Method for producing heat-treated supported aluminoxanes in aliphatic solvents using solid aluminoxanes

Abstract

A method for producing a supported single-site catalyst is provided, the method comprising 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° C. to about 200° C. for a period of about 0.5 to about 10 hours to form a supported aluminoxane slurry, and contacting the supported aluminoxane slurry with single-site catalyst components to form the supported single-site catalyst. The organic solvent comprises one or more branched aliphatic compounds having a boiling point of about 100° C. or greater, present 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

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 320,993, filed March 17, 2022, which is incorporated by reference in its entirety for all purposes.

[0002]

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

[0003]

[0003] Polyolefins are generally prepared by reacting olefin monomers in the presence of a catalyst that is composed 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. Aluminoxanes are commonly used as activators. Such catalysts are conventionally prepared 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 method. The solvent is typically removed from the resulting catalyst, but it is difficult to remove all the toluene, and therefore the polymer produced from the resulting catalyst tends to contain some toluene. Summary of the Invention [Problem to be solved by the invention]

[0004]

[0004] Recently, there has been a push to produce polyolefins containing low levels of aromatic compounds, such as toluene, especially in polyolefins intended for use in the food and beverage industry. Thus, 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 addresses this need by providing a method for preparing heat-treated supported aluminoxanes in an aliphatic solvent. [Means for solving the problem]

[0005] In one aspect, there is provided a method for producing a supported single-site catalyst, comprising the steps of: (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 to about 10 hours to form a supported aluminoxane slurry; (c) contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; Including, the organic solvent comprises 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 greater based on the total amount of organic solvent; A method is provided.

[0006]

[0006] In some embodiments, the slurry in step (a) does not contain any aromatic compounds. In some embodiments, the organic solvent comprising the one or more branched aliphatic compounds comprises an isoparaffin. In some embodiments, the organic solvent comprising the one or more branched aliphatic compounds comprises one or more C7-C12 isoparaffins. In some embodiments, the 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 a mineral oil.

[0007] In some embodiments, the solid aluminoxane activator comprises methylaluminoxane. In some embodiments, the solid aluminoxane activator is obtained from solvent stripping, precipitation, heating and distilling off the solvent and trimethylaluminum, or chemical treatment. In some embodiments, the solid aluminoxane activator has a total aluminum content in the range of about 35 to about 50 weight percent, based on the total weight of the solid aluminoxane activator.

[0008] In some embodiments, the method further comprises 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. In some embodiments, the method further comprises 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.

[0009] In some embodiments, maintaining the temperature of the slurry in step (b) is about 115° C. to about 155° C. In some embodiments, maintaining the temperature of the slurry in step (b) is about 120° C. or about 155° C.

[0010] 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% or more by weight. In some embodiments, the organic solvent is present in an amount of about 60% or more by weight, about 70% or more by weight, about 75% or more by weight, about 80% or more by weight, about 90% or more by weight, or about 95% or more by weight.

[0011] In some embodiments, the method includes separating the supported aluminoxane from the organic solvent prior to the step of contacting with the single-site catalyst component.

[0012] In some embodiments, the inorganic oxide support is heat treated (e.g., calcined). In some embodiments, the inorganic oxide support is dry. In some embodiments, the inorganic oxide support comprises silica. In some embodiments, the inorganic oxide support comprises dry silica. In some embodiments, the inorganic oxide support comprises silica in an amount of about 50% by weight or more, about 60% by weight or more, about 80% by weight or more, about 90% by weight or more, or about 99% by weight or more.

[0013]

[0013] 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.

[0014] 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 less than 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. %.

[0015] In another aspect, there is provided a method for producing a supported single-site catalyst, comprising the steps of: (a) contacting an inorganic oxide support, an organic solvent, and a solid aluminoxane activator at a temperature between about 0° C. and 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 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.; (d) adding the single-site catalyst components to the supported aluminoxane slurry to form a supported single-site catalyst; Including, the organic solvent comprises 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 greater based on the total amount of organic solvent; A method is provided.

[0016]

[0016] In some embodiments, the inorganic oxide support is dry. 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 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. %. In some embodiments, the method further comprises contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin.

[0017] In another aspect, there is provided a polyolefin produced by any one of the processes described herein.

[0018] In another aspect, there is provided a supported single-site catalyst produced by any of the methods described herein.

[0019] In another aspect, An inorganic oxide support; an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or greater, the organic solvent being present in an amount of about 50% by weight or greater based on the total amount of organic solvent; Solid aluminoxane activator A slurry is provided comprising:

[0020] In some embodiments, the slurry has a total residual solvent content of less than about 50% by weight. In some embodiments, the slurry has a total residual solvent content of less than about 5% by weight or less than about 2% by weight. In some embodiments, the slurry has a total residual aromatic solvent content of less than about 0.5% by weight.

[0021]

[0021] Other features and aspects of the present disclosure are discussed in more detail below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022]

[0022] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation on the broad aspects discussed herein. An aspect described in connection with a specific embodiment is not necessarily limited to that embodiment and may be practiced with any other embodiment.

