WO2023177433A1

WO2023177433A1 - Process for producing heat treated supported aluminoxanes in an aliphatic solvent using solid aluminoxanes

Info

Publication number: WO2023177433A1
Application number: PCT/US2022/053067
Authority: WO
Inventors: C. Gail BLAKLEY; Matthew G. Thorn; William R. Beard; John H. HAIN, JR.
Original assignee: W.R. Grace & Co.-Conn.
Priority date: 2022-03-17
Filing date: 2022-12-15
Publication date: 2023-09-21

Abstract

A process for producing a supported single-site catalyst is provided. The process includes forming a slurry comprising an inorganic oxide support, an organic solvent, and a solid aluminoxane activator; maintaining the temperature of the slurry from about 100°C to about 200°C for a time period from 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 a supported single-site catalyst. The organic solvent includes one or more branched aliphatic compound having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent.

Description

PROCESS FOR PRODUCING HEAT TREATED SUPPORTED

ALUMINOXANES IN AN ALIPHATIC SOLVENT USING SOLID

ALUMINOXANES

CROSS REFERENCE TO RELATED APPLICATIONS

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

FIELD

[0002] The present technology is generally related to polyolefin catalyst systems. More specifically, the technology is related to methods for preparing heat treated supported aluminoxanes in aliphatic solvents.

BACKGROUND

[0003] Polyolefins are commonly prepared by reacting olefin monomers in the presence of catalysts composed of a support and catalytic components deposited in the pores and on the surfaces of the support. For example, one type of polyolefin catalyst is a single-site catalyst, which typically comprises a support, an activator, and a single-site catalyst component, such as a metallocene component. Aluminoxanes are commonly used as the activator. 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 process. Although the solvent is typically removed from the resulting catalyst, it is difficult to remove all the toluene and thus polymers produced from the resulting catalysts tend to contain some toluene.

[0004] Recently, there has been a push to produce polyolefins with lower levels of aromatic compounds, such as toluene, especially in polyolefins intended for use in the food and beverage industries. As such, there is a need for producing supported single-site catalysts that contain low amounts of toluene, which may be used to produce polyolefins that contain less residual toluene. This disclosure addresses this need by providing methods for preparing heat treated supported aluminoxanes in aliphatic solvents.

SUMMARY

[0005] Provided in one aspect is a process for producing a supported single-site catalyst including:

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

(b) maintaining the temperature of the slurry from about 100°C to about 200°C for a time period from about 0.5 to about 10 hours to form a supported aluminoxane slurry; and

(c) contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; wherein the organic solvent includes one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent.

[0006] In some embodiments, the slurry in step (a) does not include any aromatic compounds. In some embodiments, the organic solvent including one or more branched aliphatic compounds includes isoparaffins. In some embodiments, the organic solvent including the one or more branched aliphatic compounds includes one or more C7-C12 isoparaffins. In some embodiments, the one or more C7-C12 isoparaffins are selected from more one or more of C7-C10 isoparaffins and C9-C12 isoparaffins. In some embodiments, the organic solvent includes mineral oil.

[0007] In some embodiments, the solid aluminoxane activator includes methylaluminoxane. In some embodiments, the solid aluminoxane activator is obtained from solvent stripping, precipitation, heating and distillation removal of the solvent and trimethylaluminum, or chemical treatment. In some embodiments, the solid aluminoxane activator has a total aluminum content in the range of from about 35 to about 50 wt % based on a total weight solid aluminoxane activator. [0008] In some embodiments, the process further includes cooling the supported aluminoxane slurry to a temperature of about 50°C or less before contacting the supported aluminoxane slurry with the single-site catalyst component. In some embodiments, the process further includes cooling the supported aluminoxane slurry to a temperature of about 25°C before contacting the supported aluminoxane slurry with the single-site catalyst component.

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

[0010] In some embodiments, the organic solvent includes one or more non-aromatic organic compounds having a boiling point greater than the highest temperature reached by the slurry in an amount of about 50 wt.% or greater. In some embodiments, the organic solvent is present in an amount of about 60 wt.% or greater, about 70 wt.% or greater, about 75 wt.% or greater, about 80 wt.% or greater, about 90 wt.% or greater, or about 95 wt.% or greater.

[0011] In some embodiments, the process includes separating the supported aluminoxane from the organic solvent before contacting it with the single-site catalyst component.

[0012] In some embodiments, the inorganic oxide support is thermally treated (such as calcination). In some embodiments, the inorganic oxide support is dried. In some embodiments, the inorganic oxide support includes silica. In some embodiments, the inorganic oxide support includes dried silica. In some embodiments, the inorganic oxide support includes silica in an amount of about 50 wt.% or more, about 60 wt.% or more, about 80 wt.% or more, about 90 wt.% or more, or about 99 wt.% or more.

[0013] In some embodiments, the single-site catalyst component includes a metallocene compound. In some embodiments, the metallocene compound includes scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel. In some embodiments, the metallocene compound includes 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 singlesite 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%.

[0015] Provided in another aspect is a process for producing a supported single-site catalyst including:

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

(b) heating the slurry to a temperature from about 100°C to about 200°C for a time period from about 0.5 to about 10 hours to form a supported aluminoxane slurry;

(c) cooling the slurry to a temperature from about 0°C to about 50°C; and

(d) adding a single-site catalyst component to the supported aluminoxane slurry to form a supported single-site catalyst; wherein the organic solvent comprises one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent.

