 20 carbon atoms, in some embodiments from about 7 to about 12 carbon atoms. In some embodiments, the solvent contains a saturated hydrocarbon. In some embodiments, the solvent contains a branched hydrocarbon. Non-limiting examples of some suitable straight chain hydrocarbons include octane, nonane, decane, dodecane, decene, tridecene, and combinations thereof. Suitable branched hydrocarbons include isoparaffins, such as C7-C12 isoparaffins, C7-C10 isoparaffins, and C10-C12 isoparaffins, and those sold under the trade name ISOPAR™ and manufactured by Exxon Mobil. Examples of ISOPAR™ include ISOPAR™ E (a mixture of C7-C10 isoparaffins) and ISOPAR™ G (a mixture of C9-C12 isoparaffins). Suitable branched hydrocarbons are isohexadecane, isododecane, 2,5-dimethyldecane, isotetradecane, and combinations thereof. The solvent may also contain mineral oil that is substantially free of aromatic content.

[0023] In some embodiments, the organic solvent comprises a cyclic or alicyclic compound, such as a C7-C20 cyclic or alicyclic compound. For example, the solvent can include cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.

[0024] The organic solvent generally comprises a non-aromatic compound having a boiling point of about 100° C. or more in an amount of more than 50% by weight based on the total amount of 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 comprises about 60% by weight or more, such as about 70% by weight or more, such as about 80% by weight or more, such as about 90% by weight or more, based on the total amount of organic solvent contained in the slurry. In some embodiments, the non-aromatic compound comprises 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, and about 90% by weight to about 100% by weight, based on the total amount of organic solvent contained in the slurry. In some embodiments, the slurry does not comprise aromatic compounds.

[0025] In addition to the non-aromatic compound, the organic solvent may contain an aromatic compound in an amount of 50% by weight or less. For example, in some embodiments, the aluminoxane activator is introduced to the support and organic solvent in the form of a solution in an aromatic component, such as toluene. When the aluminoxane is introduced as a solution in an aromatic solvent, the aluminoxane may comprise about 10 to about 50% by weight of the solution, such as about 20 to about 40% by weight of the solution. In some embodiments, when the aluminoxane is introduced as a solution in an aromatic solvent, the aluminoxane comprises about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, or about 50% by weight of the solution. The aromatic compound may also be present in the slurry even when the aluminoxane is not added, such as in a mixture with the inorganic oxide support prior to the addition of the aluminoxane. In some embodiments, the amount of aromatic compounds contained in the slurry that is not introduced as a solution of the aluminoxane is low, such as about 5 wt% or less, such as about 1 wt% or less. In some embodiments, the amount of aromatic compounds contained in the slurry that is not introduced as a solution of the aluminoxane is low, such as about 0 wt% to about 5 wt%, including about 0 wt% to about 1 wt%.

[0026] If present, the aromatic solvent preferably has a boiling point of about 100° C. or greater. For example, in some embodiments, aromatic solvents such as toluene, xylene, ethylbenzene, propylbenzene, cumene, and / or t-butylbenzene can be included in the organic solvent.

[0027] In some embodiments, the organic solvent contains toluene and branched alkanes and / or alicyclic compounds. For example, toluene may be present in an amount of about 40% to about 50% by weight, with isoparaffins and / or alicyclic compounds making up the remainder of the organic solvent.

[0028] The solvent generally has a very low amount 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 materials. In this regard, in some embodiments, the solvent is purged with air and purified before being used to produce the slurries described herein.

[0029] The single-site catalyst component can include any transition metal or metallocene single-site catalyst known in the art. For example, the single-site catalyst can include "half sandwich" and "full sandwich" compounds having one or more Cp ligands (cyclopentadienyl and ligands isotropic to cyclopentadienyl) bonded to at least one Group 3-12 metal atom and one or more leaving groups bonded to at least one metal atom.

[0030] The Cp ligands are one or more rings or ring systems, at least some of which contain a π-bond system, such as cycloalkadienyl ligands and heterocyclic analogs. The rings or ring systems typically contain atoms selected from Groups 13-16, and in some embodiments, the atoms constituting the Cp ligands are selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, with carbon constituting at least 50% of the ring members. For example, the Cp ligands may be selected from substituted and unsubstituted cyclopentadienyl ligands and ligands that are isoloval to cyclopentadienyl. Non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopento[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or "H4Ind"), substituted versions thereof (discussed and described in more detail below), and heterocyclic versions thereof.

