DE10232082A1 - Production of a supported cocatalyst for olefin polymerization comprises reaction of a compound containing a tri-valent coordinated Group 13 or 15 element with a support and a compound containing a different Group 13 or 15 element - Google Patents

Abstract

A process for the production of a supported cocatalyst for olefin polymerization comprises reaction of a compound containing a tri-valent coordinated Group 13 or 15 element, a support having functional groups that may covalently bond with the Group 13 or 15 element, and reaction of the resulting product with a compound containing a different Group 13 or 15 element. A process for the production of a supported cocatalyst (I) for olefin polymerization comprises reaction of: (a) (A) a compound containing a tri-valent coordinated Group 13 or 15 element (A1); (b) a support having functional groups such that (A) may covalently bond with it and reaction of the resulting product with; (c) a compound of formula (1). (R1)x-A2-(OH)y (1) A2 = Group 13 or 15 element that is different to A1; R1 = H, halogen, 1-20C alkyl, optionally halogenated, 1-10C alkoxy, 6-20C optionally halogenated aryl, 6-20C aryloxy, 7-40 C optionally halogenated arylalkyl or OSiR23; R2 = H, halogen, 1-20C alkyl, optionally halogenated, 1-10C alkoxy, 6-20C optionally halogenated aryl, 6-20C aryloxy, 7-40C optionally halogenated arylalkyl; y = 1 or 2; and x = 3-y. Independent claims are included for: (1) the supported cocatalyst (I); (2) a catalyst system (II) for the polymerization of olefins, prepared by contact of at least one supported cocatalyst (I) with at least one organo-transition metal compound and optionally an organometallic compound and; (3) a process for the polymerization of olefins by use of the catalyst system (II).

Description

The present invention relates to methods for preparing a supported cocatalyst for olefin polymerization which comprises reacting a compound containing a triple-coordinating element A ¹ is the 13th or 15th Group converts the Periodic Table of the Elements, with a functional group-containing carrier, which is covalently bonded to the carrier is bound, and one then the reaction product with a hydroxyl compound containing an atom of the 13th or the 15th main group of the periodic table, which is different from the element a ¹ is allowed to react. The present invention further relates to supported cocatalysts obtainable by such a process, the use of the supported cocatalysts for the preparation of a catalyst system for the polymerization of olefins, catalyst systems for the polymerization of olefins obtainable from the supported cocatalysts and processes for the polymerization of olefins in which these catalyst systems are used ,

metal compounds such as metallocene complexes are as catalysts for olefin polymerization of great Interest because they can be used to synthesize polyolefins, those with conventional Ziegler-Natta catalysts are not accessible. For example to lead such single-site catalysts to polymers with a narrow molecular weight distribution and a uniform comonomer installation. So that this with polymerization processes successfully used in the gas phase or in suspension can, it is often an advantage that the Metallocenes are used in the form of a solid, i.e. that they're on a solid support be applied. Furthermore, the supported catalysts should have a high productivity exhibit and lead to polymers with good morphology.

So that organic transition metal compounds such as metallocene complexes as catalysts for olefin polymerization are effective, it is necessary to use these as cocatalysts serving connections. A commonly used class of Cocatalysts are alumoxanes such as methylalumoxane (MAO). Have this however, the disadvantage that they used in high excess Need to become. Can continue Compounds are also used as cocatalysts, the organic transition metal compounds convert into cationic complexes.

WO 99/18135 describes catalyst systems, containing an organoboruminum compound, a metallocene and an aluminum compound, the catalyst systems also a carrier can contain. The organoboraluminum compounds are made by reacting dihydroxyorganoboranes or triorganoboroxins with organoaluminium compounds and then as such onto the carrier brought.

WO 96/04319, WO 96/23005 and WO 99/33881 describe catalyst systems, when they are first manufactured carrier reacted with a Lewis acid acting as a cocatalyst, such as trispentafluorophenylborane becomes. Subsequently becomes the modified carrier, where the Lewis acid covalently to the carrier material is bound with a metallocene or a mixture of one Metallocene and an organometallic compound implemented. In S. Charoenchaidet, S. Chavadej and E. Gulari, Macromol. Rapid Commun. 23: 426-431 (2002) described that catalyst systems with worn Cocatalysts by reacting silica gel with trispentafluorophenylborane and trityl chloride available are, a higher activity in ethylene polymerization have when the silica gel is reacted with an aluminum alkyl was brought into contact with trispentafluorophenylborane before has been.

The EP-A 1 153 938 describes catalyst systems in which a modified support is first prepared by reacting a support with an organometallic compound and a compound with functional groups containing active hydrogen. The modified support is then contacted with an organo transition metal compound and another organometallic compound. Organic compounds which contain, in addition to the functional group with active hydrogen, an electron-withdrawing group are used as compounds with active hydrogen-containing functional groups.

The procedures described above for the production of supported Catalyst systems are all quite memorable. Furthermore, the The starting materials used are usually very expensive and the polymerization activities of the Catalyst systems can still be improved.

From B. Richter, A. Meetsma, B. Hessen and J.H. Tauben, Chem. Commun. 2001, 1286-1287 it is known that by Reaction of tri-tert-butyl aluminum with a boronic acid a structurally demanding substituent crystallographically Characterizable boralumoxanes are accessible as cocatalysts for the Ethylene polymerization can act. As possible The cause of the cocatalytic action of these compounds is that The existence of edge-connected four-membered rings was discussed. However, it is not supported Polymerization is described and the activity of the catalyst system is low.

The invention was therefore the object is based on a method for producing a supported cocatalyst to find the olefin polymerization, which is not very expensive which can be used relatively inexpensive feedstocks and that leads to catalyst systems with increased polymerization activity or at the for good polymerization activity the catalyst solids only a smaller amount of expensive Input materials needed will or cheaper input materials can be used.

Accordingly, it has now been found that particularly good worn Cocatalysts for olefin polymerization are available when as cocatalysts acting connections that have at least two different triple coordinating elements of the 13th or 15th group of the periodic table of the elements included, formed directly on the surface of a support become. In this implementation, at least one of the Reactants covalently to the carrier bound. The present invention thus relates to a method to manufacture a supported Cocatalyst for olefin polymerization, in which one

• A) a compound containing a three-coordinating element A ¹ is the 13th or 15th Group of the Periodic Table of the Elements, with
•  B) a carrier having functional groups implements, wherein the compound A) is covalently bound to the carrier B), and man subsequently the reaction product with
• C) a compound of the general formula (I), (R ¹ ) x-A ² - (OH) _y (I) wherein A ^{2 is} an atom of the 13th or 15th main group of the periodic table, which is different from the element A ¹ , R ^{1 is the} same or different and is, independently of one another, hydrogen, halogen, C ₁ -C ₂₀ -alkyl, C ₁ - C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ -Halogenarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ haloalkylaryl or an OSiR ₃ ² group, in which R ^{2 is the} same or different and is hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ -haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ - Halogenarylalkyl, C ₇ -C ₄₀ -Cao-alkylaryl or C ₇ -C ₄₀ -haloalkylaryl means, y is 1 or 2 and x means 3 minus y, can react.

Furthermore, supported cocatalysts have been found by such a process, the use of the supported cocatalysts for the preparation of a catalyst system for the polymerization of olefins, catalyst systems for the polymerization of olefins obtainable from the supported cocatalysts and processes for the polymerization of olefins using these catalyst systems. The supported cocatalysts prepared according to the invention are suitable for the polymerization of olefins and, above all, for the polymerization of α-olefins, ie hydrocarbons with terminal double bonds. Suitable monomers can be functionalized olefinically unsaturated compounds such as ester or amide derivatives of acrylic or methacrylic acid, for example acrylates, methacrylates or acrylonitrile. Nonpolar olefinic compounds are preferred, including aryl-substituted? -Olefins. Particularly preferred? -Olefins are linear or branched C ₂ -C ₁₂ -1-alkenes, in particular linear C ₂ -C ₁₂ -1-alkenes such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene , 1-octene, 1-decene or branched C ₂ -C ₁₀ -1-alkenes such as 4-methyl-1-pentene, conjugated and non-conjugated dienes such as 1,3-butadiene, 1,4-hexadiene, or 1.7 -Octadiene or vinyl aromatic compounds such as styrene or substituted styrene. Mixtures of different α-olefins can also be polymerized.

