DE10017663A1 - Process for the preparation of a supported catalyst for the polymerization of olefins - Google Patents

Abstract

A method for the production of a supported catalyst for the polymerisation of olefins is characterised in that one or several compounds of general formula (Ia or b), together with a molecularly defined activator of general formula (IIa to c); [(L-H)]<+>[M')Q<1>Q<2>Q<3>Q<4>]- IIa [(Car3)]<+>[(M') Q<1>Q<2>Q<3>Q<4>]- IIb [(M')Q<1>Q<2>Q<3>] IIc are deposited on a porous support, containing 2 10 wt. % water.

Description

Process for the preparation of a supported catalyst for the polymerization of olefins, characterized in that one or more compounds of the general formulas Ia or b,

where the variables are defined as follows:
M is a transition metal of groups 5 to 10 of the periodic table of the elements,
A is selected from N, P or As,
A 'is selected from O or S,
Nu ¹ , Nu ² N or P,
X ¹ , X ² halogen or C ₁ -C ₄ alkoxy;
R ¹ , R ² unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-containing heteroaryl,
R ³ , R ^{4 are} hydrogen, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-halti Heteroaryl,
R ⁵ to R ⁷ are independently selected from hydrogen, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-containing heteroaryl, halogen, C ₁ -C ₆ alkoxy, NO ₂ , SiR ⁸ R ⁹ R ¹⁰ or OSiR ⁸ R ⁹ R ¹⁰ , adjacent residues forming a 5- to 10-membered compound with the inclusion of the parent body Ring can be connected
R ⁸ to R ¹⁰ are, independently of one another, independently of one another selected from hydrogen or unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl ;
together with a molecularly defined activator of the general formulas IIa to c

[(LH)] ⁺ [(M ') Q ¹ Q ² Q ³ Q ⁴ ] ^- IIa

[(CAr ₃ )] ⁺ [(M ') Q ¹ Q ² Q ³ Q ⁴ ] ^- IIb

[(M ') Q ¹ Q ² Q ³ ] IIc

where the variables have the following meaning:
[LH] ⁺ is a Brønsted acid, where L is an electroneutral Lewis base,
M 'is an element of group 13 of the Periodic Table of the Elements,
Q ¹ to Q ⁴ are independently selected from hydride, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or halide the restriction that at most two radicals Q ¹ and Q ² can be halide;
Ar is the same or different and is selected from unsubstituted or substituted C ₆ -C ₁₄ aryl,
deposits on a porous carrier material which contains 2 to 10% by weight of water and optionally further volatile constituents.

The present invention relates to a method for manufacturing of a supported catalyst for the polymerization of olefins. Furthermore, the present invention relates to a supported Catalyst, produced by the process according to the invention, and a process for the polymerization of olefins using tion of the catalyst according to the invention.

Polymers and copolymers of olefins are economically large of great importance because the monomers are easily accessible in large quantities Lich and because the polymers by variation of the Her  setting process or processing parameters in a wide range let vary. Special attention to the manufacturer driving applies the catalyst used. In addition to Ziegler Natta catalysts are different types of single-site catalysts tors of growing importance, with ne as central atoms ben Zr such as in metallocene catalysts (H.-H. Brintzinger et al., Angew. Chem. 1995, 107, 1255) also Ni or Pd (WO 96/23010) or Fe and Co (e.g. WO 98/27124) recently have been examined in more detail. The complexes of Ni, Pd, Fe and Co are also referred to as complexes of late transition metals.

Metallocene catalysts have for large-scale use Disadvantage. The catalysts are in contact with impurities the monomers available on an industrial scale, in the process gas and solvents used are very sensitive. As a distraction The following are, for example, moisture and oxygen and CO to call. Furthermore, the price for Zr as a central metal the technically important zirconocene very high.