[0016] In some embodiments, the inorganic oxide support is dried. In some embodiments, the inorganic oxide support is thermally 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 process further includes contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin.

[0017] Provided in another aspect is a polyolefin produced by any one of the processes described herein. [0018] Provided in another aspect is a supported single-site catalyst produced by any of the processes described herein.

[0019] Provided in another aspect is a slurry including: an inorganic oxide support; an organic solvent comprising one or more one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent; and a solid aluminoxane activator.

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

[0021] Other features and aspects of the present disclosure are discussed in greater detail below.

DETAILED DESCRIPTION

[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 to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and may be practiced with any other embodiment(s).

[0023] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are 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 up to plus or minus 10% of the particular term.

[0024] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are 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 into the specification as if it were individually recited herein. All methods described herein may be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0025] In general, the alkyl, alkenyl, aryl, or ether group, as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms may be substituted. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Thus, a substituted group will be substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; nitriles (i.e., CN); and the like.

[0026] As used herein, “alkyl” groups include straight chain and branched alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. As employed herein, “alkyl groups” include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted. An alkyl group may be substituted one or more times. An alkyl group 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 groups, and l-cyclopentyl-4-methylpentyl. Representative substituted alkyl groups may be substituted one or more times with, for example, 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 per-haloalkyl group.

[0027] Alkenyl groups are straight chain, branched or cyclic alkyl groups having 2 to about 20 carbon atoms, and further including 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 instance, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups among others. Alkenyl groups may be substituted similarly to alkyl groups. Divalent alkenyl groups, i.e., alkenyl groups with two points of attachment, include, but are not limited to, CH-CH=CH2, C=CH₂, or C=CHCH₃.

[0028] As used herein, “aryl”, or “aromatic,” groups are cyclic aromatic hydrocarbons that do 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. An aryl group with one or more alkyl groups may also be referred to as alkaryl groups. In some embodiments, aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. The phrase “aryl groups” includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like). Aryl groups may be substituted or unsubstituted.

[0029] The term “alkylaryl” refers to an aryl group with an alkyl substituent. The term “arylalkyl” refers to an alkyl group with an a d substituent. [0030] In general, the present disclosure is directed to a process 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 greater. It was discovered that an aluminoxane activator may be sufficiently immobilized on an inorganic oxide support using a slurry containing the solid aluminoxane activator, the inorganic oxide support, and an organic solvent including one or more one or more branched aliphatic compounds having a boiling point of about 100°C or greater. A single-site catalyst component can then be added to the supported aluminoxane to form a supported singlesite catalyst.

[0031] In one aspect, a process for producing a supported single-site catalyst includes:

[0032] In another aspect, a process for producing a supported single-site catalyst includes:

(c) cooling the slurry to a temperature from about 0°C to about 50°C; and

[0033] In another aspect, a slurry includes: an inorganic oxide support; an organic solvent comprising one or more one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent; and a solid aluminoxane activator.

[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 is then transferred in 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 wherein 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.

[0035] The support may be any suitable dried 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 may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, chromia, titania, zirconia, and the like. For example, inorganic oxides useful in this invention include without limitation, SiO2, AI2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, TI1O2 and double oxides thereof, e.g. SiO2 — AI2O3, SiO2 — MgO, SiO2iO2, SiO2 — TiO2 — MgO. In some embodiments, the inorganic oxide support is dried. In some embodiments, the inorganic oxide support includes silica (e.g.. dried silica). In one embodiment, the support includes silica in an amount of about of about 50 wt.% or more, about 60 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more, such as about 99 wt.% or more.

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

[0037] The specific particle size, surface area, pore diameter, pore volume, etc. of the support materials may be selected as known in the art. For example, particle sizes can range from about 0.1 to 600 micrometers, surface areas can range from about 50 to 1000 m² /g, pore diameters can range from about 50-500 angstroms and pore volumes can range from about 0.3 to 5.0 cc/g.

[0038] The inorganic oxide support is dehydrated before forming the slurry with the organic solvent and the aluminoxane activator. For example, supports may be dehydrated either chemically or by heating or calcining the support at a temperature and time sufficient to remove water. For example, drying or calcining the support will typically be conducted by heating the support to temperatures of from about 100°C to about 1000°C, such as from about 150°C to about 600°C, such as from about 200°C to about 300°C for periods of from about 1 minute to about 100 hours, such as from about 50 minutes to about 5 hours. The atmosphere during drying may be air or an inert gas. Other methods known in the art, such as azeotropic distillation, may also be used to effectively dehydrate the inorganic oxide support.

[0039] The aluminoxane activator may exist in the form of linear, cyclic, caged or polymeric structures with the simplest monomeric compounds being a tetraalkylaluminoxane such as tetramethylaluminoxane, (CH3)2A1OA1(CH3)2, or tetraethylaluminoxane, (C2H5)2A1OA1(C2H5)2. The compounds preferred for use in olefin polymerization catalysts are oligomeric materials, sometimes referred to as polyalkylaluminoxanes, which usually contain about 4 to 20 of the repeating units:

where R is Ci -Cio alkyl, such as polymethylaluminoxanes (MAOs). Although the linear and cyclic aluminoxanes are often noted as having the structures

where m and n are integers of 4 or more, the exact configuration of aluminoxanes remains unknown.