[0031] The metal atom "M" of the single-site compound may be selected from Groups 3-12 and Lanthanide atoms, or may be selected from Groups 3-10 atoms, or may be selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni, or may be selected from Groups 4, 5, and 6 atoms, or may be Ti, Zr, or Hf atoms, or may be Hf, or may be Zr. The oxidation state of the metal atom "M" may range from 0 to +7, or may be +1, +2, +3, +4, or +5, or may be +2, +3, or +4. The groups bonded to the metal atom "M" are such that the compounds described below in the structure are electrically neutral unless otherwise indicated. The Cp ligand forms at least one chemical bond with the metal atom M to form the "metallocene catalyst component". The Cp ligands differ from leaving groups attached to the metal atom M in that they do not undergo significant substitution / abstraction reactions.

[0032] In one embodiment, the single-site catalyst has the formula: (C5R x ) y R' z (C5R m )MQ n-y-1 wherein: M is a metal from Group IIIB to Group VIII of the Periodic Table of the Elements, (C5R x ) and (C5R m ) are the same or different cyclopentadienyl or substituted cyclopentadienyl groups attached to M; R is the same or different and is hydrogen or a hydrocarbyl group such as an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group containing 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C4-C6 ring; R' is a C1-C4 substituted or unsubstituted alkylene group, a dialkyl or diaryl germanium or silicon, or two (C5R x ) and (C5R m) an alkyl or aryl phosphine or amine group bridging the rings, Q is a hydrocarbyl group such as an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl group having 1 to 20 carbon atoms, a hydrocarboxy group having 1 to 20 carbon atoms, or a halogen, which may be the same or different from each other; z is 0 or 1; y is 0, 1 or 2; if y is 0 then z is 0; n is 0, 1, 2, 3, or 4 depending on the valence state of M; ny is greater than or equal to 1.

[0033] Illustrative, but non-limiting examples of metallocenes represented by the formula above include dialkyl metallocenes, such as bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diphenyl, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)hafnium dimethyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl, bis(cyclopentadienyl)zirconium di-neopentyl, bis(cyclopentadienyl)hafnium ... pentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium dimethyl; monoalkyl metallocenes, such as bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium ethyl chloride, bis(cyclopentadienyl)zirconium cyclopentadienyl phenyl chloride, bis(cyclopentadienyl)titanium methyl bromide; trialkyl metallocenes such as cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium trineopentyl, and cyclopentadienyl hafnium trimethyl; monocyclopentadienyl titanocenes such as penta Methylcyclopentadienyltitanium trichloride, pentaethylcyclopentadienyltitanium trichloride; bis(pentamethylcyclopentadienyl)titanium diphenyl, carbenes represented by the formula bis(cyclopentadienyl)titanium=CH2 and derivatives of this reagent; substituted bis(cyclopentadienyl)titanium(IV) compounds, such as bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl or dihalides; dialkyl, trialkyl,Tetra-alkyl and penta-alkyl cyclopentadienyl titanium compounds, such as bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride; silicon, phosphine, amine or carbon bridged cyclopentadiene complexes, such as dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methylphosphinedicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopentadiene, enyltitanium diphenyl or 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, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, cyclohexylidene(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, diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, ditert-butylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl) racemic-ethylenebis(1-indenyl)zirconium(IV) dichloride, racemic-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, racemic-dimethylsilylbis(1-indenyl)zirconium(IV) dichloride, racemic-dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)zirconium racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, ethylidene(1-indenyltetramethylcyclopentadienyl)zirconium(IV) dichloride, racemic-dimethylsilylbis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV) dichloride, racemic-ethylenebis(1-indenyl)hafnium(IV) dichloride, racemic-ethylenebis(4,5,6,7- tetrahydro-1-indenyl)hafnium(IV) dichloride, racemic-dimethylsilylbis(1-indenyl)hafnium(IV) dichloride, racemic-dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)hafnium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,Ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV) dichloride, racemic ethylenebis(1-indenyl)titanium(IV) dichloride, racemic ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, racemic dimethylsilylbis(1-indenyl)titanium(IV) dichloride, racemic dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)titanium racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)titanium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride, and ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV) dichloride.

