DE10232083A1 - Preparing catalyst for olefin polymerization, involves contacting organic transition metal compound(s) and mixture of organometallic compounds, and further contacting resulting mixture with cation-forming compound(s) - Google Patents

Abstract

At least one organic transition metal compound (A) is contacted with a mixture of at least two different organometallic compounds (B). The resulting mixture is further contacted with a cation-forming compound (C), to obtain a catalyst. Independent claims are included for the following: (1) use of catalyst for polymerization of olefins; (2) catalyst; and (3) polymerization of olefin using catalyst.

Description

The present invention relates to Process for the preparation of a catalyst for olefin polymerization, available by contacting at least one organic transition metal compound, one Mixture of at least two different organometallic compounds and at least one cation-forming compound, the use of the catalyst for olefin polymerization, catalysts available after these processes and processes for polymerizing olefins, where these catalysts 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 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). Farther can Compounds are also used as cocatalysts, the organo transition metal compounds convert into cationic complexes.

In the manufacture of catalysts for the Olefin polymerization based on organic transition metal compounds become common the organic transition metal compounds first reacted with an organometallic compound such as an aluminum alkyl, before working with the other components of the catalyst such as cocatalysts or carriers be brought into contact. This has been particularly difficult soluble metal compounds shown that a A number of problems such as deposit formation in the reactor or one not sufficient activity of the catalyst can occur.

The invention was therefore the object is based on a process for the preparation of catalysts for olefin polymerization to find that is inexpensive and to catalysts with a increased polymerization leads or a smaller amount of expensive with the same polymerization activity Starting materials such as boron-containing compounds or transition metal compounds needed. At the same time, polymerization should also be possible without the formation of reactor coatings.

• A) mindestens einer Organoübergangsmetallverbindung,
• B) einer Mischung aus mindestens zwei verschiedenen Organometallverbindungen und
• C) mindestens einer kationenbildenden Verbindung,

wobei man die Organoübergangsmetallverbindung A) zunächst mit der Mischung der Organometallverbindungen B) in Kontakt bringt, gefunden.Accordingly, a process for producing an olefin polymerization catalyst obtainable by contacting

• A) at least one organic transition metal compound,
• B) a mixture of at least two different organometallic compounds and
• C) at least one cation-forming compound,

wherein the organo transition metal compound A) is first brought into contact with the mixture of the organometallic compounds B).

Furthermore, the use of the Catalyst for olefin polymerization, catalysts available after these processes and processes for polymerizing olefins, where these catalysts are used, found.

The catalysts prepared according to the invention are suitable for the polymerization of olefins and especially 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 α-olefins. Particularly preferred α-olefins are linear or branched C ₂ -C ₁₂ -1-alkenes, in particular linear C ₂ -C ₁₀ -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 catalysts of 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 principle, all organic group-containing compounds of the transition metals of the 3rd to 12th group of the Periodic Table or of the lanthanides are suitable as organo transition metal compound A), which preferably have catalytic activity for olefin polymerization after reaction with components B) and C) form lysators. These are usually compounds in which at least one monodentate or multidentate ligand is bonded to the central atom via a sigma or pi bond. Suitable ligands are both those which contain cyclopentadienyl radicals and those which are free of cyclopentadienyl radicals. Chem. Rev. 2000, Vol. 100, No. 4 describes a large number of such compounds A) which are suitable for olefin polymerization. Polynuclear cyclopentadienyl complexes are also suitable for olefin polymerization.