During Ni or Pd complexes (WO 96/23010) the formation of high ver branched, less commercially interesting polymer catalysis ren, the use of Fe or Co complexes leads to formation of highly linear polyethylene. In G.J.P. Britovsek et al., J. Am. Chem. Soc. 1999, 121, 8728 and V.C. Gibson et al., J. Chem. Soc., Chem. Commun. 1998, 849 and in M. Brookhart et al., J. Am. Chem. Soc. 1998, 120, 4049 are polymerization-active complexes of Fe and Co with pyridyl-2,6-diimine ligands disclosed on Imine nitrogen are substituted with aryl groups. As Cokataly Ethers for ethylene polymerization are methylaluminoxane ("MAO") or modified methylaluminoxane ("MMAO") used, in which a certain percentage of the methyl groups are caused by Isobu tylgruppen was replaced.

However, the use of MAO or other aluminoxanes also has disadvantages:

• - MAO and other aluminoxanes must be in a large molar Excess are used, 100 to 100 times are usual Surpluses. This turns the cocatalyst into a signifi edge cost factor for the catalysts.
• - The catalysts activated with aluminoxanes are common usually active in polymerization in the current process, for example gas phase, solution, suspension or mass polymerization process, dosed and can lead to constipation, lead in particular in the metering lines.  
• - Aluminoxanes are molecularly undefined substances whose Ability to activate transition metal complexes strong depends on the manufacturing process and impurities. Wei the storage temperature and storage time play a role Role. Quality control is difficult.
• - Aluminoxanes must always be stored refrigerated because they otherwise tend to gel. Aluminoxan gels are called coka analyzers unsuitable.
• - Aluminoxanes are brought into the trade as solutions, the half has to transport a lot of otherwise worthless solvent become.
• - Aluminoxanes, especially those with C ₁ -C ₄ alkyl radicals, and their solutions are pyrophoric and require increased security.

For metallocenes, molecularly defined activators that do not have the above disadvantages have proven successful. For example, they are disclosed in EP-A 0 277 004, EP-A 0 468 537 and EP-A 0 561 479; further examples can be found in EP-A 0 426 638. These examples are salts with large, non-coordinating or only weakly coordinating anions such as, for example, the tetra-kispentafluorophenylborate anion, or strong Lewis acids such as B (C ₆ F ₅ ) ₃ (X. Yang et al., J. Am. Chem. Soc. 1991, 113, 3623). These salts are reacted with the dialkyl derivative of a tallocene. The elimination of an alkyl anion from the metallocene compound is accomplished by the counterion, which is either a Brønsted acid or a Lewis acid. It is important, however, that the metallocene dialkyl compounds commonly used are commercially available or else easily obtainable from the metallocene dichloride. This is often not the case with the corresponding complexes of late transition metals.

WO 98/27124 and WO 98/30612 relate to the polymerization of ethylene and propylene, in which case an Fe or Co complex of a tridentate pyridyldiimine ligand is first contacted with ethylene or propylene or another monomer; then MAO or an activator with a defined structure are added and finally an aluminum alkyl. The procedure is such that a complex of a late transition metal, in this case an Fe or Co complex in the presence of ethylene, is first mixed with aluminum trialkyl and then with a strong Lewis acid such as B (C ₆ F ₅ ) _3rd The low activity of the disclosed systems with 8 or 13 kg of polyethylene / (mol of Co) .h is disadvantageous. Such little active catalysts are unsuitable for technical processes.

WO 99/12981 relates to complexes of late transition metals with three dentate pyridyldiimine ligands as catalysts for the polymerization of 1-olefins. Example 29 shows the polymerization with a molecularly defined activator, especially a tetrakis pentafluorophenyl borate, and (trimethylsilylmethyl) magnesium chloride as alkylating agent. The trimethylsilylmethyl anion is sterically very demanding and must be chosen because it can prevent reductive elimination of the alkyl groups at the late transition metal. The procedure, which was also discussed in a lecture by VC Gibson at the conference "The VIII ^th International Conference on Organometallic Chemistry" from 16.-21. 08. 1998 in Munich was not technically sensible because the special reagents required for alkylation such as (trimethylsilylmethyl) magnesium chloride, trimethylsilylmethyl lithium or aluminum tris-trimethylsilylmethyl are very expensive.