[0040] Methylaluminoxanes can contain some higher alkyl groups to improve their solubility. Besides MAO, non-limiting examples of hydrocarbylaluminoxanes for use in the invention include ethylaluminoxanes (EAO), isobutylaluminoxanes (IB AO), n- propylaluminoxanes, n-octylaluminoxanes, and the like. The hydrocarbylaluminoxanes can also contain up to about 20 mole percent (based on aluminum) of moi eties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, alkyl disiloxanes and the like to improve activity, solubility and/or stability.

[0041] The solid aluminoxanes may be prepared in any manner known in the art. For example, one suitable method is by the partial hydrolysis of trialkylaluminum compounds. The trialkylaluminum compounds may be hydrolyzed by adding either free water or water containing solids, which may be either hydrates or porous materials which have absorbed water. Because it is difficult to control the reaction by adding water per se, even with vigorous agitation of the mixture, the free water is usually added in the form of a solution or a dispersion in an organic solvent. Suitable hydrates include salt hydrates, such as CuSO₄ 5H₂O, Ah (SO₄)₃ I8H2O, FeSO₄ 7H₂O, AlCh 6H2O, A1(NO₃)₃ 9H₂O, MgSO₄ 7H₂O, MgCh 6H2 O, ZnSO₄ 7H₂ O, Na₂SO₄ IOH2O, Na₃ PO₄ 12H₂O, LiBr 2H₂O, LiCl IH2O, Lil 2H₂O, Lil 3H₂O, KF 2H₂O, NaBr 2H₂O and the like, and alkali or alkaline earth metal hydroxide hydrates, such as NaOH EhO, NaOH 2H2O, Ba(OH)₂ 8H2O, KOH 2H₂O, CsOH IH2O, LiOH IH2O, and the like. Mixtures of any of the above hydrates may be used. The mole ratios of free water or water in the hydrate or in porous materials, such as alumina or silica, to total alkyl aluminum compounds in the mixture can vary widely, such as from about 2: 1 to about 1 :4, such as from about 4:3 to about 1 :3.5.

[0042] With regard to hydrolytic processes, methods for preparing solid aluminoxanes from alkyl aluminum compounds may include precipitation, heating and distillation removal of the 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. 2015/0376306, which are incorporated herein by reference with the disclosure of solid aluminoxanes. For instance, a toluene solution of methylaluminoxane may be introduced into a glass reactor equipped with a stirrer blade under nitrogen atmosphere following by dropwise addition of a suitable amount of nitrogen-replaced hexane at room temperature with stirring. The solid methylaluminoxane may then be filtered, washed with hexane, and dried under reduced pressure. In other embodiments, the solid aluminoxane may be prepared by reacting a solution including an alkylaluminoxane, a trialkylaluminum, and a hydrocarbon solvent with at least one organic compound containing a Group 15-17 element in the periodic table under heating conditions. [0043] The solid aluminoxanes can also be prepared by non-hydrolytic processes, for example, by reaction of an alkyl aluminum compound with an organic compound with one or more oxygen-containing functional groups such as carbonyl, carboxyl, and/or hydroxyl groups; examples of such compounds include PhCOMe, PhCOOH, PhCOOMe, PhsCOH and the like. Alternatively, a trialkylaluminum may be treated with carbon dioxide.

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

[0045] In some embodiments, the solid aluminoxane activator includes methylaluminoxane. In some embodiments, the solid aluminoxane activator is obtained from solvent stripping, precipitation, heating and distillation removal of the solvent and trimethylaluminum, or chemical treatment as described above.

[0046] In some embodiments, the solid aluminoxane activator has a total aluminum content in the range of from about 35 to about 50 wt % or from about 39 to about 47 wt % based on a total weight solid aluminoxane activator, including about 35 wt %, about 36 wt %, about 37 wt %, about 38 wt %, about 39 wt %, about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt %, about 45 wt %, about 46 wt %, about 47 wt %, about 48 wt %, about 49 wt %, and about 50 wt %.

[0047] In some embodiments, the solid aluminoxane activator is either free of trimethylaluminum or has a trimethylaluminum content of no more than about 30 mole %, including about 25 mole %, about 20 mole %, about 15 mole %, about 10 mole %, about about 5 mole %, and about 1 mole %. In some embodiments, the solid aluminoxane activator has a trimethylaluminum content of no more than about 20 mole % of the total aluminum present in the solid aluminoxane activator.

[0048] The organic solvent used to form the slurry containing the support material and the aluminoxane activator (e.g. the slurry in step (a)includes one or more branched aliphatic hydrocarbon compounds having a boiling point of about 100°C or more.

Such hydrocarbon compounds may saturated or unsaturated, hydrocarbons having from about 7 to about 12 carbon atoms (e.g., isoparaffins). Suitable isoparaffins, such as C7- C12 isoparaffins, C7-C10 isoparaffins, C9-C12 isoparaffins, C10-C12 isoparaffins, and those sold under the tradename ISOPAR™ and are manufactured by Exxon Mobil. Illustrative 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-dimethyl decane, isotetradecane, and combinations thereof. The organic solvent may also contain mineral oils. The slurry in step (a) is substantially free of any aromatic content or aromatic compounds.