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 unsub stituierten 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 (I) 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 ₂, -N(SiR^8A ₃)₂, -OR^8A, -OSiR^8A ₃, -SiR^8A ₃, wobeidie 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-C_{1 5}-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, -OR^14A, -OSiR^14A ₃, -SiR^14A3, 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^14A gleich oder verschieden C₁-C₁₀-Alkyl, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryloxy sein kann,
oder wobei die Reste R^4A und Z^A gemeinsam eine Gruppierung -R^15A _vA-A^A- bilden, in der
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-Anlalkylgruppe, eine C₈-C₄₀-Arylalkenylgruppe oder eine C₇-C_{4 0}-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^20A)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 A) 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 A) with at least one cyclopentadienyl type ligand, those of the general formula (I) 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 group, in which
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 has} the value at which the metallocene complex of the general formula (I) is uncharged, corresponding to the valency of M,
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 ₂ , -N (SiR ^8A ₃ ) ₂ , -OR ^8A , -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 _{1 5} 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 , -OR ^14A , -OSiR ^14A ₃ , -SiR ^14A 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 a preferably five-, six- or seven-membered heterocycle which has at least one atom from the group N, P, O or S. contains, can be connected, whereby
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 aryloxy,
or wherein the radicals R ^4A and Z ^A together form a grouping -R ^15A _v AA ^A -, in which
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 ) -, where
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 analalkyl group, a C ₈ -C ₄₀ -arylalkenyl group or a C ₇ -C _{0 4} -alkylaryl group or two adjacent radicals form, with the atoms connecting them form a 4 to 15 carbon atoms and having a saturated or unsaturated ring in each case, 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 ) 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 (I) 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 (I)

prefers.

Of the compounds of the formula (Ia), 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 form a substituted or unsubstituted unsaturated six-membered ring with the atoms connecting them.

Preferred metallocenes of the formula (Ib) 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 , 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 ₃ or Si (R ^8A ) ₃
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 (Ib) in which the cyclopentadienyl radicals are the same are.

Examples of particularly suitable compounds of the formula (Ib) 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 (Ic), 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 ^15A 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 alkyl aryloxy.

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 (Ic) are those of the formula (Ic ')

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 (Ic ') 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, where the following nomenclature applies to the place of substitution:

As preferred complex compounds (Ic ') 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 (Ic) and (Ic ') 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-trifluormethylphenyljindenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-4- [3 ', 5'-dimethylphenyljindenyl) 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.butylphenyljindenyl) 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) zirkoniumdi chloride,
Dimethylsilanediyl (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) - (2-methyl-4- [3 ', 5'-bis-tert.butylphenyljindenyl) 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 (Id), 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 -Si ^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 (Id) that are particularly suitable are those in the
M ^1A for titanium or chromium, preferably in oxidation state III and X ^A for chlorine, C ₁ -C ₄ alkyl or phenyl, or two radicals X ^A 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 -OR ^19A , -NR ^19A 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 A) 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 system 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, Nb, 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 A) suitable according to the invention are also transition metal complexes with at least one ligand of the general formulas (IIa) to (IIe),

wherein the transition metal is selected from the elements Ti, Zr, Hf, Sc, V, Nb, 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 ^9B , which can be the same or different within a ligand system of the formulas (IIa) to (IIe), represent the following groups:
R ^1B and R ^4B independently of one another for hydrocarbon or substituted hydrocarbon radicals, preference is given here to 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 (IIc) 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 (IIa) to (IId) are, for example, complexes of the transition metals Fe; Co, Ni, Pd or Pt with ligands of the formula (IIa). 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 (IIe) 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 (IIe) 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 A) 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 A) insert.

Transition metal compounds A) suitable according to the invention are also substituted monocyclopentadienyl, monoindenyl, monofluorenyl or heterocyclopentadienyl complexes of chromium, molybdenum or tungsten, with at least one of the substituents on the cyclopentadienyl ring having a rigid, not only exclusively via sp ³ hybridized carbon or silicon function bonded wearing. 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 (IIIa)

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^8C, -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, C₆-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 (III) are preferred

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

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 ^8C , -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, too

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, C ₆ -C ₂₀ -aryl, C ₇ -C ₄₀ -alkylaryl, and two geminal radicals R ^17C each 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 (III) 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(OR²⁰), 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, -OR^3D, -OSi(R^3D)₃, -SO₃R^3D, -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 (IV) ungeladen vorliegt,
L^D ein neutraler Donor und
y^D 0 bis 3.Transition metal compounds A) which are suitable according to the invention are also imidochrome compounds of the general formula (IV),

where the variables have the following meaning:
R ^D R ^1D C = NR ^2D , R ^1D C = O, R ^1D C = O (OR ²⁰ ), 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, it being possible for the organic radicals R ^1D and R ^{2D to} also carry inert substituents,
X ^D independently of one another fluorine, chlorine, bromine, iodine, -NR ^3D R ^4D , -NP (R ^3D ) ₃ , -OR ^3D , -OSi (R ^3D ) ₃ , -SO ₃ R ^3D , -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 having the value of Cr corresponding to the value at which the metallocene complex of the general formula (IV) is uncharged,
L ^{D is} a neutral donor and
y ^D 0 to 3.