Suitable olefins are also those where the double bond is part of a cyclic structure, the can have one or more ring systems. Examples include cyclopentene, Norbornene, tetracyclododecene or methylnorbornene or dienes like 5-ethylidene-2-norbornene, norbornadiene or ethylnorbornadiene.

Mixtures of two can also be used or more olefins are polymerized.

In particular, the supported cocatalysts according to the invention can be used for the polymerization or copolymerization of ethylene or propylene. C ₃ -C ₈ -? - olefins, in particular 1-butene, 1-pentene, 1-hexene and / or 1-octene, are preferably used as comonomers in the ethylene polymerization. Preferred comonomers in propylene polymerization are ethylene and / or 1-butene.

In the process according to the invention for the preparation of a supported cocatalyst, compounds A) containing a triple coordinating element A ^{1 from} the 13th or 15th group of the Periodic Table of the Elements are first reacted with support B) having functional groups.

worin
A¹ ein Atom der 13. oder 15. Hauptgruppe des Periodensystems ist, bevorzugt der 13. Hauptgruppe des Periodensystems, besonders bevorzugt Aluminium oder Bor und ganz besonders bevorzugt Aluminium ist,
R³, R⁴ und R⁵ gleich oder verschieden sind und unabhängig voneinander für Wasserstoff, Halogen, C₁-C₂₀-Alkyl, C₁-C₂₀-Halogenalkyl, C₁-C₁₀-Alkoxy, C₆-C₂₀-Aryl, C₆-C₂₀-Halogenaryl, C₆-C₂₀-Anloxy, C₇-C₄₀-Arylalky, C₇-C₄₀-Halogenarylalkyl, C₇-C₄₀-Alkylaryl, C₇-C₄₀-Halogenalkylaryl oder eine OSiR₃ ⁶-Gruppe stehen, worin
R⁶ gleich oder verschieden ist und Wasserstoff, Halogen, C₁-C₂₀-Alkyl, C₁-C₂₀-Halogenalkyl, C₁-C₁₀-Alkoxy, C₆-C₂₀-Aryl, C₆-C₂₀-Halogenaryl, C₆-C₂₀-Aryloxy, C₇-C₄₀-Arylalkyl, C₇-C₄₀-Halogenarylalkyl, C₇-C₄₀-Alkylaryl, oder C₇-C₄₀ Halogenalkylaryl bedeutet,
und R³, R⁴ und R⁵ bevorzugt für Wasserstoff, Halogen, C₆-C₁₄-Aryl, C₆-C₁₄-Halogenaryl, C₁-C₁₄-Alkyl, C₁-C₁₄-Halogenalkyl, C₇-C₃₀-Arylalky, C₇-C₃₀-Halogenarylalkyl, C₇-C₃₀-Alkylaryl oder C₇-C₃₀-Halogenalkylaryl und
besonders bevorzugt für C₆-C₁₀-Aryl, C₆-C₁₀-Halogenaryl, C₁-C₆-Alkyl, C₁-C₆-Halogenalkyl, C₇-C₂₀-Alkylaryl oder C₇-C₂₀-Halogenalkylaryl stehen.Compounds A) which have the general formula (II) are preferred,

wherein
A ^{1 is} an atom of the 13th or 15th main group of the periodic table, preferably the 13th main group of the periodic table, particularly preferably aluminum or boron and very particularly preferably aluminum,
R ³ , R ⁴ and R ^{5 are the} same or different and are independently hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ - Aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ annoxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ haloalkylaryl or an OSiR ₃ ⁶ group, wherein
R ^{6 is the} same or different and is hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl , C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, or C ₇ -C ₄₀ haloalkylaryl,
and R ³ , R ⁴ and R ^{5 are} preferably hydrogen, halogen, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ haloaryl, C ₁ -C ₁₄ alkyl, C ₁ -C ₁₄ haloalkyl, C ₇ - C ₃₀ arylalkyl, C ₇ -C ₃₀ haloarylalkyl, C ₇ -C ₃₀ alkylaryl or C ₇ -C ₃₀ haloalkylaryl and
particularly preferred for C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ haloaryl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ haloalkylaryl stand.

With preferred carriers B) are those whose functional groups are active hydrogen exhibit. Suitable functional groups are, for example, hydroxyl groups, primary and secondary amino groups, Mercapto groups, silanol groups, carboxyl groups, amido groups or Imido groups, with hydroxyl groups being preferred.

Fine carriers are preferably used as carriers organic or inorganic solids used, the corresponding have functional groups. For example, it can be layered silicates, inorganic oxides or finely divided functionalized polymer powders act.

Inorganic oxides suitable as carriers can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Oxides or mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and corresponding oxide mixtures are preferred. Other inorganic oxides that can be used alone or in combination with the last-mentioned oxidic supports are, for example, ZrO ₂ or B ₂ O ₃ . Preferred oxides are silicon dioxide, in particular in the form of a silica gel or a pyrogenic silica, or aluminum oxide. A preferred mixed oxide is, for example, calcined hydrotalcite.

The carrier materials used preferably have a specific surface area in the range from 10 to 1000 m ² / g, preferably from 50 to 500 m ² / g and in particular from 200 to 400 m ² / g and a pore volume in the range from 0.1 to 5 ml / g, preferably from 0.5 and 3.5 ml / g and in particular from 0.8 to 3.0 ml / g. The average particle size of the finely divided carriers is generally in the range from 1 to 500 μm, preferably from 5 to 350 μm and in particular from 10 to 100 μm.

The inorganic carrier can thermal treatment e.g. to remove adsorbed water be subjected. Such a drying treatment is in the Usually at temperatures in the range of 80 to 300 ° C, preferably from 100 to 200 ° C, where drying preferably under vacuum and / or in an inert gas stream, for example with nitrogen or argon. The inorganic carrier can also be calcined, then by treatment at temperatures from 200 to 1000 ° C Concentration of the OH groups on the surface adjusted and, if necessary the structure of the solid changed becomes.

Other possible carrier materials are functionalized Polymer carrier, z. B. based on polystyrenes, the functional groups for Examples can be ammonium or hydroxyl groups.

Usually compound A) is combined with carrier B) in Presence of an organic solvent, in which the carrier was suspended. Suitable solvents are aromatic or aliphatic solvents, such as Hexane, heptane, toluene or xylene or halogenated hydrocarbons, such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.

The combination is usually done at temperatures in the range from -20 ° C to 150 ° C and preferably in the range from 0 ° C to 80 ° C. The Time that you react the components brought into contact with each other leaves, is in the Usually from 10 minutes to 48 hours. Response times are preferred from 20 minutes to 6 hours and in particular from 30 minutes to 1 hour.

As compound C) with which the reaction product of compound A) is allowed to react with carrier B), those of the general formula (I) are preferred in which
A ^{2 is} an atom of the 13th main group of the periodic table, which is different from the element A ¹ and is preferably aluminum or boron and very particularly preferably boron.

Compounds of the general formula (I) in which
R ^{1 is the} same or different and is independently hydrogen, halogen, C ₆ -C ₁₄ aryl, C ₁ -C ₁₄ haloaryl, C ₁ -C ₁₄ alkyl, C ₇ -C ₃₀ haloalkyl, C ₇ -C ₃₀ arylalkyl, C ₇ -C ₃₀ haloarylalkyl, C ₇ -C ₃₀ alkylaryl or C ₇ -C ₃₀ haloalkylaryl and
in particular represents C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ haloaryl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ haloalkylaryl ,

Are also preferred also compounds of the general formula (I) in which y is the same 1 is.

Methods for producing a supported cocatalyst in which one of the elements A ¹ and A ^{2 is} aluminum and the other is boron are particularly preferred.

It is very particularly preferred if the element A ^{2 is} boron and it is particularly preferred if the compounds C) have the general formula (I ') (R ¹ ) _x -B- (OH) _y (I ') wherein
R ^{1 is the} same or different and is independently hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ -haloaryl, C ₆ -C ₂₀ -aryoxy, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
y is 1 or 2 and
x 3 minus y means.

Examples of preferred compounds of the formula (I ') are boric acids of the formula R ¹ ₂ B (OH) or boronic acids of the formula R ¹ B (OH) ₂ , in which R ^{1 is} particularly preferably C ₆ -C ₂₀ haloaryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ haloalkylaryl.

worin
R³, R⁴ und R⁵ gleich oder verschieden sind und unabhängig voneinander für C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec.-Butyl, tert.-Butyl, n-Pentyl oder n-Hexyl stehen.It is also very particularly preferred if the element A ^{1 is} aluminum and it is particularly preferred if the compounds A) have the general formula (II ')

wherein
R ³ , R ⁴ and R ^{5 are} identical or different and are independently of one another for C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, are n-pentyl or n-hexyl.