[0034] Single-site catalyst components are disclosed, 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, 5,145,819, 5,120, and 5,130,771. Nos. 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.

[0035] To form the single-site catalyst, a slurry is formed containing the support, the aluminoxane, and the organic solvent. For example, in one embodiment, the dry inorganic oxide support is mixed with a portion of the organic solvent to form the slurry. The slurry can be formed in any suitable vessel using any suitable mixing means. For example, in one embodiment, the vessel can be fitted with a condenser and an agitator or impeller. The vessel can be an open or closed reactor. The aluminoxane can then be added to the slurry. For example, in one embodiment, the aluminoxane is added in the form of a solution in an organic solvent to form a slurry containing the support, the aluminoxane, and the organic solvent. In such an embodiment, the total organic solvent includes both the organic solvent used to slurry the support and the organic solvent added with the aluminoxane.

[0036] In one embodiment, the weight ratio of the aluminoxane to the carrier added 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. In particular, when the aluminoxane is dissolved in an aromatic solvent, it should not be added in such an amount that the organic solvent obtained after addition contains more than 50% by weight of aromatic compounds.

[0037] In one embodiment, the slurry is formed at a temperature between 0° C. and 50° C., for example, about 15° C. and about 30° C. In one embodiment, the slurry is formed at a temperature of about 0° C., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. In one embodiment, the slurry is maintained at such temperature range for about 1 minute to about 2 hours, for example, about 10 minutes to about 1 hour, while mixing the slurry.

[0038] It has been found that the temperature must be maintained at about 100°C or higher for a sufficient time to fully immobilize the aluminoxane activator on the support. Thus, in one embodiment, the temperature of the slurry is increased 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 or higher, such as about 150°C or higher. Typically, the temperature remains below about 200°C. Thus, in one embodiment, the temperature of the slurry is increased to a temperature of 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, and about 150°C to about 200°C. However, depending on the solvent and reactor pressure, the temperature can be greater than about 200°C. The temperature can be maintained for about 0.5 to about 10 hours, for example, about 2 to about 6 hours, to form the supported aluminoxane slurry. In one embodiment, the temperature of the slurry is maintained below the boiling point of the organic solvent. In one embodiment, the pressure is maintained at about 130 kPa or less throughout the process, for example, about 90 to about 130 kPa and about 90 to about 110 kPa. In one embodiment, the pressure is maintained at about 90 kPa, about 95 kPa, about 100 kPa, about 105 kPa, about 110 kPa, about 115 kPa, about 120 kPa, about 125 kPa, or about 130 kPa throughout the process. However, in some embodiments, when using a closed reactor system, the pressure can be increased to above 130 kPa and the temperature can be above the atmospheric boiling point of the solvent.

[0039] After the supported aluminoxane slurry is formed, 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, after the supported aluminoxane slurry is formed, the slurry is cooled to a temperature of about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. For example, in one embodiment, the slurry is allowed to slowly cool back to room temperature.

[0040] After the supported aluminoxane slurry is formed, it is contacted with the single-site catalyst component to form the supported single-site catalyst. The single-site catalyst component can be loaded onto the supported aluminoxane by any means known in the art.

[0041] In one embodiment, for example, the slurry can be separated from the solvent, optionally stored, and later mixed with the single-site catalyst component. In another embodiment, the slurry can be mixed with the single-site catalyst component in a separate vessel. Alternatively, in another embodiment, a "one-pot" process can be used, where the single-site catalyst component is added to the supported aluminoxane slurry in the same vessel in which the slurry was formed, after the slurry has cooled.

[0042] In any of such embodiments, the single-site catalyst component can be added to the supported aluminoxane as a solution in a solvent such as toluene. The mixture of single-site catalyst component and supported aluminoxane can then be mixed, such as by stirring, for a 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 a slurry and stirred at a temperature of from about 0° C. to about 50° C., e.g., from about 15° C. to about 30° C., for from about 5 minutes to about 5 hours, e.g., from about 1 hour to about 3 hours.

[0043] Additionally, in some embodiments, the single-site catalyst component can be treated prior to mixing with the supported aluminoxane. For example, pretreatment can include treating the single-site catalyst component with Al-, Mg-, Zn-, other predominantly alkyl groups (e.g., TEA, TIBA, MgBu2, ZnEt2), borates, olefins, Lewis bases, or any combination thereof, as known in the art.