Such connections and their production are z. B. described in WO 01/09148.

Other suitable organic transition metal compounds A) 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 A) can also Mixtures of different organic transition metal compounds used become.

Furthermore, the manufacture of the catalyst as component B) a mixture of at least two different organometallic compounds are used, the method according to the invention is characterized in that the metal compound A) first brought into contact with the mixture of organometallic compounds becomes.

Suitable organometallic compounds B) are those of the general formula (V), M ¹ (R ¹ ) _r (R ² ) _s (R ³ ) _t (V) 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 .

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

Particularly preferred metal compounds of the formula (V) are n-butyllithium, n-butyl-n-octymagnesium, n-butyl-n-heptylmagnesium, Triphenyl aluminum, truesoprene 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 or trimethyl aluminum.

It is also possible to the production of the catalyst component B) or parts of the components B) add in further steps of catalyst preparation, i.e. in addition to the reaction of the organic transition metal compound A) with the mixture of organometallic compounds B) an additional one Addition of individual organometallic compounds, for example the general formula (V), or of mixtures of organometallic compounds respectively.

As component C) in the production according to the invention the catalyst uses at least one cation-forming compound. Suitable cation-forming compounds are e.g. strong neutral Lewis acids, ionic Compounds with Lewis acid cations, ionic compounds with Bronsted acids as Cations or compounds of the alumoxane type. The cation-forming Connections are common also referred to as compounds forming metallocenium ions.

Compounds of the general formula (VI) are strong, neutral Lewis acids M ² X ¹ X ² X ³ (VI) preferred in the
M ^{2 is} an element of the 13th group of the Periodic Table of the Elements, in particular B, Al or G and preferably B, and
X ¹ , X ² and X ³ for hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C- Atoms in the aryl radical or fluorine, chlorine, bromine or iodine are particularly halogenaryl, preferably pentafluorophenyl.

More examples of strong, neutral Lewis acids are mentioned in WO 00/31090.

Particularly preferred are compounds of the general formula (VI) in which X ¹ , X ² and X ^{3 are the} same, preferably tris (pentafluorophenyl) borane.

Salt-like compounds of the cation of the general formula (VII) are ionic compounds with Lewis acid cations [(Y ^{a +} ) Q ₁ Q ₂ ... Q _z ] ^{d +} (VII) suitable in which
Y represents an element of the 1st to 16th group of the Periodic Table of the Elements,
Q ₁ to Q _z for single negatively charged radicals such as C ₁ -C ₂₈ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl, each having 6 to 20 C atoms in the aryl and 1 to 28 C -Atoms in the alkyl radical, C ₃ -C ₁₀ cycloalkyl, which can optionally be substituted with C ₁ -C ₁₀ alkyl groups, halogen, C ₁ -C ₂₈ alkoxy, C ₆ -C ₁₅ aryloxy, silyl or mercaptyl groups
a for integers from 1 to 6 and
z represents integers from 0 to 5,
d corresponds to the difference a - z, whereby d is greater than or equal to 1.

Carbonium cations are particularly suitable, Oxonium cations and sulfonium cations as well as cationic transition metal complexes. In particular, the triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocenyl cation to call. They preferably have non-coordinating counterions, in particular boron compounds as also mentioned in WO 91/09882 are, preferably tetrakis (pentafluorophenyl) borate.

Salts with non-coordinating anions can also be combined by combining a boron or aluminum compound, for example an aluminum alkyl, with a second compound which can link two or more boron or aluminum atoms by reaction, e.g. B. water, and a third compound which forms an ionizing ionic compound with the boron or aluminum compound, for example triphenylchloromethane. In addition, a fourth compound can also be used with the boron or aluminum compound acts, for example pentafluorophenol, can be added.

Ionic compounds with Bronsted acids as Cations preferably also have non-coordinating counterions. As a Bronsted acid in particular protonated amine or aniline derivatives are preferred. preferred Cations are N, N-dimethylanilinium, N, N-dimethylcylohexylammonium and N, N-dimethylbenzylammonium and derivatives of the latter two.