The combination of the compound C) with the reaction product of compound A) and the carrier B) preferably in the presence of the organic solvent in which the carrier is suspended was and in which the reaction of compound A) with the carrier has been. However, it is also possible to do that first Reaction product of the compound A) with the carrier B) isolate and then the isolated or resuspended reaction product of the compound C) implement.

The combination of compound C) with the reaction product of compound A) and the carrier B) usually at temperatures in the range of -20 ° C to 150 ° C and preferably in the range of 0 ° C to 80 ° C. The Time the components react with each other at this step leaves, is in the Usually from 1 to 4.8 hours. Reaction times of are preferred 6 to 24 hours and especially 10 to 15 hours.

The molar ratio of compound A) to functional groups of the carrier B) is usually from 0.05: 1 to 100: 1, preferably from 0.2: 1 to 20: 1, in particular from 1: 1 to 5: 1.

The molar ratio of compound A) to Compound C) usually from 0.05: 1 to 20: 1, preferably from 0.2: 1 to 5: 1, in particular from 0.5: 1 to 2: 1.

The with the inventive method available, likewise cocatalysts according to the invention can be used in particular for the production of a catalyst system use for olefin polymerization. Such catalyst systems also according to the invention usually contain at least in addition to the supported cocatalysts an organic transition metal compound D).

As the organic transition metal compound D) come in principle all compounds containing organic groups of transition metals the 3rd to 12th group of the periodic table or the lanthanides in Consideration, which after reaction with those from components A) to C) available supported Cocatalysts and optionally the organometallic compounds E) for olefin polymerization form active catalysts. Usually these are compounds in which at least one one or more teeth Ligand over Sigma or Pi bond is bound to the central atom. As a ligand are both those which contain cyclopentadienyl radicals, as well as those that are free of cyclopentadienyl residues. In Chem. Rev. 2000, Vol. 100, No. 4 is a variety of such for olefin polymerization suitable compounds D). There are also multinuclear ones Cyclopentadienyl complexes for olefin polymerization is suitable.

in der die Substituenten und Indizes folgende Bedeutung haben:
M^1A Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdän oder Wolfram, sowie Elemente der 3. Gruppe des Periodensystems und der Lanthaniden,
X^1A gleich oder verschieden sind und unabhängig voneinander Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, C₂-C₁₀-Alkenyl, C₆-C₁₅-Aryl, C₇-C₄₀-Alkylaryl, C₇-C₄₀-Arylalkyl, -OR^6A oder -NR^6AR^7A bedeuten oder zwei Reste X^A miteinander verbunden sind und beispielsweise für einen substituierten oder unsubstituierten Dienliganden, insbesondere einen 1,3-Dienliganden, oder eine Biaryloxygruppierung stehen, wobei
R^6A und R^7A C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl, C₇-C₄₀-Arylalkyl, C₇-C₄₀-Alkylaryl, Fluoralkyl oder Fluoraryl mit jeweils 1 bis 16 C-Atomen im Alkylrest und 6 bis 21 C-Atomen im Arylrest ist,
n^A 1, 2 oder 3 ist, wobei n^A entsprechend der Wertigkeit von M den Wert aufweist, bei dem der Metallocenkomplex der allgemeinen Formel (III) ungeladen vorliegt,
R^1A bis R^5A unabhängig voneinander Wasserstoff, C¹-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, die ihrerseits durch C₁-C₁₀-Alkyl substituiert sein können, C₂-C₂₂-Alkenyl, C₆-C₂₂-Aryl, C₇-C₄₀-Arylalkyl, C₇-C₄₀-Alkylaryl, -NR^8A, -N(SiR^8A ₃), -OR^8A ₃, -OSiR^8A ₃, -SiR^8A ₃, wobei die Reste R^1A bis R^5A auch durch Halogen substituiert sein können und/oder je zwei Reste R^1A bis R^5A, insbesondere benachbarte Reste, mit den sie verbindenden Atomen zu einem bevorzugt fünf-, sechs- oder siebengliedrigen Ring oder einem bevorzugt fünf-, sechs- oder siebengliedrigen Heterocyclus, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält, verbunden sein können, wobei
R^8A gleich oder verschieden C₁-C₁₀-Alkyl, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryloxy sein kann und Z^A für X^A oder

steht, wobei die Reste
R^9A bis R^13A unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, die ihrerseits durch C₁-C₁₀-Alkyl substituiert sein können, C₂-C₂₂-Alkenyl, C₆-C₂₂-Aryl, C₇-C₄₀-Arylalkyl, C₇-C₄₀-Alkylaryl, -NR^14A ₂, -N(SiR^14A ₃)₂, -OSiR^14A ₃, -Sir^14A ₃, wobei die Reste R^1A bis R^5A auch durch Halogen substituiertsein können und/oder je zwei Reste R^1A bis R^5A, insbesondere benachbarte Reste, mit den sie verbindenden Atomen zu einem bevorzugt fünf-, sechs- oder siebengliedrigen Ring oder einem bevorzugt fünf-, sechs- oder siebengliedrigen Heterocyclus, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält, verbunden sein können, wobei
R^14A gleich oder verschieden C₁-C₁₀-Alkyl, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryoxy sein kann,
oder wobei die Reste R^4A und Z^A gemeinsam eine Gruppierung
R^15A

-BR^16A- , -(BNR^16AR^17A)- , -AIR^16A- , -Ge- , -Sn- , -O- , -S- , -SO- , -SO₂- , -NR^16A- , -CO- , -PR^16A- oder -(POR^16A)- ist,
wobei
R^16A, R^17A und R^18A gleich oder verschieden sind und jeweils ein Wasserstoffatom, ein Halogenatom, eine Trimethylsilylgruppe, eine C₁-C₁₀-Alkylgruppe, eine C₁-C₁₀-Fluoralkylgruppe, eine C₆-C₁₀-Fluorarylgruppe, eine C₆-C₁₀-Arylgruppe, eine C₁-C₁₀-Alkoxygruppe, eine C₇-C₁₅-Alkylaryloxygruppe, eine C₂-C₁₀-Alkenylgruppe, eine C₇-C₄₀-Arylalkylgruppe, eine C₈-C₄₀-Arylalkenylgruppe oder eine C₇-C₄₀-Alkylarylgruppe bedeuten oder wobei zwei benachbarte Reste jeweils mit den sie verbindenden Atomen einen 4 bis 15 C-Atome aufweisenden gesättigten oder ungesättigten Ring bilden, und
M^2A Silicium, Germanium oder Zinn, bevorzugt Silicium ist,
A^A -O- , -S- , -NR^19A- , -PR^19A- , -O-R^19A, -NR^19A ₂, -PR^19A ₂
oder ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem bedeutet, mit
R^19A unabhängig voneinander C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl, C₃-C₁₀-Cycloalkyl, C₇-C₁₈-Alkylaryl oder -Si(R^20AA)₃,
R^20A Wasserstoff, C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl, das seinerseits mit C₁-C₄-Alkylgruppen substituiert sein kann oder C₃-C₁₀-Cycloalkyl,
V^A 1 oder, falls A^A ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem ist, 1 oder 0
oder wobei die Reste R^4A und R^12A gemeinsam eine Gruppierung -R^15A- bilden.Suitable organo transition metal compounds D) are in particular those with at least one cyclopentadienyl-type ligand, those with two cyclopentadienyl-type ligands being commonly referred to as metallocene complexes. Of the organo transition metal compounds D) with at least one cyclopentadienyl type ligand, those of the general formula (III) are particularly suitable