[0044] In one embodiment, the weight ratio of the added catalyst components to the supported aluminoxane is from about 1:25 to about 1:200, such as from about 1:50 to about 1:100, for example, from about 1:60 to about 1:90.

[0045] The resulting solid single-site catalyst can then be separated from the solvent by any suitable means, such as by filtering, washing in a non-aromatic organic liquid, and then drying, such as by drying under vacuum.

[0046] In some embodiments, the solid single-site catalyst has a total residual solvent content of less than about 50 wt%, including less than about 40 wt%, less than about 30 wt%, less than about 20 wt%, less than about 10 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1 wt%, less than about 0.5 wt%, and less than about 0.1 wt%. In some embodiments, the solid single-site catalyst has a total residual solvent content of less than about 5 wt% or less than about 2 wt%. In some embodiments, the solid single-site catalyst has a total residual solvent content of about 0 wt% to about 50 wt%, about 0 wt% to about 5 wt%, about 0 wt% to about 2 wt%, and about 0 wt% to about 1 wt%. In some embodiments, the solid single-site catalyst has a total residual solvent 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%, and about 0.1 wt% to about 0.5 wt%. In some embodiments, the solid single-site catalyst has a total residual solvent 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%, and about 0.01 wt% to about 0.1 wt%.

[0047] In some embodiments, the total residual solvent content comprises a residual isohexane content. In some embodiments, the total residual solvent content comprises a total residual aromatic solvent content (e.g., a residual toluene content). In some embodiments, the total residual solvent content comprises a residual isohexane content. In some embodiments, the total residual solvent content comprises a total residual aromatic solvent content (e.g., a residual toluene content).

[0048] In some embodiments, the solid single-site catalyst has a total residual aromatic solvent content (e.g., toluene solvent content) of less than about 50 wt%, including less than about 40 wt%, less than about 30 wt%, less than about 20 wt%, less than about 10 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1 wt%, less than about 0.5 wt%, and less than about 0.1 wt%, and less than about 0.01 wt%. In some embodiments, the solid single-site catalyst has a total residual aromatic solvent content (e.g., toluene solvent content) of less than about 0.5 wt%. In some embodiments, the solid single-site catalyst has a total residual aromatic solvent content of about 0 wt% to about 50 wt%, about 0 wt% to about 5 wt%, about 0 wt% to about 2 wt%, and about 0 wt% to about 1 wt%. In some embodiments, the solid single-site catalyst has a total residual aromatic solvent 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%, and about 0.1 wt% to about 0.5 wt%. In some embodiments, the solid single-site catalyst has a total residual aromatic solvent 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%, and about 0.01 wt% to about 0.1 wt%.

[0049] In some embodiments, the solid single-site catalyst has a residual isohexane content of less than about 50 wt%, including less than about 40 wt%, less than about 30 wt%, less than about 20 wt%, less than about 10 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1 wt%, less than about 0.5 wt%, and less than about 0.1 wt%, and less than about 0.01 wt%. In some embodiments, the solid single-site catalyst has a residual isohexane content of less than about 0.5 wt%. In some embodiments, the solid single-site catalyst has a residual isohexane content of about 0 wt% to about 50 wt%, about 0 wt% to about 5 wt%, about 0 wt% to about 2 wt%, and about 0 wt% to about 1 wt%. 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%, and 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%, and about 0.01 wt% to about 0.1 wt%.

[0050] The invention having thus been generally described will be more readily understood with reference to the following examples, which are provided by way of illustration and are not intended to limit the invention. EXAMPLES

[0051] Five catalysts were prepared by immobilizing methylaluminoxane and a metallocene catalyst component (bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride) on dehydrated silica. After preparation of each catalyst, the relative production rates were obtained for each using the same polymerization test conditions.

[0052] A typical polymerization process was as follows: a 4-L liter autoclave was charged with isobutane (900 g), 1-hexene (28 g), TIBA (0.5 mL of a 20% solution in isohexane), catalyst (0.025 g), and ethylene (125 psi). The contents were stirred at 800 RPM using a marine impeller. The polymerization temperature was 85° C. The polymerization time was 1 hour. The resin was collected after venting and cooling the reactor after 1 hour of on-stream time. The resin was obtained after drying under vacuum at 65° C. The catalyst activity (g polymer / g catalyst per hour) was determined by dividing the amount of polymer made by the amount of catalyst added.