Preferred ionic cation-forming Compounds are primarily N, N-dimethylanilinium tetrakis (pentafluorophenyl) borates, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate.

Two or more borate anions can also be connected to one another, as in the dianion [(C ₆ F ₅ ) ₂ BC ₆ F ₄ -B (C ₆ F ₅ ) ₂ ] ^-2 , or the borate anion can be bridged with a suitable one functional group on the support surface.

Other suitable cation-forming Compounds are listed in WO 00/31090.

Suitable cation-forming compounds of the aforementioned types are, for example, also by implementation of organometallic compounds containing organic compounds at least one active hydrogen-containing functional group, available. examples for are suitable functional groups of the organic compounds Hydroxyl groups, primary and secondary Amino groups, mercapto groups, silanol groups, carboxyl groups, Amido groups or imido groups, with hydroxyl groups being preferred are.

Preferred organic compounds with hydroxyl groups are in particular those of the general formula (VIII), (R ⁴ ) _x -A- (OH) _y (VIII) in which
A is an atom of the 13th, 14th or 15th main group of the periodic table or a group consisting of 2 to 20 carbon atoms, preferably an atom of the 13th main group of the periodic table, in particular boron or aluminum, or a partially or completely halogenated C ₁ -C Is ₂₀ alkyl or C ₆ -C ₄₀ aryl group and is particularly preferably an atom of the 13th main group of the periodic table, preferably boron or aluminum and in particular boron,
R ^{4 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 or C ₇ -C ₄₀ haloalkylaryl or R ^{4 is} an OSiR ₃ ⁵ group is wherein
R ^{5 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 ^{4 is} 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 stands,
y is at least 1 and preferably 1 to 5, in particular 1 or 2 and very particularly preferably 1, and
x is an integer from 0 to 41, where x is particularly preferably 2 if y is 1 or 1 if y is 2.

Examples of preferred compounds of the formula (VIII) are boric acids of the formula R ⁴ ₂ B (OH) or boronic acids of the formula R ⁴ B (OH) ₂ .

Preferred organic compounds with hydroxyl groups are also compounds with partially or fully fluorinated aryl groups, such as pentafluorophenol or nonafluorodiphenyl-1-ol or dihydroxoctafluorodiphenyl. Such compounds C) can also be used in the form of an adduct with 1 to 10 parts of water. These are then preferably compounds which contain two OH groups, for example 4,4'-dihydroxyoctafluorodiphenyl · (s · H ₂ O), 1,2-dihydroxyoctafluorodiphenyl · (s · H ₂ O), 1,8-dihydroxyhexafluoronaphtaline · (S · H ₂ O) or 1,2-dihydroxyhexafluoronaphtaline · (s · H ₂ O), where s is a number from 1 to 10.

From the organic compounds with functional hydrogen-containing functional groups are suitable cation-forming compounds, in particular by reaction with organoaluminum compounds and particularly preferably available with aluminum trialkyls.

The amount of strong, neutral Lewis acids, ionic Compounds with Lewis Acidic Cations or Ionic Compounds with Brönsted acids as Cations preferably 0.1 to 20 equivalents, preferably 1 to 10 equivalents, based on the organic transition metal compound.

wobei
R⁶ eine C₁-C₄-Alkylgruppe bedeutet, bevorzugt eine Methyl- oder Ethylgruppe und
m für eine ganze Zahl von 5 bis 30, bevorzugt 10 bis 25 steht.As compounds of the alumoxane type, for example, the compounds described in WO 00/31090 can be used. Open-chain or cyclic alumoxane compounds of the general formulas (IX) or (X) are particularly suitable.

in which
R ^{6 represents} a C ₁ -C ₄ alkyl group, preferably a methyl or ethyl group and
m represents an integer from 5 to 30, preferably 10 to 25.

The preparation of these oligomeric Alumoxane compounds are usually made by implementing a solution of trialkyl aluminum with water. As a rule, they are included obtained oligomeric alumoxane compounds as mixtures long, both linear and cyclic chain molecules, so that m is to be regarded as the mean. The alumoxane compounds can also in a mixture with other metal alkyls, preferably with aluminum alkyls available.