in which the substituents and indices have the following meaning:
M ^1A titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, as well as elements of the 3rd group of the periodic table and the lanthanides,
X ^{1A are the} same or different and are independently fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₁₅ aryl, C ₇ -C ₄₀ alkylaryl , C ₇ -C ₄₀ arylalkyl, -OR ^6A or -NR ^6A R ^7A or two radicals X ^A are connected to one another and are, for example, a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, or a biaryloxy grouping, where
R ^6A and R ^{7A are} C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl, fluoroalkyl or fluoroaryl, each with 1 to 16 C atoms in the alkyl radical and has 6 to 21 carbon atoms in the aryl radical,
n ^{A is} 1, 2 or 3, where n ^A, corresponding to the valency of M, has the value at which the metallocene complex of the general formula (III) is uncharged,
R ^1A to R ^5A independently of one another are hydrogen, C ¹ -C ₂₂ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn can be substituted by C ₁ -C ₁₀ alkyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₂₂ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl, -NR ^8A , -N (SiR ^8A ₃ ), -OR ^8A ₃ , -OSiR ^8A ₃ , -SiR ^8A ₃ , where the radicals R ^1A to R ^{5A can} also be substituted by halogen and / or two radicals R ^1A to R ^5A , in particular adjacent radicals, with the atoms connecting them to form a preferably five-, six- or seven-membered ring or one preferably five -, Six- or seven-membered heterocycle, which contains at least one atom from the group N, P, O or S, can be connected, where
R ^{8A may be the} same or different C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl, C ₁ -C ₄ alkoxy or C ₆ -C ₁₀ aryloxy and Z ^A for X ^A or

stands, with the remains
R ^9A to R ^13A independently of one another are hydrogen, C ₁ -C ₂₂ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn can be substituted by C ₁ -C ₁₀ alkyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₂₂ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl, -NR ^14A ₂ , -N (SiR ^14A ₃ ) ₂ , -OSiR ^14A ₃ , -Sir ^14A ₃ , the radicals R ^1A to R ^{5A can} also be substituted by halogen and / or two radicals R ^1A to R ^5A , in particular adjacent radicals, with the atoms connecting them to form a preferably five-, six- or seven-membered ring or a preferably five-, six- or a seven-membered heterocycle which contains at least one atom from the group N, P, O or S, where
R ^{14A may be the} same or different C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl, C ₁ -C ₄ alkoxy or C ₆ -C ₁₀ aroxy,
or wherein the radicals R ^4A and Z ^A together form a group
R ^15A

-BR ^16A -, - (BNR ^16A R ^17A ) -, -AIR ^16A -, -Ge-, -Sn-, -O-, -S-, -SO-, -SO ₂ -, -NR ^16A -, - CO-, -PR ^16A - or - (POR ^16A ) -,
in which
R ^16A , R ^17A and R ^{18A are the} same or different and each represents a hydrogen atom, a halogen atom, a trimethylsilyl group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ fluoroalkyl group, a C ₆ -C ₁₀ fluoroaryl group, a C ₆ -C ₁₀ aryl group, a C ₁ -C ₁₀ alkoxy group, a C ₇ -C ₁₅ alkylaryloxy group, a C ₂ -C ₁₀ alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₈ -C ₄₀ arylalkenyl group or a C ₇ -C ₄₀ alkylaryl group or where two adjacent radicals each form a saturated or unsaturated ring having 4 to 15 carbon atoms with the atoms connecting them, and
M ^{2A is} silicon, germanium or tin, preferably silicon,
A ^A -O-, -S-, -NR ^19A -, -PR ^19A -, -OR ^19A , -NR ^19A ₂ , -PR ^19A ₂
or denotes an unsubstituted, substituted or fused, heterocyclic ring system, with
R ^19A independently of one another are C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, C ₃ -C ₁₀ cycloalkyl, C ₇ -C ₁₈ alkylaryl or -Si (R ^20A A) ₃ ,
R ^{20A is} hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, which in turn can be substituted by C ₁ -C ₄ alkyl groups or C ₃ -C ₁₀ cycloalkyl,
V ^A 1 or, if A ^{A is} an unsubstituted, substituted or fused, heterocyclic ring system, 1 or 0
or wherein the radicals R ^4A and R ^12A together form a group -R ^15A -.

The radicals X ^A in the general formula (III) are preferably the same, preferably fluorine, chlorine, bromine, C ₁ -C ₇ -alkyl or arylalkyl, in particular chlorine, methyl or benzyl.

bevorzugt.Of the organo transition metal compounds of the general formula (III) are

prefers.

Of the compounds of the formula (IIIa), those are particularly preferred in which
M ^1A titanium or chrome,
X ^{A is} chlorine, C ₁ -C ₄ alkyl, phenyl, alkoxy or aryloxy
n ^A the number 1 or 2 and
R ^1A to R ^{5A are} hydrogen or C ₁ -C ₄ alkyl or two adjacent radicals R ^1A to R ^5A with which they ver binding atoms form a substituted or unsubstituted unsaturated six-membered ring.

Preferred metallocenes of the formula (IIIb) are those in which
M ^{1A stands} for titanium, zirconium, hafnium or chromium,
X ^{A is} chlorine, C ₁ -C ₄ alkyl or benzyl, or two radicals X are a substituted or unsubstituted butadiene ligand,
n ^{A is} 1 or 2, preferably 2 or, if M ^{1A is} chromium, is 0,
R ^1A to R ^{5A are} hydrogen, C ₁ -C ₈ alkyl, C ₆ -C ₁₀ aryl, -NR ^8A ₂ , -OSiR ^8A ₃ , -SiR ^8A 3 or -Si (R ^8A ) ₃ and
R ^9A to R ^{13A are} hydrogen C ₁ -C ₈ alkyl, C ₆ -C ₁₀ aryl, -NR ^8A ₂ , -OSiR ^8A ₃ , -SiR ^8A or
or two radicals R ^1A to R ^5A and / or R ^9A to R ^13A together with the cyclopentadienyl ring mean an indenyl or substituted indenyl system.

In particular, the connections of the formula (IIIb) in which the cyclopentadienyl radicals are the same are.

Examples of particularly suitable compounds of the formula (IIIb) are
Bis (cyclopentadienyl) zirconium,
Bis (pentamethylcyclopentadienyl) zirconium,
Bis (methylcyclopentadienyl) zirconium,
Bis (ethyl cyclopentadienyl) zirconium,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(Indenyl) zirconium,
Bis (tetrahydroindenyl) zirconium dichloride and
Bis (trimethylsilyl) zirconium
as well as the corresponding dimethyl zirconium compounds.

Of the metallocenes of the formula (IIIc), those in which
R ^1A and R ^{9A are the} same or different and represent hydrogen or C ₁ -C ₁₀ alkyl groups,
R ^5A and R ^{13A are} identical or different and represent hydrogen, a methyl, ethyl, isopropyl or tert-butyl group,
R ^3A and R ^{11A are} C ₁ -C ₄ alkyl and
R ^2A and R ^{10A are} hydrogen
or
two adjacent radicals R ^2A and R ^3A and R ^10A and R ^11A together represent saturated or unsaturated cyclic groups ^having 4 to 44 carbon atoms,
R ^{15A stands} for -M ^2A R ^16A R ^17A - or -CR ^16A R ^17A -CR ^16A R ^17A - stands for or -BR ^16A or -BNR ^16A R ^17A - means,
M ^1A for titanium, zirconium or hafnium and
X ^{A is} identical or different to chlorine, C ₁ -C ₄ alkyl, benzyl, phenyl or C ₇ -C ₁₅ alkylanloxy.

in der
die Reste R'^A gleich oder verschieden sind und Wasserstoff, C₁-C₁₀-Alkyl oder C₃-C₁₀-Cycloalkyl, bevorzugt Methyl, Ethyl, Isopropyl oder Cyclohexyl, C₆-C₂₀-Aryl, bevorzugt Phenyl, Naphthyl oder Mesityl, C₇-C₄₀-Arylalkyl, C₇-C₄₀-Alkylaryl, bevorzugt 4-tert.-Butylphenyl oder 3,5-Di-tert.-butylphenyl, oder C₈-C₄₀-Arylalkenyl bedeuten,
R^5A und R^13A gleich oder verschieden sind und für Wasserstoff, C₁-C₆-Alkyl, bevorzugt Methyl, Ethyl, Isopropyl, n-Propyl, n-Butyl, n-Hexyl oder tert.-Butyl, stehen,
und die Ringe S und T gleich oder verschieden, gesättigt, ungesättigt oder teilweise gesättigt sind.Particularly suitable compounds of the formula (IIIc) are those of the formula (IIIc ')

in the
the radicals R ' ^{A are} identical or different and are hydrogen, C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl, preferably methyl, ethyl, isopropyl or cyclohexyl, C ₆ -C ₂₀ aryl, preferably phenyl, naphthyl or Mesityl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl, preferably 4-tert-butylphenyl or 3,5-di-tert-butylphenyl, or C ₈ -C ₄₀ arylalkenyl,
R ^5A and R ^{13A are} identical or different and represent hydrogen, C ₁ -C ₆ -alkyl, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, n-hexyl or tert-butyl,
and the rings S and T are the same or different, saturated, unsaturated or partially saturated.