[0023]

[0023] As used herein, "about" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there are any uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, "about" will mean the particular term plus or minus up to 10%.

[0024] In the context of describing elements (particularly in the context of the claims that follow), the use of the terms "a" and "an" as well as "the" and similar referents should be construed as including both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples or illustrative language provided herein (e.g., "such as") is intended merely to better describe the embodiments and does not pose a limitation on the scope of the claims, unless otherwise specified. No language in this specification should be construed as indicating any non-claimed element as essential.

[0025]

[0025] In general, alkyl, alkenyl, aryl or ether groups (e.g., alkyl groups) as defined below, in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to a non-hydrogen or non-carbon atom, may be substituted. Substituted groups also include groups in which one or more bonds to a carbon or hydrogen atom are replaced by one or more bonds to a heteroatom, including double or triple bonds. Thus, a substituted group will be substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group is substituted with one, two, three, four, five or six substituents. Exemplary substituent groups include halogens (i.e., F, Cl, Br, and I); hydroxyl; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyl (oxo); carboxyl; ester; urethane; oxime; hydroxylamine; alkoxyamine; aralkoxyamine; 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 group; nitrile (i.e., CN), and the like.

[0026] As used herein, "alkyl" groups include straight-chain or branched alkyl groups having from 1 to about 20 carbon atoms, typically from 1 to 12 carbons, or in some embodiments, from 1 to 8 carbon atoms. As used herein, "alkyl group" includes cycloalkyl groups, as defined below. Alkyl groups may be substituted or unsubstituted. Alkyl groups may be substituted one or more times. Alkyl groups may be substituted two 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, t-butyl, neopentyl, isopentyl, and 1-cyclopentyl-4-methylpentyl. Representative substituted alkyl groups may be substituted one or more times, for example, with amino, thio, hydroxy, cyano, alkoxy, and / or halo groups, such as F, Cl, Br, and I groups. As used herein, the term haloalkyl is an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a perhaloalkyl group.

[0027]

[0027] Alkenyl groups are straight chain, branched or cyclic alkyl groups having from 2 to about 20 carbon atoms and further containing at least one double bond. In some embodiments, alkenyl groups have from 1 to 12 carbons, or typically from 1 to 8 carbon atoms. Alkenyl groups may be substituted or unsubstituted. Alkenyl groups include, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and especially hexadienyl groups. Alkenyl groups may be substituted in the same manner as 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.

[0028] 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, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. Aryl groups having one or more alkyl groups are sometimes referred to as alkaryl groups. In some embodiments, aryl groups contain 6 to 14 carbon atoms, and in others 6 to 12, and even 6 to 10 carbon atoms in the ring portion of the group. The phrase "aryl group" includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, etc.). Aryl groups may be substituted or unsubstituted.

[0029]

[0029] The term "alkylaryl" refers to an aryl group with an alkyl substituent. The term "arylalkyl" refers to an alkyl group with an aryl substituent.

[0030]

[0030] In general, the present disclosure is directed to a method for producing a supported single-site catalyst using a non-aromatic solvent, such as one or more branched aliphatic compounds having a boiling point of about 100° C. or higher. It has been discovered that an aluminoxane activator can be satisfactorily immobilized on an inorganic oxide support using a slurry containing a solid aluminoxane activator, an inorganic oxide support, and an organic solvent containing one or more branched aliphatic compounds 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.

[0031] In one aspect, a method for producing a supported single-site catalyst comprises: (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 to about 10 hours to form a supported aluminoxane slurry; (c) contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; Including, The organic solvent comprises one or more branched aliphatic compounds having a boiling point of about 100° C. or greater, present in an amount of about 50% by weight or greater, based on the total amount of organic solvent.

[0032] In another aspect, a method for producing a supported single-site catalyst comprises the steps of: (a) contacting an inorganic oxide support, an organic solvent, and a solid aluminoxane activator at a temperature between about 0° C. and 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 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.; (d) adding the single-site catalyst components to the supported aluminoxane slurry to form a supported single-site catalyst; Including, The organic solvent comprises one or more branched aliphatic compounds having a boiling point of about 100° C. or greater, present in an amount of about 50% by weight or greater, based on the total amount of organic solvent.

[0033] In another embodiment, the slurry comprises: An inorganic oxide support; an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or greater, the organic solvent being present in an amount of about 50% by weight or greater based on the total amount of organic solvent; Solid aluminoxane activator Includes.

[0034]

[0034] 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 in a slurry or isolated form to a second vessel where the single-site catalyst components are added. In another embodiment, a "one-pot" process is used in which a supported aluminoxane slurry is formed and the single-site catalyst components are added to the slurry in the same vessel used to form the slurry.