So that complexes later transition metals with tridentate pyridyl diimine ligands in modern polymerization processes such as Suspen sionsverfahren, bulk polymerization process or gas phase ver can be used, it is necessary to drive them on a immobilize solid supports. Otherwise it can lead to Morpholo problems of the polymer (chunks, wall coverings, blockages in Pipes or heat exchangers) come to switch off the on location force.

WO 99/46304 relates to catalyst systems for polymerization and Copolymerization of olefins based on supported complexes later transition metals deposited on a solid support become. Aluminoxanes or. Are used as activators for the complexes molecularly defined activators used, silica gel, aluminum minium oxide or zirconium oxide as carrier materials especially before be moved. These backing materials must be manufactured before in a separate step from adsorbed water or others Substances that could damage the catalytic converter are exempted (Page 5, line 16). This additional step in catalysis However, goal preparation is complex, it takes time and one further apparatus for drying the carrier material.

So the task was

• - To provide the simplest possible process according to Supported catalysts for polymerization and copolymerization tion of Olefins Based on the Complexes Later About  transition metals and a molecularly defined activator can be put, commercially in large quantities Available and therefore inexpensive metal alkyl compounds can be used and
• - To polymerize olefins with the catalysts thus obtainable ren.

It has now been found that the object can be achieved by using water-containing carrier material with a water content of 2 to 10% by weight without thermal or chemical pretreatment. The method according to the invention can be described as follows:
One or more compounds of the general formulas Ia or Ib are used to prepare the catalyst:

in which the variables are defined as follows:
M is a transition metal of groups 5 to 10 of the periodic table of the elements,
A is selected from N, P or As,
A 'is selected from O or S,
Nu ¹ , Nu ² N or P,
X ¹ , X ² halogen or C ₁ -C ₄ alkoxy;
R ¹ , R ² unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-containing heteroaryl,
R ³ , R ^{4 are} hydrogen, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-halti Heteroaryl,
R ⁵ to R ⁷ are independently selected from hydrogen, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-containing heteroaryl, halogen, C ₁ -C ₆ alkoxy, NO ₂ , SiR ⁸ R ⁹ R ¹⁰ or OSiR ⁸ R ⁹ R ¹⁰ , adjacent residues forming a 5- to 10-membered compound with the inclusion of the parent body Ring can be connected.

The variables in the general formulas Ia and b are preferably defined as follows:
MV, Cr, Fe, Ru or Co, particularly preferably Fe;
A particularly preferably N,
A 'particularly preferably S,
Nu ¹ , Nu ² particularly preferably N,
X ¹ , X ²

• Halogen such as fluorine, chlorine, bromine or iodine, particularly preferably X ¹ and X ² are chlorine,
• - C ₁ -C ₄ alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy; particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;