The indenyl or tetrahydroindenyl ligands of the metallocenes of the formula (IIIc ') are preferably in 2-, 2,4-, 4,7-, 2,4,7-, 2,6-, 2,4,6-, 2 , 5,6-, 2,4,5,6- or 2,4,5,6,7-position, in particular in the, 2,4-position, the following nomenclature applies to the place of substitution:

Preferred complex compounds (IIIc ') are preferred bridged Bis-indenyl complexes in the rac or pseudo-rac form used, the pseudo-rac form being such complexes acts in which the two indenyl ligands without consideration all other substituents of the complex relative to each other in the rac arrangement.

Examples of particularly suitable metallocenes (IIIc) and (IIIc ') include
Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (indenyl) zirconium dichloride,
Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride,
Ethylenebis (cyclopentadienyl) zirconium dichloride,
Ethylenebis (indenyl) zirconium dichloride,
Ethylenebis (tetrahydroindenyl) zirconium dichloride,
Tetramethylethylene-9 fluorenylcyclopentadienylzirkoniumdichlorid,
Dimethylsilanediylbis (3-tert-butyl-5-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (3-tert-butyl-5-ethylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (2-methylindenyl) zirconium dichloride,
Dimethylsilanediylbis (2-isopropylindenyl) zirconium dichloride,
Dimethylsilanediylbis (2-tert.butylindenyl) zirconium dichloride,
Diethylsilandiylbis (2-methylindenyl) zirconium dibromide,
Dimethylsilanediylbis (3-methyl-5-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (3-ethyl-5-isopropylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (2-ethylindenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4,5-benzindenyl) zirconium
Methylphenylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride,
Methylphenylsilanediylbis (2-ethyl-4,5-benzindenyl) zirconium,
Diphenylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride,
Diphenylsilanediylbis (2-ethyl-4,5-benzindenyl) zirconium,
Diphenylsilanediylbis (2-methylindenyl) hafnium dichloride,
Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-ethyl-4-phenyl-indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-propyl-4- (1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-i-butyl-4- (1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-propyl-4- (9-phenanthryl) indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4-isopropylindenyl) zirconium dichloride,
Dimethylsilanediylbis (2,7-dimethyl-4-isopropylindenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4,6-düsopropylindenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4- [p-trifluoromethylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4- [3 ', 5'-dimethylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Diethylsilandiylbis (2-methyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-ethyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-propyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-n-butyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-hexyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediyl (2-isopropyl-4-phenyl-indenyl) - (2-methyl-4-phenyl-indenyl) zirconium dichloride,
Dimethylsilanediyl (2-isopropyl-4- (1-naphthyl) indenyl) - (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilanediyl (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) - (2-methyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediyl (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) - (2-ethyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediyl (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) - (2-methyl-4- [3 ', 5'-bis-tert-butylphenyl] indenyl) zirconium dichloride,
Dimethylsilanediyl (2-isopropyl-4- (4'-tert-butylphenyl) indenyl) - (2-methyl-4- [1'-naphthyl] indenyl) zirconium dichloride and
Ethylene (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) - (2-methyl-4- [4'-tert-butylphenyl] indenyl) zirconium dichloride and the corresponding dimethyl-, monochloromono (alkylaryloxy) - and di - (alkylaryloxy) zirconium compounds.

In the case of the compounds of the general formula (IIId), those in which
M ^1A for titanium or zirconium, especially titanium, and
X _{A stands} for chlorine, C ₁ -C ₄ alkyl or phenyl or two radicals X stand for a substituted or unsubstituted butadiene ligand,
R ^15A for -SiR ^16A R ^17A - or -CR ^16A R ^17A -CR ^16A R ^17A - and,
A ^{A stands} for -O-, -S- or -NR ^19A -
R ^1A to R ^3A and R ^{5A represent} hydrogen, C ₁ -C ₁₀ alkyl, preferably methyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl or -Si (R ^8A ) ₃ , or two neighboring radicals represent cyclic groups having 4 to 12 carbon atoms, all R ^1A to R ^3A and R ^5A being particularly preferably methyl.

Another group of compounds of formula (IIId) which are particularly suitable are those in the
M ^1A for titanium or chromium preferably in the oxidation state III and
X ^{A represents} chlorine, C ₁ -C ₄ -alkyl or phenyl or two radicals X ^{A represent} a substituted or unsubstituted butadiene ligand,
R ^15A for -SiR ^16A R ^17A - or -CR ^16A R ^17A -CR ^16A R ^17A - and,
A ^{A stands} for -OR ^19A , -NR ¹⁹ ₂ , -PR ^19A ₂ ,
R ^1A to R ^3A and R ^{5A represent} hydrogen, C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl or -Si (R ^8A ) ₃ , or where two adjacent radicals are Cyclic groups containing 4 to 12 carbon atoms.

The synthesis of such complex compounds can be carried out according to methods known per se, the implementation the correspondingly substituted, cyclic hydrocarbon anions with Halides of titanium, zirconium; Hafnium, vanadium, niobium, tantalum or chrome, is preferred.

Examples of corresponding manufacturing processes include in the Journal of Organometallic Chemistry, 369 (1989), 359-370 described.

Further suitable organo transition metal compounds D) are metallocenes with at least one ligand which is formed from a cyclopentadienyl or heterocyclopentadienyl with a fused-on heterocycle, wherein in the heterocycles at least one carbon atom is preferably from the group 15 or 16 of the periodic table and in particular from nitrogen or sulfur is replaced. Such compounds are described for example in WO 98/22486. These are in particular
Dimethylsilanediyl (2-methyl-4-phenyl-indenyl) - (2,5-dimethyl-N-phenyl-4-azapentalene) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride and
Dimethylsilanediylbis (2-ethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride.

wobei das Übergangsmetall ausgewählt ist aus den Elementen Ti, Zr, Hf, Sc, V, N, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt oder ein Element der Seltenerd-Metalle. Bevorzugt sind hierbei Verbindungen mit Nickel, Eisen, Kobalt und Palladium als Zentralmetall.Organic transition metal compound D) suitable according to the invention are also transition metal complexes with at least one ligand of the general formulas (IVa) to (IVe),

wherein the transition metal is selected from the elements Ti, Zr, Hf, Sc, V, N, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt or an element of the rare earth metals. Compounds with nickel, iron, cobalt and palladium as the central metal are preferred.

E ^B is an element of the 15th group of the Periodic Table of the Elements, preferably N or P, with N being particularly preferred. The two or three atoms E ^B in a molecule can be the same or different.

The radicals R ^1B to R ^19B , which can be the same or different within a ligand system of the formulas (IVa) to (IVe), represent the following groups:
R ^1B and R ^4B independently of one another are preferred for hydrocarbon or substituted hydrocarbon radicals, hydrocarbon radicals in which the carbon atom adjacent to the element E ^B is linked to at least two carbon atoms.
R ^2B and R ^3B independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, where R ^2B and R ^{3B can} also together form a ring system in which one or more heteroatoms can also be present,
R ^6B and R ^8B independently of one another for hydrocarbon or substituted hydrocarbon radicals,
R ^5B and R ^9B independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals,
where R ^6B and R ^5B or R ^8B and R ^9B together can also form a ring system,
R ^7B independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, where two R ^{7A can} also form a ring system together,
R ^10B and R ^14B independently of one another for hydrocarbon or substituted hydrocarbon radicals,
R ^11B , R ^12B , R ^{12B '} and R ^13B independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, it also being possible for two or more geminal or vicinal radicals R ^11B , R ^12B , R ^12B' and R ^13B together to form a ring system,
R ^15B and R ^18B independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R ^16B and R ^17B independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R ^19B for an organic radical which forms a 5- to 7-membered substituted or unsubstituted, in particular unsaturated or aromatic, heterocyclic ring system, in particular together with E ^B a pyridine system,
n ^1B for 0 or 1, where for compounds of the formula (IVc) for n ^1B is 0 negatively charged and
n ^2B for an integer between 1 and 4, preferably 2 or 3.