[0053] Example 1 Formation of supported aluminoxane slurry Dehydrated silica (7.5 g) was slurried in methylcyclohexane (55.8 g) in a 250 mL three-neck flask equipped with an overhead stirring arm and a condenser. MAO (17.2 g, 30 wt % in toluene) was added and the resulting slurry was stirred at room temperature for 30 minutes. The internal temperature was increased to 100° C. and held for 4 hours. The supported methylaluminoxane (sMAO) slurry was cooled back to ambient temperature.

[0054] Catalyst formation Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.22 g, 25 wt % in toluene) was added in portions to the sMAO slurry (17.2 g, 17.2 wt % solids) and stirred at room temperature for 2 hours. The solid was collected on a coarse fritted disc filter and washed with 1×20 mL of methylcyclohexane and 3×20 mL of isohexane. The solid was dried under vacuum to constant mass (0.38 wt % residual toluene, 0.24 wt % residual isohexane).

[0055] polymerization The polymerization was carried out according to the above process, and the average polymer production rate was 5,051 g / g catalyst / hour.

[0056] Example 2 Formation of supported aluminoxane slurry Dehydrated silica (7.6 g) was slurried in ISOPAR™ G (a mixture of C9-C12 isoparaffins with an aromatic content of less than 2 wt%) (41.5 g) in a 250 mL three-neck flask equipped with an overhead stirring arm and a condenser. MAO (17.3 g, 30 wt% in toluene) was added and the resulting slurry was stirred at room temperature for 30 minutes. The internal temperature was increased to 120° C. and held for 4 minutes. The sMAO slurry was cooled back to ambient temperature.

[0057] Catalyst formation Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.22 g, 25 wt % in toluene) was added in portions to the sMAO slurry (16.9 g, 18.2 wt % solids) and stirred at room temperature for 2 hours. The solids were collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ G (isoparaffin mixture) and 3×20 mL isohexane. The solids were dried under vacuum to constant mass (0.02 wt % residual toluene, 1.27 wt % residual isohexane).

[0058] polymerization The polymerization was carried out according to the above process, and the average polymer production rate was 5,576 g / g catalyst / hour.

[0059] Example 3 Formation of supported aluminoxane slurry Dehydrated silica (7.0 g) was slurried in ISOPAR™ E (a mixture of C7-C10 isoparaffins) (53.5 g) in a 250 mL three-neck flask equipped with an overhead stirring arm and a condenser. MAO (15.9 g, 30 wt % in toluene) was added and the resulting slurry was stirred at room temperature for 30 minutes. The internal temperature was increased to 120° C. and held for 4 minutes. The sMAO slurry was cooled back to ambient temperature.

[0060] Catalyst formation Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.22 g, 25 wt % in toluene) was added in portions to the sMAO slurry (14.8 g, 17.2 wt % solids) and stirred at room temperature for 2 hours. The solids were collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ E (isoparaffin mixture) and 3×20 mL isohexane. The solids were dried under vacuum to constant mass (0.02 wt % residual toluene, 0.45 wt % residual isohexane).

[0061] polymerization The polymerization was carried out according to the above process, with an average polymer production rate of 5,485 g / g catalyst / hour.

[0062] Example 4 Formation of supported aluminoxane slurry Dehydrated silica (5.7 g) was slurried in ISOPAR™ G (42.5 g) in a 250 mL three-neck flask equipped with an overhead stirring arm and a condenser. MAO (12.9 g, 30 wt % in toluene) was added and the resulting slurry was stirred at room temperature for 30 minutes. The internal temperature was increased to 150° C. and held for 4 minutes. The sMAO slurry was cooled back to ambient temperature.

[0063] Catalyst formation Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.8 g, 25 wt % in toluene) was added to the sMAO slurry and stirred at room temperature for 2 hours. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ G (isoparaffin mixture) and 3×20 mL isohexane. The solid was dried under vacuum to constant mass (0.13 wt % residual toluene, 0.62 wt % residual isohexane).

[0064] polymerization The polymerization was carried out according to the above process, and the average polymer production rate was 6,548 g / g catalyst / hour.