Furthermore, instead of the alumoxane compounds of the general formulas (IX) or (X) also modified alumoxanes are used, some of which contain hydrocarbon residues or hydrogen atoms through alkoxy, aryloxy, siloxy or amide radicals are replaced.

It has proven to be beneficial the organic transition metal compounds and to use the alumoxane compounds in such amounts that the atomic relationship between aluminum from the alumoxane compounds and the transition metal from the organic transition metal compound in the range from 10: 1 to 1000: 1, preferably from 20: 1 to 500: 1 and is in particular in the range from 30: 1 to 400: 1.

You can also mix all of them beforehand mentioned cation-forming compounds are used. preferred Mixtures contain alumoxanes, especially methylalumoxane, and an ionic compound, especially one that contains the tetrakis (pentafluorophenyl) borate anion contains and / or a strong neutral Lewis acid, especially tris (pentafluorophenyl) borane.

Preferably both the organic transition metal compound as well as the cation-forming compound in a solvent used, wherein aromatic hydrocarbons having 6 to 20 carbon atoms, in particular Xylenes and toluene are preferred.

In a preferred embodiment of the method according to the invention is used to prepare the olefin polymerization catalyst Component D) at least one carrier used. These are preferably finely divided Carrier, which is any organic or inorganic, inert solid could be. In particular, the carrier component D) a porous carrier such as talc, a layered silicate, an inorganic oxide or a fine particle Be polymer powder.

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 be subjected to a thermal treatment, for example to remove adsorbed water. Such a drying treatment is generally carried out at temperatures in the range from 80 to 300 ° C., preferably from 100 to 200 ° C., the drying preferably taking place under vacuum and / or in an inert gas stream, for example with nitrogen or argon. The inorganic carrier can also be calcined, in which case the concentration of the OH groups on the surface is adjusted by treatment at temperatures from 200 to 1000 ° C. and the structure of the solid is changed if necessary. The carrier can also be treated chemically, using conventional drying agents such as metal alkyls, preferably aluminum alkyls, chlorosilanes or SiCl ₄ , but also methylalumoxane sentence can come. Appropriate treatment methods are described, for example, in WO 00/31090.

The inorganic carrier material can also be chemically modified. For example, the treatment of silica gel with NH ₄ SiF _{6 leads} to fluorination of the silica gel surface or the treatment of silica gels with silanes which contain groups containing nitrogen, fluorine or sulfur gives correspondingly modified silica gel surfaces.

Other possible carrier materials are fine particles Polymer powder, for example from polyolefins such as polyethylene or Polypropylene or polystyrene. You should preferably before Use of adhering moisture, solvent residues or others Contamination by appropriate cleaning or drying operations be freed. It can also functionalized polymer carriers, z. B. on the basis of polystyrenes, are used on the functional groups, for example ammonium or hydroxyl groups, at least one of the catalyst components can be fixed.

In a further preferred embodiment, at least one Lewis base is used as component E). Suitable Lewis bases generally have the formula (XI) M ³ R ⁶ R ⁷ R ⁸ (XI) where
R ⁶ , R ⁷ and R ^{8 are the} same or different and represent a hydrogen atom, a C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ Haloaryl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ arylalkyl group, preferably one and two radicals or all three radicals R ³ , R ⁴ and R ⁵ via C ₂ -C ₂₀ carbon units with one another can be connected
M ^{3 is} an element of the 15th group of the Periodic Table of the Elements

R ⁶ , R ⁷ and R ⁸ are preferably C ₁ -C ₂₀ alkyl, C ₆ -C ₄₀ aryl or C ₇ -C ₄₀ alkylaryl. At least one R ⁶ , R ⁷ or R ⁸ is particularly preferably a C ₇ C ₄₀ arylalkyl group, for example benzyl.

M ³ is preferably nitrogen or phosphorus and especially nitrogen.