R ¹

, R ²

• - C ₁ -C ₁₂ alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n-dodecyl ; preferably C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;
• The substituted C ₁ -C ₁₂ -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ₁ -C ₁₂ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• - Examples of substituted cycloalkyl groups are:
  2-methylcyclopentyl, 3-methylcyclopentyl, cis-2,4-dimethylcyclopentyl, trans-2,4-dimethylcyclopentyl, cis-2,5-dimethylcyclopentyl, trans-2,5-dimethylcyclopentyl, 2,2,5,5- Tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cis-2,6-dimethylcyclohexyl, trans-2,6-dimethylcyclohexyl, cis-2,6-diisopropylcyclohexyl, trans-2,6-diisopropylcyclohexyl, 2 , 2,6,6-tetramethylcyclohexyl, 2-methoxycyclopentyl, 2-methoxycyclohexyl, 3-methoxy cyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclopentyl, 3-chlorocyclopentyl, 2,4-dichlorocyclopentyl, 2,2,4,4-tetrachlorocyclopentyl, 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,5-dichlorocyclohexyl, 2,2,6,6-tetrachlorocyclohexyl, 2-thiomethyl cyclopentyl, 2-thiomethylcyclohexyl, 3-thio-methylcy clopentyl, 3-thiomethylcyclohexyl and others Deri vate;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , identical or different substituted by one or more
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• Examples of the substituted C ₁ -C ₈ -alkyl groups are: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pen tafluorethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₅ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
• - C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• 2,6-dimethylphenyl are very particularly preferred, 2,6-diisopropylphenyl, mesityl and 2,6-dichlorophenyl;  
• - Five- to six-membered nitrogen-containing heteroa ryl radicals such as N-pyrrolyl, pyrrol-2-yl, Pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazo lyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, 2-pyri dyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazi nyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl;
• - Five- to six-membered nitrogen-containing heteroa ryl radicals such as N-pyrrolyl, pyrrol-2-yl, Pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazo lyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, 2-pyri dyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazi nyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl, the same or different substituted one or more times with
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• Examples of the substituted C ₁ -C ₈ -alkyl groups are: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pen tafluorethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
• - C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, trilsopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls group; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, benzyl radicals and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• 2,5-methyl-N-pyrrolyl are very particularly preferred, 2,5-diisopropyl-N-pyrrolyl and N-carbazolyl.

R ³

, R ⁴

• - hydrogen
• - C ₁ -C ₁₂ alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n-dodecyl ; preferably C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;
• The substituted C ₁ -C ₁₂ -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ₁ -C ₁₂ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• - Examples of substituted cycloalkyl groups are:
  2-methylcyclopentyl, 3-methylcyclopentyl, cis-2,4-dimethylcyclopentyl, trans-2,4-dimethylcyclopentyl, cis-2,5-dimethylcyclopentyl, trans-2,5-dimethylcyclopentyl, 2,2,5,5- Tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cis-2,6-dimethylcyclohexyl, trans-2,6-dimethylcyclohexyl, cis-2,6-diisopropylcyclohexyl, trans-2,6-diisopropylcyclohexyl, 2 , 2,6,6-tetramethylcyclohexyl, 2-methoxycyclopentyl, 2-methoxycyclohexyl, 3-methoxy cyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclopentyl, 3-chlorocyclopentyl, 2,4-dichlorocyclopentyl, 2,2,4,4-tetrachlorocyclopentyl, 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,5-dichlorocyclohexyl, 2,2,6,6-tetrachlorocyclohexyl, 2-thiomethyl cyclopentyl, 2-thiomethylcyclohexyl, 3-thio-methylcy clopentyl, 3-thiomethylcyclohexyl and others Deri vate;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , identical or different substituted by one or more
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• Examples of the substituted C ₁ -C ₈ -alkyl groups are: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pen tafluorethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₅ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
• - C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• 2,6-dimethylphenyl are very particularly preferred, 2,6-diisopropylphenyl, mesityl and 2,6-dichlorophenyl;
• - Five- to six-membered nitrogen-containing heteroa ryl radicals such as N-pyrrolyl, pyrrol-2-yl, Pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazo lyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, 2-pyri dyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazi nyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl;
• - Five- to six-membered nitrogen-containing heteroa ryl radicals such as N-pyrrolyl, pyrrol-2-yl, Pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazo lyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, 2-pyri dyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazi nyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl, the same or different substituted one or more times with
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• Examples of the substituted C ₁ -C ₈ -alkyl groups are: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pen tafluorethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
• - C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;
• - Silyl groups SiR ⁸ R ⁹ R ¹⁰ , where R ⁵ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, benzyl radicals and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;