[0035]

[0035] The support can be any suitable dry inorganic oxide. Such inorganic oxide support materials include metal oxides of Group IIA, IIIA, IVA or IVB, such as silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides that can be used either alone or in combination with silica, alumina or silica-alumina are magnesia, chromia, titania, zirconia, etc. 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 composite oxides thereof, such as SiO2-Al2O3, SiO2-MgO, SiO2iO2, SiO2-TiO2-MgO. In some embodiments, the inorganic oxide support is dry. In some embodiments, the inorganic oxide support comprises silica (e.g., dry silica). In one embodiment, the support comprises silica in an amount by weight of about 50% or more, such as about 60% or more, such as about 80% or more, such as about 90% or more, such as about 99% or more.

[0036] The support may be any suitable inorganic oxide that may be heat treated (e.g., subjected to calcination to remove any residual moisture). Typical conditions for calcination include performing the calcination for a time and temperature sufficient to reduce the total volatiles to a desired amount, where the total volatiles are determined by measuring the weight loss upon destructive calcination of a sample at 1000° C. (e.g., about 0.1 and 8 wt.%). In some embodiments, the calcination may be performed by heating the support to a temperature of about 150 to about 850° C., preferably about 200 to about 700° C., typically for a period of about 1 to about 600 minutes (e.g., 50 to 600 minutes), preferably about 50 to about 300 minutes. The calcination atmosphere may be air or an inert gas. Calcination should be performed under suitable conditions to avoid sintering. Calcination may be performed in a calciner selected from the group consisting of a rotary calciner, a fixed bed oven, and a multi-hearth furnace.

[0037] The specific particle size, surface area, pore diameter, pore volume, etc. of the support material may be selected as known in the art. For example, the particle size may be within the range of about 0.1 to 600 micrometers, and the surface area may be within the range of 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.

[0038]

[0038] 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 carried out 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 a period of 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. Other methods known in the art, such as azeotropic distillation, can also be used to effectively dehydrate the inorganic oxide support.

[0039]

[0039] Aluminoxane activators can exist in the form of linear, cyclic, cage or polymeric structures, but the simplest monomeric compounds are the tetraalkylaluminoxanes, e.g., tetramethylaluminoxane, (CH3)2AlOAl(CH3)2, or tetraethylaluminoxane, (C2H5)2AlOAl(C2H5)2. Preferred compounds for use in olefin polymerization catalysis are sometimes referred to as polyalkylaluminoxanes, and usually contain from about 4 to 20 repeating units:

[0040] [ka]

[0041] [Wherein, R is C1 to C 10 Linear and cyclic aluminoxanes are oligomeric materials containing alkyl groups, such as polymethylaluminoxane (MAO).

[0042] [ka]

[0043] where m and n are integers equal to or greater than 4, but the exact aluminoxane structure remains unknown.

[0044] Methylaluminoxane may contain some higher alkyl groups to improve 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, and the like. The hydrocarbyl aluminoxanes may also contain up to about 20 mole percent (based on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, alkyldisiloxanes, and the like to improve activity, solubility, and / or stability.

[0045]

[0041] Solid aluminoxanes can be prepared in any manner known in the art. For example, one suitable method is by partial hydrolysis of trialkylaluminum compounds. The trialkyl compounds can be hydrolyzed by adding either free water or a solid containing water, which can be either a hydrate or a porous material that has absorbed water. Free water is usually added in the form of a solution or a 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 the like, and hydrates of alkali metal or alkaline earth metal hydroxides such as NaOH·H2O, NaOH·2H2O, Ba(OH)2·8H2O, KOH·2H2O, CsOH·1H2O, LiOH·1H2O, and the like. Mixtures of any of the above hydrates may also be used. The molar ratio of free water in the mixture, or water in the hydrate or porous material, such as alumina or silica, to the total alkylaluminum compound may vary widely, for example, from about 2:1 to about 1:4, such as from about 4:3 to about 1:3.5.

[0046]

[0042] For the hydrolysis process, the method for preparing solid aluminoxane from alkylaluminum compounds may include precipitation, heating and distillation removal of solvent and trimethylaluminum, and chemical treatment. Such methods are described in U.S. Patent Nos. 6,255,419 and 6,518,445, and U.S. Patent Application Publication No. 2015 / 0376306, which are incorporated herein by reference for their disclosure of solid aluminoxane. For example, a toluene solution of methylaluminoxane may be introduced into a glass reactor equipped with a stirrer blade under a nitrogen atmosphere, and then a suitable amount of hexane replaced with nitrogen may be added dropwise at room temperature while stirring. The solid methylaluminoxane is then filtered, washed with hexane, and dried under reduced pressure. In another embodiment, the solid aluminoxane may be prepared by reacting a solution containing alkylaluminoxane, trialkylaluminum, and a hydrocarbon solvent with at least one organic compound containing an element of Groups 15 to 17 of the periodic table under heating conditions.

[0043] Solid 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 may be treated with carbon dioxide.

[0047]

[0044] Such solid aluminoxanes can be prepared by precipitation, as described in U.S. Pat. No. 8,404,880, Chem. Mater., 2016, 28, 7444-7450, and Macromol. Chem. Phys., 2004, 205, 1394-1401, which are incorporated herein by reference for their disclosure of solid aluminoxanes. In some embodiments, the solid aluminoxanes are obtained by heating an aromatic hydrocarbon solution containing polyalkylaluminoxanes and trimethylaluminum to precipitate a solid polyalkylaluminoxane composition. In some embodiments, the solid aluminoxanes are obtained by controlled hydrolysis of trimethylaluminum (TMA) with benzoic acid, followed by pyrolysis.