Examples of components used as component E) Lewis bases are methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, Diphenylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline or N, N-dimethylcyclohexylamine. Particularly preferred Lewis bases are, for example, benzylamine, N-benzyldimethylamine, N-benzyldiethylamine, N-benzylbutylamine, N-benzyl-tert-butylamine, N'-benzyl-N, N-dimethylethylenediamine, N-benzylethylenediamine, N-benzylisopropylamine, N-benzylmethylamine, N-benzylethylamine, N-benzyl-1-phenylethylamine, N-benzyl-2-phenylethylamine or N-benyl piperazine.

Is preferred when using a Lewis base E) this first with the carrier implemented and the modified carrier with the other components brought into contact.

The manufacturing method according to the invention the catalysts are made by contacting components A) to C) and optionally D) and E) in any order, wherein all components can be added individually one after the other however also possible is that initially individual Components are mixed together and then these mixtures brought into contact with other mixtures and / or individual components provided, however, that the metal compound A) first combined with the mixture of organometallic compounds B) is before the reaction product with another component or a mixture of further components of the catalyst in contact brought.

A preferred course of action at the contacting is with the organic compound at least an active hydrogen-containing functional group C) initially with the organometallic compound B), with a subset of the organometallic compound B) or, when using a mixture of different organometallic compounds, in contact with at least one of the components of component B) bring to.

Usually the components are combined in the presence of an organic one Solvent, in which the carrier D) used with preference, the reaction products of the carrier or the resulting catalyst solids are 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 assembly of the components usually takes place at temperatures in the range from -20 ° C to 150 ° C and preferably in the range of 0 ° C up to 100 ° C. If not when contacting the components all at the same time can be combined, the temperature in the individual steps be the same in each case. The temperature of each Steps can but also differ.

The time you get in touch components brought to react with each other is usually 1 minute up to 48 hours. Reaction times of 10 minutes to are preferred 6 hours. If the components are contacted step by step, are the response times for the individual steps usually from 1 minute to 6 hours and preferably from 10 minutes to 2 hours.

In what proportions are the components preferably used?

The molar ratio of any used Lewis base E) for cation-forming compound C) is preferred from 0.05: 1 to 2: 1, in particular from 0.1: 1 to 1: 1.

The molar ratio of organo transition metal compound A) Cation-forming compound C) is preferably from 1: 0.1 to 1: 1000 especially from 1: 1 to 1: 100.

When using a support D), it is 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 copolymerized monomer is usually in the range from 1: 0.1 to 1: 200.

Furthermore, as an additive during or after making a supported one Catalyst a small amount of an olefin, preferably a? -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. Solution procedures, 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 characterized by catalysts for olefin polymerization from that it is less expensive and can be achieved with a reduced amount expensive feedstocks such as transition metal compounds or boron-containing compounds to produce catalysts with a good polymerization activity. In particular, it is used to manufacture catalysts for olefin polymerization suitable for the preparation of organic transition metal compounds with low solubility in usual solvents be used. Furthermore enables it also to produce catalysts with an increased polymerization activity.

Examples

example 1

a) Synthesis of the supported cocatalyst

5 ml of trimethyl aluminum (2 M in toluene, 10 mmol) were placed in 45 ml of toluene. At -10 ° C were too this solution a solution of 7 g bis (pentafluorophenyl) borinic acid (20 mmol) in 50 ml toluene over 15 minutes slowly admitted. It was brought to room temperature and one Hour stirred. 7 g of silica gel (XPO 2107, Grace) were suspended in 30 ml of toluene and for this purpose 1.4 ml of N, N-dimethylbenzylamine were added at room temperature added. It was at 0 ° C chilled and slowly added the solution prepared above. Then was warmed to room temperature and stirred for 3 hours. The suspension was then filtered and washed with heptane. The Residue was in an oil pump vacuum dried to constant weight. The result was 11.2 g of one white Support material.

b) Support of the organo transition metal compound

To a suspension of 37 mg of dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl) -indenyl) zirconium dichloride (50 μmol) 250 μmol were dissolved in 25 ml of toluene Trimethyl aluminum (20% in a high-boiling dearomatized Hydrocarbon mixture) and 250 μmol triisobutylaluminum (20th % in a high-boiling dearomatized hydrocarbon mixture) was given and it was at 50 ° C. Stirred for 1 hour. Subsequently 2.2 g of that in Example 1a) were prepared at room temperature carrier added. The catalyst solution was stirred for 1 hour and then the solvent in an oil pump vacuum deducted. The result was an orange, free-flowing powder.