Particularly suitable transition metal complexes with ligands of the general formulas (IVa) to (IVd) are, for example, complexes of the transition metals Fe, Co, Ni, Pd or Pt with ligands of the formula (IVa). Diimine complexes of Ni or Pd are particularly preferred, for example:
Di (2,6-di-i-propyl-phenyl) -2,3-dimethyldiazabutadien-palladium dichloride,
Di (di-i-propyl-phenyl) -2,3-dimethyldiazabutadiennickeldichlorid,
Di (2,6-di-i-propyl-phenyl) -2,3-dimethyldiazabutadienpalladiumdimethyl,
Di (2,6-di-i-propyl-phenyl) -2,3-dimethyldiazabutadiennickeldimethyl,
Di (2,6-dimethyl-phenyl) -2,3-dimethyldiazabutadienpalladiumdichlorid,
Di (2,6-dimethyl-phenyl) -2,3-dimethyldiazabutadiennickeldichlorid,
Di (2,6-dimethyl-phenyl) -2,3-dimethyldiazabutadienpalladiumdimethyl,
Di (2,6-dimethyl-phenyl) -2,3-dimethyldiazabutadiennickeldimethyl,
Di (2-methyl-phenyl) -2,3-dimethyldiazabutadienpalladiumdichlorid,
Di (2-methyl-phenyl) -2,3-dimethyldiazabutadiennickeldichlorid,
Di (2-methyl-phenyl) -2,3-dimethyldiazabutadienpalladiumdimethyl,
Di (2-methyl-phenyl) -2,3-dimethyldiazabutadiennickeldimethyl,
Diphenyl-2,3-dimethyldiazabutadienpalladiumdichlorid,
Diphenyl-2,3-dimethyldiazabutadiennickeldichlorid,
Diphenyl-2,3-dimethyldiazabutadienpalladiumdimethyl,
Diphenyl-2,3-dimethyldiazabutadiennickeldimethyl,
Di (2,6-dimethyl-phenyl) -azanaphtenpalladiumdichlorid,
Di (2,6-dimethyl-phenyl) -azanaphtennickeldichlorid,
Di (2,6-dimethyl-phenyl) -azanaphtenpalladiumdimethyl,
Di (2,6-dimethyl-phenyl) -azanaphtennickeldimethyl,
1,1'-Dipyridylpalladiumdichlorid,
1,1'-Dipyridylnickeldichlorid,
1,1'-dipyridyl palladium dimethyl or
1,1'-Dipyridylnickeldimethyl.

Particularly suitable connections (IVe) are those described in J. Am. Chem. Soc. 120, pp. 4049 ff. (1998), J. Chem. Soc., Chem. Commun. 1998, 849. As preferred Complexes with ligands (IVe) can be 2,6-bis (imino) pyridyl complexes of transition metals Use Fe, Co, Ni, Pd or Pt, especially Fe.

As the organic transition metal compound D) can also iminophenolate complexes are used, the ligands for example starting from substituted or unsubstituted Salicylaldehydes and primary Amines, especially substituted or unsubstituted arylamines, getting produced. Also transition metal complexes with Pi ligands that contain one or more heteroatoms in the Pi system, such as the Boratabenzolligand, the pyrrolyl anion or the phospholyl anion, can be used as organic transition metal compounds D) insert.

Transition metal compounds D) which are suitable according to the invention are also substituted monocyclopentadienyl, monoindenyl, monofluorenyl or heterocyclopentadienyl complexes of chromium, molybdenum or tungsten, at least one of the substituents on the cyclopentadienyl ring being a rigid, not only exclusively sp ^3- hybridized carbon or silicon atom Carries donor function. The most direct link to the donor function contains at least one sp or sp ² hybridized carbon atom, preferably one to three sp ² hybridized carbon atoms. The direct link preferably contains an unsaturated double bond, an aromatic or forms a partially unsaturated or aromatic heterocyclic system with the donor.

The cyclopentadienyl ring in these transition metal compounds can also be a heterocyclopentadienyl ligand, ie at least one C atom can also be replaced by a hetero atom from group 15 or 16. In this case, a C ₅ ring carbon atom is preferably replaced by phosphorus. In particular, the cyclopentadienyl ring is substituted with further alkyl groups, which can also form a five or six-membered ring, such as, for example, tetrahydroindenyl, indenyl, benzindenyl or fluorenyl.

An element of come as a donor 15th or 16th group of the periodic table containing neutral functional Groups, e.g. Amine, imine, carboxamide, carboxylic acid ester, ketone (oxo), ether, Thioketone, phosphine, phosphite, phosphine oxide, sulfonyl, sulfonamide, or unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring systems into consideration.

eingesetzt, worin
M^C Chrom, Molybdän oder Wolfram bedeutet und
Z^C durch die folgende allgemeine Formel (Va)

beschrieben ist, worin die Variablen folgende Bedeutung besitzen:
E^1C–E^5C Kohlenstoff oder, für maximal ein Atom E^1C bis E^5C, Phosphor oder Stickstoff,
A^C -NR^5CR^6C, -PR^5CR^6C, -OR^5C, -SR^5C oder ein unsubstituiertes, substituiertes oder kondensiertes, partiell ungesättigtes heterocyclisches oder heteroaromatisches Ringsystem,
R^C eine der folgenden Gruppen:

und zusätzlich, falls A^c ein unsubstituiertes, substituiertes oder kondensiertes, partiell ungesättigtes heterocyclisches oder heteroaromatisches Ringsystem ist, auch

wobei
L^1C, L^2C Silicium oder Kohlenstoff bedeutet,
k^C 1 oder, wenn A^1c ein unsubstituiertes, substituiertes oder kondensiertes, partiell ungesättigtes heterocyclisches oder heteroaromatisches Ringsystem ist, auch 0 ist,
X^C unabhängig voneinander Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, C₂-C₁₀- Alkenyl, C₆-C₂₀-Aryl, C₇-C₄₀-Alkylaryl, -NR^15CR^16C, -OR^15C, -SR^15C, -SO₃R^15C, -OC(O)R^15C, -CN, -SCN, β-Diketonat, -CO, BF₄ ^–, PF₆ ^– oder sperrige nichtkoordinierende Anionen bedeuten,
R^1C–R^16C unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, C₇-C₄₀-Alkylaryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6-20 C-Atomen im Arylrest, SiR^17C ₃, wobei die organischen Reste R^1B-R^16B auch durch Halogene substituiert sein können und je zwei geminale oder vicinale Reste R^1C-R^16C auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können,
R^17C unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, ₆-C₂₀-Aryl, C₇-C₄₀-Alkylaryl, und je zwei geminale Reste R^17C auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können,
n^c 1, 2 oder 3 und
m^C 1, 2 oder 3 bedeuten.Substituted monocyclopentadienyl, monoindenyl, monofluorenyl or heterocyclopentadienyl complexes of the general formula (V) are preferred

used where
M ^{C means} chromium, molybdenum or tungsten and
Z ^C by the following general formula (Va)

in which the variables have the following meaning:
E ^1C –E ^5C carbon or, for a maximum of one atom E ^1C to E ^5C , phosphorus or nitrogen,
A ^C -NR ^5C R ^6C , -PR ^5C R ^6C , -OR ^5C , -SR ^5C or an unsubstituted, substituted or condensed, partially unsaturated heterocyclic or heteroaromatic ring system,
R ^C one of the following groups:

and additionally, if A ^{c is} an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system, also

in which
L ^1C , L ^{2C means} silicon or carbon,
k ^C 1 or, if A ^{1c is} an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system, is also 0,
X ^C independently of one another fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ alkylaryl, -NR ^15C R ^16C , -OR ^15C , -SR ^15C , -SO ₃ R ^15C , -OC (O) R ^15C , -CN, -SCN, β-diketonate, -CO, BF ₄ ^- , PF ₆ ^- or bulky non-coordinating anions,
R ^1C -R ^16C independently of one another hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ alkylaryl, alkylaryl with 1 to 10 carbon atoms in the Alkyl radical and 6-20 C atoms in the aryl radical, SiR ^17C ₃ , where the organic radicals R ^1B -R ^{16B can} also be substituted by halogens and two geminal or vicinal radicals R ^1C -R ^16C also to form a five- or six-membered ring can be connected
R ^17C independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, ₆ -C ₂₀ -aryl, C ₇ -C ₄₀ -alkylaryl, and two geminal radicals R ^17C also form a five- or six-membered ring can be connected
n ^c 1, 2 or 3 and
m is ^C 1, 2 or 3.