[0065] Example 5 (Comparative) Formation of supported aluminoxane slurry Dehydrated silica (7.4 g) was slurried in ISOPAR™ G (55.8 g) in a 250 mL three-neck flask equipped with an overhead stirring arm and a condenser. MAO (16.9 g, 30 wt % in toluene) was added and the resulting slurry was stirred at room temperature for 30 minutes. The internal temperature was increased to 60° C. and held for 4 minutes. The sMAO slurry was cooled back to ambient temperature.

[0066] Catalyst formation Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (1.0 g, 25 wt % in toluene) was added to the sMAO slurry and stirred at room temperature for 2 hours. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ G (isoparaffin mixture) and 3×20 mL isohexane. The solid was dried under vacuum to constant mass.

[0067] polymerization The polymerization was carried out according to the above process, and the average polymer production rate was 3,302 g / g catalyst / hour.

[0068] Example 6 (Comparative) Formation of supported aluminoxane slurry Dehydrated silica (5.7 g) was slurried in ISOPAR™ G (36.3 g) in a 250 mL three-neck flask equipped with an overhead stirring arm and a condenser. MAO (13.0 g, 30 wt % in toluene) was added and the resulting slurry was stirred at room temperature for 4.5 hours.

[0069] Catalyst formation Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.8 g, 25 wt % in toluene) was added to the sMAO slurry and stirred at room temperature for 2 hours. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ G (isoparaffin mixture) and 3×20 mL isohexane. The solid was dried under vacuum to constant mass.

[0070] polymerization Polymerization was carried out according to the above process, with an average polymer production rate of 3,339 g / g catalyst / hour.

[0071] Item 1. A process for producing a supported single-site catalyst, comprising: forming a slurry comprising a dry inorganic oxide support, an organic solvent, and an aluminoxane activator; maintaining the temperature of the slurry at about 100° C. to about 200° C. for about 0.5 to about 10 hours to form a supported aluminoxane slurry; contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; The process wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point of about 100° C. or greater in an amount of about 50% by weight or greater, based on the total amount of organic solvent.

[0072] Item 2. The process of item 1, wherein the organic solvent comprises one or more branched aliphatic compounds.

[0073] Item 3. The process of item 2, wherein the one or more branched aliphatic compounds comprise isoparaffins.

[0074] Item 4. The process of item 1, wherein the organic solvent comprises a mineral oil.

[0075] Item 5. The process of item 1, wherein the organic solvent comprises one or more alicyclic compounds.

[0076] Item 6. The process of item 5, wherein the one or more alicyclic compounds comprises methylcyclohexane.

[0077] Item 7. The process of any one of items 1 to 6, wherein the aluminoxane activator comprises methylaluminoxane.

[0078] Item 8. The process according to any one of items 1 to 7, wherein the organic solvent comprises one or more aromatic compounds in an amount of about 5% by weight to about 45% by weight based on the total amount of the organic solvent.

[0079] Item 9. The process of item 8, wherein the one or more aromatic compounds include toluene.

[0080] Item 10. The process of any one of items 1 to 9, further comprising cooling the supported aluminoxane slurry to a temperature of about 50° C. or less prior to contacting the supported aluminoxane slurry with the single-site catalyst component.

[0081] Item 11. The process according to any one of items 1 to 10, 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% by weight or more.

[0082] Item 12. The process of any one of items 1 to 11, wherein an aluminoxane activator is added to an aromatic solvent to form a slurry.

[0083] Item 13. The process of any one of items 1 to 12, wherein the process includes separating the supported aluminoxane from the organic solvent prior to contacting the supported aluminoxane with the single-site catalyst component.

[0084] Item 14. The process of any one of items 1 to 13, wherein the inorganic oxide comprises silica.

[0085] Item 15. The process of any one of items 1 to 14, wherein the single-site catalyst component comprises a metallocene compound.

[0086] Item 16. The process of any one of items 1 to 15, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt.%.

[0087] Item 17. The process of item 16, wherein the supported single-site catalyst has a total residual solvent content of less than about 5 wt.% or about 2 wt.%.

[0088] Item 18. The process of any one of items 1 to 17, wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt.%.