c) polymerization

A dry 16 liter reactor was first with nitrogen and then rinsed with propylene and then with 10 liters of liquid Propylene and 5 standard liters of hydrogen filled. 13.3 ml of triisobutyl aluminum were added (20% in a high-boiling dearomatized hydrocarbon mixture) added and the mixture was stirred for 15 minutes. Then were 0.23 g of the catalyst solid prepared in Example 1 b) suspended in 20 ml of heptane and over a lock was placed in the reactor, rinsing with 15 ml of heptane. The reaction mixture was brought to the polymerization temperature of 65 ° C heated and polymerized for 1 hour. 1860 g of powdered polypropylene resulted. This corresponds to a productivity of 8.1 kg PP / g catalyst solid. The reactor showed no deposits on the inner wall and on the stirrer.

Comparative Example A

a) Synthesis of the supported cocatalyst

It was produced in Example 1a) supported Cocatalyst used.

b) Support of the organo transition metal compound

The procedure was as in Example 1 b) however, instead of the mixture of 250 µmol trimethyl aluminum and 250 µmol triisobutyl aluminum now 500 μmol Trimethyl aluminum used. The result was an orange, free flowing Powder.

c) polymerization

The polymerization was carried out as in Example 1c), however, 1.15 g of the in Comparative Example Ab) catalyst solid prepared used in 20 ml of heptane. 3610 g of powdery product resulted Polypropylene. This corresponds to a productivity of 3.1 kg PP / g catalyst solid. After the polymerization, deposits appeared on the inside of the reactor and on the stirrer.

Example 2

a) Catalyst synthesis

30 mg of dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride, 0.15 ml of triethyl aluminum and 0.26 ml of a 20% by weight solution of triisobutylaluminum in a high-boiling dearomatized hydrocarbon mixture were suspended in 20 ml of toluene and at 50 ° C until a clear one was obtained solution touched. Subsequently became the yellow solution brought to room temperature and with 0.69 ml of a 20 wt .-% solution of trimethyl aluminum in a high-boiling dearomatized Hydrocarbon mixture and 1 g of bis (pentafluorophenyl) boric acid added. After stirring for an hour 0.1 ml of dimethylbenzylamine was added and others Stir for 30 min the addition of 2 g of silica gel (XPO 2107 from Grace). After 1 h further stirring became the solvent in a vacuum at 50 ° C distilled off. The result was 3.09 g of a salmon-colored, flowable powder.

b) polymerization

A dry 2 l reactor was initially used Nitrogen and then rinsed with propylene and then with 1.5 l of liquid Filled with propylene. For this purpose, 3 ml of a 20 wt .-% solution of trüsobutylaluminum in a high-boiling dearomatized hydrocarbon mixture was added and it was Stirred for 15 minutes. Subsequently were 250 mg of the catalyst system prepared in Example 2a) suspended in 20 ml of heptane, and via a lock into the reactor given, rinsing with 15 ml of heptane. The reaction mixture was heated to the polymerization temperature of 65 ° C and polymerized for 1 hour. 450 g of powdery product resulted Polypropylene. This corresponds to a productivity of 1.8 kg PP / g catalyst solid or an activity of 2.4 kg PP / mmol B or 158 kg PP / mmol Zr x h. The reactor showed no toppings on the inner wall or on the stirrer.

Example 3

a) Catalyst synthesis

0.69 ml of trimethyl aluminum were in 10 ml of toluene and 1 g of bis (pentafluorophenyl) boric acid were added at room temperature. After stirring for an hour 0.1 ml of dimethylbenzylamine were added at room temperature and stirring was continued for 15 minutes. Subsequently became a solution of 30 mg of dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride, 0.15 ml triethyl aluminum and 0.26 ml triisobutyl aluminum in 20 ml of toluene added. After stirring for 15 minutes at room temperature 2.5 g of silica gel (XPO 2107 from Grace) were added and it was Stirred for 1 h at room temperature. Subsequently became the solvent in a vacuum at 50 ° C distilled off. The result was 3.57 g of a salmon-red, flowable powder.