[0049] The organic solvent generally comprises one or more non-aromatic compounds having boiling points of about 100°C or greater in an amount greater than 50 wt.% relative to 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, non-aromatic compounds constitute from about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more of the organic solvent relative to the total amount of organic solvent contained in the slurry. In some embodiments, non-aromatic compounds constitute from about 60 wt.% to about 100 wt.%, including from about 70 wt.% to about 100 wt.%, from about 80 wt.% to about 100 wt.%, and from about 90 wt.% to about 100 wt.%, of the organic solvent relative to the total amount of organic solvent contained in the slurry. In some embodiments, the slurry is free of aromatic compounds.

[0050] 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 substances. In this regard, in some embodiments, the solvent is purged of air and purified prior to being used to produce a slurry as described herein.

[0051] The single site-catalyst component can comprise any transition metal or metallocene single site catalyst known in the art. For example, single-site catalysts can include "half sandwich" and "full sandwich" compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom.

[0052] The Cp ligands are one or more rings or ring system(s), at least a portion of which includes 7t-bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues. The ring(s) or ring system(s) typically comprise atoms selected from Groups 13 to 16 atoms, and, in some embodiments, the atoms that make up the Cp ligands are selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum, and combinations thereof, where carbon makes up at least 50% of the ring members. For example, the Cp ligand(s) may be selected from substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl. Nonlimiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H- cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4, 5,6,7- tetrahydroindenyl, or "H4 Ind"), substituted versions thereof (as discussed and described in more detail below), and heterocyclic versions thereof.

[0053] The metal atom "M" of the single-site compound may be selected from Groups 3 through 12 atoms and lanthanide Group atoms; or may be selected from Groups 3 through 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" can range from 0 to +7; or may be +1, +2, +3, +4 or +5; or may be +2, +3 or +4. The groups bound to the metal atom "M" are such that the compounds described below in the structures are electrically neutral, unless otherwise indicated. The Cp ligand(s) forms at least one chemical bond with the metal atom M to form a "metallocene catalyst component." The Cp ligands are distinct from the leaving groups bound to metal atom M in that they are not highly susceptible to substitution/abstraction reactions.

[0054] In some embodiments, the single-site catalyst component includes a metallocene compound. In some embodiments, the metallocene compound includes scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel. In some embodiments, the metallocene compound includes titanium, zirconium, or hafnium.

[0055] In one embodiment, the single-site catalyst may be represented by the following formula:

(C₅R )_JR'₁(C_jR_B,)MQ_B-J,_ , wherein:

M is a metal of Groups IIIB to VIII of the Periodic Table of the Elements; (Cs c) and (CsRm) are the same or different cyclopentadienyl or substituted cyclopentadienyl groups bonded to M; R is the same or different and is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 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 radical, a dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or amine radical bridging two (CsRx) and (CsRm) rings;

Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and may be the same or different from each other; z is 0 or 1; y is 0, 1 or 2; z is 0 when y is 0; n is 0, 1, 2, 3, or 4 depending upon the valence state of M; and n-y is >1.

[0056] Illustrative but non-limiting examples of the metallocenes represented by the above formula are 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 dineopentyl, bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium dimethyl; the mono alkyl 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(cyclopentadienyl)titanium methyl bromide; the 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; monocyclopentadienyls titanocenes such as, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride; bis(pentamethylcyclopentadienyl) titanium diphenyl, the carbene 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(l ,2- dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(l ,2- diethylcyclopentadienyl)titanium diphenyl or dichloride; silicon, phosphine, amine or carbon bridged cyclopentadiene complexes, such as dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride, methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl titanium diphenyl or dichloride and other dihalide complexes, and the like; as well as 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, ditertbutylmethylene (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(cyclopentadienyl) (fluorenyl)hafnium dichloride, 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, ditertbutylmethylene(cyclopentadienyl) (fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl) (fluorenyl)titanium dichloride, diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride, racemic-ethylene bis (1-indenyl) zirconium (IV) di chloride, racemic-ethylene bis (4, 5, 6, 7- tetrahydro-l-indenyl) zirconium (IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) zirconium (IV) dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-l-indenyl) zirconium (IV) dichloride, racemic- 1,1, 2, 2- tetramethylsilanylene bis (1-indenyl) zirconium (IV) dichloride, racemic- 1,1, 2, 2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-l- indenyl) zirconium (IV), dichloride, ethylidene (1-indenyl tetramethylcyclopentadi enyl) zirconium (IV) di chloride, racemic- dimethylsilyl bis (2-methyl-4-t-butyl-l- cyclopentadienyl) zirconium (IV) dichloride, racemic-ethylene bis (1-indenYl) hafnium (IV) dichloride, racemic-ethylene bis (4,5,6,7-tetrahydro-l-indenyl) hafnium (IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) hafnium (IV) dichloride, racemic- dimethylsilyl bis (4,5,6,7-tetrahydro-l- indenyl) hafnium (IV) dichloride, racemic- 1,1, 2,2- tetramethylsilanylene bis (1-indenyl) hafnium (IV) dichloride, racemic- 1, 1,2,2- tetramethylsilanylene bis (4,5,6,7-tetrahydro-l- indenyl) hafnium (IV), dichloride, ethylidene (l-indenyl-2,3,4,5-tetramethyl-l-cyclopentadienyl) hafnium (IV) dichloride, racemic- ethylene bis (1-indenyl) titanium (IV) dichloride, racemic-ethylene bis (4,5,6,7- tetrahydro-l-indenyl) titanium (IV) dichloride, racemic- dimethylsilyl bis (1-indenyl) titanium (IV) dichloride, racemic- dimethylsilyl bis (4,5,6,7-tetrahydro-l-indenyl) titanium (IV) dichloride, racemic- 1,1, 2, 2-tetramethylsilanylene bis (1-indenyl) titanium (IV) dichloride racemic- 1,1, 2, 2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-l-indenyl) titanium (IV) dichloride, bis(l-methy-3-butylcyclopentadienyl) zirconium dichloride, and ethylidene (l-indenyl-2,3,4,5-tetramethyl-l-cyclopentadienyl) titanium IV) dichloride.