[0048]

[0045] In some embodiments, the solid aluminoxane activator comprises methylaluminoxane. As noted above, in some embodiments, the solid aluminoxane activator is obtained from solvent stripping, precipitation, heating and distilling off the solvent and trimethylaluminum, or chemical treatment.

[0049] In some embodiments, the solid aluminoxane activator has a total aluminum content in the range of about 35 to about 50 weight percent, or about 39 to about 47 weight percent, including about 35 weight percent, about 36 weight percent, about 37 weight percent, about 38 weight percent, about 39 weight percent, about 40 weight percent, about 41 weight percent, about 42 weight percent, about 43 weight percent, about 44 weight percent, about 45 weight percent, about 46 weight percent, about 47 weight percent, about 48 weight percent, about 49 weight percent, and about 50 weight percent, based on the total weight of the solid aluminoxane activator.

[0050] In some embodiments, the solid aluminoxane activator is either free of trimethylaluminum or has a trimethylaluminum content of about 30 mol% or less, 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 about 20 mol% or less of the total aluminum present in the solid aluminoxane activator.

[0051] 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 can 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 those sold under the trade name ISOPAR™ and manufactured by Exxon Mobil. Illustrative examples of ISOPAR™ include ISOPAR™ E (a mixture of C7-C10 isoparaffins) and ISOPAR™ E (a mixture of C7-C10 isoparaffins). G (a 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.

[0052]

[0049] The organic solvent generally comprises one or more non-aromatic compounds 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 compounds comprise about 60% or more by weight, such as about 70% or more by weight, such as about 80% or more by weight, such as about 90% or more by weight, based on the total amount of organic solvent contained in the slurry. In some embodiments, the non-aromatic compounds comprise about 60% to about 100% by weight of the organic solvent, including about 70% to about 100% by weight, about 80% to about 100% by weight, and about 90% to about 100% by weight, based on the total amount of organic solvent contained in the slurry. In some embodiments, the slurry is free of aromatic compounds.

[0053]

[0050] The solvent generally has a very small 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 of air or purified before being used to generate the slurry as described herein.

[0054]

[0051] 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.

[0055]

[0052] The Cp ligand is one or more rings or ring systems, at least some of which include π-bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues. The rings or ring systems typically include atoms selected from group 13 to group 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, with carbon accounting for at least 50% of the ring members. For example, the Cp ligand can be selected from substituted and unsubstituted cyclopentadienyl ligands, and ligands isotropic to cyclopentadienyl. Non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[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.

[0056] The metal atom "M" of the single-site compound may be selected from group 3-12 and lanthanide group atoms, or may be selected from group 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 group 4, 5 and 6 atoms, or may be Ti, Zr or Hf atom, or may be Hf, or may be Zr. The oxidation state of the metal atom "M" may be in the range of 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 compound of the following structure is 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 are not highly susceptible to substitution / abstraction reactions.

[0057]

[0054] 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.

[0058] In one embodiment, the single-site catalyst has the formula:

[0059] [ka]

[0060] [In the formula, 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 attached to M; R is the same or different and is hydrogen or a hydrocarbyl group containing 1 to 20 carbon atoms, such as an alkyl, alkenyl, aryl, alkylaryl or arylalkyl group, or two carbon atoms are joined together to form a C4-C6 ring; R' is a combination of two (C5R x ) ring and (C5R m ) ring, and a C1-C4 substituted or unsubstituted alkylene group, a dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or amine group, Q is a hydrocarbyl group, for example 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 1 or greater] It can be represented by:

[0061]

[0056] For purposes of illustration of the metallocenes represented by the above formula, non-limiting examples 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 ... bis(cyclopentadienyl)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 phenyl chloride, bis(cyclo 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 pentamethylcyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, Ethylcyclopentadienyltitanium 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 dihalide; dialkyl, trialkyl, tetra-alkyl and penta-alkylcyclopentadienyltitanium compounds, such as bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride; cyclopentadiene complexes bridged with silicon, phosphine, amine or carbon, such as dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methylphosphinedicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopentadienyltitanium 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 diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, ditert-butylmethylene(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, di-tert-butylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl) cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(2,5 dimethylcyclopentadienylfluorenyl)titanium dichloride, 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(I V) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)zirconium(IV) dichloride, 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(IV) dichloride racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-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.

[0062]

[0057] Single-site catalyst components can be prepared using the methods 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, 5,145,819, 5,120, and 5,130, and are not intended to be limiting unless otherwise specified. 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 regarding such components are incorporated herein by reference.

[0063] To form the single-site catalyst, a slurry containing the support, the aluminoxane, and the organic solvent is formed. For example, in one embodiment, the dry inorganic oxide support is mixed with a portion of the organic solvent to form a 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 a stirrer 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 the 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.