2,5-methyl-N-pyrrolyl, 2,5-diisopropyl-N-pyrrolyl and N-carbazolyl are very particularly preferred
R ⁵

to R ⁷

are selected independently

• - hydrogen,
• - C ₁ -C ₁₂ alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n-dodecyl ; preferably C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;
• The substituted C ₁ -C ₁₂ -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ₁ -C ₁₂ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• - Examples of substituted cycloalkyl groups are:
  2-methylcyclopentyl, 3-methylcyclopentyl, cis-2,4-dimethylcyclopentyl, trans-2,4-dimethylcyclopentyl, cis-2,5-dimethylcyclopentyl, trans-2,5-dimethylcyclopentyl, 2,2,5,5- Tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl cis-2,6-dimethylcyclohexyl, trans-2,6-dimethylcyclohexyl, cis-2,6-diisopropylcyclohexyl, trans-2,6-diisopropylcyclohexyl, 2, 2,6,6-tetramethylcyclohexyl, 2-methoxycyclopentyl, 2-methoxycyclohexyl, 3-methoxy cyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclopentyl, 3-chlorocyclopentyl, 2,4-dichlorocyclopentyl, 2,2,4,4-tetrachlorocyclopentyl, 2 -Chlorcyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,5-dichlorocyclohexyl, 2,2,6,6-tetrachlorocyclohexyl, 2-thiomethyl cyclopentyl, 2-thiomethylcyclohexyl, 3-thio-methylcy clopentyl, 3-thiomethylcyclohexyl and other deri vate;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , identical or different substituted by one or more
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• Examples of the substituted C ₁ -C ₈ -alkyl groups are: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pen tafluorethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₅ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
• - C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• 2,6-dimethylphenyl are very particularly preferred, 2,6-diisopropylphenyl, mesityl and 2,6-dichlorophenyl;
• - Five- to six-membered nitrogen-containing heteroa ryl radicals such as N-pyrrolyl, pyrrol-2-yl, Pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazo lyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, 2-pyri dyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazi nyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl;
• - Five- to six-membered nitrogen-containing heteroa ryl radicals such as N-pyrrolyl, pyrrol-2-yl, Pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazo lyl, 2,2,4-ttiazol-3-yl, 1,2,4-triazol-4-yl, 2-pyri dyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazi nyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl,  N-indolyl and N-carbazolyl, the same or different substituted one or more times with
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• - The substituted C ₁ -C ₈ -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;  
• - C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, benzyl radicals and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• 2,5-methyl-N-pyrrolyl are very particularly preferred, 2,5-diisopropyl-N-pyrrolyl and N-carbazolyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, fluorine and chlorine are preferred,
• - C ₁ -C ₆ alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-Bu toxy, n-pentoxy, iso-pentoxy, n -Hexoxy and iso-He xoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy,
• - NO _2,
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylyls; the trimethylsilyl group and the tert-butyldi methylsilyl group are particularly preferred;
• - Silyloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₈ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferably the trimethylsilyloxy, Triethylsily loxy-, triisopropylsilyloxy, Diethylisopropylsily loxy-, Dimethylthexylsilyloxy-, tert-butyldimethyl silyloxy, tert-butyldiphenylsilyloxy, Tribenzylsi are lyloxy-, Triphenylsilyloxy- and tri-para-xylylsi lyloxygruppe; the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred.

In a particular embodiment of the present invention, two adjacent radicals can form a 5- to 10-membered ring with the inclusion of the parent aromatic. For example, in formula Ia R ⁵ and R ⁶ or in formula Ib R ⁵ and R ⁷ together can be: - (CH ₂ ) ₃ - (trimethylene), - (CH ₂ ) ₄ - (tetramethylene), - (CH ₂ ) ₅ - (pentamethylene), - (CH ₂ ) ₆ - (hexamethylene), -CH ₂ -CH = CH-, -CH ₂ -CH = CH-CH ₂ -, -CH = CH-CH-CH = CH- , -O-CH ₂ -O-, -O-CH (CH ₃ ) -O-, -O-CH- (C ₆ H ₅ ) -O-, -O-CH ₂ -CH ₂ -O-, - OC (CH ₃ ) ₂ -O-, -N CH ₃ -CH ₂ -CH ₂ -NCH ₃ -, -NCH ₃ -CH ₂ -NCH ₃ - or -O-Si (CH ₃ ) ₂ -O-.