[0057] Single site catalyst components are described, for example, in U.S. Pat. Nos. 2,864,843; 2,983,740; 4,665,046: 4,874,880; 4,892,851; 4,931,417; 4,952,713; 5,017,714: 5,026,798; 5,036,034; 5,064,802; 5,081,231; 5,145,819; 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, whose teachings with respect to such components are incorporated herein by reference.

[0058] 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 dried inorganic oxide support is mixed with a portion of the organic solvent to form a slurry. The slurry may be formed in any suitable vessel using any suitable mixing means. For example, in one embodiment, the vessel may be fitted with a condenser and a stirrer or impeller. The vessel may 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, aluminoxane, and organic solvent. In such embodiments, the total organic solvent includes both the organic solvent used to slurry the support and the organic solvent added with the aluminoxane.

[0059] In one embodiment, the weight ratio of aluminoxane added to the support is from about 0.5: 1 to about 5:1, such as from about 1 : 1 to about 3: 1, such as from about 2: 1 to about 2.5: 1. Notably, if the aluminoxane is dissolved in an aromatic solvent, it should not be added in an amount such that the resulting organic solvent after the addition contains more than 50 wt.% of aromatic compounds.

[0060] It was discovered that, in order to sufficiently immobilize the aluminoxane activator on the support, the temperature of the slurry at step (b) must be maintained at about 100°C or greater for a sufficient time period. Therefore, in one embodiment, the temperature of the slurry is raised to a temperature of about 100°C or greater, such as about 110°C or greater, such as about 120°C or greater, such as about 130°C or greater, such as about 140°C, such as about 150°C or greater, and such as about 150°C or greater,. Typically, the temperature remains less than about 200°C. In some embodiments, maintaining the temperature of the slurry at 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 at step (b) is about 120°C or about 155°C. In some embodiments, maintaining the temperature of the slurry at step (b) is from about 100°C to about 200°C, including from about 110°C to about 200°C, from about 120°C to about 200°C, from about 130°C to about 200°C, from about 140°C to about 200°C, and from about 150°C to about 200°C. However, depending on the solvent and the pressure of the reactor, the temperature may be greater than about 200°C. The temperature may be maintained for a time period from about 0.5 to about 10 hours, such as from about 2 hours to about 6 hours to form a supported aluminoxane slurry. In some embodiments, the time period is about 0.5 hour, 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, such as from about 90 to about 130kPa or from about 90 to about 110 kPa, throughout the process. 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 elevated above 130 kPa and brought to temperatures above the atmospheric boiling point of the solvent.

[0061] After the supported aluminoxane slurry is formed, the slurry may be cooled to a temperature of about 50°C or lower, such as from about 15°C to about 50°C or from 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 allowed to gradually cool back to room temperature.

[0062] After the supported aluminoxane slurry is formed, it is contacted with a singlesite catalyst component to form the supported single-site catalyst. The single-site catalyst component may be loaded onto the supported aluminoxane in any manner known in the art.

[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, after the slurry is cooled, the single site catalyst component is added to the supported aluminoxane slurry in the same vessel the slurry was formed in. [0064] In any of such 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 the single-site catalyst component and supported aluminoxane can then be mixed, such as by stirring, for a time period sufficient to load 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 at a temperature from about 0°C to about 50°C, such as from about 15°C to about 30°C for a time from about 5 min to about 5 hours, such as from about 1 hour to about 3 hours.

[0065] Additionally, in some embodiments, the single site catalyst component may be treated prior to combining with the supported aluminoxane. For example, pretreatments could include treating the single site catalyst component with A1-, Mg-, Zn-, other main group alkyls (e.g., TEA, TIB A, MgBu2, ZnEt2), borates, olefins, Lewis bases, or any combination thereof, as known in the art.

[0066] In one embodiment, the weight ratio of the catalyst component added to the supported aluminoxane is from about 1 :25 to about 1 :200, such as from about 1 :50 to about 1 :100, such as from about 1 :60 to about 1 :90.

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

[0068] 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 from about 0 wt% to about 50 wt%, from about 0 wt% to about 5% wt, from about 0 wt% to about 2 wt%, and from about 0 wt% to about 1 wt%. In some embodiments, the solid single-site catalyst has a total residual solvent content of from about 0.1 wt% to about 50 wt%, from about 0.1 wt% to about 5% wt, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, and from about 0.1 wt% to about 0.5 wt%. In some embodiments, the solid single-site catalyst has a total residual solvent content of from about 0.01 wt% to about 50 wt%, from about 0.01 wt% to about 5% wt, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.01 wt% to about 0.5 wt%, and from about 0.01 wt% to about 0.1 wt%.