[0064] In one embodiment, the weight ratio of the aluminoxane added to the support is about 0.5:1 to about 5:1, such as about 1:1 to about 3:1, such as 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 an amount such that the organic solvent obtained after addition contains more than 50% by weight of aromatic compounds.

[0065] It has been discovered that in order to adequately immobilize 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 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, and such as about 150° C. or higher. Typically, the temperature remains below about 200° C. In some embodiments, maintaining the temperature of the slurry in step (b) is from about 100° C. to about 200° C. or from 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, maintaining the temperature of the slurry in step (b) is 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., and about 150° C. to about 200° C. However, depending on the solvent and reactor pressure, the temperature may be greater than about 200° C. The temperature may be maintained for a period of about 0.5 to about 10 hours, such as about 2 hours to about 6 hours, to form a supported aluminoxane slurry. In some embodiments, the time 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 is kept 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, or 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 may be increased to above about 130 kPa to provide temperatures above the atmospheric boiling point of the solvent.

[0066] After the supported aluminoxane slurry is formed, the slurry can be cooled to a temperature of about 50° C. or less, for example, 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 to about 30° C. For example, in one embodiment, the slurry is gradually cooled back to room temperature.

[0067]

[0062] After the supported aluminoxane slurry is formed, it is contacted with a single-site catalyst component to form the supported single-site catalyst. The single-site catalyst component can be supported on the supported aluminoxane by any method known in the art.

[0068]

[0063] In one embodiment, for example, the slurry may be separated from the organic solvent, optionally stored, and later combined with the single-site catalyst component. In another embodiment, the slurry may be combined with the single-site catalyst component in a separate vessel. Alternatively, in another embodiment, a "one-pot" process may be used in which 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.

[0069] In any of these embodiments, the single-site catalyst component may 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 may then be mixed, such as by stirring, for a sufficient period of time to support the catalyst component on the support. For example, the single-site catalyst component may be added to the supported aluminoxane in a slurry and stirred for a period of time from about 5 minutes to about 5 hours, such as from about 1 hour to about 3 hours, at a temperature of from about 0° C. to about 50° C., such as from about 15° C. to about 30° C.

[0070]

[0065] Additionally, in some embodiments, the single-site catalyst component may be treated prior to combining with the supported aluminoxane. For example, pretreatment may include treating the single-site catalyst component with Al, Mg, Zn, other main group alkyl salts (e.g., TEA, TIBA, MgBu2, ZnEt2), borates, olefin salts, Lewis base salts, or any combination thereof, as known in the art.

[0071] In one embodiment, the weight ratio of 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.

[0072]

[0067] The resulting solid single-site catalyst may then be separated from the solvent by any suitable means, for example by filtering, washing in a non-aromatic organic liquid and then drying, for example by drying under vacuum.

[0073] In some embodiments, the solid single-site catalyst has a total residual solvent 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, and less than about 0.1% by weight. In some embodiments, the solid single-site catalyst has a total residual solvent content of less than about 5% by weight or less than about 2% by weight. In some embodiments, the solid single-site catalyst has a total residual solvent content of about 0% to about 50% by weight, about 0% to about 5% by weight, about 0% to about 2% by weight, and about 0% to about 1% by weight. In some embodiments, the solid single-site catalyst has a total residual solvent content of about 0.1% to about 50% by weight, about 0.1% to about 5% by weight, about 0.1% to about 2% by weight, about 0.1% to about 1% by weight, and about 0.1% to about 0.5% by weight. In some embodiments, the solid single-site catalyst has a total residual solvent content of about 0.01% to about 50% by weight, about 0.01% to about 5% by weight, about 0.01% to about 2% by weight, about 0.01% to about 1% by weight, about 0.01% to about 0.5% by weight, and about 0.01% to about 0.1% by weight.

[0074]

[0069] 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).

[0075] 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% 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, and less than about 0.1% by weight, and less than about 0.01% by weight. 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% by weight. In some embodiments, the solid single-site catalyst has a total residual aromatic solvent content of about 0% to about 50% by weight, about 0% to about 5% by weight, about 0% to about 2% by weight, and about 0% to about 1% by weight. 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%.

[0076] 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, and less than about 0.1% by weight, and 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% to about 50% by weight, about 0% to about 5% by weight, about 0% to about 2% by weight, and about 0% to about 1% by weight. In some embodiments, the solid single-site catalyst has a residual isohexane content of about 0.1% to about 50% by weight, about 0.1% to about 5% by weight, about 0.1% to about 2% by weight, about 0.1% to about 1% by weight, and about 0.1% to about 0.5% by weight. In some embodiments, the solid single-site catalyst has a residual isohexane content of about 0.01% to about 50% by weight, about 0.01% to about 5% by weight, about 0.01% to about 2% by weight, about 0.01% to about 1% by weight, about 0.01% to about 0.5% by weight, and about 0.01% to about 0.1% by weight.