Due to the production process of the complexes with the general formulas Ia and b, those in which R ¹ and R ² and Nu ¹ and Nu ^{2 are} each chosen identically are particularly preferred.

The following complexes of the general formula Ia are very particularly preferred:
[2,6-diacetylpyridine-bis- (2,6-diisopropylanil)] - FeCl ₂
[2,6-diacetylpyridine-bis- (2,6-diisopropylanil)] - CoCl ₂
[2,6-diacetylpyridine-bis- (mesitylanil)] - FeCl ₂
[2,6-diacetylpyridine-bis- (mesitylanil)] - CoCl ₂
[2,6-diacetylpyridine-bis- (mesitylanil)] - RuCl ₂
[2,6-diacetylpyridine-bis (2-methyl-5-iso-propylpyrrol-1-yli min)] - FeCl ₂
[2,6-diacetylpyridine-bis (2-methyl-5-iso-propylpyrrol-1-yli min)] - CoCl ₂
[2,6-diacetylpyridin-bis (2,5-diisopropylpyrrol-1-ylimin)] - CoCl ₂
[2,6-diacetylpyridin-bis (2,5-diisopropylpyrrol-1-ylimin)] - FeCl ₂
as well as the corresponding dibromides.

Very particularly preferred examples of complexes of the general formula Ib are:
[2,5-diacetylfuran-bis (2,6-diisopropylanil)] - FeCl ₂
[2,5-diacetylfuran-bis- (2,6-diisopropylanil)] - CoCl ₂
[2,5-diacetylfuran bis (mesitylanil)] - FeCl ₂
[2,5-diacetylfuran bis (mesitylanil)] - CoCl ₂
[2,5-diacetylfuran bis (mesitylanil)] - RuCl ₂
[2,5-diacetylfuran-bis- (2-methyl-5-iso-propylpyrrol-1-yli min)] - FeCl ₂
[2,5-diacetylfuran-bis- (2-methyl-5-iso-propylpyrrol-1-yli min)] - CoCl ₂
[2,5-diacetylfuran-bis- (2,5-diisopropylpyrrol-1-ylimin)] - CoCl ₂
[2,5-diacetylfuran-bis- (2,5-diisopropylpyrrol-1-ylimin)] - FeCl ₂
[2,5-diacetylthiophene-bis- (2,6-diisopropylanil)] - FeCl ₂
[2,5-diacetylthiophene bis (2,6-diisopropylanil)] - CoCl ₂
[2,5-diacetylthiophene-bis- (mesitylanil)] - FeCl ₂
[2,5-diacetylthiophene-bis- (mesitylanil)] - CoCl ₂
[2,5-diacetylthiophene bis (mesitylanil)] - RuCl ₂
[2,5-diacetylthiophene-bis- (2-methyl-5-iso-propylpyrrol-1-yli min)] - FeCl ₂
[2,5-diacetylthiophene-bis- (2-methyl-5-iso-propylpyrrol-1-yli min)] - CoCl ₂
[2,5-diacetylthiophene-bis (2,5-diisopropylpyrrol-1-ylimin)] - CoCl ₂
[2,5-diacetylthiophene-bis- (2,5-diisopropylpyrrol-1-ylimin)] - FeCl ₂
as well as the corresponding dibromides.