[0069] In some embodiments, total residual solvent content comprises residual isohexanes content. In some embodiments, total residual solvent content comprises total residual aromatic solvent content (e.g., residual toluene content). In some embodiments, total residual solvent content comprises residual isohexanes content. In some embodiments, total residual solvent content comprises total residual aromatic solvent content (e.g., residual toluene content).

[0070] 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 from about 0 wt% to about 50 wt%, from about 0 wt% to about 5% wt, from about 0 wt% to about 2 wt%, and from about 0 wt% to about 1 wt%. In some embodiments, the solid single-site catalyst has a total residual aromatic solvent content of from about 0.1 wt% to about 50 wt%, from about 0.1 wt% to about 5% wt, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, and from 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 from about 0.01 wt% to about 50 wt%, from about 0.01 wt% to about 5% wt, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.01 wt% to about 0.5 wt%, and from about 0.01 wt% to about 0.1 wt%.

[0071] In some embodiments, the solid single-site catalyst has a residual isohexanes content 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 isohexanes content of less than about 0.5 wt%. In some embodiments, the solid single-site catalyst has a residual isohexanes content of from about 0 wt% to about 50 wt%, from about 0 wt% to about 5% wt, from about 0 wt% to about 2 wt%, and from about 0 wt% to about 1 wt%. In some embodiments, the solid single-site catalyst has a residual isohexanes content of from about 0.1 wt% to about 50 wt%, from about 0.1 wt% to about 5% wt, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, and from about 0.1 wt% to about 0.5 wt%. In some embodiments, the solid single-site catalyst has a residual isohexanes content of from about 0.01 wt% to about 50 wt%, from about 0.01 wt% to about 5% wt, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.01 wt% to about 0.5 wt%, and from about 0.01 wt% to about 0.1 wt%.

[0072] Provided in another aspect is a polyolefin produced by any one of the processes 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 substituted or unsubstituted C2to C40 alpha olefins, including C2to C20 alpha olefins, and C2to C12 alpha olefins and may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In some embodiments, the monomer comprises an optional co-monomer(s) comprising one or more of ethylene or C4to C40 olefins, C4to C20 olefins, Ceto C12 olefins that may be (i) linear, branched, or cyclic and/or (ii) strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

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

EXAMPLES

[0074] The catalysts described below were prepared by immobilizing methylaluminoxane and a metallocene catalyst component (e.g., Bis(l-methy-3- butylcyclopentadienyl) zirconium dichloride and Rac-Dimethylsilylbis(2-methyl-4- phenyl-indenyl) zirconium dichloride) on dehydrated silica having a nominal size, surface area, and pore volume of 33 microns, 280 m²/g and 1.6 mL/g, respectively. After forming each catalyst, the relative production rates were obtained using the same polymerization test conditions for each.

[0075] A typical ethylene 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 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. Resin was collected after venting and cooling the reactor after the 1-hour run time. Resin was obtained after drying under vacuum at 65 °C.

Catalyst activity (g polymer/g catalyst per hour) was determined by dividing the amount of polymer made by the amount of catalyst added.

[0076] A typical propylene polymerization process was as follows: A 4-L liter autoclave was charged with propylene (1030 g), hydrogen (50 mg), TIBA (0.5 mL of 20% solution in isohexane), and catalyst (0.005 g). The contents were stirred at 800 RPM using a marine impeller. The polymerization temperature was 70 °C. The polymerization time was 1 hour. Resin was collected after venting and cooling the reactor after the 1-hour run time. Resin was obtained after drying under vacuum at 65 °C. Catalyst activity (g polymer/g catalyst per hour) was determined by dividing the amount of polymer made by the amount of catalyst added.

[0077] Comparative Example A (one pot procedure)

Formation of Supported Aluminoxane Slurry and Catalyst

[0078] Dehydrated silica (6.6 g) was slurried in toluene (57.6 g) in a 250mL, 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 held for 4 hours. The ‘sMAO slurry’ was cooled back down to ambient temperatures. Bis(l-methyl-3-butylcyclopentadienyl) zirconium dichloride (0.23 g) was added and stirred for 2 hours. The solids were collected on a coarse fritted disc filter and washed 1x20 mL toluene and 3x20 mL isohexanes. The solids were dried under vacuum until constant mass.

[0079] Polymerization was conducted according to the process described above. The average polymer production rate was 6,023 g/g catalyst/hour.

[0080] Example 1

Formation of Supported Aluminoxane Slurry

[0081] Dehydrated silica (6.6 g) was slurried in ISOPAR™ G (42.5 g) in a 250mL, 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 raised to 120°C and the reaction held for 4 hours. The ‘sMAO slurry’ was cooled back down to ambient temperatures.

Formation of Catalyst 1

[0082] Bis(l-methyl-3-butylcyclopentadienyl) zirconium dichloride (0.05 g) was added an aliquot of the sMAO slurry (14.7 g, 15.8 wt% solids) and stirred for 2 hours. The solids were collected on a coarse fritted disc filter and washed 1x20 mL Isopar G and 3x20 mL isohexanes. The solids were dried under vacuum until constant mass (0.03 wt% residual toluene, 1.66 wt% residual isohexanes).