[0077] In another aspect, there is provided a polyolefin produced by any one of the methods described herein. Specifically, the resulting supported solid single-site catalyst may also be contacted with an olefin monomer to produce a polyolefin. Suitable monomers include, but are not limited to, C2 to C6 20 Alpha olefins and C2-C 12 Substituted or unsubstituted C2-C, including alpha olefins 40 Alpha olefins include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In some embodiments, the monomer is ethylene or a C4-C olefin which may be (i) linear, branched or cyclic and / or (ii) strained or unstrained, monocyclic or polycyclic.40 Olefins, C4-C 20 Olefins, C6-C 12 It may contain optional comonomers, including one or more olefins, and may optionally contain heteroatoms and / or one or more functional groups.

[0078]

[0073] The invention having thus been generally described, it will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to limit the invention. EXAMPLES

[0079] The following catalysts were prepared by mixing methylaluminoxane and metallocene catalyst components (e.g., bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride, and Rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride) at 33 microns, 280 microns, and 100 microns, respectively. 2 The catalysts were prepared by immobilization on dehydrated silica having a nominal size, surface area, and pore volume of 1.6 mL / g and 1.6 mL / g. After each catalyst was formed, the same polymerization test conditions were used for each to obtain relative production rates.

[0080] A typical ethylene polymerization process is 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 RRM using a marine impeller. The polymerization temperature was 85° C. The polymerization time was 1 hour. After 1 hour of run time, the reactor was degassed and cooled and the resin was collected. 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.

[0081] A typical propylene polymerization process is as follows: A 4 L liter autoclave was charged with propylene (1030 g), hydrogen (50 mg), TIBA (0.5 mL of a 20% solution in isohexane) and catalyst (0.005 g). The contents were stirred at 800 RRM using a marine impeller. The polymerization temperature was 70° C. The polymerization time was 1 hour. After 1 hour of run time, the reactor was degassed and cooled and the resin was collected. The resin was obtained after drying at 65° C. under vacuum. The catalyst activity (g polymer / g catalyst per hour) was determined by dividing the amount of polymer made by the amount of catalyst added.

[0082] Comparative Example A (One-pot Procedure) Formation of Supported Aluminoxane Slurry and Catalyst Dehydrated silica (6.6 g) was slurried in toluene (57.6 g) in a 250 mL 3-neck flask fitted with an overhead stirring arm and condenser. Solid MAO (5.3 g) was charged and stirred at room temperature for 30 minutes. The internal temperature was raised to 120° C. and the reaction was held for 4 hours. The "sMAO slurry" was cooled back to ambient temperature. Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.23 g) was added and stirred for 2 hours. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL toluene and 3×20 mL isohexane. The solid was dried under vacuum to constant mass.

[0083] Polymerization was carried out according to the above process, with an average polymer production rate of 6,023 g / g catalyst / hour.

[0084] Example 1 Formation of supported aluminoxane slurry Dehydrated silica (6.6 g) was slurried in ISOPAR™ G (42.5 g) in a 250 mL 3-neck flask fitted with an overhead stirring arm and condenser. Solid MAO (4.5 g) was charged and the reaction mixture was stirred at room temperature for 30 minutes. The internal temperature was increased to 120° C. and the reaction was held for 4 hours. The "sMAO slurry" was cooled back to ambient temperature.

[0085] Formation of catalyst 1 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 h. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL Isopar G and 3×20 mL isohexane. The solid was dried under vacuum to constant mass (0.03 wt % residual toluene, 1.66 wt % residual isohexane).

[0086] Polymerization was carried out according to the above process, with an average polymer production rate of 5,769 g / g catalyst / hr.

[0087] Formation of catalyst 2 Rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)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 solid was collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ G and 3×20 mL isohexane. The solid was dried under vacuum to constant mass.

[0088] The polymerization was carried out according to the process described above for polymerizing propylene. The average polymer production rate was 20,044 g / g catalyst / hour.

[0089] Example 2 Formation of Supported Aluminoxane Slurry and Catalyst 3 Dehydrated silica (5.0 g) was slurried in ISOPAR™ G (37.7 g) in a 250 mL 3-neck flask fitted with an overhead stirring arm and condenser. Solid MAO (4.0 g) was charged and stirred at room temperature for 30 minutes. The internal temperature was raised to 150° C. and the reaction was held for 4 hours. The “sMAO slurry” was cooled back to ambient temperature. Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.18 g) was added and stirred for 2 hours. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL ISOPAR™ G and 3×20 mL isohexane. The solid was dried under vacuum to constant mass (0.13 wt % residual toluene, 1.62 wt % residual isohexane).

[0090] Polymerization was carried out according to the above process, with an average polymer production rate of 4,839 g / g catalyst / hr.

[0091] Example 3 Formation of Supported Aluminoxane Slurry and Catalyst 4 Dehydrated silica (4.1 g) was slurried in methylcyclohexane (40.4 g) in a 250 mL 3-neck flask fitted with an overhead stirring arm and condenser. Solid MAO (3.3 g) was charged and stirred at room temperature for 30 minutes. The internal temperature was raised to 100° C. and the reaction was held for 4 hours. The “sMAO slurry” was cooled back to ambient temperature. Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (0.15 g) was added and stirred for 2 hours. The solid was collected on a coarse fritted disk filter and washed with 1×20 mL methylcyclohexane and 3×20 mL isohexane. The solid was dried under vacuum to constant mass (0.28 wt % residual toluene, 1.85 wt % residual isohexane).