[0089] Item 19. A process for producing a supported single-site catalyst, comprising: contacting a dry inorganic oxide support, an organic solvent, and an aluminoxane activator at a temperature of from about 0° C. to about 50° C. to form a slurry; heating the slurry to a temperature of about 100° C. to about 200° C. for about 0.5 to about 10 hours to form a supported aluminoxane slurry; Cooling the slurry to a temperature of about 0° C. to about 50° C.; adding a single-site catalyst component to the supported aluminoxane slurry to form a supported single-site catalyst; The process wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point of about 100° C. or greater in an amount of about 50% by weight or greater, based on the total amount of organic solvent.

[0090] Item 20. The process of item 19, wherein the organic solvent comprises one or more branched aliphatic compounds.

[0091] Item 21. The method of item 20, wherein the one or more branched aliphatic compounds include isoparaffins.

[0092] Item 22. The process of item 19, wherein the organic solvent comprises mineral oil.

[0093] Item 23. The process of item 19, wherein the organic solvent comprises one or more alicyclic compounds.

[0094] Item 24. The process of item 23, wherein the one or more alicyclic compounds comprises methylcyclohexane.

[0095] Item 25. The process of any one of items 19 to 24, wherein the aluminoxane activator comprises methylaluminoxane.

[0096] Item 26. The process of any one of items 19 to 25, wherein the organic solvent comprises one or more aromatic compounds in an amount of about 5% by weight to about 45% by weight based on the total amount of the organic solvent.

[0097] Item 27. The process of item 26, wherein the one or more aromatic compounds include toluene.

[0098] Item 28. The process of any one of items 19 to 27, 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% by weight or more.

[0099] Item 29. The process of any one of items 19 to 28, wherein an aluminoxane activator is added to an aromatic solvent to form a slurry.

[0100] Item 30. The process of any one of items 19 to 29, wherein the inorganic oxide comprises silica.

[0101] Item 31. The process of any one of items 19-30, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt%.

[0102] Item 32. The process of item 31, wherein the supported single-site catalyst has a total residual solvent content of less than about 5 wt.% or about 2 wt.%.

[0103] Item 33. The process of any one of items 19 to 32, wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt.%.

[0104] Item 34. The process of any one of items 1 to 33, further comprising contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin.

[0105] Item 35. A polyolefin produced by the process according to item 34.

[0106] Item 36. A supported single-site catalyst produced by the process of any one of items 1 to 33.

[0107] Item 37. A slurry comprising: A dry inorganic oxide support; an organic solvent comprising one or more non-aromatic organic compounds having a boiling point of about 100° C. or higher in an amount of about 50% by weight or higher based on the total amount of the organic solvent; and an aluminoxane activator.

[0108] Item 38. The slurry according to item 37, wherein the one or more non-aromatic organic compounds having a boiling point of about 100° C. or more are present in an amount of about 75% by weight or more based on the total amount of organic solvent.

[0109] Item 39. The slurry according to item 37 or 38, wherein the organic solvent comprises one or more branched aliphatic compounds.

[0110] Item 40. The slurry of item 39, wherein the one or more branched aliphatic compounds include isoparaffins.

[0111] Item 41. The slurry according to item 37 or 38, wherein the organic solvent comprises a mineral oil.

[0112] Item 42. The slurry according to item 37 or 38, wherein the organic solvent comprises one or more alicyclic compounds.

[0113] Item 43. The slurry according to item 42, wherein the one or more alicyclic compounds include methylcyclohexane.

[0114] Item 44. The slurry according to any one of Items 37 to 43, wherein the aluminoxane activator comprises methylaluminoxane.

[0115] Item 45. The slurry according to any one of Items 37 to 44, wherein the inorganic oxide includes silica.

[0116] Item 46. The process of any one of items 37 to 45, wherein the slurry has a total residual solvent content of less than about 50% by weight.

[0117] Item 47. The process of item 46, wherein the slurry has a total residual solvent content of less than about 5% by weight or less than about 2% by weight.

[0118] Item 48. The process of any one of items 37 to 47, wherein the slurry has a total residual aromatic solvent content of less than about 0.5 wt.%.

[0119] While certain embodiments have been illustrated and described, it should be understood that changes and modifications may be made therein by those skilled in the art without departing from the technology in its broader aspects as defined in the following claims.