[0083] Polymerization was conducted according to the process described above. The average polymer production rate was 5,769 g/g catalyst/hour.

Formation of Catalyst 2

[0084] Rac-Dimethylsilylbis(2-methyl-4-phenyl-indenyl) zirconium dichloride (0.04 g) was added an aliquot of the sMAO slurry (16.3 g, 15.8 wt% solids) and stirred for 2 hours. The solids were collected on a coarse fritted disc filter and washed 1x20 mL ISOPAR™ G and 3x20 mL isohexanes. The solids were dried under vacuum until constant mass.

[0085] Polymerization was conducted according to the process described above for polymerizing propylene. The average polymer production rate was 20,044 g/g catalyst/hour. [0086] Example 2

Formation of Supported Aluminoxane Slurry and Catalyst 3

[0087] Dehydrated silica (5.0 g) was slurried in ISOPAR™ G (37.7 g) in a 250mL, 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 held for 4 hours. The ‘sMAO slurry’ was cooled back down to ambient temperatures. Bis(l-methyl-3-butylcyclopentadienyl) zirconium di chloride (0.18 g) was added and stirred for 2 hours. The solids were collected on a coarse fritted disc filter and washed 1x20 mL ISOPAR™ G and 3x20 mL isohexanes.

The solids were dried under vacuum until constant mass (0.13 wt% residual toluene, 1.62 wt% residual isohexanes).

[0088] Polymerization was conducted according to the process described above. The average polymer production rate was 4,839 g/g catalyst/hour.

[0089] Example 3

Formation of Supported Aluminoxane Slurry and Catalyst 4

[0090] Dehydrated silica (4.1 g) was slurried in methylcyclohexane (40.4 g) in a 250mL, 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 held for 4 hours. The ‘sMAO slurry’ was cooled back down to ambient temperatures. Bis(l-methyl-3-butylcyclopentadienyl) zirconium di chloride (0.15 g) was added and stirred for 2 hours. The solids were collected on a coarse fritted disc filter and washed 1x20 mL methylcyclohexane and 3x20 mL isohexanes. The solids were dried under vacuum until constant mass (0.28 wt% residual toluene, 1.85 wt% residual isohexanes).

[0091] Polymerization was conducted according to the process described above. The average polymer production rate was 6,057 g/g catalyst/hour.

[0092] Para. 1. A process 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;

(c) contacting the supported aluminoxane slurry with a single-site catalyst component to form a supported single-site catalyst; wherein the organic solvent comprises one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent.

[0093] Para. 2. The process according to Para. 1, wherein the slurry in step (a) does not comprise any aromatic compounds.

[0094] Para. 3. The process according to any one of Paras. 1-2, wherein the organic solvent comprising one or more branched aliphatic compounds comprises isoparaffins.

[0095] Para. 4. The process according to any one of Paras. 1-3, wherein the organic solvent comprising the one or more branched aliphatic compounds comprises one or more C7-C12 isoparaffins.

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

[0097] Para. 6. The process according to any one of Paras. 1-5, wherein the organic solvent comprises mineral oil.

[0098] Para. 7. The process according to any of the preceding Paras., wherein the solid aluminoxane activator comprises methylaluminoxane.

[0099] Para. 8. The process according Para. 7, wherein the solid aluminoxane activator is obtained from solvent stripping precipitation, heating and distillation removal of the solvent and trimethylaluminum, or chemical treatment. [0100] Para. 9. The process according to any one of Paras.7-8, wherein the solid aluminoxane activator has a total aluminum content in the range of from about 35 to about 50 wt % based on a total weight solid aluminoxane activator.

[0101] Para. 10. The process according to any of the preceding Paras., 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.

[0102] Para. 11. The process according to any of the preceding Paras., further comprising cooling the supported aluminoxane slurry to a temperature of about 25°C before contacting the supported aluminoxane slurry with the single-site catalyst component.

[0103] Para. 12. The process according to any of the preceding Paras., wherein maintaining the temperature of the slurry at step (b) is from about 115°C to about 155°C.

[0104] Para. 13. The process according to Para. 12, wherein maintaining the temperature of the slurry at step (b) is about 120°C or about 155°C.

[0105] Para. 14. The process according to any of the preceding Paras., wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point greater than the highest temperature reached by the slurry in an amount of about 50 wt.% or greater.

[0106] Para. 15. The process according to any of the preceding Paras., wherein the organic solvent is present in an amount of about 60 wt.% or greater, about 70 wt.% or greater, about 75 wt.% or greater, about 80 wt.% or greater, about 90 wt.% or greater, or about 95 wt.% or greater.

[0107] Para. 16. The process according to any of the preceding Paras., wherein the process comprises separating the supported aluminoxane from the organic solvent before contacting it with the single-site catalyst component.

[0108] Para. 17. The process according to any of the preceding Paras., wherein the inorganic oxide support comprises silica. [0109] Para. 18. The process according to Para. 17, wherein the inorganic oxide support comprises dried silica.

[0110] Para. 19. The process according to any one of Paras. 17-18, wherein the inorganic oxide support comprises silica in an amount of about 50 wt.% or more, about 60 wt.% or more, about 80 wt.% or more, about 90 wt.% or more, or about 99 wt.% or more.