[0092] Polymerization was carried out according to the above process, with an average polymer production rate of 6,057 g / g catalyst / hr.

[0093]

[0092] Paragraph 1. A method for producing a supported single-site catalyst, 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 to about 10 hours to form a supported aluminoxane slurry; (c) contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; Including, the organic solvent comprises 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 greater based on the total amount of organic solvent; method.

[0094]

[0093] Paragraph 2. The method of paragraph 1, wherein the slurry in step (a) does not contain any aromatic compounds.

[0095]

[0094] Paragraph 3. The method of any one of Paragraphs 1-2, wherein the organic solvent comprising the one or more branched aliphatic compounds comprises an isoparaffin.

[0096]

[0095] Paragraph 4. The method of any one of Paragraphs 1 to 3, wherein the organic solvent comprising the one or more branched aliphatic compounds comprises one or more C7 to C12 isoparaffins.

[0097]

[0096] Paragraph 5. The method of Paragraph 4, wherein the one or more C7 to C12 isoparaffins are selected from one or more of C7 to C10 isoparaffins and C9 to C12 isoparaffins.

[0098]

[0097] Paragraph 6. The method of any one of Paragraphs 1 to 5, wherein the organic solvent comprises a mineral oil.

[0098] Paragraph 7. The method of any of the preceding paragraphs, wherein the solid aluminoxane activator comprises methylaluminoxane.

[0099]

[0099] Paragraph 8. The method of Paragraph 7, wherein the solid aluminoxane activator is obtained from solvent stripping, precipitation, heating and distilling off the solvent and trimethylaluminum, or chemical treatment.

[0100]

[0100] Paragraph 9. The method of any one of Paragraphs 7-8, wherein the solid aluminoxane activator has a total aluminum content in the range of about 35 to about 50 weight percent, based on the total weight of the solid aluminoxane activator.

[0101]

[0101] Paragraph 10. The method of any of the preceding paragraphs, further comprising the step of cooling the supported aluminoxane slurry to a temperature of about 50° C. or less prior to the step of contacting the supported aluminoxane slurry with the single-site catalyst component.

[0102]

[0102] Paragraph 11. The method of any of the preceding paragraphs, further comprising the step of cooling the supported aluminoxane slurry to a temperature of about 25° C. prior to the step of contacting the supported aluminoxane slurry with the single-site catalyst component.

[0103]

[0103] Paragraph 12. The method of any of the preceding paragraphs, wherein the step of maintaining the temperature of the slurry in step (b) is from about 115°C to about 155°C.

[0104]

[0104] Paragraph 13. The method of paragraph 12, wherein the step of maintaining the temperature of the slurry in step (b) is about 120°C or about 155°C.

[0105]

[0105] Paragraph 14. The method of 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% by weight or greater.

[0106]

[0106] Paragraph 15. The method of any of the preceding paragraphs, wherein the organic solvent is present in an amount of about 60% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80% by weight or more, about 90% by weight or more, or about 95% by weight or more.

[0107]

[0107] Paragraph 16. The method of any of the preceding paragraphs, comprising a step of separating the supported aluminoxane from the organic solvent prior to the step of contacting with the single-site catalyst component.

[0108]

[0108] Paragraph 17. The method of any of the preceding paragraphs, wherein the inorganic oxide support comprises silica.

[0109]

[0109] Paragraph 18. The method of paragraph 17, wherein the inorganic oxide support comprises dry silica.

[0110] Paragraph 19. The method of any one of Paragraphs 17-18, wherein the inorganic oxide support comprises silica in an amount of about 50% by weight or more, about 60% by weight or more, about 80% by weight or more, about 90% by weight or more, or about 99% by weight or more.

[0110]

[0111] Paragraph 20. The method of any of the preceding Paragraphs, wherein the single-site catalyst component comprises a metallocene compound.

[0111]

[0112] 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.

[0112]

[0113] Paragraph 22. The method of Paragraph 21, wherein the metallocene compound comprises titanium, zirconium or hafnium.

[0113]

[0114] Paragraph 23. The method of any one of the preceding Paragraphs, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt.%.

[0114]

[0115] Paragraph 24. The method of Paragraph 23, wherein the supported single-site catalyst has a total residual solvent content of less than about 5 wt.% or about 2 wt.%.

[0115]

[0116] Paragraph 25. The method of any one of the preceding Paragraphs, wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt.%.

[0116]

[0117] Paragraph 26. A method for producing a supported single-site catalyst, 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 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.; (d) adding the single-site catalyst components to the supported aluminoxane slurry to form a supported single-site catalyst; Including, the organic solvent comprises 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 greater based on the total amount of organic solvent; method.

[0117]

[0118] Paragraph 27. The method of claim 26, wherein the inorganic oxide support is heat treated.

[0119] Paragraph 28. The method of any one of Paragraphs 26-27, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt.%.