[0120] The embodiments illustratively described herein may be suitably practiced in the absence of any element(s), limitation(s) not specifically disclosed herein. Thus, for example, terms such as "comprising", "including", "containing" and the like should be read expansively and without limitation. In addition, the terms and expressions used herein are used as terms of description and not of limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the shown and described features or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase "consisting essentially of" will be understood to include those elements specifically recited, as well as those additional elements that do not materially affect the basic and novel features of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0121] The present disclosure is not limited with respect to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope of the present invention. In addition to those recited herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the present disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0122] Additionally, when features or aspects of the disclosure are described in terms of a Markush group, one of skill in the art will recognize that the disclosure is also thereby described in terms of any individual members or subgroups of members of the Markush group.

[0123] As will be understood by those skilled in the art, for any and all purposes, especially in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations thereof. It can be easily recognized that any recited range fully describes and allows for the same range to be subdivided into at least two, three, four, five, ten, etc. As a non-limiting example, each range discussed herein can be easily subdivided into a lower third, a middle third, an upper third, etc. Also, as will be understood by those skilled in the art, all terms such as "up to," "at least," "greater than," "less than," etc. refer to ranges that include the numbers recited and can then be subdivided into the subranges discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member.

[0124] All publications, patent applications, issued patents, and other documents referenced herein are incorporated 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 the descriptions incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0125] Other embodiments are within the scope of the following claims.

Claims

1. 1. A process for producing a supported single-site catalyst, said process comprising: forming a slurry comprising a dry inorganic oxide support, an organic solvent, and an aluminoxane activator; maintaining the temperature of the slurry at about 100°C to about 200°C for about 0.5 to about 10 hours to form a supported aluminoxane slurry; contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; The process wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point of about 100° C. or higher in an amount of about 50% by weight or higher, based on the total amount of the organic solvent.

2. 10. The process of claim 1, wherein the organic solvent comprises one or more branched aliphatic compounds, including isoparaffins.

3. 10. The process of claim 1, wherein the organic solvent comprises one or more alicyclic compounds, including mineral oil or methylaluminoxane.

4. 10. The process of claim 1, wherein the aluminoxane activator comprises methylaluminoxane.

5. 10. The process of claim 1, wherein the organic solvent comprises one or more aromatic compounds in an amount of about 5% to about 45% by weight, based on the total amount of the organic solvent.

6. 6. The process of claim 5, wherein the one or more aromatic compounds comprise toluene.

7. 10. The process of claim 1, 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.

8. 10. The process of claim 1, 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% by weight or greater.

9. 10. The process of claim 1, wherein the aluminoxane activator is added to an aromatic solvent to form the slurry.

10. 10. The process of claim 1, wherein the process comprises separating the supported aluminoxane from the organic solvent prior to contacting the supported aluminoxane with the single-site catalyst component.

11. 10. The process of claim 1, wherein the inorganic oxide comprises silica and / or the single-site catalyst component comprises a metallocene compound.

12. 10. The process of claim 1, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt.% and / or the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt.%.

13. 1. A process for producing a supported single-site catalyst, said process comprising: contacting a dry inorganic oxide support, an organic solvent, and an aluminoxane activator at a temperature of from about 0° C. to about 50° C. to form a slurry; heating the slurry to a temperature of about 100° C. to about 200° C. for about 0.5 to about 10 hours to form a supported aluminoxane slurry; cooling the slurry to a temperature of about 0°C to about 50°C; adding a single-site catalyst component to the supported aluminoxane slurry to form a supported single-site catalyst; The process wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point of about 100° C. or higher in an amount of about 50% by weight or higher, based on the total amount of the organic solvent.

14. 10. The process of claim 1, further comprising contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin.

15. 15. A polyolefin produced by the process of claim 14.

16. 10. A supported single-site catalyst produced by the process of claim 1.

17. A slurry comprising: a dry inorganic oxide support; an organic solvent comprising one or more non-aromatic organic compounds having a boiling point of about 100° C. or higher in an amount of about 50% by weight or higher, based on the total amount of the organic solvent; an aluminoxane activator.

18. 20. The slurry of claim 17, wherein the one or more non-aromatic organic compounds having a boiling point of about 100°C or greater are present in an amount of about 75% by weight or greater, based on the total amount of the organic solvent.

19. 18. The slurry of claim 17, wherein the aluminoxane activator comprises methylaluminoxane and / or the inorganic oxide comprises silica.

20. 18. The process of claim 17, wherein the slurry has a total residual solvent content of less than about 50 wt% and / or the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%.