Chromium is particularly suitable as the transition metal M ^C.

Examples of organic transition metal compounds of the formula (V) are
1- (8-quinolyl) -2-methyl-4-methylcyclopentadienylchrom (III) dichloride,
1- (8-quinolyl) -3-isopropyl-5-methylcyclopentadienylchrom (III) dichloride,
1- (8-quinolyl) -3-tert-butyl-5-methylcyclopentadienylchrom (III) dichloride,
1- (8-quinolyl) -2,3,4,5-tetramethylcyclopentadienylchrom (III) dichloride,
1- (8-quinolyl) tetrahydroindenylchrom (III) dichloride,
1- (8-quinolyl) indenylchrom (III) dichloride,
1- (8-quinolyl) -2-methylindenylchrom (III) dichloride,
1- (8-quinolyl) -2-isopropylindenylchrom (III) dichloride,
1- (8-quinolyl) -2-ethylindenylchrom (III) dichloride,
1- (8-quinolyl) -2-tert.butylindenylchrom (III) dichloride,
1- (8-quinolyl) benzindenylchrom (III) dichloride,
1- (8-quinolyl) -2-methylbenzindenylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) - 2-methyl-4-methylcyclopentadienylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) - 2,3,4,5-tetramethylcyclopentadienylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) tetrahydroindenylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) indenylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) - 2-methylindenylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) - 2-isopropylindenylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) - 2-ethylindenylchrom (III) dichloride,
1- (8- (2-methylquinolyl)) - 2-tert.butylindenylchrom (III) dichloride,
1- (8- (2-Methylquinolyl)) benzindenylchrome (III) dichloride or
1- (8- (2-methylquinolyl)) - 2-methylbenzindenylchrom (III) dichloride.

The Production of Functional Cyclopentadienyl Ligands has been known for a long time. Different synthetic routes for this Complex ligands are e.g. by M. Enders et. al. in Chem. Ber. (1996), 129, 459-463 or P. Jutzi and U. Siemeling in J. Orgmet. Chem. (1995), 500, 175-185.

The metal complexes, in particular the chromium complexes, can be obtained in a simple manner if the corresponding metal salts, such as metal chlorides, are reacted with the ligand anion (for example analogously to the examples in DE-A 197 10 615 ).

worin die Variablen folgende Bedeutung haben:
R^D R^1DC=NR^2D, R^1DC=O, R^1DC=O(OR^2D), R^1DC=S, (R^1D)₂P=O, (OR^1D)₂P=O, SO₂R^1D, R^1DR^2DC=N, NR^1DR^2D oder BR^1DR^2D, C₁-C₂₀-Alkyl, C₁-C₂₀-Cycloalkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, C₇-C₄₀-Alkylaryl, Wasserstoff, falls dieser an ein Kohlenstoffatom gebunden ist, wobei die organischen Reste R^1D und R^2D auch inerte Substituenten tragen können,
X^D unabhängig voneinander Fluor, Chlor, Brom, Jod, -NR^3DR^4D, -NP(R^3D)₃, -OR³, -OSi(R³)₃, -SO₃R³, -OC(O)R^3D, β-Diketonat, BF₄ ^–, PF₆ ^–, oder sperrige schwach oder nicht koordinierende Anionen,
R^1D-R^4D unabhängig voneinander C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, C₇-C₄₀-Alkylaryl, Wasserstoff, falls dieser an ein Kohlenstoffatom gebunden ist, wobei die organischen Reste R^1D bis R^4D auch inerte Substituenten tragen können,
n^D 1 oder 2,
m^D 1, 2 oder 3 ist, wobei m^1D entsprechend der Wertigkeit von Cr den Wert aufweist, bei dem der Metallocenkomplex der allgemeinen Formel (VI) ungeladen vorliegt,
L^D ein neutraler Donor und
y^D 0 bis 3.Transition metal compounds D) which are suitable according to the invention are also imidochrome compounds of the general formula (VI),

where the variables have the following meaning:
R ^D R ^1D C = NR ^2D , R ^1D C = O, R ^1D C = O (OR ^2D ), R ^1D C = S, (R ^1D ) ₂ P = O, (OR ^1D ) ₂ P = O, SO ₂ R ^1D , R ^1D R ^2D C = N, NR ^1D R ^2D or BR ^1D R ^2D , C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C _20- aryl, C ₇ -C ₄₀ -alkylaryl, hydrogen, if this is bound to a carbon atom, where the organic radicals R ^1D and R ^{2D can} also carry inert substituents,
X ^D independently of one another fluorine, chlorine, bromine, iodine, -NR ^3D R ^4D , -NP (R ^3D ) ₃ , -OR ³ , -OSi (R ³ ) ₃ , -SO ₃ R ³ , -OC (O) R ^3D , β-diketonate, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ^1D -R ^4D independently of one another C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ alkylaryl, hydrogen, if this is bonded to a carbon atom, where the organic radicals R ^1D to R ^{4D can} also carry inert substituents,
n ^D 1 or 2,
m ^{D is} 1, 2 or 3, m ^1D corresponding to the valence of Cr having the value at which the metallocene complex of the general formula (VI) is uncharged,
L ^{D is} a neutral donor and
y ^D 0 to 3.

Such connections and their production are e.g. described in WO 01/09148.

Other suitable organic transition metal compounds D) are transition metal complexes with a tridentate macrocyclic ligand such as
[1,3,5-tri (methyl) -1,3,5-triazacyclohexane] chromium trichloride,
[1,3,5-tri (ethyl) -1,3,5-triazacyclohexane] chromium trichloride,
[1,3,5-tri (octyl) -1,3,5-triazacyclohexane] chromium trichloride,
[1,3,5-tri (dodecyl) -1,3,5-triazacyclohexane] chromium trichloride and
[1,3,5-tri (benzyl) -1,3,5-triazacyclohexane] chromium trichloride,

As component D) can also Mixtures of different organic transition metal compounds used become.

Furthermore, preferred catalyst systems according to the invention contain, in addition to the supported cocatalyst and the organo transition metal compound, at least one organometallic compound E). Suitable organometallic compounds E) are those of the general formula (VII), M ¹ (R ¹ ) _r (R ² ) _s (R ³ ) _t (VII) in the
M ¹ denotes an alkali metal, an alkaline earth metal or a metal from the 13th group of the periodic table, ie boron, aluminum, gallium, indium or thallium,
R ^{1 is} hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, halo C ₁ -C ₁₀ alkyl, halo C ₆ -C ₁₅ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₁ -C ₁₀ -alkoxy or halo-C ₇ -C ₄₀ -alkylaryl, halo-C ₇ -C ₄₀ -arylalkyl or halo-C ₁ -C ₁₀ -alkoxy,
R ² and R ^{3 are} hydrogen, halogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, halogen C ₁ -C ₁₀ alkyl, halogen C ₆ -C ₁₅ aryl, C ₇ -C ₄₀ Arylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₁ -C ₁₀ -alkoxy or halo-C ₇ -C ₄₀ -alkylaryl, halo-C ₇ -C ₄₀ -arylalkyl or halo-C ₁ -C ₁₀ -alkoxy,
r is an integer from 1 to 3
and
s and t are integers from 0 to 2, the sum r + s + t corresponding to the valence of M ¹ .

Mixtures of different types can also be used Metal compounds of formula (VII) are used.

Of the metal compounds of the general formula (VII), those are preferred in which
M ^{1 means} lithium, boron, magnesium or aluminum and
R ¹ , R ² and R ^{3 are} C ₁ -C ₁₀ alkyl.

Particularly preferred metal compounds of the formula (VII) are n-butyllithium, n-butyl-n-octymagnesium, n-butyl-n-heptylmagnesium, Triphenyl aluminum, triisoprene aluminum, tri-n-octyl aluminum, tri-n-hexyl aluminum, Tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-propyl aluminum, Tri-iso-propyl aluminum, triethyl aluminum, trispentafluorophenylborane and trimethyl aluminum and mixtures thereof.

Mixtures of different types can also be used Metal compounds of formula (VII) are used.