[0111] Para. 20. The process according to any of the preceding Paras., wherein the single-site catalyst component comprises a metallocene compound.

[0112] Para. 21. The process according to Para. 20, wherein the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel.

[0113] Para. 22. The process according to Para. 21, wherein the metallocene compound comprises titanium, zirconium, or hafnium.

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

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

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

[0117] Para. 26. A process for producing a supported single-site catalyst comprising:

(c) cooling the slurry to a temperature from about 0°C to about 50°C; and

[0118] Para. 27. The process according to claim 26, wherein the inorganic oxide support is thermally treated.

[0119] Para. 28. The process of any one of Paras. 26-27, wherein the supported singlesite catalyst has a total residual solvent content of less than about 50 wt%.

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

[0121] Para. 30. The process of any one of Paras. 26-29, wherein the supported singlesite catalyst has a total residual aromatic solvent content of less than about 0.5 wt%.

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

[0123] Para. 32. A polyolefin produced by the process according to Para. 31.

[0124] Para. 33. A supported single-site catalyst produced by the process of any one of Paras. 1-31.

[0125] Para. 34. A slurry comprising: an inorganic oxide support; an organic solvent comprising one or more one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent; and a solid aluminoxane activator.

[0126] Para. 35. The process of Para. 34, wherein the slurry has a total residual solvent content of less than about 50 wt%. [0127] Para. 36. The process of Para. 35, wherein the slurry has a total residual solvent content of less than about 5 wt% or about 2 wt%.

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

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

[0130] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding 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. Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0131] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations may be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. 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 this disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which can 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.

[0132] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0133] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range may be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein may be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which may be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0134] All publications, patent applications, issued patents, and other documents referred to in this specification are herein 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 that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

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

Claims

WHAT IS CLAIMED IS:

1. A process for producing a supported single-site catalyst comprising:

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

3. The process according to any one of claims 1-2, wherein the organic solvent comprising one or more branched aliphatic compounds comprises isoparaffins.

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

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

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

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

8. The process according claim 7, wherein the solid aluminoxane activator is obtained from solvent stripping precipitation, heating and distillation removal of the solvent and trimethylaluminum, or chemical treatment. process according to any one of claims 7-8, wherein the solid aluminoxane activator has a total aluminum content in the range of from about 35 to about 50 wt % based on a total weight solid aluminoxane activator. process according to any one of claims 1-9, further comprising cooling the supported aluminoxane slurry to a temperature of about 50°C or less before contacting the supported aluminoxane slurry with the single-site catalyst component. process according to any one of claims 1-10, further comprising cooling the supported aluminoxane slurry to a temperature of about 25°C before contacting the supported aluminoxane slurry with the single-site catalyst component. process according to any one of claims 1-11, wherein maintaining the temperature of the slurry at step (b) is from about 115°C to about 155°C. process according to claim 12, wherein maintaining the temperature of the slurry at step (b) is about 120°C or about 155°C. process according to any one of claims 1-13, wherein the organic solvent comprises one or more non-aromatic organic compounds having a boiling point greater than the highest temperature reached by the slurry in an amount of about 50 wt.% or greater. process according to any one of claims 1-14, wherein the organic solvent is present in an amount of about 60 wt.% or greater, about 70 wt.% or greater, about 75 wt.% or greater, about 80 wt.% or greater, about 90 wt.% or greater, or about 95 wt.% or greater. process according to any one of claims 1-15, wherein the process comprises separating the supported aluminoxane from the organic solvent before contacting it with the single-site catalyst component. process according to any one of claims 1-16, wherein the inorganic oxide support comprises silica. process according to claim 17, wherein the inorganic oxide support comprises dried silica. process according to any one of claims 17-18, wherein the inorganic oxide support comprises silica in an amount of about 50 wt.% or more, about 60 wt.% or more, about 80 wt.% or more, about 90 wt.% or more, or about 99 wt.% or more. process according to any one of claims 1-19, wherein the single-site catalyst component comprises a metallocene compound. process according to claim 20, wherein the metallocene compound comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, or nickel. process according to claim 21, wherein the metallocene compound comprises titanium, zirconium, or hafnium. process according to any one of claims 1-22, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt%, and/or wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%. rocess for producing a supported single-site catalyst comprising:

(c) cooling the slurry to a temperature from about 0°C to about 50°C; and

(d) adding a single-site catalyst component to the supported aluminoxane slurry to form a supported single-site catalyst; wherein the organic solvent comprises one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent. process according to claim 24, wherein the inorganic oxide support is thermally treated. process according to any one of claims 24-25, wherein the supported single-site catalyst has a total residual solvent content of less than about 50 wt%, and/or wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%. process according to any one of claims 24-26, further comprising contacting the supported single-site catalyst with an olefin monomer to produce a polyolefin. olyolefin produced by the process according to claim 27. pported single-site catalyst produced by the process of any of claims 1-27. urry comprising: an inorganic oxide support; an organic solvent comprising one or more one or more branched aliphatic compounds having a boiling point of about 100°C or greater and is present in an amount of about 50 wt.% or greater with respect to the total amount of the organic solvent; and a solid aluminoxane activator. process according to claim 30, wherein the slurry has a total residual solvent content of less than about 50 wt%, and/or wherein the supported single-site catalyst has a total residual aromatic solvent content of less than about 0.5 wt%.