WO2007005400A2 - Compositions de sel d'aluminoxanate possedant une stabilite amelioree dans des solvants aromatiques et aliphatiques - Google Patents

Compositions de sel d'aluminoxanate possedant une stabilite amelioree dans des solvants aromatiques et aliphatiques Download PDF

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WO2007005400A2
WO2007005400A2 PCT/US2006/024905 US2006024905W WO2007005400A2 WO 2007005400 A2 WO2007005400 A2 WO 2007005400A2 US 2006024905 W US2006024905 W US 2006024905W WO 2007005400 A2 WO2007005400 A2 WO 2007005400A2
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aluminoxanate
composition
carbon atoms
soluble
twenty carbon
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PCT/US2006/024905
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English (en)
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WO2007005400A3 (fr
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Samuel A. Sangokoya
Steven P. Diefenbach
Christopher Daly
Larry S. Simeral
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Albemarle Corporation
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Priority to DE112006001733T priority Critical patent/DE112006001733T5/de
Publication of WO2007005400A2 publication Critical patent/WO2007005400A2/fr
Publication of WO2007005400A3 publication Critical patent/WO2007005400A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences

Definitions

  • the present invention relates to aluminoxate salt compositions. More particularly, the present invention relates to soluble aluminoxanate salt compositions that are of particular utility in the formation of new catalyst systems. This invention is also directed to methods for the preparation of such soluble aluminoxanate salt compositions and catalyst systems, and to the use of such catalyst systems in the polymerization of olefinic monomers.
  • Aluminoxane compositions are widely used in combination with various types of metallocenes and transition metal compounds to prepare catalyst systems for polymerizing olefinic monomers.
  • certain limitations are associated with standard aluminoxane solutions, such as instability to gel formation and poor solubility, especially in aliphatic solvents.
  • methylaluminoxane (MAO) the most commonly used aluminoxane, has lower solubility in organic solvents than higher alkylaluminoxanes and tends to be cloudy or gelatinous due to oligomerization and agglomerization.
  • Attempts to improve the solubility of methylaluminoxane include hydrolyzing a mixture of trimethylaluminum with a C 2 -C 20 alkylaluminum compound such as, for example, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum or a triarylaluminum to produce a modified MAO.
  • modified MAOs are described, for example, in U.S. Patent. No. 5,157,008. While modified MAOs have improved solubility in commercial solvents, these compounds often have poor solution stability.
  • U.S. Patent Nos. 5,565,395; 5,670,682; and 5,922,631 and WO 03/082879 describe various aluminoxanate salts and liquid clathrate compositions.
  • these aluminoxanate salts and liquid clathrate compositions are soluble in certain solvents, they are practically insoluble in standard industrial solvents, for example, aliphatic and aromatic solvents.
  • the present invention is directed to soluble aluminoxanate salt compositions, methods for preparing soluble aluminoxanate salt compositions, supported and unsupported catalyst compositions comprising soluble aluminoxanate salt compositions, methods for preparing these catalyst compositions, and methods for polymerizing olefinic monomers using these catalyst compositions.
  • ionic aluminoxanate salts and liquid clathrate compositions can be modified such that they are soluble in aliphatic and aromatic solvents.
  • the present invention encompasses a soluble aluminoxanate salt composition comprising the contact product of:
  • L is a stabilizing ligand
  • R is, independently, a hydrocarbyl group having from one to about twenty carbon atoms
  • AO is an aluminoxane moiety
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide; and m is 1, 2, or 3, inclusive;
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • Z is, independently, a halide, a pseudohalide, or an alkyl group having from about three to about twenty carbon atoms
  • the present invention also encompasses a soluble aluminoxanate salt composition having the general formula
  • L is a stabilizing ligand
  • R is a hydrocarbyl group having from one to about twenty carbon atoms
  • R 1 is an alkyl group having from about four to about twenty carbon atoms
  • AO is an aluminoxane moiety
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide; and m is 1, 2, or 3, inclusive.
  • L is a stabilizing Iigand
  • Me is a methyl group
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • MAO is a methylaluminoxane moiety; and m is 1 , 2, or 3, inclusive.
  • Yet another aspect of this invention encompasses a mixed aluminoxanate composition
  • a mixed aluminoxanate composition comprising:
  • L is a stabilizing Iigand
  • R is a hydrocarbyl group having from one to about twenty carbon atoms
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • AO is an aluminoxane moiety or a mixture of aluminoxane moieties
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide; and m is 1, 2, or 3, inclusive.
  • the present invention further comprises a catalyst composition comprising a soluble aluminoxanate salt composition and at least one complex of a transition metal of Group 3, 4, 5, 6, 7, 8, 9, 10, or 11 of the Periodic Table of Elements, including the lanthanide and actinide series.
  • the catalyst composition can be unsupported or supported on an organic or inorganic carrier material.
  • This invention also encompasses a method for polymerizing olefinic monomers comprising contacting under polymerization conditions at least one olefinic monomer and a catalyst system comprising a soluble aluminoxanate salt composition of the present invention and at least one transition metal complex.
  • Figure 1 is a visual representation of an octamethyltrisiloxane-complexed dimethylaluminum methylaluminoxane (DMAMOMTS).
  • Figure 2 illustrates the proton NMR spectra of the ionic aluminoxanate of Figure 1, and its methylaluminoxane and octamethyltrisiloxane precursors.
  • Figure 3 illustrates the 29 Si NMR spectra of the ionic aluminoxanate of Figure 1 , and its octamethyltrisiloxane precursor.
  • Figure 4 illustrates the 27 AI NMR spectra of the ionic aluminoxanate of Figure 1 , and its methyialuminoxane precursor.
  • Figure 5 illustrates the proton NMR spectra of conventional methylaluminoxane and a crown-ether-complexed dimethylaluminum methylaluminoxanate.
  • Figure 6 illustrates the 29 Si NMR spectra of the ionic aluminoxanate of Figure 1 treated with tri-n-octylaluminum and conventional methylaluminoxane treated with tri-n- octylaluminum.
  • Figure 7 illustrates the 29 Si NMR spectra of the ionic aluminoxanate of Figure 1 treated with triisobutylaluminum and conventional methylaluminoxane treated with triisobutylaluminum.
  • Figure 8 illustrates the proton NMR spectra of the ionic aluminoxanate of Figure 1 treated with tri-n-octylaluminum and conventional methylaluminoxane treated with tri-n- octylaluminum.
  • Figure 9 illustrates the 27 AI NMR spectra of the ionic aluminoxanate of Figure 1 treated with tri-n-octylaluminum and conventional methylaluminoxane treated with tri-n- octylaluminum.
  • the present invention provides soluble aluminoxanate salt compositions, methods for preparing soluble aluminoxanate salt compositions, supported and unsupported catalyst compositions comprising soluble aluminoxanate salt compositions, and methods for polymerizing olefins using catalyst compositions comprising soluble aluminoxanate salt compositions.
  • Soluble aluminoxanate salt compositions in accordance with the present invention comprise the contact product of:
  • L is a stabilizing ligand
  • R is, independently, a hydrocarbyl group having from one to about twenty carbon atoms
  • AO is an aluminoxane moiety
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide; and m is 1, 2, or 3 inclusive;
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • Z is, independently, a halide, a pseudohalide, or an alkyl group having from about three to about twenty carbon atoms
  • Soluble aluminoxanate salt compositions in accordance with another aspect of the present invention have the general formula
  • L is a stabilizing ligand
  • R is a hydrocarbyl group having from one to about twenty carbon atoms;
  • R' is an alkyl group having from about four to about twenty carbon atoms;
  • AO is an aluminoxane moiety;
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide; and m is 1 , 2, or 3, inclusive.
  • a further aspect of the present invention encompasses a soluble methylaluminoxanate composition having the general formula
  • L is a stabilizing ligand
  • Me is a methyl group
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • MAO is a methylaluminoxane moiety; and m is 1 , 2, or 3, inclusive.
  • Yet another aspect of this invention encompasses a mixed aluminoxanate composition comprising
  • L is a stabilizing ligand
  • R is a hydrocarbyl group having from one to about twenty carbon atoms
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • AO is an aluminoxane moiety or a mixture of aluminoxane moieties
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide
  • m is 1, 2, or 3, inclusive.
  • Ionic aluminoxanate compositions employed in the present invention include aluminoxanate salts having a chelated dihydrocarbylaluminum group as the cation and an aluminoxanate moiety as the anion.
  • Dihydrocarbylaluminum aluminoxanate salts have the following general formula: wherein
  • L is a stabilizing ligand
  • R is, independently, a hydrocarbyl group having from one to about twenty carbon atoms
  • AO is an aluminoxane moiety
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide; and m is 1, 2, or 3, inclusive.
  • stabilizing ligands include, but are not limited to, monosiloxanes, polysiloxanes, monoethers, polyethers, monothioethers, polythioethers, a multidentate ligand comprising oxygen coordinating atoms, nitrogen coordinating atoms, phosphorous coordinating atoms, sulfur coordinating atoms, oxygen crown ether ligands, nitrogen crown ether ligands, nitrogen and oxygen crown ether ligands, or any combination thereof.
  • crown ether structures include, but are not limited to, 12-crown-4, 15-crown-5, or 18-crown-6.
  • Stabilizing ligands can be either bidentate or monodentate ligands.
  • R is an alkyl, cycloalkyl, aryl, or aralkyl group.
  • R is a C 1 . s alkyl group.
  • R is a methyl group.
  • X is an alkyl group which can be the same as or different from the R group. Examples of X groups which can be employed in the present invention include, but are not limited to, alkyl, cycloalkyl, aryl, or aralkyl groups, halides, or pseudohalides.
  • Pseudohalides include, but are not limited to, oxyhalide groups, hydrocarbyloxy groups, amido groups (e.g., — NR 2 ), hydrocarbylthio groups (e.g., -SR groups), and the like.
  • Hydrocarbyloxy groups comprise, without limitation, — OR groups such as alkoxy, aryloxy, cycloalkoxy, arylalkoxy, and the like.
  • X is a methyl group or fluoride.
  • Aluminoxane moieties can include any suitable hydrocarbylaluminoxanes having at least one hydrocarbyl moiety having from one to about twenty carbon atoms, for example, alkylaluminoxanes, cycloalkylaluminoxanes, arylaluminoxanes, aralkylaluminoxanes, or any combination thereof.
  • Hydrocarbylaluminoxanes can exist in the form of linear or cyclic polymers with the simplest monomeric compound being a tetraalkylaluminoxane such as tetramethylaluminoxane, (CH 3 ) 2 AI — O — AI(CH 3 ) 2 , or tetraethylaluminoxane, (C 2 H 5 ) 2 Al — O — AI(C 2 H 5 ) 2 .
  • the aluminoxanes can be oligomeric materials, sometimes referred to as polyalkylaluminoxanes, containing the repeating unit
  • Aluminoxanes employed in the present invention can contain linear, cyclic, cross-linked species, or any combination thereof.
  • hydrocarbylaluminoxanes which can be employed in the present invention include, but are not limited to, methylaluminoxa ⁇ es (MAO), modified MAOs, ethylaluminoxanes (EAO), isobutylaluminoxanes (IBAO), n-propylaluminoxanes, n- octylaluminoxanes, phenylaluminoxanes, or any combination thereof.
  • WO 03/082466 describes a crystal structure of a discrete hydrocarbyl haloaluminoxane, having the general formula Me 9 AI 1S O 13 CI 1 S, which can also be used as a suitable aluminoxane moiety in the present invention.
  • the hydrocarbylaluminoxanes can contain up to about 20 mole percent (based on aluminum atoms) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, aryl disiloxanes, alkyl disiloxanes and the like to further improve activity, solubility and/or stability.
  • Aluminoxanes can be prepared as known in the art by the partial hydrolysis of hydrocarbylaluminum compounds.
  • Hydrocarbylaluminum compounds or mixture of compounds capable of reacting with water to form an aluminoxane can be employed in the present invention.
  • hydrocarbylaluminum compounds include, but are not limited to, trialkylaiuminum, triarylaluminum, mixed alkyl-aryl aluminum, or any combination thereof.
  • the hydrocarbylaluminum compounds can be hydrolyzed by adding either free water or water-containing solids, which can be either hydrates or porous materials which have absorbed water.
  • Suitable hydrates include, but are not limited to, salt hydrates such as, for example, CuSO 4 -5H 2 O, AI 2 (SO 4 VIeH 2 O, FeSO 4 « 7H 2 O, AICI 3 « 6H 2 O, AI(NO 3 ) 3 '9H 2 O, MgSO 4 -7H 2 O, MgCI 2 « 6H 2 O, ZnSO 4 -7H 2 O, Na 2 SO 4 -IOH 2 O, Na 3 PO 4 -12H 2 O, LiBr « 2H 2 O, LiOH 2 O, Lil « 2H 2 O, Lil « 3H 2 O, KF « 2H 2 O, NaBr « 2H 2 O, or any combination thereof.
  • salt hydrates such as, for example, CuSO 4 -5H 2 O, AI 2 (SO 4 VIeH 2 O, FeSO 4 « 7H 2 O, AICI 3 « 6H 2 O, AI(NO 3 ) 3 '9H 2 O, MgSO 4 -7H 2 O, Mg
  • Alkali or alkaline earth metal hydroxide hydrates are also suitable hydrates and include, but are not limited to, NaOH-H 2 O, NaOH « 2H 2 O, Ba(OH) 2 » 8H 2 O, KOH « 2H 2 O, CsOH-H 2 O, LiOH*H 2 O, or any combination thereof. Mixtures of salt hydrates and alkali or alkaline earth metal hydroxide hydrates can also be used.
  • the molar ratios of free water or water in the hydrate or in porous materials such as alumina or silica to total alkylaluminum compounds in the mixture can vary widely, such as for example, from about 2:1 to about 1 :4. In another aspect, molar ratios can range from about 4:3 to about 2:7.
  • Suitable hydrocarbylaluminoxanes and processes for preparing hydrocarbyl- aluminoxanes are described in U.S. Patent Nos. 4,908,463; 4,924,018; 5,003,095; 5,041 ,583; 5,066,631; 5,099,050; 5,157,008; 5,157,137; 5,235,081; 5,248,801 , and 5,371,260.
  • Methylaluminoxanes can contain varying amounts, for example, from about 5 to about 35 mole percent, of the aluminum value as unreacted trimethylaluminum (TMA).
  • Ionic aluminoxanates are substantially free of occluded non-ionic organoaluminum compounds such as alkylaluminums and non-ionic alkylaluminoxane species.
  • the ionic aluminoxanate contains, if any, less than about 5 mole percent of aluminum in the form of trialkylaiuminum as determined by proton NMR. In one aspect, the ionic aluminoxanate contains, if any, less than about 1 mole percent of aluminum in the form of trialkylaiuminum.
  • ionic aluminoxanate compositions include those in which the composition has a siloxane or polysiloxane ligand and in which the composition is characterized by a downfield shift in 1 H NMR as compared to the NMR of the aluminoxane from which the ionic aluminoxanate was prepared ("parent aluminoxane").
  • Ionic aluminoxanate compositions of the present invention can further be characterized by (i) a 27 AI NMR with at least one large and broad peak shifted upfield from the parent aluminoxane peak, and (ii) at least one smaller peak shifted downfield from the parent aluminoxane peak.
  • aluminoxanate compositions are characterized by an increase in conductivity of at least 10 micro-mhos as compared to the parent aluminoxane.
  • ionic aluminoxanate compositions can be prepared by contacting, in any order, (i) at least one suitable aromatic solvent; (ii) at least one aluminoxane; and (iii) at least one hydrocarbylpolysiloxane.
  • suitable aluminoxanes include, but are not limited to, hydrocarbylaluminoxanes, such as one or more alkylaluminoxanes, one or more cycloalkylaluminoxanes, one or more arylaluminoxanes, one or more aralkylaluminoxanes, or any combination thereof.
  • aluminoxanes having alkyl groups having from one to about eight carbon atoms are used, such as methylaluminoxane.
  • the hydrocarbylpolysiloxane can have from about 3 to about 18 silicon atoms in the molecule which are separated from each other by an oxygen atom such that there is a linear, branched, or cyclic backbone of alternating silicon and oxygen atoms, with the remainder of the four valence bonds of each silicon atom individually satisfied by hydrocarbyl groups or hydrogen atoms.
  • the univalent hydrocarbyl groups of the polysiloxane each contain, independently, up to about 18 carbon atoms, for example, alkyl, cycloalkyl, aryl, oraralkyl groups.
  • polysiloxanes include, but are not limited to, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane.
  • Suitable aromatic solvents include, but are not limited to, benzene, toluene, xylene, ethylbenzene, cumene, tetrahydronaphthalene, or any mixtures of aromatic solvents, such as BTX.
  • ionic aluminoxanate compositions can be prepared by contacting, in any order, (i) at least one suitable aromatic solvent; (ii) at least one aluminoxane; and (iii) at least one aliphatic or crown polyether, to form a clathrate.
  • suitable aluminoxanes include, but are not limited to, hydrocarbylaluminoxanes, such as one or more alkylaluminoxanes, one or more cycloalkylaluminoxanes, one or more arylaluminoxanes, one or more aralkylaluminoxanes, or any combination thereof.
  • aluminoxanes having alkyl groups having from one to about eight carbon atoms are used, such as methylaluminoxane.
  • suitable aliphatic or crown polyethers which can be employed in the present invention include, but are not limited to, dimethoxyethane, diethoxyethane, 1-ethoxy-2-methoxyethane, dipropoxyethane, 1 ,2-dimethoxypropane, 1,3- dimethyoxypropane, 1 ,2-dimethoxybutane, 2,3-dimethoxybutane, 1,3,5-trimethoxypropane, 18-crown-6 polyether, or analogs and homologs thereof.
  • Suitable aromatic solvents include, but are not limited to, benzene, toluene, xylene, ethylbenzene, cumene, tetrahydronaphthalene, or any mixtures of aromatic solvents, such as BTX.
  • Preparation of ionic aluminoxanate clathrates generally results in a two-phase liquid system, wherein the denser lower liquid is typically the clathrate, and is readily separated from the supernatant liquid upper layer by conventional separation techniques.
  • Exemplary processes for preparing the ionic aluminoxanate compositions include, for example, the following steps:
  • An effective amount of organic, inorganic, or organometallic compound as used herein is an amount which is sufficient to form a stable clathrate, but insufficient to cause the aluminoxanate to be incapable of activating a transition metal complex catalyst system.
  • the volume of aromatic organic solvent used relative to the initial liquid clathrate is variable, and is not critical as long as it is sufficient to form a stirrable solution.
  • solid ionic aluminoxanate compositions are optionally prepared by:
  • solid ionic aluminoxanate compositions are prepared by:
  • solid ionic aluminoxanate compositions are prepared by:
  • liquid non-solvents which can be employed in the present invention include, but are not limited to, liquid paraffinic or cycloparaffinic hydrocarbons, such as liquid pentane, hexane, heptane, octane, nonane, decane, cyclopentane, alkylcyclopentanes, cyclohexane, alkylcyclohexanes, or any combination thereof.
  • the addition of non-solvent should be in an amount sufficient to produce the desired yield of precipitated solids. This amount can be determined by adding the non-solvent in portions and observing whether addition of further non-solvent results in more precipitate formation.
  • the solid ionic aluminoxanate composition can be prepared by:
  • steps (1)-(5) recovering precipated solids as in step (2a), (3c), or (4d).
  • the preparation processes described in steps (1)-(5) can be conducted at ambient room temperatures (e.g., 25°C to 30°C) or at suitably reduced or elevated temperatures, for example, in the range of about 10 c C to about 100 0 C. In one aspect of the present invention, the preparation is carried out at temperatures in a range of about 20 0 C to about 80 0 C.
  • the precipitated ionic aluminoxanate solids formed in steps (2a), (3c), and (4d) will typically have a higher electrical conductivity than an unprecipitated liquid clathrate, such as the liquid clathrate in step (1b). Accordingly, the solid ionic aluminoxanate compositions are more ionic than the liquid clathrate ionic aluminoxanate compositions. Similarly, the recovered solids of step (5c) will have a higher electrical conductivity than the precipitated solids formed in steps (2a), (3c), and (4d). The precipitated solids can be rewashed with fresh aromatic solvent as many times as necessary to achieve the desired electrical conductivity, or until no additional increase in electrical conductivity is observed.
  • Alkylaluminum compounds employed in the present invention include trialkylaluminum compounds and substituted trialkylaluminum compounds having the following general formula:
  • R' is an alkyl group having from about four to about twenty carbon atoms
  • Z is, independently, a halide, a pseudohalide, or an alkyl group having from about three to about twenty carbon atoms.
  • Suitable alkylaluminum compounds include, but are not limited to, tributylaluminum, triisobutylaluminum, tri-n-octylaluminum, or any combination thereof.
  • Substituted alkylaluminum compounds include, but are not limited to, dialkylaluminum halides and alkylaluminum dihalides.
  • the halide substituent can be selected from bromide, chloride, or fluoride. In one aspect, the halide substituent is fluoride.
  • pseudohalide groups which can be employed in the present invention include, but are not limited to, are oxyhalide groups, hydrocarbyloxy groups ( — OR groups such as alkoxy, aryloxy, cycloalkoxy, arylalkoxy, etc.), amido groups ( — NR 2 ), hydrocarbylthio groups ( — SR groups), azides, cyanide, cyanate, thiocyanate, isocyanate, isothiocyanate, and the like.
  • oxyhalide groups — OR groups such as alkoxy, aryloxy, cycloalkoxy, arylalkoxy, etc.
  • amido groups — NR 2
  • hydrocarbylthio groups — SR groups
  • azides cyanide, cyanate, thiocyanate, isocyanate, isothiocyanate, and the like.
  • Inert organic solvents employed in the present invention include any suitable aromatic solvents, aliphatic solvents, halogenated solvents, or any combination thereof.
  • aliphatic solvents employed in the present invention have from 1 to 12 carbon atoms.
  • Examples of aliphatic solvents include, but are not limited to, pentane, isopentane, cyclopentane, alkylcyclopentane, hexane, cyclohexane, alkylcyclohexane, heptane, octane, decane, dodecane, hexadecane, octadecane, or any combination thereof.
  • aliphatic solvents can be employed in the present invention and include, but are not limited to, isopar C and isopar E.
  • aromatic solvents include, but are not limited to, benzene, chlorobenzene, ethylbenzene, toluene, xylene, cumene, or any combination thereof.
  • the soluble aluminoxanate salt composition can optionally be supported on any suitable organic or inorganic carrier.
  • Support materials used in accordance with this invention can be any finely divided inorganic solid support such as talc, clay, silica, alumina, silica-alumina, or any combination thereof.
  • Support materials can also include particulate, organic resinous support materials including, but not limited to, spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination or modification thereof.
  • support materials are inorganic particulate supports or carrier materials such as magnesium halides, inorganic oxides and mixed inorganic oxides, aluminum silicates, inorganic compositions containing inorganic oxides, or any combination thereof.
  • inorganic compositions containing inorganic oxides include kaolinite, attapulgtite, montmorillonite, illite, bentonite, halloysite, similar refractory clays, or any combination thereof.
  • examples of inorganic oxides include, but are not limited to, silica, alumina, silica-alumina, magnesia, titania, zirconia, or any combination thereof.
  • the support is anhydrous or substantially anhydrous.
  • Inorganic oxides can be dehydrated to remove water.
  • the support can also be calcined or chemically treated with known conventional reagents to remove hydroxyl groups and/or water from the carrier.
  • Suitable conventional reagents include, but are not limited to, aluminum alkyls, lithium alkyls, silylchloride, aluminoxanes, ionic aluminoxanates, or any combination thereof.
  • the specific particle size, surface area, and pore volume of the support material determine the amount of support material that is desirable to employ in preparing the catalyst compositions, as well as affect the properties of polymers formed with the aid of the catalyst compositions. These properties are frequently taken into consideration in choosing a support material for use in a particular aspect of the invention.
  • a suitable support material such as silica typically will have a particle diameter in a range of about 0.1 to about 600 microns, or in a range of about 0.3 to about 100 microns; a surface area in a range of about 50 m 2 /g to about 1000 m 2 /g, or, in another aspect of the present invention, in a range of about 100 m 2 /g to about 500 m 2 /g; and a pore volume in a range of about 0.3 cc/g to about 5.0 cc/g, or, in another aspect of the present invention, in a range of about 0.5 cc/g to about 3.5 cc/g.
  • the support material can be heat treated at about 100 0 C to about 1000 0 C for a period of about 1 hour to about 100 hours, or, in another aspect of the present invention, from about 3 to about 24 hours.
  • the treatment can be carried out in a vacuum or while purging with a dry inert gas such as nitrogen.
  • the support material can be chemically dehydrated.
  • Chemical dehydration is accomplished by slurrying the support in an inert low-boiling solvent, such as, for example, heptane, in the presence of a dehydrating agent, such as, for example, triethylaluminum, in a moisture and oxygen-free environment.
  • an inert low-boiling solvent such as, for example, heptane
  • a dehydrating agent such as, for example, triethylaluminum
  • This invention encompasses methods for preparing soluble aluminoxanate salts comprising contacting at least one ionic aluminoxanate, at least one inert organic solvent, and at least one alkylaluminum compound, in any order.
  • the soluble aluminoxanate salt is obtained when the components are contacted in any sequence or order.
  • a two-phase ionic aluminoxanate liquid clathrate system is prepared by contacting (i) at least one aluminoxane compound; (ii) an effective amount of at least one organic, inorganic, organometallic compound, or any combination thereof; and (iii) an aromatic organic solvent to form a liquid clathrate system. Subsequently, the liquid clathrate system is contacted with an alkylaluminum compound to form the soluble aluminoxanate salt composition. The less dense upper layer can optionally be removed before adding the alkylaluminum compound.
  • the ionic aluminoxanate solids can be removed from the liquid clathrate system by:
  • the ionic aluminoxanate solids can first be contacted with an alkylaluminum compound to form a mixture, after which the mixture is subsequently contacted with an organic solvent to form the soluble aluminoxanate salt composition.
  • an ionic aluminoxanate solid is first contacted with an aromatic solvent to form a liquid clathrate, and the clathrate is subsequently contacted with an alkylaluminum compound to form the soluble aluminoxanate salt composition.
  • the ionic aluminoxanate solids and an aliphatic solvent are first contacted together to form a slurry, and the slurry is subsequently contacted with the alkylaluminum compound to form the soluble aluminoxanate salt composition.
  • the soluble aluminoxanate salt compositions are typically prepared at temperatures in a range of about 2O 0 C to about 80 0 C.
  • the present invention further encompasses methods to produce supported soluble aluminoxanate salt compositions comprising contacting at least one ionic aluminoxanate, at least one inert organic solvent, at least one alkylaluminum compound, and at least one organic or inorganic support material, in any order.
  • the soluble aluminoxanate salt composition is prepared and subsequently contacted with a support material to form the supported composition.
  • the supported composition can be prepared by forming a slurry of (i) the soluble aluminoxanate salt composition dissolved in an aromatic or aliphatic solvent and (ii) a particulate support or carrier material.
  • the supported composition can be prepared by forming a slurry of (i) an ionic aluminoxanate liquid clathrate system and (ii) an alkylaluminum supported on a particulate carrier material.
  • any other sequential combination is suitable for forming the supported soluble aluminoxanate salt compositions of the present invention.
  • Preparation of the soluble aluminoxanate salt is generally conducted under a conventional inert atmosphere using substantially inert anhydrous materials.
  • temperatures for preparation are in a range from about 20 0 C to about 80 0 C, although higher and lower temperatures are also suitable.
  • the molar ratio of the aluminum atoms derived from the ionic aluminoxanate compound to the aluminum atoms derived from the alkylaluminum compound is in a range of about 2:1 to about 1000:1. In another aspect, the molar ratio is in a range of about 10:1 to about 50:1.
  • This invention encompasses supported and unsupported catalyst compositions prepared using soluble aluminoxanate salt compositions.
  • Catalyst systems employed in one aspect of the present invention comprise the contact product of
  • L is a stabilizing ligand
  • R is, independently, a hydrocarbyl group having from one to about twenty carbon atoms
  • R' is, independently, an alkyl group having from about four to about twenty carbon atoms
  • AO is an aluminoxane moiety
  • X is a hydrocarbyl group having from one to about twenty carbon atoms, a halide, or a pseudohalide,
  • Z is, independently, a halide, a pseudohalide, or an alkyl group having from about three to about twenty carbon atoms,
  • MAO is a methylalumi ⁇ oxane moiety
  • Me is a methyl group
  • m is 1 , 2, or 3, inclusive.
  • each R can be the same or different.
  • each R' can be the same or different.
  • Soluble aluminoxanate salt compositions of the present invention can be used with any known transition metal catalyst compound in which the transition metal is a Group 3 to 11 transition metal of the Periodic Table of Elements, including compounds of a metal of the lanthanide or actinide series.
  • the Periodic Table of Elements referred to herein is that appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News.
  • Suitable catalyst compounds can also be described as d- and f- block metal compounds. See, for example, the Periodic Table of Elements appearing on page 225 of Moeller, et al., Chemistry, Second Edition, Academic Press, copyright 1984.
  • the metal constituent is a compound of Fe, Co, Ni, Pd, or V.
  • the metal constituent is a compound of the metals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W).
  • the metal constituent is a Group 4 metal, for example, titanium, zirconium, or hafnium.
  • the transition metal catalyst compounds used in this invention can be one or more of any Ziegler-Natta catalyst compound, any metallocene, any compound of constrained geometry, any late transition metal complex, or any other transition metal compound or complex reported in the literature or otherwise generally known in the art to be an effective catalyst compound when suitably activated, including mixtures of at least two different types of such transition metal compounds or complexes, such as for example a mixture of a metallocene and a Ziegler-Natta olefin polymerization catalyst compound.
  • transition metal compounds of the metals of Groups 3, 4, 5, and 6 which can be used as the transition metal component of the catalyst compositions of this invention are the compounds of such metals as scandium, titanium, zirconium, hafnium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, thorium and uranium, often referred to as Ziegler-Natta type olefin polymerization catalysts.
  • M represents the transition metal atom or a transition metal atom cation containing one or two oxygen atoms such as vanadyl, zirconyl, or uranyl
  • X represents a halogen atom
  • OR represents a hydrocarbyloxy group having up to about 18 carbon atoms, or up to about 8 carbon atoms, or an alkyl of up to about 4 carbon atoms, such as an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or aralkyl group
  • n and m are positive integers except that either one of them (but not both) can be zero
  • n + m is the valence state of the transition metal.
  • Hydrocarbyloxides and mixed halide/hydrocarbyloxides of the transition metals which can be employed in the present invention include, but are are not limited to, Ti(OCH 3 ) 4 , Ti(OCH 3 )CI 3 , Ti(OCH 3 )Br 3 , Ti(OCHa) 2 I 2 , Ti(OC 2 Hg) 4 , Ti(OC 2 Hg) 3 CI, Ti(OC 2 H 5 )CI 3 , Ti(OC 2 H 5 )Br 3 , Ti(OC 4 H 9 )Br 3 , Ti(OC 2 H 5 )I 3 , Ti(OC 3 H 7 ) 2 CI 2 , Ti(O-iso-C 3 H 7 ) 3 CI, Ti(0-iso-C 3 H 7 ) 2 CI 2 , Ti(O-iso- C 3 H 7 )CI 3 , Ti(OC 4 Hg) 3 CI, Ti(OC 4 Hg) 2 CI 2 , Ti(OC 4 H 9 )CI 3
  • Carboxylic acid salts and various chelates of the transition metal can also be employed.
  • Examples of such salts and chelates include, but are not limited to, zirconyl acetate, uranyl butyrate, chromium acetate, chromium(III) oxy-2-ethylhexanoate, chromium(lll) 2-ethylhexanoate, chromium(lll) dichloroethylhexanoate, chromium(ll) 2-ethylhexanoate, titanium(IV) 2-ethylhexanoate, bis(2,4-pentanedionate)titanium oxide, bis(2,4-pentanedionate)titanium dichloride, bis(2,4-pentanedionate)titanium dibutoxide, vanadyl acetylacetonate, chromium acetylacetonate, niobium
  • transition metal alkyls including but not limited to, tetramethyl titanium, methyl titanium trichloride, tetraethyl zirconium, or tetraphenyl titanium can be employed in the present invention.
  • transition metal compounds of the well- known Ziegler-Natta catalyst compounds are those of the Group 4 metals, including the alkoxides, halides, and mixed halide/alkoxide compounds.
  • suitable transition metal compounds include, but are not limited to, TiCI 4 , ZrCI 4 , HfCI 4 , or TiCI 3 . These compounds can also be used in chelated form in order to facilitate solubility.
  • Metallocenes are another broad class of olefin polymerization catalyst compounds with which the soluble aluminoxanate salt compositions can be used in forming the catalyst compositions of this invention.
  • the term "metallocene” includes metal derivatives which contain at least one cyclopentadienyl (Cp) moiety.
  • Suitable metallocenes are well known in the art and include the metallocenes of Groups 3, 4, 5, 6, including lanthanide and actinide metals. For example and without limitation, the metallocenes which are described in U.S. Patent Nos.
  • Metallocene structures in this specification are to be interpreted broadly, and include structures containing 1, 2, 3, or 4 Cp or substituted Cp rings.
  • metallocenes suitable for use in this invention can be represented by Formula (I):
  • B a C Pb MX c Y d (I) where Cp, independently in each occurrence, is a cyclopentadienyl-moiety-containing group which typically has in the range of 5 to about 24 carbon atoms; B is a bridging group or ansa group that links two Cp groups together or alternatively carries an alternate coordinating group such as alkylaminosilylalkyl, silylamido, alkoxy, siloxy, aminosilylalkyl, or analogous monodentate hetero atom electron donating groups; M is a d- orf-block metal atom; each X and each Y is, independently, a group that is bonded to the d- or f-block metal atom; a is 0 or 1 ; b is an integer from 1 to 3; c is at least 2; and d is 0 or 1. The sum of b, c, and d is sufficient to form a stable compound, and often is the coordination number of the d-
  • Cp is, independently, a cyclopentadienyl, indenyl, fluorenyl or related group that can ff-bond to the metal, or a hydrocarbyl-, halo-, halohydrocarbyl-, hydrocarbylmetalloid-, and/or halohydrocarbylmetalloid-substituted derivative thereof.
  • Cp typically contains up to 75 non-hydrogen atoms.
  • B if present, is typically a silylene (-SiR 2 -), benzo (C B H 4 ⁇ ), substituted benzo, methylene (-CH 2 -), substituted methylene, ethylene (-CH 2 CH 2 -), or substituted ethylene bridge.
  • M is a metal atom of Groups 4-6.
  • M is a Group 4 metal atom, such as hafnium, zirconium, or titanium.
  • X can be a divalent substituent such as an alkylidene group, a cyclometallated hydrocarbyl group, or any other divalent chelating ligand, two loci of which are singly bonded to M to form a cyclic moiety which includes M as a member.
  • Each X, and if present, Y can be, independently in eacn occurrence, a halogen atom, a hydrocarbyl group (alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, aralkyl, etc.), hydrocarbyloxy, (alkoxy, aryloxy, efc.) siloxy, amino or substituted amino, hydride, acyloxy, triflate, and similar univalent groups that form stable metallocenes.
  • the sum of b, c, and d is a whole number, and is often from 3-5.
  • M is a Group 4 metal or an actinide metal
  • b is 2
  • the sum of c and d is 2, c being at least 1.
  • M is a Group 3 or lanthanide metal, and b is 2, c is 1 and d is zero.
  • M is a Group 3 or lanthanide metal, and b is 2, c is 1 and d is zero.
  • Also useful in this invention are compounds analogous to those of Formula (I) where one or more of the Cp groups are replaced by cyclic unsaturated charged groups isoelectronic with Cp, such as borabenzene or substituted borabenzene, azaborole or substituted azaborole, and various other isoelectronic Cp analogs. See for example
  • b is 2, i.e., there are two cyclopentadienyl-moiety containing groups in the molecule, and these two groups can be the same or they can be different from each other.
  • metallocenes of the type described in WO 98/32776 are metallocenes of the type described in WO 98/32776. These metallocenes are characterized in that one or more cyclopentadienyl groups in the metallocene are substituted by one or more polyatomic groups attached via a N, O, S, or P atom or by a carbon-to-carbon double bond.
  • metallocenes to which this invention is applicable include, but are not limited to: bis(cyclopentadienyl)zirconium dimethyl; bis(cyclopentadienyl)zirconium dichloride; bis(cyclopentadienyl)zirconium monomethylmonochloride; bis(cyclopentadienyl)titanium dichloride; bis(cyclopentadienyl)titaniunr) difluoride; cyclopentadienylzirconium tri-(2-ethylhexanoate); bis(cyclopentadienyl)zirconium hydrogen chloride; bis(cyclopentadienyl)hafnium dichloride; racemic and meso dimethylsilanylene-bis(methylcyclopentadienyl)hafnium dichloride; racemic dimethylsilanylene-bis(indenyl)hafnium dichloride; racemic ethylene-bis(in
  • organometallic catalytic compounds with which the soluble aluminoxanate salt compositions can be used in forming the catalyst compositions of this invention are the late transition metal catalyst described, for example, in U.S. Patent Nos. 5,516,739 to Barborak, et al.; 5,561,216 to Barborak, et al.; 5,866,663 to Brookhart, et al; 5,880,241 to Brookhart, et al; and 6,114,483 to Coughlin, et al.
  • Such catalysts are sometimes referred to herein collectively as "a Brookhart-type late transition metal catalyst compound or complex".
  • transition metal catalyst compounds and catalyst complexes that can be used in the practice of this invention include catfluoro nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands such as described in Johnson et al. WO 96/23010; palladium and nickel catalysts containing selected bidentate phosphorus- containing ligands such as described in EP 381 ,495; catfluoro ⁇ -diimine-based nickel and palladium complexes such as described by Johnson et al. in J. Am. Chem. Soc, 1995, 117, 6414, see also Brown et al. WO 97/17380; nickel complexes such as described by Johnson et al.
  • transition metal compounds include the following: 2,6-bis-[1-(1-methylphenylirnino)ethyl]pyridine iron[ll] chloride; 2,6-bis[1-(1-ethylphenylimino)ethyl]pyridine iron[ll] chloride; 2,6-bis[1-(1-isopropylphenylimino)ethyl]pyridine iron[ll] chloride; 2,6-bis-(1-(2-methylphenylimino)ethyl)pyridine iron(II) chloride; N,N'-di(trimethylsilyl)benzamidinato copper(ll); tridentate Schiff base complexes of cobalt and iron described by Mashima in Shokubai 1999, vol.
  • nickel compounds of the type described in U. S. Patent 5,880,323 nickel(II) acetylacetonate; bis(acetonitrile)dichloro palladium(ll); bis(acetonitrile)bis(tetrafluoroborate)palladium(II); (2,2'-bipyridine)dichloro palladium(ll); bis(cyclooctadienyl) nickel(O); pallad ⁇ um(ll) acetylacetonate; bis(salicylaldiminato) complexes of the type described by Matsui et. al. in Chemistry Letters
  • transition metal compounds which can be used in forming the catalysts of this invention are transition metal compounds which can be represented by the formula:
  • MX n Ym where M is a transition metal of Group 4 to 8, of the Periodic Table of Elements, including the lanthanide series and actinide series, and Y is, independently, a halide or pseudohalide, n is the valence of M 1 and m is an integer of from 0 to n-1.
  • Pseudohalide which is a term of art, refers to anionic non-halogenides with salt-like characteristics.
  • Non-limiting examples of suitable pseudohalide groups are oxyhalide groups, hydrocarbyloxy groups ( — OR groups such as alkoxy, aryloxy, cycloalkoxy, arylalkoxy, etc.), amido groups ( — NR 2 ), hydrocarbylthio groups ( — SR groups), azides, cyanide, cyanate, thiocyanate, isocyanate, isothiocyanate, and the like.
  • M is a transition metal of Group 4 to 8 of the Periodic Table of Elements. In another aspect, M is a Group 4 metal.
  • transition metal compounds include, but are not limited to, transition metal halides and oxyhalides such as titanium dibromide, titanium tribromide, titanium tetrabromide, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium trifluoride, titanium tetrafluoride, titanium diiodide, titanium tetraiodide, zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium tetrafluoride, zirconium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride
  • suitable alkoxides and mixed halide/alkoxides of the transition metals which can be employed in the present invention include, but are not limited to, Ti(OCH 3 ) 4 , Ti(OC 2 Hg) 4 , Ti(OC 2 Hs) 3 CI, Ti(OC 2 Hg)CI 3 , Ti(0-iso-C 3 H 7 )CI 3 , Ti(OC 4 Hg) 3 Cl, Ti(OC 3 H 7 ) 2 CI 2 , Ti(O-iso-C 3 H 7 ) 2 CI 2 , Ti(OC 17 H 18 ) 2 Br 2 , Zr(OC 2 Hg) 4 , Zr(OC 4 Hg) 4 , Zr(OC 5 Hn) 4 , ZrCI 3 (OC 2 H 5 ), ZrCI(OC 4 Hg) 3 , Hf(OC 4 Hg) 4 , Hf(OC 4 Hg) 3 CI, VO(OC 2 Hs) 3 , Cr(O-iso-C 4 H 9
  • transition metal compounds which can be used include, but are not limited to, amides such as Ti(NMe 2 J 4 , Zr(NMe 2 ) 4 , Ti(NEt 2 J 4 , Zr(NEt 2 J 4 , and Ti(NBu 2 ) 4 ; or carboxylic acid salts such as titanium oxalate, cobalt acetate, chromium acetate, nickel formate, thallium oxalate, and uranyl formate.
  • the transition metal compounds are the halides, oxyhalides, alkoxides, or mixed halide-alkoxides of the Group 4 to 6 metals.
  • the transition metal compounds are the trivalent or tetravalent Group 4 metal halides and the vanadium oxyhalides.
  • the Periodic Table of Elements referred to is that appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News.
  • the catalyst composition can optionally be supported on any suitable organic or inorganic carrier.
  • Support materials used in accordance with this invention can be any finely divided inorganic solid support, such as talc, clay, silica, alumina, silica-alumina, or any combination thereof.
  • Support materials can also include particulate, organic resinous support materials including, but not limited to, spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination or modification thereof.
  • the specific particle size, surface area, and pore volume of the support material determine the amount of support material that is desirable to employ in preparing the catalyst compositions, as well as affect the properties of polymers formed with the aid of the catalyst compositions. These properties are frequently taken into consideration in choosing a support material for use in a particular aspect of the invention.
  • This invention encompasses methods for preparing supported and unsupported catalyst compositions comprising contacting at least one soluble aluminoxanate salt composition and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements.
  • the catalyst composition can be produced by contacting at least one ionic aluminoxanate compound, at least one organometallic compound having at least one long chain alkyl substituent, for example, an alkyl aluminum compound, at least one organic solvent, and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements
  • the catalyst composition can be produced by contacting at least one ionic aluminoxanate compound, at least one organometallic compound having at least one long chain alkyl substituent, for example, an alkyl aluminum compound, at least one organic solvent, at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements, and at least one organic or inorganic support
  • the supported or unsupported catalyst composition is obtained when the components are contacted in any sequence or order.
  • the components can be fed to a reactor or separate vessel separately, in any order, or any two or more can be premixed and fed as a mixture, with the remaining components being fed before, during, or after the mixture is fed to the reactor.
  • Unsupported catalyst compositions in accordance with the present invention can be produced by contacting the transition metal complex with the soluble aluminoxanate salt composition before, during, or after its formation.
  • the transition metal complex can be contacted with any one or any combination of (a) the ionic aluminoxanate composition; (b) the alkylaluminum compound; or (c) the organic solvent.
  • the transition metal complex can be added at any time during the formation of the soluble aluminoxanate salt composition.
  • the transition metal complex can be contacted with the soluble aluminoxanate salt composition after it is formed.
  • Temperatures for the preparation of unsupported catalyst compositions are in a range of about -100 c C to about 300 0 C. In another aspect, preparation temperatures are in a range of about O 0 C to about 80 0 C. Typically, the preparation is carried out at temperatures in a range of 2O 0 C to about 50 0 C, or at ambient room temperature. Holding times to allow for the completion of catalyst formation can range from about 10 seconds to about 60 minutes, depending on the reaction variables.
  • Supported catalyst compositions are similarly formed by contacting the support material with the catalyst composition before, during, or after its formation. Preparation can include contacting, in any order, the transition metal compound, a soluble aluminoxanate salt composition, and a support material in one or more suitable solvents or diluents.
  • Suitable solvents and/or diluents include, but are not limited to, straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, or octane; cyclic and acyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, or methylcyclopentane; or aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, or xylene.
  • straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, or octane
  • cyclic and acyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, or methylcyclopentane
  • Mixtures of different types of solvents and/or diluents can also be used, such as a mixture of one or more acyclic aliphatic hydrocarbons and one or more cycloaliphatic hydrocarbons; a mixture of one or more acyclic aliphatic hydrocarbons and one or more aromatic hydrocarbons; a mixture of one or more cycloaliphatic hydrocarbons and one or more aromatic hydrocarbons; or a mixture of one or more acyclic aliphatic hydrocarbons, one or more cycloaliphatic hydrocarbons, and one or more aromatic hydrocarbons.
  • the support material can first be contacted with the soluble aluminoxanate salt composition to form a supported aluminoxanate which is subsequently contacted with the transition metal complex.
  • the support material can first be contacted with the transition metal complex to form a supported complex which is subsequently contacted with a soluble aluminoxanate salt composition.
  • the soluble aluminoxanate salt and the transition metal complex can be contacted together, and the resulting composition can be subsequently contacted with a support material.
  • the support material can be contacted with either the soluble aluminoxanate salt composition or the transition metal complex during its formation.
  • the support material can be contacted with one or more of the components used to form the soluble aluminoxanate or with one or more of the components used to form the transition metal complex.
  • catalyst components and catalyst compositions are generally handled under a conventional inert atmosphere using substantially inert anhydrous materials, for example, in a moisture-free, oxygen-free environment such as argon, nitrogen, or helium.
  • Temperatures for each stage of the preparation of supported catalyst compositions of this invention are in a range of about -100°C to about 300 0 C.
  • preparation temperatures are in a range of about 0 0 C to about 8O 0 C.
  • the preparation is carried out temperatures in a range of 2O 0 C to about 50 0 C, or at ambient room temperature. Holding times to allow for the completion of catalyst formation can range from about 10 seconds to about 60 minutes, depending on the reaction variables.
  • the concentration of transition metal compound on the support is typically in a range of about 0.01 wt% to about 50 wt%. In another aspect of the present invention, the concentration of transition metal compound on the support is in a range of about 0.1 wt% to about 20 wt%, based upon the weight of the support.
  • Modified supported catalysts can be prepared in accordance with this invention by combining, in any order, at least one transition metal compound, at least one soluble aluminoxanate salt composition, at least one modifier, and a support material, in a suitable solvent and/or diluent.
  • a modifier can be defined as any compound containing a Lewis acidic or basic functionality. Examples of compounds containing a Lewis acidic or basic functionality include, but are not limited to, tetraethoxysilane, phenyltri(ethoxy)silane, bis-tert- butylhydroxytoluene (BHT), or N,N-dimethylaniline.
  • the modified supported catalyst is formed by contacting a soluble aluminoxanate salt composition and the modifier in a suitable solvent to produce a slurry.
  • a transition metal compound is subsequently added to the slurry.
  • Suitable temperatures for these contacting steps are in a range of about -100 0 C to about 300°C, or, in another aspect of the present invention, in a range of about 0 0 C to about 100 0 C. Holding times to allow for the completion of the reaction can range from about 10 seconds to about 60 minutes, depending on the reaction variables.
  • the mixture comprising the transition metal, modifier, and soluble aluminoxanate salt can then be contacted with the support material.
  • the molar ratio of soluble aluminoxanate salt composition to transition metal compound is generally in a range of about 1 :1 to about 20000:1 , or, in another aspect of the present invention, in a range of about 10:1 to about 1000:1.
  • the molar ratio of soluble aluminoxanate salt to modifier is in a range of about 1 :1 to about 20000:1 , or, in another aspect of the present invention, in a range of about 10:1 to about 1000:1.
  • the concentration of transition metal compound on the support is typically in a range of 0.01 wt% to about 50 wt%, or, in another aspect of the present invention, in a range of about 0.1 wt% to about 20 wt%, based upon the weight of the support.
  • the amount of soluble aluminoxanate salt composition used varies depending upon the application and reaction conditions. Soluble aluminoxanate salt is typically used in an amount sufficient to produce molar ratio of aluminum atoms derived from the soluble aluminoxanate salt to transition metal is in a range of about 20:1 to about 2000:1. In another aspect, the molar ratio is in a range of about 20:1 to about 500:1.
  • This invention encompasses a method for polymerizing olefinic monomers comprising contacting at least one olefinic monomer and a catalyst system comprising a soluble aluminoxanate salt composition and at least one transition metal complex.
  • Catalyst compositions in accordance with the present invention are useful for the homopolymerization or copolymerization of olefinic monomers, for example, ⁇ -olefin monomers, cyclic olefin monomers, or vinylaromatic monomers.
  • Polymerizations using the catalysts of this invention can be carried out in any manner known in the art. Such polymerization processes include, but are not limited to, slurry polymerizations, gas phase polymerizations, solution polymerizations, and the like, including multi-reactor combinations thereof. Thus, any polymerization zone known in the art to produce ethylene-containing polymers can be utilized. For example, a stirred reactor can be utilized for a batch process, or the reaction can be carried out continuously in a loop reactor or in a continuous stirred reactor.
  • the polymerization reactor can be any suitable type of reactor, for example, a gas phase reactor, tubular reactor, solution phase reactor, or a combination of two or more reactors.
  • the polymerization reaction typically occurs in an inert atmosphere, that is, in an atmosphere substantially free of oxygen and under substantially anhydrous conditions, as the reaction begins. Therefore a dry, inert atmosphere, for example, dry nitrogen or dry argon, is typically employed in the polymerization reactor.
  • a dry, inert atmosphere for example, dry nitrogen or dry argon
  • Conventional temperatures for polymerization are in a range of about 0 c C to about 160 0 C and conventional pressures for polymerization are in a range of about 1 kg/cm 2 to about 50 kg/cm 2 .
  • the polymerization can be carried out at both ambient temperature and pressure.
  • controlled admission of hydrogen gas is also suitable.
  • a particulate catalyst is typically dispersed in a suitable liquid reaction medium which can be composed of one or more ancillary solvents or an excess amount of liquid monomer.
  • suitable ancillary solvents include, but are not limited to, aliphatic and aromatic liquid hydrocarbons such as heptane, isooctane, decane, toluene, xylene, ethylbenzene, mesitylene, or any combination thereof.
  • Slurry polymerization temperatures for this invention typically are in a range of about 0 0 C to about 160 0 C, with a polymerization reaction temperature more typically operating between about 4O 0 C to about 11O 0 C.
  • the polymerization can take place under atmospheric, subatmospheric, or superatmospheric conditions, or any other polymerization reaction condition can be any pressure that does not adversely affect the polymerization reaction.
  • Typical diluents include, but are not limited to, isobutane, pentane, isopentane, hexane, heptane, toluene, or any combination thereof.
  • Gas phase polymerizations are typically conducted at temperatures in a range of about 50 0 C to about 160 0 C, under superatmospheric pressures. However, the polymerization can take place at any temperature or pressure that does not adversely affect the polymerization reaction.
  • These gas phase polymerizations can be performed in a stirred or fluidized bed of catalyst in a pressure vessel adapted to permit the separation of product particles from unreacted gases. Thermostated ethylene, comonomer, hydrogen, and an inert diluent gas such as nitrogen can be introduced or reciruclated to maintain the particles at the desired polymerization reaction temperature.
  • An aluminum alkyl such as triethylaluminum
  • the alkylaluminum is typically employed as a solution in a suitable dry liquid hydrocarbon solvent such as toluene or xylene. Concentrations of such solutions are typically in a range of about 5 x 10 "5 molar (M), but solutions of greater or lesser concentrations can be used.
  • Polymer product can be withdrawn continuously or semi- continuously at a rate that maintains a constant product inventory in the reactor. [00090] Polymerization reactions in accordance with the present invention are carried out using a catalytically effective amount of a novel catalyst composition of this invention.
  • the amount of catalyst used depends on several factors, such as the type of polymerization being conducted, the polymerization conditions being used, and the type of reaction equipment in which the polymerization is being conducted.
  • the catalyst composition is used in a range of about 0.000001 to about 0.01 percent by weight of transition, lanthanide, or actinide metal based on the total weight of the monomer(s) being polymerized.
  • conditions can be used for preparing unimodal or multimodal polymers.
  • multimodal polymers can be produced by using a mixture of different catalysts having different propagation and termination rate constants.
  • the product polymer can be recovered from the polymerization reactor by any suitable means.
  • the product is typically recovered by a physical separation technique, for example, decantation.
  • the recovered polymer is generally washed with one or more suitable volatile solvents to remove residual polymerization solvent or other impurities, and then dried, typically under reduced pressure, with or without the addition of heat.
  • the product after removal from the gas phase reactor is typically freed of residual monomer by means of a nitrogen purge, and can possibly be used without further catalyst deactivation or catalyst removal.
  • Polymers produced in accordance with this invention can be homopolymers, typically of ⁇ -olefins such as ethylene, propylene, 1-butene, styrene, or any combination thereof. Polymers can also be copolymers of two or more monomers, one of which is typically an ⁇ -olefin. Monomers useful in forming copolymers include one or more different ⁇ -olefin, diolefin, cyclic olefin, acetylenic, or functional olefin monomers.
  • Non-limiting examples of olefins that can be polymerized in the presence of a catalyst composition of the present invention include ⁇ -olefins having from 2 to about 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1- dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.
  • Typical diolefin monomers which can be used to form terpolymers with ethylene and propylene include, but are not limited to, butadiene, hexadiene, norbornadiene, or any combination thereof.
  • Suitable acetylenic monomers include 1-heptyne or 1-octyne.
  • ethylene can be copolymerized with at least one ⁇ -olefin having 3 to 8 carbon atoms, for example, propylene.
  • room temperature means a temperature in a range of about 25 0 C to about 30°C.
  • Activator Conductivity in Tables III and IV is expressed as micro Mohs/centimeter ( ⁇ S/cm).
  • MAO methylaluminoxane
  • OMTS octamethyltrisiloxane
  • Figure 3 compares the 29 Si NMR spectra of OMTS (Spectrum A) and DMAMOMTS (Spectrum B) in 1 ,3 dichlorobenzene with deuteromethylene chloride for NMR lock.
  • Conventional MAO contains no silicon species, and thus, generates no 29 Si NMR signals.
  • Spectrum B shows two unusual downfield chemical shifts in the 29 Si NMR at about 29 and 39 ppm with respect to the tetramethylsilane (TMS) reference and a significant shifted (> about 5ppm) from OMTS alone.
  • FIG. 4 compares the 27 AI NMR spectra of MAO (Spectrum A) and DMAMOMTS (Spectrum B) in 1 ,3 dichlorobenzene with deuteromethylene chloride for NMR lock.
  • DMAMOMTS is ultimately derived from a conventional MAO, a significant difference in their chemical composition is clearly illustrated in Figure 4. For example, the broad feature seen at about 0 parts per million (ppm) in Spectrum A is narrowed and shifted to about -20 ppm in Spectrum B.
  • the narrow feature at about 150 ppm in Spectrum A is significantly diminished and shifted slightly downfield in Spectrum B.
  • the upfield peak in Spectrum B corresponds to the anionic aluminoxanate species and the downfield peak corresponds to the cationic four coordinate aluminum species.
  • Figure 5 compares the proton NMR spectra of MAO (Spectrum A) and DMAM « 18-CE-6 (Spectrum B) in 1,3 dichlorobenzene with deuteromethylene chloride for NMR lock. Again, a significant difference in the chemical composition of MAO and DMAM'18-CE-6 is clearly illustrated in Figure 5.
  • DMAMOMTS was produced as described in Example 1 from a mixture of about 30% MAO in toluene (725 g, 3729 mmol Al) and OMTS (44.1 g, 186.5 mmol).
  • the resulting clathrate composition was treated, without phase cut or wash, with tri-n-octylaluminum (TNOA, 47.6 g, 130.5 mmol).
  • TNOA tri-n-octylaluminum
  • the two layers became one phase.
  • the mixture was heated at about 80 0 C for about two hours and filtered to obtain a clear, colorless solution with an aluminum concentration of about 14.3 wt%.
  • This composition did not show signs of solid or gel formation at room temperature or at about -20 0 C after 52 weeks. Although gel formation was not monitored past 52 weeks, it is believed that this composition will not show signs of solid or gel formation at these temperatures for longer periods of time.
  • DMAMOMTS was produced as described in Example 1 from a mixture of about 30% MAO in toluene (725 g, 3729 mmol Al) and OMTS (44.1 g, 186.5 mmol). After phase cut and wash, the clathrate layer was treated with excess cyclohexane to obtain ionic methylaluminoxanate solids. The solids were then treated with about 800 ml toluene. The new washed clathrate was treated with TNOA (47.6 g, 139.5 mmol) and the mixture was heated at about 80 0 C for about two hours. A clear, colorless solution of soluble methylaluminoxanate salt in toluene was formed, which did not show signs of solid or gel formation at room temperature after 52 weeks.
  • DMAMOMTS was produced as described in Example 1 from a mixture of about 30% MAO in toluene (719.2 g, 3696.6 mmol) and OMTS (43.72 g, 184.83 mmol).
  • the resulting two-phase clathrate composition was treated without wash or phase cut with TNOA (94.44 g, 258.76 mmol).
  • the mixture was heated at about 8O 0 C for about two hours.
  • the mixture was subsequently subjected to solvent swap by first removing toluene under reduced pressure.
  • the resulting thick oil composition was treated with about 500 ml of isohexane, followed by vacuum distillation to remove the last traces of toluene. Again, a thick oil resulted.
  • TNOA-modified DMAMOMTS and TNOA-modified MAO were prepared as in Examples 6 and 7.
  • the 29 Si NMR spectra of these species in 1 ,2 dichlorobenzene with perdeuterobenzene for NMR lock are presented in Figure 6.
  • the TNOA-modified MAO spectrum shows no silicon species Or 29 Si NMR signals.
  • the TNOA-modified DMAMOMTS spectrum shows the characteristic 29 and 39-ppm shifts seen in the 29 Si NMR of DMAM'OMTS ( Figure 3).
  • TIBA-modified DMAMOMTS and TiBA-modified MAO were prepared as in Examples 8 and 9.
  • the 29 Si NMR spectra of these species in 1 ,2 dichlorobenzene with perdeuterobenzene for NMR lock are presented in Figure 7.
  • the TIBA- modified MAO spectrum shows no silicon species or 29 Si NMR signals.
  • FIG. 8 compares the proton NMR spectra for TNOA-modified DMAM'OMTS and TNOA-modified MAO in 1 ,2 dichlorobenzene with perdeuterobenzene for NMR lock. There are several noticeable differences in the spectra. For example, the TNOA-modified MAO spectrum does not show the peak corresponding to the OMTS cation complex present in the TNOA-modified DMAMOMTS spectrum.
  • the TNOA-modified MAO spectrum does not have any of the same sharp peak features seen in the TNOA-modified DMAMOMTS spectrum. Further, the TNOA-modified MAO spectrum shows a peak corresponding to trimethylaluminum, while the TNOA-modified DMAMOMTS spectrum does not have such a feature.
  • Figure 9 compares the 27 AI NMR spectra for TNOA-modified DMAM'OMTS and TNOA-modified MAO in 1,2 dichlorobenzene with perdeuterobenzene for NMR lock.
  • the broad feature seen at about 0 ppm in the TNOA-modified MAO spectrum is narrowed and shifted to about -20 ppm in the TNOA-modified DMAMOMTS spectrum.
  • a similar phenomenon was observed in the comparison of the 27 AI NMR spectra of MAO and DMAMOMTS, shown in Figure 4.
  • Comparative ethylene polymerizations were conducted using conventional MAO, modified MAO, and soluble methylaluminoxanate salts of the present invention as co- catalysts. All polymerizations were carried out using rac ethylenebis(indenyl)zirconium(IV) dimethyl (ZDM) as the catalyst in an amount sufficient to produce a catalyst system having ratio of aluminum (Al) atoms to zirconium (Zr) atoms of about 50:1. In each trial, polymerizations were allowed to proceed for about 15 minutes at a temperature of about 70 0 C and an ethylene pressure of about 50 psi using isohexane as diluent. The results of the polymerization trials are shown in Table I.
  • catalyst systems employing soluble aluminoxanate salts of the present invention as co-catalysts exhibit polymerization activities almost four times that of catalyst systems employing conventional MAO as co-catalyst (Trial 1 ).
  • catalyst systems employing the soluble aluminoxanate salts of the present invention as co-catalysts exhibit polymerization activities almost three times that of catalyst systems employing analogous modified MAO compositions as co-catalysts (Trials 2 and 5).
  • TNOA-modified and TIBA-modified DMAMOMTS exhibit no gel formation at room temperature for at least 52 weeks. This date strongly suggests that TNOA-modified and TIBA-modified DMAM'OMTS will be stable at room temperature for even longer periods of time.
  • conventional MAO and analogous modified MAOs exhibit gel formation after less than 10 weeks and less than 20 weeks at room temperature, respectively.
  • soluble aluminoxanate compositions have greatly improved solution stability over both conventional MAO and analogous modified MAOs.
  • Example 15 Comparative experiments were conducted as in Example 15 to evaluate and compare the electrical conductivities of conventional MAO, modified MAO, and soluble methylaluminoxanate salts of the present invention, as well as catalyst compositions formed using each of these activators.
  • the solvent was removed from the activator solutions to unmask any potential solvent interference with the conductivity measurements.
  • Catalyst systems were prepared by combining each activator (after solvent removal) with rac ethylenebis(indenyl)zirconium(IV) dimethyl (ZDM) in an amount sufficient to produce a catalyst system having ratio of aluminum (Al) atoms to zirconium (Zr) atoms of about 50:1.
  • Example 13 the activators and catalyst systems were added to chlorobenzene in an amount sufficient to produce a sample solution having an aluminum content of about 2 wt%.
  • the electrical conductivity of each sample solution was determined at room temperature using a VWR Digital Conductivity Meter. The results are illustrated below in Table IV.
  • Table IV Activator and Catalyst Conductivity

Abstract

L'invention concerne des compositions de sel d'aluminoxanate soluble, des procédés de préparation de compositions de sel d'aluminoxanate soluble, des compositions de catalyseur contenant des compositions de sel d'aluminoxanate soluble, et des procédés de polymérisation d'oléfines au moyen des compositions de catalyseur contenant des compositions de sel d'aluminoxanate soluble. Les compositions de sel d'aluminoxanate de cette invention sont solubles dans des solvants aromatiques et aliphatiques et présentent une stabilité de solution améliorée et une efficacité d'activateur supérieure par rapport aux aluminoxanes classiques ou modifiés.
PCT/US2006/024905 2005-07-01 2006-06-27 Compositions de sel d'aluminoxanate possedant une stabilite amelioree dans des solvants aromatiques et aliphatiques WO2007005400A2 (fr)

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