In the production of the catalyst systems according to the invention is usually first the supported cocatalyst obtainable from components A), B) and C) manufactured and then this with the organic transition metal compound D) contacted. When using an organometallic compound E) you can do this first with the organo transition metal compound D) contact and then the reaction product with the supported cocatalyst react. It can however also components D) and E) in succession in any Order with the worn Cocatalyst are combined. It is also possible that the organometallic compound E) in the polymerization in the polymerization reactor with the the implementation of the supported Cocatalyst with the organic transition metal compound D) catalyst solid obtained is contacted, wherein however, it is still possible is an organometallic compound in the preparation of the catalyst solid E}, the same or different from that in the polymerization reactor added organometallic compound E) can be used.

Usually the components are combined in the presence of an organic one Solvent, in which the carrier, the carrier's reaction products or the resulting catalyst test substance is suspended. suitable solvent are aromatic or aliphatic solvents, such as Hexane, heptane, toluene or xylene or halogenated hydrocarbons, such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.

The order of joining the components are arbitrary. All components can be used individually be added in succession. It is also possible that first individual components together are mixed and then these mixtures with other mixtures and / or individual components are brought into contact.

The assembly of the components usually takes place at temperatures in the range of -20 ° C to 150 ° C and preferably in the range of 0 ° C up to 80 ° C. The time you put the components in contact with each other can react, is in the Usually from 1 minute to 48 hours. Response times are preferred from 10 minutes to 6 hours.

The molar ratio of organo transition metal compound D) to compound A) is usually from 1: 0.1 to 1: 1000 and preferably from 1: 1 to 1: 100.

When using an organometallic compound E) is the molar ratio from organometallic compound E) to organo transition metal compound D) usually from 800: 1 to 1: 1 and preferably from 200: 1 to 2: 1.

The one after contacting the supported cocatalyst with the organo transition metal compound and any other components that may be available are usually solid obtained as a moist solid or a suspension. This reaction product can as such, optionally with other components of the Catalyst system, are used for the polymerization of olefins. Usually however, the reaction product is worked up further, preferably by drying the solid. In the presence of a suspension the solid beforehand additionally, for example, by filtration, are separated from the liquid phase. The drying usually takes place at temperatures above the Room temperature. A vacuum is preferably applied during drying. The dried catalyst solid can be used as such or resuspended be used for the polymerization.

It is also possible to prepolymerize the catalyst solid first with α-olefins, preferably linear C ₂ -C ₁₀ -1-alkenes and in particular with ethylene or propylene, and then to use the resulting prepolymerized catalyst solid in the actual polymerization. The mass ratio of the catalyst solid used in the prepolymerization to the addition polymer is usually based monomer in the range of 1: 0.1 to 1: 200.

Furthermore, as an additive during or after making the worn Catalyst system a small amount of an olefin, preferably an α-olefin, for example vinylcyclohexane, styrene or phenyldimethylvinylsilane, as a modifying component, an antistatic or a suitable one inert compound such as a wax or oil can be added. The molar relationship of additives to organic transition metal compounds A) is usually from 1: 1000 to 1000: 1, preferably from 1: 5 to 20: 1.

The polymerization can be done in a known manner Way in bulk, in suspension, in the gas phase or in a supercritical Medium in the usual, for the Polymerization of olefins used reactors are carried out. It can be carried out discontinuously or preferably continuously in one or several stages. There are solution processes, suspension processes, stirred Gas phase process or gas phase fluidized bed process into consideration. As a solvent or suspending agents inert hydrocarbons, for example isobutane, or else Monomers themselves can be used.

The polymerizations can take place at temperatures in the range of -60 to 300 ° C and press in the range of 0.5 to 3000 bar. Are preferred Temperatures in the range from 50 to 200 ° C, in particular from 60 to 100 ° C, and pressures in the range from 5 to 100 bar, in particular from 15 to 70 bar. The middle ones Residence times are usually from 0.5 to 5 hours, preferably from 0.5 to 3 hours. It can at the polymerization also includes molecular weight regulators, for example hydrogen, or usual Additives such as antistatic agents can also be used.

The manufacturing method according to the invention from worn Cocatalyst is characterized in that it is not very expensive. The Procedure allows it, with a reduced amount of expensive feedstocks such as boron Compounds or transition metal compounds or with cheaper feedstocks catalyst systems with a good polymerization activity manufacture. Furthermore enables it is also possible to produce catalyst systems with an increased polymerization activity.

Examples

example 1

a) Synthesis of the supported cocatalyst

1.58 g of silica gel (XPO 2107, from Grace; 8 h at 130 ° C dried) were suspended in 15 ml of toluene at ambient temperature and mixed with 2.9 ml of triethyl aluminum (1.9 M in toluene, 5.6 mmol). The suspension was stirred for 30 minutes and then 1.18 g (5.6 mmol) of pentafluorophenylboronic acid was added. The reaction mixture was about Stirred at night and then filtered off. The residue was washed 5 times with 20 ml of toluene and in an oil pump vacuum to constant weight dried. 2.89 g of a white free-flowing powder were obtained receive.

b) Support of the organo transition metal compound

556.9 mg of that in Example 1a) manufactured supported Cocatalyst were suspended in 7 ml of toluene and mixed with a solution of 30.8 mg (52.4 μmol) Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl added in 7 ml of toluene. The reaction mixture was for one hour touched and then filtered off. The residue was washed twice with 1 ml of toluene and in an oil pump vacuum dried.

c) polymerization

A dry 1 liter reactor was initially used Nitrogen and then rinsed with propylene and then filled with 350 g of propylene and 2 ml (4 mmol) of a 2 M triisobutylaluminum-hexane solution. Then were 91 mg of the catalyst solid prepared in Example 1 b) in by blowing with argon over a Lock placed in the reactor. The reaction mixture was on the polymerization temperature of 65 ° C heated and polymerized for 1 hour. The polymerization was started by venting the remaining propylene stopped. 295 g of a fine-grain polymer were obtained. The inside walls of the Reactor showed no deposits. The catalyst activity was 3.2 kg PP / g catalyst solid per hour.

Claims (8)

A process for preparing a supported cocatalyst for olefin polymerization which comprises A) a compound containing a three-coordinating element A ¹ is the 13th or 15th Group of the Periodic Table of the Elements, with B) reacting a carrier having functional groups, the compound A) being covalently bound to the carrier B), and then the reaction product with C) a compound of the general formula (I), (R ¹ ) _x -A ² - (OH) _y (I) wherein A ^{2 is} an atom of the 13th or 15th main group of the periodic table, which is different from the element A ¹ , R ^{1 is the} same or different and is, independently of one another, hydrogen, halogen, C ₁ -C ₂₀ -alkyl, C ₁ - C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ Haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ haloalkylaryl or an OSiR ₃ ² group in which R ^{2 is} identical or different and is hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ - C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ -Halogenarylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -Halogenalkylaryl means, y is 1 or 2 and x means 3 minus y, can react. The method of claim 1, wherein the compound A) has the general formula (11),

wherein A ^{1 is} an atom of the 13th or 15th main group of the periodic table, which is different from the element A ² , R ³ , R ⁴ and R ^{5 are the} same or different and independently of one another for hydrogen, halogen, C ₁ -C ₂₀ -Alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl , C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ haloalkylaryl or an OSiR ₃ ⁶ group in which R ^{6 is the} same or different and is hydrogen, halogen, C ₁ -C ₂₀ Alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl , C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, or C ₇ -C ₄₀ haloalkylaryl, and the functional groups of the support B) are those with active hydrogen. The method of claim 1 or 2, wherein one of the elements A ¹ and A ^{2 is} aluminum and the other is boron. Process according to claims 1 to 3, wherein a carrier B) with active hydrogen-containing functional groups with compounds A) of the formula (II '),

in which R ³ , R ⁴ and R ^{5 are} identical or different and independently of one another are C ₁ -C ₆ alkyl, and the reaction product is then reacted with a compound C) of the general formula (I '), (R ¹ ) _x -B- (OH) _y (I ') wherein R ^{1 is the} same or different and is independently hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl , C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ haloalkylaryl, y is 1 or 2 and x 3 minus y means to react. supported Cocatalyst available by a method according to claims 1 to 4. Use of a manufactured according to claims 1 to 4 supported Cocatalyst for the production of a catalyst system for polymerization of olefins. Catalyst system for the polymerization of olefins, obtainable by Contact at least one supported cocatalyst after Claim 6 with D) at least one organic transition metal compound and e) optionally an organometallic compound, Process for the polymerization of olefins, using a catalyst system according to claim 7.