b) polymerization

A dry 16 liter reactor was first with nitrogen and then rinsed with propylene and then with 10 liters of liquid Filled with propylene. For this purpose, 6 ml of a 20 wt .-% solution of trüsobutylaluminum in a high-boiling dearomatized hydrocarbon mixture was added and it was Stirred for 15 minutes. Subsequently 5 NL of hydrogen were metered in and it was again 15 minutes touched. 250 mg of the catalyst system prepared in Example 3a) were suspended in 20 ml of heptane, and via a lock into the reactor given, rinsing with 15 ml of heptane. The reaction mixture was heated to the polymerization temperature of 65 ° C and polymerized for 1 hour. The result was 2.1 kg powder Polypropylene. This corresponds to a productivity of 8.4 kg PP / g catalyst solid or an activity of 11 kg PP / mmol B or 740 kg PP / mmol Zr x h. The reactor showed no toppings on the inner wall or on the stirrer.

Example 4

a) Catalyst synthesis

1.5 g of silica gel (XPO 2107 from Grace) were suspended in 20 ml of toluene. After that, 0.15 ml of a 20% by weight solution of triethyl aluminum and 0.26 ml of a 20% by weight solution of Triisobutylaluminum in a high-boiling dearomatized hydrocarbon mixture added, then 30 mg of dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride and 0.2 ml of dimethylbenzylamine. Then was heated to 50 ° C and until a clear solution is obtained touched. A mixture of 1 g of bis (pentafluorophenyl) boric acid, 0.69, was added at room temperature ml of a 20% by weight solution of trimethyl aluminum in a high-boiling dearomatized Hydrocarbon mixture and 10 ml of toluene. After stirring for 1 h The solvent became room temperature in a vacuum at 50 ° C distilled off. 2.37 g of a salmon-colored, flowable powder were obtained.

b) polymerization

A dry 2 l reactor was initially used Nitrogen and then rinsed with propylene and then with 1.5 l of liquid Filled with propylene. For this purpose, 3 ml of a 20 wt .-% solution of trüsobutylaluminum in a high-boiling dearomatized hydrocarbon mixture was added and it was Stirred for 15 minutes. Subsequently were 250 mg of the catalyst system prepared in Example 4a) suspended in 20 ml of heptane, and via a lock into the reactor given, rinsing with 15 ml of heptane. The reaction mixture was heated to the polymerization temperature of 65 ° C and polymerized for 1 hour. The result was 169 g powder Polypropylene. This corresponds to a productivity of 0.7 kg PP / g catalyst solid or an activity of 0.6 kg PP / mmol B or 40 kg PP / mmol Zr x h. The reactor showed no toppings on the inner wall or on the stirrer.

Claims (10)

Process for the preparation of a catalyst for olefin polymerization, available by contacting A) at least one organic transition metal compound, B) a mixture of at least two different organometallic compounds and C) at least one cation-forming compound, in which the organic transition metal compound A) first less mixture of the organometallic compounds B) in contact. Process for the preparation of an olefin polymerization catalyst according to claim 1, wherein as a further component D) at least A carrier used becomes. Process for the preparation of an olefin polymerization catalyst according to claim 1 or 2, wherein as a further component E) at least a Lewis base is used. Process for the preparation of an olefin polymerization catalyst according to the claims 1 to 3, the cation-forming compound being a strong neutral Lewis acid an ionic compound with a Lewis acidic cation, an ionic compound with Bronsted acid as a cation or a compound is of the alumoxane type. Process for the preparation of an olefin polymerization catalyst according to the claims 1 to 4, wherein the cation-forming compound in the preparation of the catalyst by reacting a compound with at least an active hydrogen-containing functional group an organometallic compound is obtained. Process for the preparation of an olefin polymerization catalyst according to claim 5, characterized in that the connection with at least an active hydrogen-containing functional group Compound containing hydroxyl groups. Process for the preparation of an olefin polymerization catalyst according to claim 6, characterized in that the hydroxyl groups on a Element of the 13th, 14th or 15th main group of the periodic table bound are. Use of a manufactured according to claims 1 to 7 Catalyst for the polymerization of olefins. Catalyst available by a method according to claims 1 to 7. Process for the polymerization of olefins using a catalyst is used according to claim 9.