[0118]

[0120] Paragraph 29. The method of Paragraph 28, wherein the supported single-site catalyst has a total residual solvent content of less than about 5 wt.% or about 2 wt.%.

[0119]

[0121] Paragraph 30. The method of any one of Paragraphs 26-29, wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt.%.

[0120]

[0122] Paragraph 31. The method of any one of Paragraphs 26 to 30, further comprising contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin.

[0121]

[0123] Paragraph 32. A polyolefin produced by a process according to paragraph 31.

[0124] Paragraph 33. A supported single-site catalyst produced by the method of any one of Paragraphs 1 to 31.

[0122]

[0125] Paragraph 34. Inorganic oxide supports; an organic solvent comprising one or more branched aliphatic compounds having a boiling point of about 100° C. or greater, the organic solvent being present in an amount of about 50% by weight or greater based on the total amount of organic solvent; Solid aluminoxane activator A slurry comprising:

[0123]

[0126] Paragraph 35. The method of Paragraph 34, wherein the slurry has a total residual solvent content of less than about 50% by weight.

[0124]

[0127] Paragraph 36. The method of Paragraph 35, wherein the slurry has a total residual solvent content of less than about 5% by weight or about 2% by weight.

[0125]

[0128] Paragraph 37. The method of any one of Paragraphs 34-36, wherein the slurry has a total residual aromatic solvent content of less than about 0.5 wt.%.

[0126]

[0129] While certain specific embodiments have been illustrated and described, it is to be understood that changes and modifications may be made therein by those of ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0127]

[0130] The embodiments illustratively described herein may suitably be practiced in the absence of any element(s) or limitation(s) not specifically disclosed herein. Thus, for example, terms such as "comprising," "including," "containing," and the like, should be read openly and without limitation. In addition, the terms and expressions used herein are used as terms of description and not as terms of limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the features shown and described, 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" is understood to include the elements specifically recited and additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0128]

[0131] The present disclosure is not limited in terms of 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 listed herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art from the above description. Such modifications and variations are intended to be included within the scope of the appended claims. The present disclosure should be limited only by the terms of the appended claims, together with the full scope of equivalents entitled to 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 terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0129]

[0132] In addition, when features or aspects of the disclosure are described in terms of a Markush group, those skilled 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.

[0130]

[0133] As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein encompass any and all possible subranges and combinations of these subranges. Any recited range is fully described and can be readily recognized as being capable of being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third, upper third, etc. As will also be understood by those skilled in the art, all language such as "up to," "at least," "greater than," "less than," etc., refers to a range that includes the recited numbers and can be subsequently broken down into subranges as discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member.

[0131]

[0134] All publications, patent applications, issued patents, and other documents mentioned in this specification are hereby incorporated by reference to the same extent 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 text incorporated by reference are excluded to the extent that they conflict with definitions in this disclosure.

[0132]

[0135] Other embodiments are set forth in the following claims.

Claims

1. 1. A method for producing a supported single-site catalyst, 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 to about 10 hours to form a supported aluminoxane slurry; (c) contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; Including, the organic solvent comprises 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 based on the total amount of organic solvent; method.

2. 10. The method of claim 1, wherein the slurry in step (a) is free of any aromatic compounds.

3. 10. The method of claim 1, wherein the organic solvent comprising one or more branched aliphatic compounds comprises an isoparaffin.

4. The method described in claim 3, wherein the isoparaffin is selected from one or more of C7 to C10 isoparaffins and C9 to C12 isoparaffins.

5. The method of claim 1 , wherein the organic solvent comprises mineral oil.

6. The method of claim 1 , wherein the solid aluminoxane activator comprises methylaluminoxane.

7. 7. The method of claim 6, wherein the solid aluminoxane activator is obtained from solvent stripping, precipitation, heating and distilling off the solvent and trimethylaluminum, or chemical treatment.

8. 7. The method of claim 6, wherein the solid aluminoxane activator has a total aluminum content in the range of about 35 to about 50 weight percent, based on the total weight of the solid aluminoxane activator.

9. 10. The method of claim 1, further comprising the step of cooling the supported aluminoxane slurry to a temperature of about 50°C or less prior to the step of contacting the supported aluminoxane slurry with the single-site catalyst component.

10. 10. The method 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.

11. 10. The method of claim 1, wherein the organic solvent is present in an amount of about 60% by weight or greater.

12. 10. The method of claim 1, further comprising the step of separating the supported aluminoxane from the organic solvent prior to the step of contacting with the single-site catalyst component.

13. The method of claim 1 , wherein the inorganic oxide support comprises silica.

14. The method of claim 1 , wherein the single-site catalyst component comprises a metallocene compound.

15. 15. The method of claim 14, wherein the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel.

16. 10. The method 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.%.

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

18. 20. A polyolefin produced by the method of claim 17.

19. 10. A supported single-site catalyst produced by the method of claim 1.

20. an inorganic oxide support; 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 based on the total amount of organic solvent; Solid aluminoxane activator and , a slurry comprising: