DE112006001733T5 - Aluminoxanate salt compositions with improved stability in aromatic and aliphatic solvents - Google Patents

Abstract

Soluble aluminoxane salt composition containing the contact product of
(a) at least one ionic aluminoxanate having the general formula [L _m R ₂ Al] ⁺ [(AO) X] ^- , in the
L is a stabilizing ligand,
Each R is independently a hydrocarbon group having one to about twenty carbon atoms,
AO is an aluminoxane proportion,
X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and
m is 1, 2 or 3, inclusive,
(b) at least one alkylaluminum compound having the general formula Al (R ') (Z) (Z), in the
R 'is an alkyl group having from about four to about twenty carbon atoms, and each Z is independently a halide, a pseudohalide or an alkyl group having from about three to about twenty carbon atoms, and
(C) comprises at least one inert, organic solvent.

Description

FIELD OF THE INVENTION

The The present invention relates to aluminoxanate salt compositions. The present invention particularly relates to soluble Aluminoxanate salt compositions useful in the preparation of novel catalyst systems are particularly useful. This invention also relates Process for the preparation of such soluble aluminoxanate salt compositions and catalyst systems and the use of such catalyst systems in the polymerization of olefinic monomers.

BACKGROUND OF THE INVENTION

Aluminoxane compositions are widely used in combination with various types of metallocenes and transition metal compounds for the preparation of catalyst systems for polymerizing olefinic monomers. However, there are certain limitations associated with standard aluminoxane solutions, such as instability to gelation and poor solubility, especially in aliphatic solvents. Methylaluminoxane (MAO), the most commonly used aluminoxane, also has lower solubility in organic solvents than higher alkylaluminoxanes and tends to be cloudy and gelatinous due to oligomerization and agglomeration. Attempts to improve the solubility of methylaluminoxane have involved hydrolyzing a mixture of trimethylaluminum with a C ₂ to C ₂₀ alkylaluminum compound, such as triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-tri- octylaluminum or a triarylaluminum to produce a modified MAO. Such modified MAOs are for example in the US-A-5 157 008 described. Although modified MAOs have improved solubility in commercial solvents, these compounds often have poor solution stability.

The US-A-5 565 395 . US-A-5,670,682 and U.S. Patent No. 5,922,631 and the WO 03/082879 describe various aluminoxanate salts and liquid clathrate compositions. However, while 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.

It There is therefore a need for aluminoxane compositions which are known in aliphatic and aromatic solvents soluble are. There is also a need for catalyst systems for polymerizing olefinic ones Monomers using such aluminoxane compositions. The The present invention addresses this need and other needs.

BRIEF SUMMARY OF THE INVENTION

The The present invention relates to soluble aluminoxanate salt compositions, Process for the preparation of soluble aluminoxanate salt compositions, supported and unsupported catalyst compositions, comprising soluble aluminoxanate salt compositions, Process for the preparation of these catalyst compositions and Process for polymerizing olefinic monomers using of these catalyst compositions. In the course of the investigation Aluminoxanatzusammensetzungen was found that ionic Aluminoxanate salts and liquid clathrate compositions can be modified so that they are in aliphatic and aromatic solvents.

• (a) mindestens einer ionischen Aluminoxanatzusammensetzung mit der allgemeinen Formel [L_mR₂Al]⁺(AO)X]^–, in der L ein stabilisierender Ligand ist, R jeweils unabhängig eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen ist, AO ein Aluminoxananteil ist, X eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen, ein Halogenid oder ein Pseudohalogenid ist, und m 1, 2 oder 3, einschließlich, ist;
• (b) mindestens einer organometallischen Verbindung, wie einer Alkylaluminiumverbindung mit der allgemeinen Formel Al(R')(Z)(Z), in der R' eine Alkylgruppe mit etwa vier bis etwa zwanzig Kohlenstoffatomen ist, und Z jeweils unabhängig ein Halogenid, ein Pseudohalogenid oder eine Alkylgruppe mit etwa drei bis etwa zwanzig Kohlenstoffatomen ist, und
• (c) mindestens einem inerten organischen Lösungsmittel umfasst.

The present invention, in one aspect, comprises a soluble aluminoxanate salt composition comprising the contact product of:

• (a) at least one ionic aluminoxane composition having the general formula [L _m R ₂ Al] ⁺ (AO) X] ^- , wherein L is a stabilizing ligand, each R is independently a hydrocarbon group having one to about twenty carbon atoms, AO is an aluminoxane moiety, X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and m is 1, 2 or 3 , including, is;
• (b) at least one organometallic compound, such as an alkylaluminum compound having the general formula Al (R ') (Z) (Z), wherein R 'is an alkyl group having from about four to about twenty carbon atoms, and each Z is independently a halide, a pseudohalide or an alkyl group having from about three to about twenty carbon atoms, and
• (c) at least one inert organic solvent.

The present invention also includes a soluble aluminoxanate salt composition having the general formula: [L _m (R) (R ') Al] ⁺ [(AO) X] ^- , in the
L is a stabilizing ligand,
R is a hydrocarbon group having one to about twenty carbon atoms,
R 'is an alkyl group having from about four to about twenty carbon atoms,
AO is an aluminoxane proportion,
X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and
m is 1, 2 or 3, inclusive.

Another aspect of this invention comprises a soluble methylaluminoxane saltate composition having the general formula: [L _m (Me) (R ') Al] ⁺ [((MAO) Me] ^- , in the
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.

• (a) eine lösliche Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(R)(R')Al]⁺[(AO)X]^–
• (b) eine lösliche Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(R)(R)Al]⁺[(AO)X]^–
• (c) eine lösliche Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(R')(R')Al]⁺[(AO)X]^– oder
• (d) irgendeine Kombination derselben umfasst, in denen: L ein stabilisierender Ligand ist, R eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen ist, R' eine Alkylgruppe mit etwa vier bis etwa zwanzig Kohlenstoffatomen ist, AO ein Aluminoxanatanteil oder eine Mischung von Aluminoxananteilen ist, und X eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen, ein Halogenid oder ein Pseudohalogenid ist, und m 1, 2 oder 3, einschließlich, ist.

Another aspect of this invention comprises a mixed aluminoxane composition which

• (a) a soluble aluminoxanate salt composition having the general formula [L _m (R) (R ') Al] ⁺ [(AO) X] ^-
• (b) a soluble aluminoxanate salt composition having the general formula [L _m (R) (R) Al] ⁺ [(AO) X] ^-
• (c) a soluble aluminoxanate salt composition having the general formula [L _m (R ') (R') Al] ⁺ [(AO) X] ^- or
• (d) any combination thereof wherein: L is a stabilizing ligand, R is a hydrocarbon group having one to about twenty carbon atoms, R 'is an alkyl group having from about four to about twenty carbon atoms, AO is an aluminoxaneate moiety or a mixture of aluminoxane moieties and X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and m is 1, 2 or 3, inclusive.

The The present invention further comprises a catalyst composition, the one soluble aluminoxanate salt composition and at least a Group 3, 4, 5 transition metal complex, 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements including the lanthanide and actinide series. The catalyst composition Can be strapless or on an organic or inorganic Supported support material.

These The invention also encompasses a process for polymerizing olefinic Monomers in which at least one olefinic monomer and a Catalyst system comprising a soluble according to the invention Aluminoxanate salt composition and at least one transition metal complex comprises contacting under polymerization conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

1 Figure 4 is a visual representation of a dimethylaluminum methylaluminoxane complexed with octamethyltrisiloxane (DMAM · OMTS).

2 illustrates the proton NMR spectra of the ionic aluminoxanate of 1 and its methylaluminoxane and octamethyltrisiloxane precursors.

3 illustrates the ²⁹ Si NMR spectra of the ionic aluminoxanate of 1 and its octamethyltrisiloxane precursor.

4 illustrates the ²⁷ Al NMR spectra of the ionic aluminoxanate of 1 and its methylaluminoxane precursor.

5 illustrates the proton NMR spectra of conventional methylaluminoxane and a crown ether complexed dimethylaluminum methylaluminoxane.

6 illustrates the ²⁹ Si NMR spectra of the ionic aluminoxanate of 1 which has been treated with tri-n-octylaluminum and a conventional methylaluminoxane which has been treated with tri-n-octylaluminum.

7 illustrates the ²⁹ Si NMR spectra of the ionic aluminoxanate of 1 which has been treated with triisobutylaluminum and a conventional methylaluminoxane which has been treated with triisobutylaluminum.

8th illustrates the proton NMR spectra of the ionic aluminoxanate of 1 which has been treated with tri-n-octylaluminum and a conventional methylaluminoxane which has been treated with tri-n-octylaluminum.

9 illustrates the ²⁷ Al NMR spectra of the ionic aluminoxanate of 1 which has been treated with tri-n-octylaluminum and a conventional methylaluminoxane which has been treated with tri-n-octylaluminum.

DETAILED DESCRIPTION THE INVENTION

The present invention provides soluble aluminoxanate salt compositions, Process for the preparation of soluble aluminoxanate salt compositions, supported and unsupported catalyst compositions, comprising soluble aluminoxanate salt compositions, and methods for polymerizing olefins using Catalyst compositions, the soluble aluminoxanate salt compositions include.

Soluble aluminoxanate salt compositions and components

• (a) mindestens einer ionischen Aluminoxanatzusammensetzung mit der allgemeinen Formel [L_mR₂Al]⁺[(AO)X]^–, in der L ein stabilisierender Ligand ist, R jeweils unabhängig eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen ist, AO ein Aluminoxananteil ist, X eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen, ein Halogenid oder ein Pseudohalogenid ist, und m 1, 2 oder 3, einschließlich, ist;
• (b) mindestens einer organometallischen Verbindung, wie einer Alkylaluminiumverbindung mit der allgemeinen Formel Al(R')(Z)(Z), in der R' eine Alkylgruppe mit etwa vier bis etwa zwanzig Kohlenstoffatomen ist, und Z jeweils unabhängig ein Halogenid, ein Pseudohalogenid oder eine Alkylgruppe mit etwa drei bis etwa zwanzig Kohlenstoffatomen ist, und
• (c) mindestens einem inerten, organischen Lösungsmittel.

Soluble aluminoxane salt compositions of the invention comprise the contact product of:

• (a) at least one ionic aluminoxane composition having the general formula [L _m R ₂ Al] ⁺ [(AO) X] ^- , wherein L is a stabilizing ligand, each R is independently a hydrocarbon group having one to about twenty carbon atoms, AO is an aluminoxane moiety, X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and m is 1, 2 or 3 , including, is;
• (b) at least one organometallic compound, such as an alkylaluminum compound having the general formula Al (R ') (Z) (Z), wherein R 'is an alkyl group having from about four to about twenty carbon atoms, and each Z is independently a halide, a pseudohalide or an alkyl group having from about three to about twenty carbon atoms, and
• (c) at least one inert, organic solvent.

Soluble aluminoxane salt compositions according to another aspect of the present invention have the general formula [L _m (R) (R ') Al] ⁺ [(AO) X] ^- in the
L is a stabilizing ligand,
R is a hydrocarbon group having one to about twenty carbon atoms,
R 'is an alkyl group having from about four to about twenty carbon atoms,
AO is an aluminoxane proportion,
X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and
m is 1, 2 or 3, inclusive.

Another aspect of the present invention comprises a soluble methylaluminoxane novelty composition having the general formula [L _m (Me) (R ') Al] ⁺ [((MAO) Me] ^- , in the
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.

• (a) eine lösliche Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(R)(R')Al]⁺[(AO)X]^–
• (b) eine lösliche Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(R)(R)Al]⁺[(AO)X^– ;
• (c) eine lösliche Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(R')(R')Al]⁺[(AO)X]^– oder
• (d) irgendeine Kombination derselben umfasst, in denen: L ein stabilisierender Ligand ist, R eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen ist, R' eine Alkylgruppe mit etwa vier bis etwa zwanzig Kohlenstoffatomen ist, AO ein Aluminoxanatanteil oder eine Mischung von Aluminoxananteilen ist, und X eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen, ein Halogenid oder ein Pseudohalogenid ist, und m 1, 2 oder 3, einschließlich, ist.

Another aspect of this invention comprises a mixed aluminoxane composition which

• (a) a soluble aluminoxanate salt composition having the general formula [L _m (R) (R ') Al] ⁺ [(AO) X] ^-
• (b) a soluble aluminoxanate salt composition having the general formula [L _m (R) (R) Al] ⁺ [(AO) X ^- ;
• (c) a soluble aluminoxanate salt composition having the general formula [L _m (R ') (R') Al] ⁺ [(AO) X] ^- or
• (d) comprises any combination thereof in which: L is a stabilizing ligand, R is a hydrocarbon group having 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, and X is a hydrocarbon moiety having from one to about twenty carbon atoms, a halide or a pseudohalide is, and m is 1, 2 or 3, inclusive.

The ionic aluminoxane composition

Aluminoxane aluminate acetate compositions used in the invention include aluminoxanate salts having a chelated dihydrocarbylaluminum group as a cation and an aluminoxane anionate as an anion. Dihydrocarbylaluminum aluminoxanate salts have the following general formula: [L _m R ₂ Al] ⁺ [(AO) X] ^- , in the
L is a stabilizing ligand,
Each R is independently a hydrocarbon group having one to about twenty carbon atoms,
AO is an aluminoxane proportion,
X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and
m is 1, 2 or 3, inclusive.

Examples of stabilizing ligands include, but are not limited to, monosiloxanes, polysiloxanes, monoethers, polyethers, monothioethers, polythioethers, a polydentate ligand comprising coordinating oxygen atoms, coordinating nitrogen atoms, coordinating phosphorus atoms, coordinating sulfur atoms, oxygen crown ether ligands, nitrogen crown ether ligands , Nitrogen and oxygen crown ether ligands or any combination thereof. Examples of crown ether structures include, but are not limited to, 12-crown-4, 15-crown-5 or 18-crown-6. Stabilizing ligands may be bidentate or monodentate ligands. When L is a bidentate ligand, m is 1. When L is a monodentate ligand, m is 2. In one aspect of the present invention, R is an alkyl, cycloalkyl, aryl, or aralkyl group. In another aspect, R is a C ₁ to C ₈ alkyl group. R is a methyl group according to another aspect of the present invention. X is, in another aspect of the present invention, an alkyl group which may be the same as or different from the R group. Examples of X groups which may be used 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, hydrocarbonoxy groups, amido groups (e.g., -NR ₂ ), hydrocarbylthio groups (e.g., -SR groups), and the like. Hydrocarbonoxy groups include, without limitation, -OR groups such as alkoxy, aryloxy, cycloalkoxy, arylalkoxy, and the like. X is, in one aspect of the present invention, a methyl group or fluoride.

wobei R eine C₁- bis C₁₀-Alkylgruppe ist und n eine Zahl von etwa 4 bis etwa 20 ist. Erfindungsgemäß verwendete Aluminoxane können lineare, cyclische, vernetzte Spezies oder irgendeine Kombination derselben enthalten. Beispiele für Kohlenwasserstoffaluminoxane, die erfindungsgemäß verwendet werden können, schließen Methylaluminoxane (MAO), modifizierte MAOs, Ethylaluminoxane (EAO), Isobutylaluminoxane (IBAO), n-Propylaluminoxane, n-Octylaluminoxane, Phenylaluminoxane oder irgendeine Kombination davon ein, sind jedoch nicht darauf eingeschränkt. Die WO 03/082466 beschreibt eine Kristallstruktur eines diskreten Kohlenwasserstoffhalogenaluminoxans mit der allgemeinen Formel Me₉Al₁₆O₁₃Cl₁₃, das auch als erfindungsgemäß geeigneter Aluminoxananteil verwendet werden kann. Die Kohlenwasserstoffaluminoxane können bis zu etwa 20 Mol.% (bezogen auf Aluminiumatome) von Anteilen enthalten, die von Aminen, Alkoholen, Ethern, Estern, Phosphor- und Carbonsäuren, Thiolen, Aryldisiloxanen, Alkyldisiloxanen und dergleichen abgeleitet sind, um die Aktivität, Löslichkeit und/oder Stabilität weiter zu verbessern.Aluminoxane (AO) moieties may include any suitable hydrocarbyl aluminoxanes having at least one hydrocarbon moiety of from one to about twenty carbon atoms, for example, alkylaluminoxanes, cycloalkylaluminoxanes, arylaluminoxanes, aralkylaluminoxanes, or any combination thereof. Hydrocarbon aluminoxanes may be in the form of linear or cyclic polymers, the simplest monomeric compound being a tetraalkylaluminoxane, such as tetramethylaluminoxane, (CH ₃ ) ₂ -Al-O-Al (CH ₃ ) ₂ , or tetraethylaluminoxane, (C ₂ H ₅ ) ₂ Al-O-Al (C ₂ H ₅ ) ₂ . The aluminoxanes, according to one aspect of the invention, may be oligomeric materials, sometimes referred to as polyalkylaluminoxanes, containing the following repeating unit:

wherein R is a C ₁ to C ₁₀ alkyl group and n is a number from about 4 to about 20. Aluminoxanes used in the present invention may contain linear, cyclic, crosslinked species or any combination thereof. Examples of hydrocarbylaluminoxanes which can be used in the present invention include methylaluminoxanes (MAO), modified MAOs, ethylaluminoxanes (EAO), isobutylaluminoxanes (IBAO), n-propylaluminoxanes, n-octylaluminoxanes, phenylaluminoxanes or any combination thereof but not limited thereto. The WO 03/082466 describes a crystal structure of a discrete Kohlenwasserstoffhalogenaluminoxans with the general formula Me ₉ Al ₁₆ O ₁₃ Cl ₁₃ , which can also be used as the present invention suitable Aluminoxananteil. The hydrocarbyl aluminoxanes may contain up to about 20 mole% (based on aluminum atoms) of portions derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, aryldisiloxanes, alkyldisiloxanes, and the like, for the activity, solubility, and / or to further improve stability.

Aluminoxanes, as known in the art, can be prepared by partial hydrolysis of hydrocarbylaluminum compounds. Hydrocarbon aluminum compounds or a mixture of compounds which can react with water to form an aluminoxane can be used in the present invention. Hydrocarbon aluminum compounds include, but are not limited to, trialkylaluminum, triarylaluminum, mixed alkyl-arylaluminum, or any combination thereof. The hydrocarbylaluminum compounds can be hydrolyzed by adding either free water or hydrous solids, which may be hydrates or porous materials that have absorbed water. Because it is difficult to control the reaction by adding water even with vigorous stirring of the mixture, the free water may be added in the form of a solution or dispersion in an organic solvent. Suitable hydrates include, but are not limited to, salt hydrates such as CuSO ₄ .5H ₂ O, Al ₂ (SO ₄ ) ₃ .18H ₂ O, FeSO ₄ .7H ₂ O, AlCl ₃ .6H ₂ O, Al (NO _{3) 3} · 9H ₂ O, MgSO ₄ · 7H ₂ O, MgCl ₂ · 6H ₂ O, ZnSO ₄ · 7H ₂ O, Na ₂ SO ₄ · 10H ₂ O, Na ₃ PO ₄ · 12H ₂ O, LiBr · 2H ₂ O, LiCl · H ₂ O, LiI · 2H ₂ O, LiI · 3H ₂ O, KF · 2H ₂ O, NaBr · 2H ₂ O, or any combination thereof. 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 may 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 from about 2: 1 to about 1: 4. Molar ratios, in another aspect, may range from about 4: 3 to about 2: 7.

Suitable hydrocarbyl aluminoxanes and processes for the preparation of hydrocarbyl aluminoxanes are disclosed in U.S. Pat US-A-4 908 463 ; U.S. Patent 4,924,018 ; US-A-5 003 095 ; US-A-5 041 583 ; US-A-5 066 631 ; US-A-5 099 050 ; US-A-5 157 008 ; US-A-5 157 137 ; US-A-5,235,081 ; US-A-5,248,801 and US-A-5,371,260 described. Methylaluminoxanes may contain varying amounts, for example from about 5 to about 35 mole percent, of the aluminum value as unreacted trimethylaluminum (TMA).

Ionian Aluminoxanates are essentially free of occluded, non-ionic Organoaluminum compounds such as alkylaluminum compounds and nonionic alkylaluminoxane species. The ionic aluminoxanate contains less than about 5 mol%, if any. Aluminum in the form of trialkylaluminum, determined by proton NMR. In one aspect, the ionic contains Aluminoxanate, if any, less than about 1 mole% in the form of trialkylaluminum.

Ionic aluminoxane compositions, according to one aspect of the present invention, include those in which the composition has a siloxane or polysiloxane ligand and wherein 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 were prepared ("Stammaluminoxan"). Ionic aluminoxaneate compositions of the present invention may be further characterized by (i) ²⁷ Al-NMR having at least one large and broad peak upfield from the parent aluminoxane peak, and (ii) at least one minor peak downfield from the parent aluminoxane peak , The large and broad peak corresponds to the anion of the ionic aluminoxanate and the smaller peak corresponds to the cation of the ionic aluminoxanate composition. Aluminoxane compositions, according to another aspect of the present invention, are characterized by a conductivity increase of at least 10 mirco-ohms compared to the parent aluminoxane.

According to one aspect of the present invention, ionic aluminoxanate compositions can be prepared by reacting in any order (I) at least one suitable aromatic solvent; (ii) at least one aluminoxane and (iii) at least one hydrocarbylpolysiloxane are contacted with each other. 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. Typically, aluminoxanes having alkyl groups of one to about eight carbon atoms are used, such as methylaluminoxane. The hydrocarbylpolysiloxane can contain from about 3 to about 18 silicon atoms in the Mo Have lekül separated by an oxygen atom, so that a linear, branched or cyclic skeleton of alternating silicon and oxygen atoms results, with the remainder of the four valence bonds of each silicon atom is individually saturated by hydrocarbon groups or hydrogen atoms. The monovalent hydrocarbon groups of the polysiloxane each independently contain up to about 18 carbon atoms, for example, alkyl, cycloalkyl, aryl, or aralkyl groups, in accordance with another aspect of the present invention. Examples of 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.

According to one Another aspect of the present invention may be ionic Aluminoxanatzusammensetzungen be prepared by in any Order (I) at least one suitable aromatic solvent; (ii) at least one aluminoxane and (iii) at least one aliphatic one or crown polyethers are brought into contact with each other to to form a clathrate. Suitable aluminoxanes include without being limited to hydrocarbylaluminoxanes, such as one or more alkylaluminoxanes, one or more cycloalkylaluminoxanes, one or more arylaluminoxanes, one or more aralkylaluminoxanes or some combination of it. Typically, aluminoxanes used with alkyl groups having one to about eight carbon atoms, such as methylaluminoxane. Examples of suitable aliphatic or crown polyethers used in the present invention can be, without limitation dimethoxyethane, diethoxyethane, 1-ethoxy-2-methoxyethane, Dipropoxyethane, 1,2-dimethoxypropane, 1,3-dimethoxypropane, 1,2-dimethoxybutane, 2,3-dimethoxybutane, 1,3,5-trimethoxypropane, 18-crown-6-polyether or Analogues and homologs thereof. To suitable aromatic solvents include, but are not limited to, benzene, Toluene, xylene, ethylbenzene, cumene, tetrahydronaphthalene or any Blends of aromatic solvents, such as BTX.

• (1a) Bilden eines stabilen flüssigen Clathrats, wie es beispielsweise in den US-A-5 670 682 und US-A-5 922 631 beschrieben ist, durch Kontaktieren von (i) mindestens einer Aluminoxanverbindung, (ii) einer wirksamen Menge von mindestens einer organischen, anorganischen, organometallischen Verbindung oder irgendeiner Kombination davon und (iii) einem aromatischen organischen Lösungsmittel; und
• (1b) einmaliges oder mehrmaliges Waschen des flüssigen Clathrats mit einem aromatischen Lösungsmittel, wobei jeweils ein Zweiphasensystem gebildet wird, das aus einer unteren Schicht aus viskoser Flüssigkeit, die aus der Aluminoxanatzusammensetzung und eingeschlossenem aromatischem Lösungsmittel zusammengesetzt ist, und einer oberen Schicht aus einer Flüssigkeit mit geringerer Dichte zusammengesetzt ist, die entfernt und verworfen wird.

The preparation of ionic aluminoxanate clathrates generally results in a two-phase liquid system in which the denser bottom liquid is typically the clathrate and can be easily separated from the overlying liquid top phase by conventional separation techniques. Exemplary methods of preparing the aluminoxane aluminoxane compositions include, for example, the following steps:

• (1a) forming a stable liquid clathrate, such as in the US-A-5,670,682 and U.S. Patent No. 5,922,631 (ii) an effective amount of at least one organic, inorganic, organometallic compound or any combination thereof and (iii) an aromatic organic solvent; and
• (1b) washing the liquid clathrate one or more times with an aromatic solvent to form a two-phase system each consisting of a lower layer of viscous liquid composed of the aluminoxane composition and entrapped aromatic solvent and an upper layer of liquid composed of lower density which is removed and discarded.

A effective amount of the organic, inorganic or organometallic Compound, as used here, is a lot to be used for Formation of a stable clathrate is sufficient but insufficient to the aluminoxane is incapable of activating a transition metal complex catalyst system close. The volume of the aromatic, organic used Solvent relative to the initial liquid Clathrate is variable and not crucial as long as it is sufficient to form a stirrable solution.

• (2a) Gewinnen der Aluminoxanat-Feststoffe aus der viskosen Flüssigkeit in der obigen Stufe (1b) durch (i) Ausfällen der Feststoffe durch Mischen mit einem flüssigen Nicht-Lösungsmittel, wie einem flüssigen Paraffin- oder Cycloparaffin-Kohlenwasserstoff mit der viskosen Flüssigkeit, Isolieren der Feststoffe durch irgendeine geeignete physikalische Flüssigkeit/Feststoff-Trennung, wie durch Filtrieren, Zentrifugieren oder Dekantieren, und vorzugsweise Trocknen der Feststoffe, beispielsweise unter Vakuum bei Umgebungsraumtemperatur; (ii) gegebenenfalls Verdünnen der viskosen Flüssigkeit mit einem geeigneten aromatischen Lösungsmittel, gefolgt von Sprühtrocknen der viskosen Flüssigkeit, typischerweise bei einer Temperatur bis zu etwa 50°C; (iii) Entfernen des eingeschlossenen aromatischen Lösungsmittels aus der viskosen Flüssigkeit durch Vakuumdestillation oder (iv) Entfernen der Flüssigkeit mit geringerer Dichte und des eingeschlossenen aromatischen Lösungsmittels aus der in (b) gebildeten zweiphasigen Flüssigkeit.

Solid ionic aluminoxanate compositions are optionally prepared according to another aspect of the present invention by:

• (2a) recovering the aluminoxaneate solids from the viscous liquid in the above step (1b) by (i) precipitating the solids by mixing with a liquid non-solvent such as a liquid paraffin or cycloparaffinic hydrocarbon with the viscous liquid, isolating the solids by any suitable physical liquid / solid separation, such as by filtering, centrifuging or decanting, and preferably drying the solids, for example under vacuum at ambient room temperature; (ii) optionally diluting the viscous liquid with a suitable aromatic solvent, followed by spray-drying the viscous liquid, typically at a temperature up to about 50 ° C; (iii) removing the entrapped aromatic solvent from the viscous liquid through Va or (iv) removing the lower density liquid and the entrapped aromatic solvent from the biphasic liquid formed in (b).

• (3a) gründliches Waschen des in der obigen Stufe (1a) gebildeten flüssigen Clathrats unter Bildung eines zweiphasigen flüssigen Systems;
• (3b) Entfernen der oberen Schicht aus Flüssigkeit mit geringerer Dichte und
• (3c) Entfernen des aromatischen Lösungsmittels aus der unteren viskosen Flüssigkeit durch Vakuumdestillation, um teilchenförmige Aluminoxanat-Feststoffe zu isolieren.

Solid ionic aluminoxane compositions are prepared according to another aspect of the present invention by:

• (3a) thoroughly washing the liquid clathrate formed in the above step (1a) to form a biphasic liquid system;
• (3b) removing the upper layer of lower density liquid and
• (3c) Removal of the aromatic solvent from the lower viscous liquid by vacuum distillation to isolate particulate aluminoxanate solids.

• (4a) gründliches Waschen des in der obigen Stufe (1a) gebildeten flüssigen Clathrats unter Bildung eines zweiphasigen flüssigen Systems;
• (4b) Entfernen der oberen Schicht aus Flüssigkeit mit geringerer Dichte;
• (4c) Mischen eines inerten, flüssigen Nicht-Lösungsmittels mit der viskosen Flüssigkeit, um eine Aufschlämmung zu bilden, die aus ausgefällten Aluminoxanat-Feststoffen und einer flüssigen Phase zusammengesetzt ist, und
• (4d) Gewinnen der ausgefällten Feststoffe aus der flüssigen Phase.

Solid ionic aluminoxane compositions are prepared according to another aspect of the present invention by:

• (4a) thoroughly washing the liquid clathrate formed in the above step (1a) to form a biphasic liquid system;
• (4b) removing the upper layer of lower density liquid;
• (4c) mixing an inert liquid non-solvent with the viscous liquid to form a slurry composed of precipitated aluminoxanate solids and a liquid phase, and
• (4d) recovering the precipitated solids from the liquid phase.

Examples for liquid non-solvents, the can be used according to the 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 the non-solvent should be sufficient Amount done to the desired yield of precipitated To produce solids. This amount can be determined by the non-solvent added in portions and care is taken to see if the addition of more non-solvent leads to further precipitation formation.

• (5a) Mischen der in Stufe (2a), (3c) oder (4d) ausgefällten Feststoffe mit frischem aromatischem Lösungsmittel, um ein Clathrat zu bilden;
• (5b) Waschen das Clathrats wie in Stufe (1b);
• (5c) Gewinnen ausgefällter Feststoffe, wie in Stufe (2a), (3c) oder (4d).

The solid ionic aluminoxane composition can be prepared according to another aspect of the present invention by:

• (5a) mixing the solids precipitated in step (2a), (3c) or (4d) with fresh aromatic solvent to form a clathrate;
• (5b) washing the clathrate as in step (1b);
• (5c) recovering precipitated solids as in step (2a), (3c) or (4d).

The in the stages (1) to (5) described manufacturing method at ambient room temperatures (eg 25 ° C to 30 ° C) or suitably reduced or elevated temperatures be, for example, in the range of about 10 ° C to about 100 ° C. The production is carried out according to a Aspect of the present invention at temperatures in the range of about 20 ° C to about 80 ° C performed.

The Precipitated, ionic aluminoxanate solids, which in The stages (2a), (3c) and (4d) have been formed as a rule a higher electrical conductivity than a non-precipitated liquid clathrate, like this liquid clathrate in step (1b). The solid, ionic Aluminoxanatzusammensetzungen are thus more ionic as the liquid clathration aluminoxane admixtures. The solids recovered from step (5c) are similar Way a higher electrical conductivity than the precipitated formed in steps (2a), (3c) and (4d) Solids. The precipitated solids can as often as necessary again with fresh aromatic solvent be washed to the desired electrical conductivity to reach, or until no further increase in electrical conductivity is observed.

The alkylaluminum compound

Alkylaluminum compounds used in the present invention include trialkylaluminums and substituted trialkylaluminums having the following general formula: Al (R ') (Z) (Z), in the
R 'is an alkyl group having from about four to about twenty carbon atoms, and
Each 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 may be selected from bromide, chloride or fluoride. The halide substituent is fluoride in one aspect. Examples of pseudohalide groups useful in the present invention include, but are not limited to, oxyhalide groups, hydrocarbonoxy 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.

The inert organic solvent

Used according to the invention inert, organic solvents exclude any suitable aromatic solvents, aliphatic solvents, halogenated solvent or any combination thereof one. In accordance with the invention, used aliphatic solvents in accordance with one aspect of the present invention 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. According to the invention Mixtures of aliphatic solvents can be used and close without being limited to Isopar C and Isopar E one. Examples of aromatic Solvents include but are not limited to to be benzene, chlorobenzene, ethylbenzene, toluene, xylene, cumene or any combination thereof.

Optional carrier materials

The soluble aluminoxanate salt composition may optionally on any suitable organic or inorganic carrier to be supported. Any finer, more inorganic, firmer Carriers such as talc, clay, silica, alumina, Silica-alumina or any combination thereof, can carrier materials used in the invention be. Backing materials may also be particulate, include organic, resinous support materials, including, but not limited to spherical, particulate or finely divided Polyethylene, polyvinyl chloride, polystyrene or any combination or modification thereof. Support materials are according to a Another aspect of this invention is inorganic, particulate Supports or support materials, such as magnesium halides, inorganic oxides and mixed inorganic oxides, aluminum silicates, inorganic compositions containing inorganic oxides, or any combination thereof. Non-limiting Examples of inorganic compositions, the inorganic Include kaolinite, attapulgite, montmorillonite, Il lit, bentonite, halloysite, similar heat resistant Tone or any combination of them. Examples of inorganic oxides include but are not limited to silica, alumina, silica-alumina, Magnesia, titania, zirconia or any combination from that. According to one aspect of the invention is the Support anhydrous or substantially anhydrous. inorganic Oxides can be dehydrated to remove water. The carrier can also be calcined or with known conventional reagents be chemically treated to hydroxyl groups and / or water of to remove the carrier. To suitable conventional Reagents include aluminum alkyls, lithium alkyls, silyl chloride, Aluminoxanes, ionic aluminoxanates or any combination of it, without being limited to it.

The specific particle size, surface area, and pore volume of the support material determine the amount of support material desirably to be used in the preparation of the catalyst compositions and affect the properties of polymers formed using the catalyst compositions. These properties are often considered in the choice of a carrier material for use in accordance with a particular aspect of the invention. A suitable support material, such as silica, typically has a particle diameter in the range of about 0.1 to about 600 microns, or in a range of about 0.3 to about 100 microns, a surface in the range of about 50 m ² / g to about 1000 m ² / g or according to 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 the range of about 0.3 cm ³ / g to about 5.0 cm ³ / g or, according to another aspect of the present invention in a range of about 0.5 cm ³ / g to about 3.5 cm ³ / g. It is also desirable to use supports with pore diameters in the range of about 50Å to about 500Å. The carrier material, to ensure its use in dehydrated form, may be at about 100 ° C about 1000 ° C for a period of about one hour to about 100 hours or, according to another aspect of the present invention, from about 3 to about 24 hours. The treatment can be carried out in vacuo or under a dry inert gas purging, such as nitrogen.

The Support material may alternatively be chemically dehydrated become. Chemical dehydration is effected by the carrier in an inert, low-boiling solvent, such as for example heptane, in the presence of a dehydrating agent, such as triethylaluminum, in a moisture and oxygen free Is slurried environment.

Production of the soluble Aluminoxanatsalzzusammensetzung

These Invention encompasses processes for preparing soluble aluminoxanate salts, in which at least one ionic aluminoxanate, at least one inert, organic solvent and at least one Alkylaluminiumverbindung in any order with each other in Be brought in contact. The soluble aluminoxanate salt is obtained according to this aspect when the components brought into contact with each other in any order or sequence become.

According to one Another aspect of the present invention is a two-phase, ionic aluminoxanate-liquid clathrate system prepared, by (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 brought into contact with each other to form a liquid clathrate system. The Liquid clathrate system is connecting with one Alkylaluminium compound brought into contact with the soluble Aluminoxanate salt composition. The upper layer with lower density may optionally be removed before the Alkylaluminiumverbindung is added.

• (i) Dekantieren der oberen Schicht mit geringerer Dichte; Ausfällen der Feststoffe durch Mischen eines flüssigen Nicht-Lösungsmittels, wie eines flüssigen Paraffin- oder Cycloparaffin-Kohlenwasserstoffs, mit der viskosen Flüssigkeit; Isolieren der Feststoffe durch irgendeine geeignete physikalische Flüssigkeit/Feststoff-Trennung, wie durch Filtrieren, Zentrifugieren oder Dekantieren, und vorzugsweise Trocknen der Feststoffe, beispielsweise unter Vakuum bei Umgebungsraumtemperatur;
• (ii) Dekantieren der oberen Schicht mit geringerer Dichte; gegebenenfalls Verdünnen der viskosen Flüssigkeit mit einem geeigneten aromatischen Lösungsmittel, gefolgt von Sprühtrocknen der viskosen Flüssigkeit, typischerweise bei einer Temperatur bis zu etwa 50°C;
• (iii) Dekantieren der oberen Schicht mit geringerer Dichte und Entfernen des eingeschlossenen aromatischen Lösungsmittels aus der viskosen Flüssigkeit durch Vakuumdestillation oder
• (iv) Entfernen der Flüssigkeit mit geringerer Dichte und des eingeschlossenen aromatischen Lösungsmittels aus der zweiphasigen Flüssigkeit unter Verwendung von irgendeinem in der Technik bekannten geeigneten Verfahren.

The ionic aluminoxanate solids may alternatively be removed from the liquid clathrate system by:

• (i) decanting the lower density upper layer; Precipitation of the solids by mixing a liquid non-solvent, such as a liquid paraffin or cycloparaffinic hydrocarbon, with the viscous liquid; Isolating the solids by any suitable physical liquid / solid separation, such as by filtration, centrifugation or decantation, and preferably drying the solids, for example under vacuum at ambient room temperature;
• (ii) decanting the lower density upper layer; optionally diluting the viscous liquid with a suitable aromatic solvent, followed by spray-drying the viscous liquid, typically at a temperature up to about 50 ° C;
• (iii) decanting the lower density upper layer and removing the entrapped aromatic solvent from the viscous liquid by vacuum distillation or
• (iv) removing the lower density liquid and the entrapped aromatic solvent from the biphasic liquid using any suitable method known in the art.

The ionic aluminoxanate solids can be first with a Alkylaluminum compound to form a mixture in contact be brought, after which the mixture subsequently with an organic solvent is brought into contact, to form the soluble aluminoxanate salt composition. According to one Another aspect of the invention is an ionic aluminoxanate solid first in contact with an aromatic solvent brought to form a liquid clathrate, and the Clathrate is then treated with an alkylaluminium compound contacted to form the soluble aluminoxanate salt composition to build. The ionic aluminoxanate solids and an aliphatic Alternatively, solvents are first formed to form a Slurry contacted, and the slurry then comes into contact with the alkylaluminum compound brought to the soluble aluminoxanate salt composition to build. The soluble aluminoxanate salt compositions typically at temperatures in the range of about 20 ° C produced to about 80 ° C.

The present invention further includes methods of making supported, soluble aluminoxanate salt compositions wherein 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 are contacted in any order. In one aspect, the soluble aluminoxanate salt composition is prepared and then contacted with a carrier material to form the carrier-supported composition. The carrier-based Zu For example, composition may be prepared by forming a slurry of (i) the soluble aluminoxanate salt composition dissolved in aromatic or aliphatic solvent and (ii) a particulate carrier or carrier material. In another aspect, the supported composition can be prepared by forming a slurry of (i) an ionic alumino xanate liquid clathrate system and (ii) an alkylaluminum supported on a particulate support material. In addition, any other sequential combination is suitable for preparing the supported aluminoxane salt soluble compositions of this invention.

The Preparation of the soluble aluminoxane salt is generally using a conventional inert atmosphere using of essentially inert, anhydrous materials. The temperatures for the production are typically in a range from about 20 ° C to about 80 ° C, although higher or lower temperatures are suitable are.

The Molar ratio of the aluminum atoms, which differ from the ionic Derive aluminoxanate compound, to the aluminum atoms that are derived from the alkylaluminum compound is in the range of about 2: 1 to about 1000: 1. The molar ratio is according to one another aspect ranges from about 10: 1 to about 50: 1.

catalyst compositions and components

• (I) einer löslichen Aluminoxanatsalzzusammensetzung ausgewählt aus: (a) mindestens einer löslichen Aluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m((R)(R')Al]⁺[(AO)X]^–, (b) mindestens einer löslichen Aluminoxanatsalzzusammensetzung, die das Kontaktprodukt von (i) mindestens einer ionischen Aluminoxanatzusammensetzung mit der allgemeinen Formel [L_mR₂Al]⁺[(AO)X]^– (ii) mindestens einer organometallischen Verbindung, wie einer Alkylaluminiumverbindung mit der allgemeinen Formel Al(R')(Z)(Z), und (iii) mindestens einem inerten, organischen Lösungsmittel umfasst; (c) mindestens einer löslichen Methylaluminoxanatsalzzusammensetzung mit der allgemeinen Formel [L_m(Me)(R')Al]⁺[(MAO)Me]^– und (d) mindestens einer gemischten Aluminoxanatzusammensetzung, die (i) ein lösliches Aluminoxanat mit der allgemeinen Formel L_m(R)(R')Al]⁺[(AO)X]^– (ii) ein lösliches Aluminoxanat mit der allgemeinen Formel [L_m(R)(R)Al]⁺[(AO)X^–, (iii) ein lösliches Aluminoxanat mit der allgemeinen Formel [L_m(R')(R')Al]⁺(AO)X]^– oder (iv) irgendeine Kombination davon umfasst, und
• (II) mindestens einem Komplex eines Übergangsmetalls der Gruppe 3, 4, 5, 6, 7, 8, 9, 10 oder 11 des Periodensystems der Elemente einschließlich der Lanthanidreihen und der Actinidreihen, wobei L ein stabilisierender Ligand ist, R jeweils unabhängig eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen ist, R' jeweils unabhängig eine Alkylgruppe mit etwa vier bis etwa zwanzig Kohlenstoffatomen ist, AO ein Aluminoxananteil ist, X eine Kohlenwasserstoffgruppe mit einem bis etwa zwanzig Kohlenstoffatomen, ein Halogenid oder ein Pseudohalogenid ist, und Z jeweils unabhängig ein Halogenid, ein Pseudohalogenid oder eine Alkylgruppe mit etwa drei bis etwa zwanzig Kohlenstoffatomen ist, MAO ein Methylaluminoxananteil ist, Me eine Methylgruppe ist, und m 1, 2 oder 3, einschließlich, ist.

This invention includes supported and unsupported catalyst compositions made using soluble aluminoxanate salt compositions. Catalyst systems used according to one aspect of the present invention comprise the contact product of:

• (I) a soluble aluminoxanate salt composition selected from: (a) at least one soluble aluminoxanate salt composition having the general formula [L _m ((R) (R ') Al] ⁺ [(AO) X] ^- , (b) at least one soluble aluminoxanate salt composition comprising the contact product of (i) at least one ionic aluminoxane composition having the general formula [L _m R ₂ Al] ⁺ [(AO) X] ^- (ii) at least one organometallic compound, such as an alkylaluminum compound having the general formula Al (R ') (Z) (Z), and (iii) at least one inert organic solvent; (c) at least one soluble methylaluminoxane saltate composition having the general formula [L _m (Me) (R ') Al] ⁺ [(MAO) Me] ^- and (d) at least one mixed aluminoxane composition comprising (i) a soluble aluminoxanate having the general formula L _m (R) (R ') Al] ⁺ [(AO) X] ^- (ii) a soluble aluminoxanate having the general formula [L _m (R) (R) Al] ⁺ [(AO) X ^- , (iii) a soluble aluminoxanate having the general formula [L _m (R ') (R') Al] ⁺ (AO) X] ^- or (iv) any combination thereof, and
• (II) 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 the Elements including the lanthanide series and the actinide series, wherein L is a stabilizing ligand, R each independently is a hydrocarbon group of one to about twenty carbon atoms, each R 'independently is an alkyl group of about four to about twenty carbon atoms, AO is an aluminoxane moiety, X is a hydrocarbon group of one to about twenty carbon atoms, a halide or a pseudohalide, and Z is each independently a halide, a pseudohalide or an alkyl group having from about three to about twenty carbon atoms, MAO is a methylaluminoxane moiety, Me is a methyl group, and m is 1, 2 or 3, inclusive.

If multiple R groups in a given component or in different ones Components of a composition are present, according to the invention each R be the same or different. If in a similar way several R 'groups in a given component or in different ones Components of a composition are present, each R ' be the same or different.

Transition metal complexes

Soluble aluminoxane salt compositions of this invention may be used with any known transition metal catalyst compound in which the transition metal is a transition metal of Group 3 to 11 of the Periodic Table of the Elements, including the lanthanide or actinide series. The periodic table of elements meant here is that on Page 27 of the issue of Chemical & Engineering News of 4 February 1985 is specified. Suitable catalyst compounds can also be described as d- and f-block metal compounds. See for example the periodic table of the elements on page 225 of Moeller et al., Chemistry, 2nd Ed., Academic Press, Copyright 1984 , The metal component according to one aspect of the present invention is a compound of Fe, Co, Ni, Pd or V. In another aspect, the metal component is a compound of the metals of Groups 4 to 6 (Ti, Zr, Hf, V, Nb, Ta , Cr, Mo and W). The metal component in another aspect is a Group 4 metal such as titanium, zirconium or hafnium.

The Transition metal catalyst compounds used in the invention Thus, one or more of any Ziegler-Natta catalyst compound, any metallocene, any compound with strained geometry, any late transition metal complex or any other transition metal compound or any other transition metal complex, of which in the literature was reported or otherwise general in the art for it they are known to be effective upon appropriate activation Catalyst compound are, including mixtures of at least two different types of such transition metal compounds or complexes, such as a mixture of a metallocene and a Ziegler-Natta olefin polymerization catalyst compound.

The transition metal compounds of Group 3, 4, 5, and 6 metals which can be used as the transition metal component of the catalyst compositions of this invention include the compounds of metals such as scandium, titanium, zirconium, hafnium, cerium, vanadium, niobium, tantalum, chromium, molybdenum Tungsten, thorium and uranium, often referred to as Ziegler-Natta type olefin polymerisation catalysts. Compounds of this type can be represented by the formula MX _n (OR) _m , in which M is the transition metal atom or a transition metal atom cation containing one or two oxygen atoms, such as vanadyl, zirconyl or uranyl, X is a halogen atom, OR is a Hydrocarbonoxy group having up to about 18 carbon atoms or up to about 8 carbon atoms or an alkyl having up to 4 carbon atoms, such as an alkyl, cycloalkyl, cycloalkylalkyl, aryl or aralkyl group, n and m are positive integers, except that a of them (but not both) can be zero, and n + m is the valency state of the transition metal. Illustrative of some of the transition metal compounds that can be used in the present invention include, but are not limited to, titanium dibromide, titanium tribromide, titanium tetrabromide, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium trifluoride, titanium tetrafluoride, titanium diiodide, titanium triiodide, titanium tetraiodide, zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium tetrafluoride, Zirkoniumtetraiodid, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, Hafniumtetraiodid, Hafniumtrichlorid, Hafniumtribromid, Hafniumtriiodid, vanadium dichloride, vanadium trichloride, vanadium tetrachloride, vanadium tetrabromide, vanadium tribromide, Vanadiumdibromid, Vanadiumtrifluorid, vanadium tetrafluoride, vanadium pentafluoride, Vanadiumdiiodid, Vanadiumtriiodid, vanadium tetraiodide, vanadyl chloride, Vanadylbromid, Niobium pentabromide, niobium pentachloride, niobium pentafluoride, tantalum pentabromide, tantalum pentachloride, tan talpentafluoride, chromium (II) bromide, chromium (III) bromide, chromium (II) chloride, chromium (III) chloride, chromium (II) fluoride, chromium (III) fluoride, molybdenum dibromide, molybdenum trib sulfide, molybdenum tetrabromide, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexafluoride, lanthanum trichloride, cerium (III) fluoride, cerium (III) chloride, cerium (III) bromides, cerium (III) iodides, cerium (IV) fluoride, uranium trichloride, uranium tetrachloride , Uranium tribromide, urantetrabromide, thorium tetrachloride, thorium tetrabromide or any combination thereof. Hydrocarbon oxides and mixed halides / hydrocarbon oxides of transition metals which can be used in the invention include, but are not limited to Ti (OCH _{3) 4,} Ti (OCH ₃₎ Cl _3, Ti (OCH ₃₎ Br _3, Ti (OCH _{3) 2} I ₂ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) Cl 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 Cl ₂ , Ti (O-iso-C ₃ H ₇ ) ₃ Cl, Ti (O-iso-C ₃ H ₇ ) ₂ Cl ₂ , Ti (O-iso-C ₃ H ₇ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₃ Cl, Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) Cl ₃ , Ti ( OC ₆ H ₅ ) Cl ₃ , Ti (Op-CH ₃ C ₆ H ₄ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) ₂ Cl ₂ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (O-cyclo-C ₆ H ₁₁ ) Cl ₃ , Ti (OC ₈ H ₁₇ ) ₂ Br ₂ , Ti (O ₂ -EtHex) ₄ , Ti (OC ₁₂ H ₂₅ ) Cl ₃ , Ti (OC ₁₇ H ₁₈ ) ₂ Br ₂ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , Zr (OC ₅ H ₁₁ ) ₄ , ZrCl (OC ₂ H ₅ ) ₃ , ZrCl ₂ (OC ₂ H ₅ ) ₂ , ZrCl ₃ (OC ₂ H ₅ ), ZrCl (OC ₄ H ₉ ) ₃ , ZrCl ₂ (OC ₄ H ₉ ) ₂ , ZrCl ₃ (OC ₄ H ₉ ), Hf (OC ₄ H ₉ ) ₄ , Hf (OC ₄ H ₉ ) ₃ Cl, VO (OC ₂ H ₅ ) ₃ , VOCl (OCH ₃ ) ₂ , VO Cl (OC ₂ H ₅ ) ₂ , VOCl (OC ₃ H ₇ ) ₂ , VOCl (O-iso-C ₃ H ₇ ) ₂ , VOCl ₂ (OCH ₃ ), VOCl ₂ (OC ₂ H ₅ ), VOCl ₂ ( OC ₃ H ₇ ), VOCl ₂ (O-iso-C ₃ H ₇ ), VOBr (OCH ₃ ) ₂ , VOBr (OC ₂ H ₅ ) ₂ , VOBr (O-iso-C ₄ H ₉ ) ₂ , VOBr ₂ (OC ₃ H ₇ ), VOBr ₂ (O-iso-C ₃ H ₇ ), VOBr ₂ (OC ₄ H ₉ ), VOBr ₂ (O-iso-C ₄ H ₉ ), VOI (OCH ₃ ) ₂ , VOI (OC ₂ H ₅ ) ₂ , VOI ₂ (OCH ₃ ), VOI ₂ (O-cyclo-C ₃ H ₅ ), VOI ₂ (OC ₅ H ₁₁ ), VOI ₂ (O-cyclo-C ₆ H ₁₁ ), Cr (O-iso-C ₄ H ₉ ) ₃ , Mo (OC ₂ H ₅ ) ₃ or any combination thereof. Carboxylic acid salts and various chelates of the transition metal can also be used. Examples of such salts and chelates include, but are not limited to, zirconyl acetate, uranyl butyrate, chromium acetate, chromium (III) oxy-2-ethylhexanoate, chromium (III) 2-ethylhexanoate, chromium (III) dichloroethylhexanoate, chromium (II) 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 acetylacetonate, zirconyl acetylacetonate , Chromoctylacetoacetat or any combination thereof. Transition metal alkyls including tetramethyltitanium, methyltitanium trichloride, tetraethylzirconium or tetraphenyltitanium may also be used in the present invention, but are not limited thereto.

In one aspect of the present invention, transition metal compounds of the well-known Ziegler-Natta catalyst compounds are those of Group 4 metals including the alkoxides, halides, and mixed halide / alkoxide compounds. Suitable transition metal compounds include, for example but not limited to, TiCl _4, ZrCl _4, HfCl ₄ or TiCl. ₃ These compounds can also be used in chelated form to improve solubility. Suitable chelated catalysts of this type are known and described in the literature.

Metallocenes are another general class of olefin polymerization catalyst compounds with which the soluble aluminoxanate salt compositions can be used to form the catalyst compositions of this invention. The term "metallocene" here includes metal derivatives containing at least one cyclopentadienyl (Cp) moiety. Suitable metallocenes are well known in the art and include the group 3, 4, 5 and 6 metallocenes, including lanthanide and actinide metals. For example, according to the invention and without limitation, the metallocenes used in the US-A-2,864,843 ; US-A-2,983,740 ; US-A-4,665,046 ; U.S. Patent 4,874,880 ; U.S. Patent 4,892,851 ; US-A-4,931,417 ; US-A-4 952 713 ; US-A-5 017 714 ; US-A-5,026,798 ; US-A-5 036 034 ; US-A-5 084 802 ; US-A-5 081 231 ; US-A-5,145,819 ; US-A-5,162,278 ; US-A-5,245,019 ; US-A-5,268,495 ; US-A-5,276,208 ; US-A-5 304 523 ; US-A-5,324,800 ; US-A-5,329,031 ; US-A-5,329,033 ; US-A-5,330,948 . US-A-5 347 025 ; U.S.-A-5,347,026 and US-A-5,347,752 are described.

The metallocene structures are to be interpreted broadly in this specification and include structures containing 1, 2, 3, or 4 Cp or substituted Cp rings. Metallocenes suitable for use according to the invention can thus be represented by formula (I): B _a Cp _b MX _c Y _d (I)

In each Cp independently represents a cyclopentadienyl moiety on each occurrence containing group, which is typically in the range of 5 to has about 24 carbon atoms; B is a bridge group or ansa group is that connects two cp groups together or alternatively carries an alternating coordinating group, such as alkylaminosilylalkyl, silylamido, alkoxy, siloxy, aminosilylalkyl or analogous monodentate heteroatom electron donor groups; M is a d or f block metal atom; every X and every Y respectively independently is a group attached to the d or f block metal atom is bound; 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 enough to form a stable connection and is often the Coordination number of the d- or f-block metal atom.

Each Cp is independently a cyclopentadienyl, indenyl, fluorenyl or related group capable of forming an n bond to the metal, or a hydrocarbon, halogen, halohydrocarbon, hydrocarbon metalloid and / or halohydrocarbon metalloid-substituted derivative thereof. Cp typically contains up to 75 non-hydrogen atoms. B, if present, is typically a silylene - (- SiR ₂ -), benzo (C ₆ H ₄ -), substituted benzo, methylene - (- CH ₂ -), substituted methylene, ethylene - (- CH ₂ CH ₂ -) or substituted ethylene bridge. In one aspect, M is a metal atom of Groups 4-6. In another aspect, 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 cyclometalated hydrocarbon group or any other bivalent chelating ligand whose two loci are linked to M via a single bond to form a cyclic moiety that includes M as a member. Each X and, if present, Y may each independently be a halogen atom, a hydrocarbon group (alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, aralkyl, etc.) each at each occurrence, hydrocarbyloxy (alkoxy, aryloxy, etc.), siloxy -, amino or substituted amino, hydride, acyloxy, triflate and similar monovalent groups which form stable metallocenes. The sum of b, c and d is an integer and often 3 to 5. When M is a group 4 metal or an actinide metal and b is 2, the sum of c and d is 2, and c is at least 1. If M is a group 3- or lanthanide metal and b is 2, c is 1 and d is zero. When M is a Group 5 metal and b is 2, the sum of c and d is 3 and c is at least 2.

Also useful in the present invention are compounds analogous to those of formula (I) wherein one or more of the Cp groups are replaced by cyclic unsaturated charged groups which are isoelectronic with Cp, such as borabenzene or substituted borabenzene, azaborole or substituted Araborol and various other isoelectronic Cp analogs. See, for example, Krishnamurti et al. US-A-5 554 775 and US-A-5,756,611 ,

In a group of metallocenes is b 2, d. H. There are two cyclopentadienyl moieties containing groups in the molecule, and these two groups may be the same or different.

Another subgroup of suitable metallocenes which may be used in the practice of the invention are metallocenes of the type disclosed in U.S. Pat WO 98/32776 described type. These metallocenes are characterized in that one or more cyclopentadienyl groups in the metallocene are substituted by one or more polyatomic groups bonded through an N, O, S or P atom or through a carbon-carbon double bond. Examples of such substituents on the cyclopentadienyl ring include -OR, -SR, -NR ₂ , -CH =, -CR = and -PR ₂ where R may be the same or different and is a substituted or unsubstituted C ₁ to C ₁₆ . Hydrocarbon group, a tri-C ₁ -C ₈ hydrocarbylsilyl group, a tri-C ₁ -C ₈ hydrocarbyloxysilyl group, a mixed C ₁ -C ₈ hydrocarbyl and C ₁ -C ₈ hydrocarbyloxysilyl group, a tri-C ₁ -C ₈ -hydrocarbylgermyl group, a tri-C ₁ -C ₈ hydrocarbylgermyl group, or a mixed C ₁ -C ₆ hydrocarbyl and C ₁ -C ₈ hydrocarbyloxygermyl group.

Examples of metallocenes to which this invention is applicable include, but are not limited to:
Bis (cyclopentadienyl) zirconium dichloride;
Bis (cyclopentadienyl) zirconium dichloride;
Bis (cyclopentadienyl) zirkoniummonomethylmonochlorid;
Bis (cyclopentadienyl) titanium dichloride;
Bis (cyclopentadienyl) titanium difluoride;
Cyclopentadienylzirkoniumtri (2-ethylhexanoate);
Bis (cyclopentadienyl) zirkoniumhydrogenchlorid;
hafnium dichloride, bis (cyclopentadienyl);
racemic and meso-dimethylsilanylene-bis (methylcyclopentadienyl) hafnium dichloride;
racemic dimethylsilanylene-bis (indenyl) hafnium dichloride;
racemic ethylene-bis (indenyl) zirconium dichloride;
(η ⁵ -indenyl) hafnium trichloride;
(η ⁵ -C ₅ Me ₅ ) hafnium trichloride;
racemic dimethylsilanylene-bis (indenyl) thorium dichloride;
racemic dimethylsilanylene bis (4,7-dimethyl-1-indenyl) zirconium dichloride;
racemic dimethylsilanylene-bis (indenyl) uranium dichloride;
racemic dimethylsilanylene-bis (2,3,5-trimethyl-1-cyclopentadienyl) zirconium dichloride;
racemic dimethylsilanylene (3-methylcyclopentadienyl) hafnium dichloride;
racemic dimethylsilanylene-bis (1- (2-methyl-4-ethyl) indenyl) zirconium dichloride;
racemic dimethylsilanylene bis (2-methyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride;
Bis (pentamethylcyclopentadienyl) thorium;
Bis (pentamethylcyclopentadienyl) uranium dichloride;
(tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride;
(tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyanopenta-dienyl) silane chromium dichloride;
(tert-butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane titanium dichloride;
(tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane-methyltitan bromide;
(tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylurandichloride;
(tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride;
(Methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethane diylcer dichloride;
(Methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethane diyl titanium dichloride;
(Ethylamido) (tetramethyl-η ⁵ -cyclopentadienyl) methylene titanium dichloride;
(tert-butylamido) dibenzyl (tetramethyl-η ⁵ -cyclopenta-dienyl) -silane-benzyl-vanadium chloride;
(Benzylamido) dimethyl (indenyl) silanetitanium dichloride;
(Phenylphosphido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanebenzyltitanium chloride;
rac-dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride;
rac-ethylenebis (1-indenyl) zirconium dichloride;
Bis (methylcyclopentadienyl) titanium dimethyl;
Bis (methylcyclopentadienyl) zirconium dimethyl;
Bis (n-butylcyclopentadienyl) zirconium dichloride;
Bis (dimethylcyclopentadienyl) zirconium dichloride;
Bis (diethylcyclopentadienyl) zirconium dimethyl;
Bis (methyl-n-butylcyclopentadienyl) zirconium dichloride;
Bis (n-propylcyclopentadienyl) zirconium dimethyl;
Bis (2-propylcyclopentadienyl) zirconium dimethyl;
Bis (methylethylcyclopentadienyl) zirconium dimethyl;
Bis (indenyl) zirconium dichloride;
Bis (methylindenyl) zirconium dimethyl;
Dimethylsilylenebis (indenyl) zirconium dichloride;
Dimethylsilylenebis (2-methylindenyl) zirconium dimethyl;
Dimethylsilylenebis (2-ethylindenyl) zirconium dimethyl;
Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl;
1,2-ethylenebis (indenyl) zirconium dichloride;
1,2-ethylenebis (methylindenyl) zirconium dimethyl;
2,2-propylidenebis (cyclopentadienyl) (fluorenyl) zirconium dichloride;
Dimethylsilylenebis (6-phenylindenyl) zirconium dichloride;
Bis (methylindenyl) zirkoniumbenzylmethyl;
Ethylenebis [2- (tert-butyldimethylsiloxy) -1-indenyl] zirconium dichloride;
Dimethylsilylenebis (indenyl) chlorzirkoniummethyl;
5- (cyclopentadienyl) -5- (9-fluorenyl) 1-hexene zirconium dimethyl;
Dimethylsilylenebis (2-methylindenyl) hafnium dimethyl;
Dimethylsilylenebis (2-ethylindenyl) hafnium dimethyl;
Dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dimethyl;
2,2-propylidenebis (cyclopentadienyl) (fluorenyl) hafnium dimethyl;
Bis (9-fluorenyl) (methyl) (vinyl) silanzirkoniumdimethyl;
Bis (9-fluorenyl) (methyl) (prop-2-enyl) silanzirkoniumdimethyl;
Bis (9-fluorenyl) (methyl) (but-3-enyl) silanzirkoniumdimethyl;
Bis (9-fluorenyl) (methyl) (hex-5-enyl) silanzirkoniumdimethyl;
Bis (9-fluorenyl) (methyl) (oct-7-enyl) silanzirkoniumdimethyl;
(Cyclopentadienyl) (1-allylindenyl) zirconium dimethyl;
Bis (1-allylindenyl) zirconium dimethyl;
(9- (prop-2-enyl) fluorenyl) (cyclopentadienyl) zirconium dichloride;
(9- (prop-2-enyl) fluorenyl) (pentamethylcyclopentadienyl) zirconium dichloride;
Bis (9- (prop-2-enyl) fluorenyl) zirconium dichloride;
(9- (cyclopent-2-enyl) fluorenyl) (cyclopentadienyl) zirconium dichloride;
Bis (9- (cyclopent-2-enyl) (fluorenyl) zirconium dichloride;
5- (2-methylcyclopentadienyl) -5 (9-fluorenyl) -1-hexenzirkoniumdimethyl;
1- (9-fluorenyl) -1- (cyclopentadienyl) -1- (but-3-enyl) -1- (methyl) methanzirkoniumdimethyl;
5- (Fluorenyl) -5- (cyclopentadienyl) -1-hexenhafniumdimethyl;
(9-fluorenyl) (1-allylindenyl) dimethylsilanzirkoniumdimethyl;
1- (2,7-di (α-methylvinyl) (9-fluorenyl) -1- (cyclopentadienyl) -1,1-dimethylmethanezirkoniumdimethyl;
1- (2,7-di (cyclohex-1-enyl) (9-fluorenyl)) - 1- (cyclopentadienyl) -1,1-methanzirkoniumdimethyl;
5- (cyclopentadienyl) -5- (9-fluorenyl) -1-hexentitandimethyl;
5- (cyclopentadienyl) -5- (9-fluorenyl) 1-hexentitandimethyl;
Bis (9-fluorenyl) (methyl) (vinyl) silane titanium dimethyl;
Bis (9-fluorenyl) (methyl) (prop-2-enyl) silane titanium dimethyl;
Bis (9-fluorenyl) (methyl) (but-3-enyl) silane titanium dimethyl;
Bis (9-fluorenyl) (methyl) (hex-5-enyl) silane titanium dimethyl;
Bis (9-fluorenyl) (methyl) (oct-7-enyl) silane titanium dimethyl;
(Cyclopentadienyl) (1-allylindenyl) titanium dimethyl;
Bis (1-allylindenyl) titanium dimethyl;
(9- (prop-2-enyl) fluorenyl) (cyclopentadienyl) hafnium dimethyl;
(9- (prop-2-enyl) fluorenyl) (pentamethylcyclopentadienyl) hafnium dimethyl;
Bis (9- (prop-2-enyl) fluorenyl) hafnium dimethyl;
(9- (cyclopent-2-enyl) fluorenyl) (cyclopentadienyl) hafnium dimethyl;
Bis (9- (cyclopent-2-enyl) (fluorenyl) hafnium dimethyl;
5- (2-methylcyclopentadienyl) -5 (9-fluorenyl) -1-hexenhafniumdimethyl;
5- (fluorenyl) -5- (cyclopentadienyl) -1-octenhafniumdimethyl;
(9-fluorenyl) (1-allylindenyl) dimethylsilanhafniumdimethyl;
(Tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium (1,3-pentadiene);
(Cyclopentadienyl) (9-fluorenyl) diphenylmethanzirkoniumdimethyl;
(Cyclopentadienyl) (9-fluorenyl) diphenylmethanhafniumdimethyl;
Dimethylsilanylene-bis (indenyl) thoriumdimethyl;
Dimethylsilanylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride;
Dimethylsilanylene-bis (indenyl) urandimethyl;
Dimethylsilanylene-bis (2-methyl-4-ethyl-1-indenyl) zirconium dichloride;
Dimethylsilanylene-bis (2-methyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride;
(tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dimethyl;
(tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane hexane;
(tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dimethyl;
(Phenyiphosphido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dimethyl;
[Dimethylsilanediylbis (indenyl)] scandiummethyl or any combination thereof. In many cases, metallocenes such as the above are present as racemic mixtures, but according to the invention pure enantiomeric forms or mixtures in which a given enantiomeric form is enriched can be used.

Other organometallic catalytic compounds with which the soluble aluminoxanate salt compositions are used to form the catalyst compositions of this invention are the late transition metal catalysts described, for example, in U.S. Pat US-A-5 516 739 Barborak et al .; US-A-5 561 216 Barborak et al .; US-A-5 866 663 Brookhart et al .; US-A-5,880,241 by Brookhart et al. and US-A-6 114 483 by Coughlin et al. are described. Such catalysts are sometimes collectively referred to herein as "Brookhart-type late transition metal catalyst compound or complex".

Other transition metal catalyst compounds and catalyst complexes which can be used in the practice of the invention include catfluorophenyl, palladium, iron and cobalt complexes containing diimine and bisoxazoline ligands as described in Johnson et al. WO 96/23010 described; Palladium and nickel catalysts containing selected bidentate phosphorus-containing ligands, as in US Pat EP-A-381 495 described; Catfluoro-adiimine-based nickel and palladium complexes, such as Johnson et al. in J. Am. Chem. Soc., 1995, 117, 6414 , see also Brown et al. WO 97/17380 ; Nickel complexes as described by Johnson et al. in the US-A-5714556 described; catalytic cobalt (III) cyclopentadienyl systems, such as Schmidt et al. in J. Am. Chem. Soc., 1985, 107, 1443 , and from Brookhart et al. in Macromolecules, 1995, 28, 5378 described; Anfluor-, phosphorus, oxygen donor ligands to nickel (II), as von Klabunde in the US-A-4,716,205 . US-A-4,906,754 . US-A-5 030 606 and U.S.-A-5,175,326 described; Group 8-10 Transition metal complexes coordinated with a bidentate ligand as described in U.S. Pat WO 98/40374 described; Transition metal complexes containing bidentate ligands containing pyridine or quinoline moieties, as in US Pat US-A-5 637 660 described; Quinolinoxy or pyridinoxy-substituted Group 4 transition metal trihalides, as described in U.S. Pat US-A-6 020 493 described; Nickel complexes, such as bis (ylide) nickel complexes, such as Starzewski et al. in Angew. Chem. Int. Ed. Eng1., 1987, 26, 63 , and the US-A-4,691,036 described; neutral N, O, P or S donor ligands in combination with a nickel (0) compound and an acid, as in U.S. Pat WO 97/02298 described; Aminobis (imino) phosphorane nickel catalysts as described by Fink et al. in the US-A-4,724,273 described.

Illustrative, non-limiting, further examples of various types of transition metal compounds which may be used include the following:
2,6-bis [1- (1-methylphenylimino) ethyl] pyridineisen [II] chloride;
2,6-bis [1- (1-ethylphenylimino) ethyl] pyridineisen [II] chloride;
2,6-bis [1- (1-isopropylphenylimino) ethyl] pyridineisen [II] chloride;
2,6-bis (1- (2-methylphenylimino) ethyl) pyridineisen (II) chloride;
N, N'-di (trimethylsilyl) benzamidinatokupfer (II);
Tridentate Schiff base complexes of cobalt and iron derived from Mashima in Shokubai 1999, Volume 41, page 58 , have been described,
Nickel compounds of the in U.S. Patent 5,880,323 type described;
Nickel (II) acetylacetonate;
Bis (acetonitrile) dichloropalladium (II);
Bis (acetonitrile) bis (tetrafluoroborate) palladium (II);
(2,2'-bipyridine) dichloropalladium (II);
Bis (cyclooctadienyl) nickel (0);
Palladium (II) acetylacetonate;
Bis (salicylaldiminato) complexes of the Matsui et al. in Chemistry Letters 2000, pages 554-555 , type described;
Kobaltdioctoat;
cobaltocene;
(Cyclopentadienyl) (triphenylphosphino) cobalt (II) diiodide;
Nickel compounds of the in JP-A-09-272709 type described, or any combination thereof.

In one aspect of the present invention, transition metal compounds that can be used to form the catalysts of the present invention are transition metal compounds that can be represented by the following formula: MX _n Y _m wherein M is a transition metal of Group 4 to 8 of the Periodic Table of the Elements including the lanthanide series and actinide series, and each Y is independently a halide or pseudohalide, n is the valency of M, and m is an integer of 0 to n-1. Pseudohalide, a term in the art, refers to anionic non-halides with salt-like characteristics. Non-limiting examples of pseudohalide groups useful in the present invention include oxyhalide groups, hydrocarbonoxy 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, according to one aspect of the present invention, a transition metal of Group 4 to 8 of the Periodic Table of the Elements. M is a group 4 metal according to another aspect. Examples of suitable 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 tri-fluoride, titanium tetrafluoride, titanium diiodide, titanium tetraiodide, zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium dichloride, zirconium trichloride , zirconium tetrachloride, zirconium tetrafluoride, Zirkoniumtetraiodid, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, Hafniumtetraiodid, Hafniumtrichlorid, Hafniumtribromid, Hafniumtriiodid, hafnium, vanadium dichloride, vanadium trichloride, vanadium tetrachloride, Vanadiumtrifluorid, vanadium tetrafluoride, vanadium pentafluoride, Vanadiumtriiodid, vanadium oxytrichloride, Vanadiumoxytribromid, niobium pentabromide, niobium pentachloride, niobium pentafluoride, Tantalpentabromid , Tantalum pentachloride, tantalum pentafluoride, chromium (II) bromide, chromium (III) bromide, chromium (II) chloro id, chromium (III) chloride, chromium (II) fluoride, chromium (III) fluoride, molybdenum dibromide, molybdenum tribromide, molybdenum tetrabromide, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexafluoride, lanthanum trichloride, cerium (III) fluoride, cerium (III) chloride, Cerium (III) bromide, cerium (III) iodide, cerium (IV) fluoride, uranium trichloride, uranium tetrachloride, uranium tribromide, uranium tetrabromide, thorium tetrachloride, thorium tetrabromide, or any combination thereof. Suitable alkoxides and mixed halide / alkoxides of the transition metals that can be used in the present invention include, but are not limited to, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O-iso-C ₃ H ₇ ) Cl _3, Ti (OC ₄ H ₉ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti ( O-iso-C ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₁₇ H ₁₈ ) ₂ Br ₂ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , Zr (OC ₅ H ₁₁ ) ₄ , ZrCl ₃ (OC ₂ H ₅ ), ZrCl (OC ₄ H ₉ ) ₃ , Hf (OC ₄ H ₉ ) ₄ , Hf (OC ₄ H ₉ ) ₃ Cl, VO (OC ₂ H ₅ ) ₃ , Cr (O -iso-C ₄ H ₉ ) ₃ , Mo (OC ₂ H ₅ ) ₃ or any combination thereof. Other transition metal compounds which may be used include amides such as Ti (NMe ₂ ) ₄ , Zr (NMe ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Zr (NEt ₂ ) _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, without being limited thereto. According to one aspect of the present invention, the transition metal ver the halides, oxyhalides, alkoxides or mixed halide alkoxides of Group 4 to 6 metals.

According to another aspect of the present invention, the transition metal compounds are the halides of trivalent or tetravalent metals of Group 4 and the vanadium oxyhalides. The said periodic table of elements is that on Page 27 of the Chemical & Engineering Neves issue of 4 February 1985 ,

Optional carrier materials

The Catalyst composition may optionally be on any suitable supported organic or inorganic carrier be. Support materials used according to the invention may be any finely divided, inorganic, solid carrier, such as talc, clay, silica, alumina, silica-alumina or any combination thereof. support materials may also be particulate, organic, resinous Include support materials including, but not limited to spherical, particulate or finely divided polyethylene, polyvinyl chloride, polystyrene or any combination or modification thereof.

The specific particle size, surface area and the pore volume of the carrier material determine the amount on carrier material which is desirably for Preparation of the catalyst compositions should be used and influence the properties of polymers using the Catalyst compositions are formed. These properties are used in the choice of a carrier material considered in a particular aspect of the invention frequently.

Preparation of the catalyst composition

These Invention includes methods for the preparation of supported and unsupported catalyst compositions in which at least one soluble aluminoxanate salt composition and at least one complex of a transition metal of the groups 3 to 11 of the Periodic Table of the Elements are brought into contact. The catalyst composition may according to a other aspect are prepared by at least one ionic Aluminoxane compound, at least one organometallic compound with at least one long-chain alkyl substituent, for example an alkylaluminum compound, at least one organic solvent and at least one complex of a transition metal of the groups 3 to 11 of the Periodic Table of the Elements are brought into contact, according to another aspect of the present invention For example, the catalyst composition can be prepared by at least an ionic aluminoxanate compound, at least one organometallic Compound with a long-chain alkyl substituent, for example an alkylaluminum compound, at least one organic solvent, at least one complex of a transition metal of the groups 3 to 11 of the Periodic Table of the Elements and at least one organic or inorganic carrier material are brought into contact. The supported or unsupported catalyst composition is obtained according to this aspect when the components be contacted in any order or order. For example, the components may be in any order separately fed to a reactor or a separate vessel or any two or more can be premixed and are fed as a mixture, with the remaining Components before, during or after feeding the Mixture be fed into the reactor.

invention carrierless catalyst compositions can prepared by the transition metal complex, during or after its formation with the soluble Aluminoxanatsalzzusammensetzung is brought into contact. The transition metal complex For example, before the soluble aluminoxane salt composition is formed with any or any combination of (a) the ionic aluminoxane composition; (b) the alkylaluminum compound or (c) contacted with the organic solvent become. The transition metal complex may alternatively be any Time during the formation of the soluble aluminoxanate salt composition be added. The transition metal complex can also in contact with the soluble aluminoxanate salt composition after being made.

The temperatures for preparing carrierless catalyst compositions are in the range of about -100 ° C to about 300 ° C. The production temperatures in another aspect range from about 0 ° C to about 80 ° C. The preparation is typically conducted at temperatures ranging from 20 ° C to about 50 ° C or at ambient room temperature. The residence times to allow the completion of the catalyst formation can vary depending on the reaction variables in the range of about 10 seconds to about 60 minutes.

carrier-supported Catalyst compositions are similarly formed by the carrier material with the catalyst composition before, during or after their formation is brought into contact. In the preparation, in any order, the transition metal compound, a soluble aluminoxanate salt composition and a carrier material in one or more suitable solvents or diluents be brought into contact. To suitable solvents and / or diluents belong without it be restricted, straight-chain and branched hydrocarbons, such as isobutane, butane, pentane, hexane, heptane or octane; cyclic and acyclic hydrocarbons, such as cyclohexane, cycloheptane, Methylcyclohexane or methylcyclopentane; o the aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene or xylene. It can also mixtures of different types of solvents and / or diluents, such as Mixture of one of the several 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 one Mixture of one or more acyclic aliphatic hydrocarbons, one or more cycloaliphatic hydrocarbons and a or more aromatic hydrocarbons.

The Backing material may first be coated with the soluble aluminoxanate salt composition be contacted to a carrier-based Aluminoxanat, which subsequently with the transition metal complex is brought into contact. The carrier material may alternatively first contacted with the transition metal complex be used to form a carrier-supported complex, followed by the soluble aluminoxanate salt composition is brought into contact. According to another Aspect of this invention may be the soluble aluminoxanate salt and the transition metal complex brought into contact with each other and the resulting composition can subsequently be brought into contact with a carrier material. The Carrier material may according to another Aspect of the present invention with either the soluble Aluminoxanate salt composition or the transition metal complex be contacted during his education. The Support material can, for example, with one or more of the Components are brought into contact, which contribute to the formation of the soluble Aluminoxanats be used, or with one or more of Components that contribute to the formation of the transition metal complex be used.

Because the catalyst components and catalyst compositions sensitive are against moisture and oxygen, these are Components and compositions generally under a conventional inert atmosphere, essentially inert, anhydrous materials, for example in a moisture-free, oxygen-free environment, such as argon, nitrogen or helium become. The temperatures are in production for each stage of unsupported catalyst compositions in the range from about -100 ° C to about 300 ° C. The production temperatures According to another aspect, they are in the range of about 0 ° C to about 80 ° C. The production becomes typical at temperatures in the range of 20 ° C to about 50 ° C or at ambient room temperature. The residence times, to allow the completion of the catalyst formation, can depend on the reaction variables ranging from about 10 seconds to about 60 minutes.

The Concentration of the transition metal compound on the support typically ranges from about 0.01% to about 50% Wt .-%. According to another aspect of the present Invention is the concentration of the transition metal compound on the support in the range of about 0.1% by weight to about 20 wt .-%, based on the weight of the carrier.

modified Supported catalysts can be prepared according to the invention be prepared by adding at least one transition metal compound in any order, at least one soluble aluminoxanate salt composition, at least one modifier and a carrier material in a suitable solvent and / or diluent be brought into contact. A modifier can be used as any Connection can be defined, which is a Lewissaure or basic Contains functionality. examples for Compounds that have a Lewis acid or basic functionality include tetraethoxysilane, phenyltri (ethoxy) silane, bis-tert-butylhydroxytoluene (BHT) or N, N-dimethylaniline, without being limited thereto to be.

The modified supported catalyst is formed in accordance with one aspect of the present invention by contacting a soluble aluminoxanate salt composition and the modifier in a suitable solvent to produce a slurry. After that, a Transition metal compound added to the slurry. Suitable temperatures for these contacting steps are in the range of about -100 ° C to about 300 ° C or, in another aspect of the present invention, in the range of about 0 ° C to about 100 ° C. The residence times to complete the reaction may range from about 10 seconds to about 60 minutes, depending on the reaction variables. The mixture comprising the transition metal, the modifier and the soluble aluminoxanate salt may then be brought into contact with the support material.

in the Case of Modified Supported Catalysts is the molar ratio of soluble aluminoxanate salt composition to transition metal compound generally in the range from about 1: 1 to about 20,000: 1 or according to one 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 the range of about 1: 1 to about 20,000: 1 or according to another Aspect of the present invention in a range of about 10: 1 to about 1000: 1. The concentration of the transition metal compound on the support is typically in the range of 0.01 Wt .-% to about 50 wt .-%, or according to another Aspect of the present invention in a range of about 0.1 Wt .-% to about 20 wt .-%, based on the weight of the carrier.

The used amount of soluble aluminoxanate salt composition varies depending on the application and the reaction conditions. Soluble aluminoxane salt is typically in one sufficient amount used to a molar ratio of Aluminum atoms derived from the soluble aluminoxanate salt derive to transition metal in the range of about 20: 1 to to produce about 2000: 1. The molar ratio is according to one another aspect ranging from about 20: 1 to about 500: 1.

polymerization

These Invention comprises a process for polymerizing olefinic Monomers in which at least one olefinic monomer and a catalyst system, a soluble aluminoxanate salt composition and at least a transition metal complex, brought into contact become. Inventive catalyst compositions are for homopolymerization or copolymerization of olefinic monomers useful, for example, α-olefin monomers, cyclic Olefin monomers or vinylaromatic monomers.

polymerizations using catalysts of the invention may be performed in any manner known in the art become. Such polymerization processes include, without be limited to slurry polymerizations, Gas phase polymerizations, solution polymerizations and the like, including multi-reactor combinations thereof. Thus, it may be any in the art for producing ethylene-containing Polymer known polymerization zone can be used. It can for example, a stirred reactor for a batch process be used, or the reaction can be continuous in one Loop reactor or in a continuous, stirred Reactor be performed. The polymerization reactor may 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 that is substantially free of oxygen and under substantially anhydrous conditions when the reaction begins. Therefore, a dry, inert atmosphere is typically used in the polymerization reactor, for example, dry nitrogen or dry argon. Conventional polymerization temperatures range from about 0 ° C to about 160 ° C, and conventional polymerization pressures range from about 1 kg / cm ² to about 50 kg / cm ² . The polymerization can generally be carried out at ambient temperature and pressure. In some cases, to control the properties of the resulting polymer, the controlled addition of hydrogen gas is also suitable.

In slurry polymerizations, typically a particulate catalyst is dispersed in a suitable liquid reaction medium, which may be composed of one or more co-solvents or an excess amount of liquid monomer. Suitable co-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. The slurry polymerization temperatures in this invention are typically in the range of about 0 ° C to about 160 ° C, with a polymerization reaction temperature typically in the range of about 40 ° C to about 110 ° C. The polymerization may be under atmospheric, subatmospheric or superatmospheric conditions, or any other polymerization reaction condition may be any Be 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 ranging from about 50 ° C to about 160 ° C under superatmospheric pressures. However, the polymerization may be at any temperature or pressure that does not interfere with the polymerization reaction. These gas phase polymerizations can be carried out in a stirred or fluidized catalyst bed in a beaker adapted to allow separation of the product particles from unreacted gases. Thermostatized ethylene, comonomer, hydrogen and an inert diluent gas such as nitrogen may be introduced or recirculated to maintain the particles at the desired polymerization reaction temperature. An aluminum alkyl such as triethylaluminum may be added as a scavenger for water, oxygen and other impurities. The alkylaluminum in these cases is typically used as a solution in a suitable dry hydrocarbon liquid solvent such as toluene or xylene. The concentrations of these solutions are typically in the range of about 5x10 ^-5 molar (M), but solutions of higher or lower concentration can be used. The polymer product may be withdrawn continuously or semi-continuously at a rate which maintains a constant product inventory in the reactor.

invention Polymerization reactions are carried out using a catalytic effective amount of a new invention Catalyst composition performed. The used The amount of catalyst depends on several factors, such as carried out polymerization, the polymerization conditions used and the type of reaction apparatus in which the polymerization is carried out. The catalyst composition becomes in one aspect according to one aspect of this invention from about 0.000001 to about 0.01 weight percent transition metal, Lanthanide or Actinidmetall used, based on the total weight of the polymerized monomer (s).

If carried out according to the invention polymerization may be conditions for producing unimodal or multimodal polymers are used. Multimodal polymers can For example, be prepared by mixing a mixture of different Catalysts with different growth and termination rate constants be used.

To the polymerization and deactivation of the catalyst may be the product polymer with the aid of any suitable means from the polymerization reactor be won. If the process with a slurry or dispersion of the catalyst in a liquid medium is performed, the product is typically through obtained a physical separation technique, such as decantation. The recovered polymer will generally be one or more washed with suitable volatile solvents, residual polymerization solvent or others Remove impurities, and then dried, typically under reduced pressure with or without heat. If the process is carried out as gas-phase polymerization is, the product is after removal from the gas phase reactor typically freed from residual monomer with a nitrogen shower and may possibly be without further catalyst deactivation or catalyst removal can be used.

Produced according to the invention Polymers may be homopolymers, usually of α-olefins such as ethylene, propylene, 1-butene, styrene or any combination from that. Polymers can also be copolymers of two or more Monomers, one of which is typically an α-olefin is. Monomers useful for the preparation of comonomers, include one or more different α-olefin, Diolefin, cyclic olefin, acetylenic or functional olefin monomers one. Non-limiting examples of olefins, in the presence of a catalyst composition according to the invention can be polymerized include α-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 Diolefinonomere to the Preparation of terpolymers used with ethylene and propylene butadiene, hexadiene, norbornadiene or any combination thereof, without limitation to be. Suitable acetylenic monomers include 1-heptine or 1-octyne. Ethylene may according to one aspect of the present invention with at least one α-olefin with 3 to 8 carbon atoms are copolymerized, for example Propylene.

Examples

The following examples are given for purposes of illustration and are not meant to be limiting meanings for the scope of this invention. Room temperature, as discussed earlier and hereinafter, means a temperature in the range of about 25 ° C to about 30 ° C. The conductivity of the activator is given in Tables III and IV in Mohms / cm (μS / cm).

GENERAL PROCEDURE

NMR characterization

instruments

All spectra were obtained on Bruker DPX400 instruments operating at 400 MHz for ¹ H NMR, 79.5 MHz for ²⁹ Si NMR, and 104.3 MHz for ²⁷ Al NMR. The proton spectra were obtained using a 5 mm QNP probe. The ²⁹ Si spectra were obtained with a 10 mm broadband observation probe and the ²⁷ Al spectra were obtained with a 10 mm ²⁷ Al probe without ²⁷ Al NMR background artifacts.

All spectra were obtained with conventional pulse sequences. The proton and ²⁷ Al spectra were obtained with 1 pulse experiments, while the ²⁹ Si spectra were obtained with a DEPT45 sequence. In all cases, the probe fine tuning and matching were suitably recorded.

sample preparation

All Samples were rinsed in dry nitrogen Box made. All solvents were over dried 4 Å molecular sieves and dried in the rinsed Box stored. For the solid MAO and DMAM OMTS samples was 1,3-dichlorobenzene with deuteromethylene chloride for NMR lock used. In all cases, the fixed ones dissolved Completely on samples. For modified MAO and modified DMAM • OMTS samples 1,2-dichlorobenzene with perdeuterobenzene was used as NMR lock.

example 1

Preparation of an octamethyltrisiloxane-complexed Dimethylaluminum methylaluminoxane (DMAM · OMTS)

A Solution of about 30% by weight of methylaluminoxane (MAO) in toluene (60 g, 308 mmol AL) was treated with octamethyltrisiloxane at room temperature (OMTS, 3.65 g, 15.4 mmol). There was clathration, and Two immiscible liquid phases were observed. The liquid system was left overnight at room temperature touched. The upper layer was removed by decantation. The bottom layer was filled with three samples of about 100 ml of toluene washed. After each wash, the lower layer became denser. To the third wash was two samples of about 100 ml of cyclohexane added to the solid ionic Aluminoxanatzusammensetzung (DMAN · OMTS) precipitate. This solid product was filtered off and washed with Washed cyclohexane.

The product was subjected to spectroscopic characterization after thorough washing and precipitation as described above. This product was found to be an octamethyltrisiloxane-complexed dimethylaluminum methylaluminoxane [Me ₂ Al • OMTS) ⁺ (MAO • Me) ^- ], which may also be referred to as an OMTS-complexed dimethylaluminum salt of a methylaluminoxane (DMAM • OMTS). A visual representation of this product is in 1 shown.

Example 2

Characterization of an octamethyltrisiloxane-complexed Dimethylaluminum methylaluminoxane (DMAM · OMTS)

The proton NMR spectra of DMAM.OMTS, as prepared in Example 1, and its MAO and OTMS precursors in 1,3-dichlorobenzene with deuteromethylene chloride as the NMR lock are in 2 where spectrum A shows conventional MAO, spectrum B shows OMTS and spectrum C shows DMAM · OMTS. Spectrum C clearly demonstrates the presence of OMTS complexed with a dimethylaluminum species by comparative integration of the OMTS and (Me ₂ Al) ⁺ peaks [(6: 2): 2]. The OMTS peaks in spectrum C are also significantly shifted (at least about 0.2 ppm) compared to spectrum B for OMTS alone. Spectrum A for conventional MAO shows no indication of the features visible in Spectrum C.

3 compares the ²⁹ Si NMR spectra of OMTS (Spectrum A) and DMAM-OMTS (Spectrum B) in 1,3-dichlorobenzene with deuteromethylene chloride as the NMR lock. Conventional MAO does not contain any silicon species and thus does not produce ²⁹ Si NMR signals. Spectrum B shows two unusual chemical downfield shifts in ²⁹ Si NMR at about 29 and 39 ppm relative to the reference tetramethylsilane (TMS) and a significantly (> about 5 ppm) shifted signal from OMTS alone. Theoretical calculations by Professor Jack Tossell of the University of Maryland have shown that the experimental chemical shifts in the ²⁹ Si NMR spectrum fit perfectly with the cationic species [Me ₂ Al • OMTS] ⁺ of DNAM-OMTS.

4 compares the ²⁷ Al-MR spectra of MAO (spectrum A) and DMAM-OMTS (spectrum B) in 1,3-dichlorobenzene with deuteromethylene chloride as the NMR lock. Although DMAM · OMTS is ultimately derived from a conventional MAO, in 4 clearly shown a significant difference in their chemical composition. For example, the broad signal seen at about 0 ppm in spectrum A is narrower in spectrum B and shifted to about -20 ppm. The narrow signal at about 150 ppm in spectrum A is also significantly reduced in spectrum B and shifted slightly downfield. The high-field peak in spectrum B corresponds to the anionic aluminoxane species, and the low-peak peak corresponds to the cationic, four-coordinate aluminum species.

Example 3

Characterization of an 18-crown-6-ether complexed Dimethylaluminum methylaluminoxane (DMAM · 18-CE-6)

A Solution of MAO in toluene (20.5 g, 105.4 mmol Al) at room temperature with 18-crown-6-ether (18-CE-6, 1.4 g, 5.26 mmol) treated. There was clathration, and there were two immiscible observed liquid phases. There was further toluene (about 60 g), because the lower clathrate layer is very thick was. The liquid system was added overnight Room temperature stirred. The upper phase was decanted away. The lower phase was filled with three samples of about 100 ml Washed toluene. The upper toluene phase was decanted removed, and the viscous lower phase was filled with 2 samples of approximately Treated 100 m of cyclohexane to give the solid ionic aluminoxanate composition (DMAM-18-CE-6) precipitate. This solid product was filtered off and washed with cyclohexane.

5 compares the ¹ H NMR spectra of MAO (spectrum A) and DMAM-18-CE-6 (spectrum B) in 1,3-dichlorobenzene with deuteromethylene chloride as NMR lock. A significant difference in the chemical composition of MAO and DMAM-18-CE-6 is in 5 again clearly visible.

Example 4

Toluene-soluble aluminoxanate salt compositions

DMAM- · OMTS was prepared as described in Example 1 from a mixture of about 30% MAO in toluene (725 g, 3729 mmol Al) and OMTS (44.1 g, 188.5 mmol). The resulting clathrate composition became without phase separation or washing with tri-n-octylaluminum (TNOA, 47.6 g, 130.5 mmol). The two layers became one Phase. The mixture was heated to about 80 ° C for about two hours and filtered to give a clear, colorless solution with a Aluminum concentration of about 14.3 wt .-% to obtain. This composition showed at room temperature or about -20 ° C 52 weeks no signs of solid or gel formation. Although no gel formation was observed after 52 weeks, it is believed that this composition over at these temperatures longer periods no signs of solid matter or gelation will show.

Example 5

Toluene-soluble aluminoxanate salt compositions

A Solution of about 30% by weight MAO in toluene (725 g, 3729 mmol Al) was described with OMTS (44.1 g, 186.5 mmol) as in Example 1 react. After phase separation and washing was the (lower) clathrate layer with about 800 ml of toluene and TNOA (47.8 g, 139.5 mmol). The resulting solution was heated to about 80 ° C for two hours, a clear, colorless solution of soluble methylaluminoxanate salt in toluene, which after 52 weeks at room temperature no Showed signs of solid or gel formation.

Example 6

Stability of the solution TNOA-modified DMAM · OMTS

DMAM- · OMTS was prepared 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 clathrate layer became after phase separation and wash with cyclohexane in excess, to obtain ionic methylaluminoxanate solids. Then were the solids are treated with about 800 ml of toluene. The new, washed Clathrate was treated with TNOA (47.6 g, 139.5 mmol), and the Mixture was heated to about 80 ° C for about two hours. It became a clear, colorless solution of soluble Methylaluminoxanatsalz formed in toluene, which after 52 weeks at Room temperature no signs of solid or gel formation showed.

Comparative Example 7

Stability of the solution of TNOA-modified MAO compositions

A Solution of about 30% MAO in toluene (129 g, 663 mmol Al) was treated with TNOA (8.47 g, 23.2 mmol Al). The used TNOA amount is equivalent to the amount needed to form an analogous soluble aluminoxanate salt composition at about -20 ° C to render solution stable. The mixture was at about 80 ° C for about two hours heated. The clear, colorless solution was filtered, TNOA-modified MAO solution in toluene with an Al concentration of about 14.0% by weight. In marked contrast to the The analog TNOA-modified DMAM OMTS composition described in Example 6 began this composition after ten weeks at room temperature signs to show for gelation.

Example 8

Stability of the solution TIBA-modified DMAM · OMTS

A Dissolve about 30% by weight MAO in toluene (252.2 g, 1296.3 mmol Al) was treated with OMTS (64.82 g, 15.33 mmol) as in Example 1 described reacted react. The resulting biphasic clathrate composition was treated with triisobutylaluminum (TIBA, 25.72 g, 129.63 mmol). The two-layered solution became a single phase. The mixture was at about 80 ° C for about two hours heated. It became a clear colorless after filtration Solution of soluble methylaluminoxane salt in Toluene, which showed no signs after 52 weeks at room temperature for solid or gel formation showed.

Comparative Example 9

Stability of the solution TIBA-modified MAO compositions

A Solution of about 30% MAO in toluene (162 g, 833 mmol Al) was treated with TIBA (16.52 g, 83.27 mmol Al). The used TIBA amount was equivalent to the amount needed was an analogous soluble aluminoxanate salt composition at about -20 ° C to render solution stable. The mixture was then filtered to give a TIBA-modified MAO solution to obtain in toluene with an Al concentration of about 14.2 wt .-%. In marked contrast to the analog, described in Example 8, TIBA-modified DMAM · OMTS composition started this Composition after six weeks at room temperature signs for Show gelation.

Example 10

In aliphatic hydrocarbons soluble Aluminoxanatsalzzusammensetzungen

DMAM · OMTS was prepared as described in Example 1 from a mixture of about 30% MAO in toluene (719.2 g, 3696.6 mmol Al) and OMTS (43.72 g, 184.83 mmol). The resulting biphasic clathrate composition was treated without washing or phase separation with TNOA (94.44 g, 258.76 mmol). The mixture was heated to about 80 ° C for about two hours. The mixture was then solvent exchanged 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. It resulted in turn a thick oil. The oil was treated with about 707 g of isohexane to give a clear, colorless solution of soluble methylaluminoxanate salt in isohexane which showed no signs of solid or solid after 52 weeks at room temperature or at about -20 ° C Gel formation showed.

Example 11

In aliphatic hydrocarbons soluble aluminoxanate salt compositions

A Solution of about 30% MAO in toluene (719 g, 3696 mmol Al) was treated with OMTS (43.7 g, 184.8 mmol Al). The clathrate layer was treated with excess isohexane after phase separation and washing, to obtain ionic methylaluminoxanate solids. The resulting Solids were suspended in about 800 g of isohexane to make a slurry to produce. To the slurry was added TNOA (94.4 g, 258.76 mmol) was added, and it was heated to about 2 hours Heated to 80 ° C. The solution was filtered, a clear, colorless solution of soluble methylaluminoxanate salt in isohexane, which after about 52 weeks at room temperature or at -20 ° C no signs of Solid or gel formation showed.

Example 12

NMR characterization of modified DMAM · OMTS and modified MAO

TNOA-modified DMAM · OMTS 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 NMR spectroscopy are in 6 shown. The TNOA-modified MAO spectrum shows no silicon species or ²⁹ Si NMR signals. The TNOA-modified DMAM OMTS spectrum shows the characteristic 29 and 39 ppm shifts observed in ²⁹ Si NMR by DMAM.OMTS (FIG. 3 ) demonstrate. However, compared to the spectrum of unmodified DMAM · OMTS, the TNOA-modified DMAM OMTS spectrum showed a splitting of the 29 and 29 ppm peaks, showing mixed alkyl groups on some of the cationic aluminum species.

TIBA-modified DMAM · OMTS 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 NMR spectroscopy are in 7 shown. As in Example 11, the TIBA-modified MAO spectrum shows no silicon species or ²⁹ Si NMR signals. The TIBA-modified DMAMOMTS spectrum also showed the characteristic 29- and 39-ppm shifts with split peaks, indicating mixed alkyl groups on some of the cationic aluminum species.

8th compares the proton NMR spectra for TNOA-modified DMAM · OMTS and TNOA-modified MAO in 1,2-dichlorobenzene with perdeuterobenzene NMR spectra. There are several perceptible 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 DMAM OMTS spectrum. The TNOA-modified MAO spectrum does not have the same sharp peak signals seen in the TNOA-modified DMAM OMTS spectrum. The TNOA-modified MAO spectrum also shows a peak corresponding to trimethylaluminum, while the spectrum of TNOA-modified DMAM.OMTS does not have this feature.

9 compares the ²⁷ Al NMR spectra for TNOA-modified DMAM · OMTS and TNOA-modified MAO in 1,2-dichlorobenzene with perdeuterobenzene NMR spectra. The broad signal in the spectrum of TNOA-modified MAO, shown at about 0 ppm, is narrower in the spectrum of TNOA-modified DMAM OMTS and is shifted to about -20 ppm. A similar phenomenon was observed when comparing the ²⁷ Al spectra of MAO and DMAM · OMTS, shown in 4 ,

Example 13

Polymerization Activity: Comparison modified DMAM · OMTS and modified MAO

Comparative ethylene polymerizations were performed with conventional MAO, modified MAO and soluble methylaluminoxanate salts of the invention as cocatalysts. All polymerizations were carried out using rac-ethylenebis (indenyl) zirconium (IV) dimethyl (ZDM) as catalyst in a sufficient amount to form a catalyst system having a ratio of aluminum (Al) atoms to zirconium (Zr) atoms of about 50: 1 to produce. In each experiment, the polymerizations were carried out for about 15 minutes at a temperature of about 70 ° C and an ethylene pressure of about 50 psi with Ver run off isohexane as a diluent. The results of the polymerization experiments are shown in Table I. Table I: Polymerization activity Experiment No. activator Polymer (g) Activity kg polymer / g Zr / hour Activity kg polymer / mmol Zr / hour 1 30% by weight MAO in toluene (control) 22.5 459 41.9 2 30% by weight MAO / 3.5% by weight TNOA in toluene 30.3 622 56.7 3 20 wt .-% DMAM / 3.5 wt .-% TNOA in toluene 79.7 1626 148.3 4 20 wt% DMAM · OMTS / 7.0 wt% TNOA in isohexane 67.3 1363 124.3 5 30% by weight MAO / 10% by weight TIBA in toluene 24.3 494 45.1 6 30 wt% DMAM · OMTS / 10 wt% TIBA in toluene 66.7 1360 124.1

Catalyst systems the soluble Aluminoxanatsalze invention used as cocatalysts (runs 3, 4 and 6) showed how is illustrated above, polymerization activities, which were almost quadruple of catalyst systems, the conventional ones MAO used as cocatalyst (Experiment 1). Catalyst systems the soluble aluminoxanate salts of the invention used as cocatalysts also showed polymerization activities, which corresponded to almost three times of catalyst systems, the used analog modified MAO compositions as cocatalysts (Experiments 2 and 5).

Example 14

Stability of the solution: Comparison of MAO, Modified MAO and Modified DMAM · OMTS

• ^* Versuche 3, 4 und 6 zeigten nach dem Beobachtungszeitraum von 52 Wochen keine Gelbildung.

Aliquots of the activator solutions of Example 13 were placed in glass bottles in a substantially dry nitrogen box and stored for at least 52 weeks at room temperature. The stability of each activator solution is shown below in Table II. Table II: Stability of the solution Experiment No. activator first sign of gelation (weeks) 1 30% by weight MAO in toluene (control) <10 2 30% by weight MAO / 3.5% by weight TNOA in toluene <20 3 20 wt% DMAM · OMTS / 3.5 wt% TNOA in toluene N / A ^* 4 20 wt% DMAM · OMTS / 7.0 wt% TNOA in isohexane N / A ^* 5 30% by weight MAO / 10% by weight TIBA in toluene <20 6 30 wt% DMAM · OMTS / 10 wt% TIBA in toluene N / A ^*

• ^* Experiments 3, 4 and 6 showed no gel formation after the observation period of 52 weeks.

As shown by the above data show TNOA-modified and TIBA-modified DMAM · OMTS (experiments 3, 4 and 6) Room temperature for at least 52 weeks, no gelation. These dates strongly suggest that TNOA-modified and TIBA-modified DMAM · OMTS for even longer periods of time be stable at room temperature. In marked difference conventional MAOs and analogously modified MAOs showed this less than 10 weeks or less than 20 weeks at Room temperature gelation. Soluble aluminoxane compositions thus have opposite both conventional MAO as well similarly modified MAOs significantly improved solution stability.

Example 15

Conductivity: Comparison of MAO, Modified MAO and Modified DMAM · OMTS

Comparative experiments were performed to evaluate and compare the electrical conductivities of conventional MAO, modified MAO and soluble methylaluminoxanate salts of the present invention. In these experiments, the activator solutions prepared in Example 13 were mixed with chlorobenzene in an amount sufficient to produce a sample solution having an aluminum content of about 2% by weight. With a VWR digital conductivity meter, the electrical conductivity of each of the six test solutions was determined at room temperature. The results are shown below in Table III. Table III: Conductivity of the activator Experiment No. activator Conductivity of the activator (μS / cm) 1 30% by weight MAO in toluene (control) 1.7 2 30% by weight MAO / 3.5% by weight TNOA in toluene 2.6 3 20 wt% DMAM · OMTS / 3.5 wt% TNOA in toluene 46.9 4 20 wt% DMAM · OMTS / 7.0 wt% TNOA in isohexane 46.7 5 30% by weight MAO / 10% by weight TIBA in toluene 1.4 6 30 wt% DMAM · OMTS / 10 wt% TIBA in toluene 42.9

As shown by the above conductivity measurements, have the soluble aluminoxane compositions according to the invention, although they are ultimately derived from conventional MAOs, significantly different chemical compositions.

This difference is emphasized by the inherent conductivity of soluble aluminoxane compositions, while MAO compositions are essentially nonconductive. Analogous modification of MAO with alkylaluminum compounds also results in compositions which are nonconductive and thus different from the soluble aluminoxanate salt compositions of the present invention.

Example 16

Conductivity: Comparison of MAO, Modified MAO and Modified DMAM · OMTS

Comparative experiments were performed as in Example 15 to compare the electrical conductivities of conventional MAO, modified MAO, and soluble methylaluminoxanate salts of the present invention, as well as catalyst compositions formed with each of these activators. In these experiments, the solvent was removed from the activator solutions to reveal any potential disruption of solvent conductivity measurements. The catalyst systems were prepared by combining each activator (after solvent removal) with rac-ethylenebis (indenyl) zirconium (IV) dimethyl (ZDM) catalyst in an amount sufficient to produce a catalyst system with a ratio of aluminum (Al) atoms to produce zirconium (Zr) atoms of about 50: 1. The activators and catalyst systems were added to chlorobenzene in a sufficient amount as in Example 13 to produce a sample solution having an aluminum content of about 2% by weight. With a VWR digital conductivity meter, the electrical conductivity of each sample solution was determined at room temperature. The results are shown in the following Table IV. Table IV: Conductivity of activator and catalyst activator Conductivity of the activator (μS / cm) Conductivity of the catalyst (μS / cm) Change in conductivity (Δ μS / cm) MAO 1.5 23.5 22 MAO / TNOA 1.8 31.3 29.5 DMAM- OMTS 48.0 46.8 -1.2 DMAM- OMTS / TNOA 55.5 63.2 7.7

The shown above conductivity results of the activator were similar to those obtained in Example 15. Interestingly, the TNOA-modified DMAM is OMTS indeed more conductive than its insoluble, ionic precursor DMAM · OMTS. TNOA-modified DMAM · OMTS also performs in combination with ZDM to a catalyst system with higher conductivity as catalyst systems using MAO or modified MAO were formed. This higher conductivity of the catalyst system leads to a higher Polymerization activity as shown in Table I. It is thus speculated that the ionic character of the aluminoxanate salts contributes to their ability to transition metal catalysts to activate effectively.

Summary

The present invention provides soluble aluminoxanate salt compositions, Process for the preparation of soluble aluminoxanate salt compositions, Catalyst compositions comprising soluble aluminoxanate salt compositions and methods of polymerizing olefins using of catalyst compositions comprising soluble aluminoxanate salt compositions to disposal. Aluminoxanate salt compositions of the present invention Invention are soluble in aromatic and aliphatic Solvents and have an improved solution stability and a superior activator efficiency compared to conventional aluminoxanes or modified aluminoxanes on.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (28)

A soluble aluminoxanate salt composition comprising the contact product of (a) at least one ionic aluminoxanate having the general formula [L _m R ₂ Al] ⁺ [(AO) X] ^- , wherein L is a stabilizing ligand, each R is independently a hydrocarbon group having one to about twenty carbon atoms, AO is an aluminoxane moiety, X is a hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and m is 1, 2 or 3 , including, is; (b) at least one alkylaluminum compound having the general formula Al (R ') (Z) (Z), wherein R 'is an alkyl group having from about four to about twenty carbon atoms, and each Z is independently a halide, a pseudohalide or an alkyl group having from about three to about twenty carbon atoms, and (c) at least one inert organic solvent. A composition according to claim 1, wherein the inert, organic solvents an aliphatic solvent, an aromatic solvent, a halogenated solvent or any combination thereof. A composition according to claim 1, wherein L is a monosiloxane, a polysiloxane, a monoether, a polyether, a monothioether, is a polythioether or a polydentate ligand, the Oxygen coordinating atoms, nitrogen coordinating atoms, Phosphorus coordinating atoms, sulfur coordinating atoms or includes any combination thereof. A composition according to claim 1, wherein L on Polysiloxane, a polyether, an oxygen-crown ether ligand, nitrogen-crown ether ligand or a nitrogen and oxygen crown ether ligand; R is an alkyl group having one to about eight carbon atoms, and X is fluoride or an alkyl group of one to about eight Carbon atoms. A composition according to claim 1 wherein AO is an aluminoxane having at least one hydrocarbylaluminum moiety, the one has up to twenty carbon atoms. A composition according to claim 1 wherein AO is a hydrocarbylaluminoxane selected from alkylaluminoxanes, cycloalkylaluminoxanes, Arylaluminoxanes, aralkylaluminoxanes or any combination it is. A composition according to claim 1, wherein the ratio of aluminum atoms derived from the ionic aluminoxanate, to aluminum atoms derived from the alkylaluminum compound in the Range from about 2: 1 to about 1000: 1. Carrier-based composition, which is the composition according to claim 1 and a organic or inorganic carrier material. A composition according to claim 8, wherein the inorganic Carrier material talc, clay, modified clay, silicon dioxide, Alumina, silica-alumina, magnesia, titania, Zirconia, magnesium halides, aluminum silicates, kaolinite, Attapulgite, montmorillonite, illite, bentonite, haloysite or any Combination of it is. A composition according to claim 8, wherein the organic Carrier material spherical, particulate or finely divided polyethylene, polyvinyl chloride, polystyrene or any combination of it is. Catalyst composition containing the composition according to claim 1 and a complex of a transition metal Group 3, 4, 5, 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements including the lanthanide series and the actinide series includes. A catalyst composition according to claim 11 which furthermore an organic or inorganic carrier material includes. A catalyst composition comprising the contact product of (a) at least one soluble aluminoxanate salt composition having the general formula [L _m (R) (R ') Al] ⁺ [(AO) X] ^- , wherein L is a stabilizing ligand, R is a hydrocarbon group having 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 hydrocarbon group having one to about twenty carbon atoms, a halide or is a pseudohalide, and m is 1, 2 or 3, inclusive; and (b) at least one transition metal complex of group 3, 4, 5, 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements including the lanthanide series and the actinide series. A catalyst composition according to claim 13, which further comprises a carrier material. A catalyst composition according to claim 13, which further comprising an inert organic solvent. A soluble methylaluminoxane saltate composition having the general formula [L _m ] (Me) (R ') Al] ⁺ [(MAO) Me] ^- , wherein L is a stabilizing ligand, Me is a methyl group, R 'is an alkyl group of about four to about twenty carbon atoms, MAO is a methylaluminoxane moiety and m is 1, 2 or 3, inclusive. The composition of claim 16, further comprising at least an inert, organic solvent. Catalyst composition containing the composition according to claim 16 and a complex of a transition metal Group 3, 4, 5, 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements including the lanthanide series and the actinide series includes. A process for preparing a soluble aluminoxanate salt composition comprising, in an environment that is substantially inert and anhydrous, (a) at least one ionic aluminoxanate having the general formula [L _m R ₂ Al] ⁺ [(AO) X] ^- , (b) at least one inert organic solvent; and (c) at least one alkylaluminum compound having the general formula Al (R ') (Z) (Z), wherein L is a stabilizing ligand, each R is independently a hydrocarbon group having 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 hydrocarbon group having one to about twenty carbon atoms, a halide or a pseudohalide, and each Z is independently a halide, a pseudohalide or an alkyl group having from about three to about twenty carbon atoms, and m is 1, 2 or 3 , including, is to be contacted. The method of claim 19, wherein the inert, organic solvents an aliphatic solvent wherein (a) and (b) are first to form a slurry be contacted and the slurry subsequently is brought into contact with (c). The method of claim 19, wherein the inert, organic solvents, an aromatic solvent wherein (a) and (b) are first formed to form a liquid Clathrats are brought into contact and the liquid clathrate then contacted with (c). The method of claim 19, wherein L is a monosiloxane, a polysiloxane, a monoether, a polyether, a monothioether, is a polythioether or a polydentate ligand, the Oxygen coordinating atoms, nitrogen coordinating atoms, Phosphorus coordinating atoms, sulfur coordinating atoms or any Combination thereof includes. The method of claim 19, wherein the AO is a hydrocarbylaluminoxane selected from alkylaluminoxanes, cycloalkylaluminoxanes, Arylaluminoxanes, aralkylaluminoxanes or any combination thereof is. The method of claim 19, further comprising the ionic Aluminoxanat is obtained by adding a second aromatic solvent from an aluminoxanate-containing liquid clathrate Will get removed. Process for the preparation of a polyolefin polymer, in which, under polymerization conditions, at least one olefinic A monomer and at least one catalyst composition according to claim 13, 19, 20, 29, 30 or 34 are brought into contact. A composition according to claim 1 which has increased has ionic character, compared with a corresponding conventional Aluminoxane, measured by electrical conductivity. A composition according to claim 1 which has been increased Stability in aliphatic and aromatic solvents has, compared with a corresponding conventional aluminoxane. A catalyst composition according to claim 19 or 29, which has increased ionic character, compared with a corresponding catalyst composition which is a conventional Aluminoxane used, measured by electrical conductivity.