The complexes of the general formulas Ia and b can be subtracted Synthesize literary regulations; Find sample regulations for example in J. Cham. Soc., Chem. Commun. 1998, 849 and J. Am. Chem. Soc. 1998, 120, 4049 and in DE-A 199 39 415, publi adorns on. . . .

Furthermore, a molecularly defined activator of the general formulas IIa to c is used, the activators being able to be represented as follows:

[(LH)] ⁺ [(M ') Q ¹ Q ² Q ³ Q ⁴ ] ^- IIa

[(CAr ₃ )] ⁺ [(M ') Q ¹ Q ² Q ³ Q ⁴ ] ^- IIb

[(M ') Q ¹ Q ² Q ³ ] IIc

[LH] ⁺ is a Brønsted acid, where L is an electroneutral Lewis base, for example an amine of the general formula NR ⁸ R ⁹ R ¹⁰ , a phosphane of the general formula PR ⁸ R ⁹ R ¹⁰ or an ether of the general formula OR ¹ R ² , the radicals R ¹ and R ² and R ⁸ to R ^{10 being selected} independently of one another from the same group as defined above. Preferred Lewis bases L are tertiary amines or phosphines, particularly preferred Lewis bases L are tri-n-butylamine, N, N-dimethyl aniline and N, N-dimethylbenzylamine.
M 'is an element of group 13 of the Periodic Table of the Elements, B and Al are preferred.
Q ¹ to Q ⁴ is independently selected from

• - hydride,
• - C ₁ -C ₁₂ alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n-dodecyl ; preferably C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;
• Examples of the substituted C ₁ -C ₁₂ -alkyl groups are: mono- or poly-halogenated C ₁ -C ₁₂ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pen tafluorethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• - Examples of substituted cycloalkyl groups are:
  2-methylcyclopentyl, 3-methylcyclopentyl, cis-2,4-dimethylcyclopentyl, trans-2,4-dimethylcyclopentyl, cis-2,5-dimethylcyclopentyl, trans-2,5-dimethylcyclopentyl, 2,2,5,5- Tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl cis-2,6-dimethylcyclohexyl, trans-2,6-dimethylcyclohexyl, cis-2,6-diisopropylcyclohexyl, trans-2,6-diisopropylcyclohexyl, 2, 2,6,6-tetramethylcyclohexyl, 2-methoxycyclopentyl, 2-methoxycyclohexyl, 3-methoxy cyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclopentyl, 3-chlorocyclopentyl, 2,4-dichlorocyclopentyl, 2,2,4,4-tetrachlorocyclopentyl, 2 -Chlorcyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,5-dichlorocyclohexyl, 2,2,6,6-tetrachlorocyclohexyl, 2-thiomethyl cyclopentyl, 2-thiomethylcyclohexyl, 3-thio-methylcy clopentyl, 3-thiomethylcyclohexyl and other deri vate;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; unsubstituted or substituted with
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , identical or different substituted by one or more
• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• - The substituted C ₁ -C ₈ -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ -CyCloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• C ₇ -C ₁₅ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1- Methyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine and particularly preferred Fluorine.
• - Halide with the proviso that a maximum of two radicals Q ¹ and Q ² can be halide.

All radicals Q ¹ to Q ⁴ are very particularly preferably the same and selected from pentafluorophenyl, 3,5-bis-perfluoromethylphenyl or ortho-perfluorobiphenyl.
Ar is the same or different and selected from unsubstituted or substituted C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl , 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, identical or different substituted by one or more

• - C ₁ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• - The substituted C ₁ -C ₈ -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ₁ -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be preferred are cyclopentyl, cyclohexyl and cycloheptyl;
• - C ₇ -C ₁₅ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Halogen, for example fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine and particularly preferred Fluorine, or
• - NO ₂ .

Ar is preferably phenyl.

Mixtures of two or more molecularly defined ones can also be used Add activators of the general formulas IIa to IIc.

The compound or compounds of the general formulas Ia or b and the molecularly defined activators of the general my formulas IIa to c are usually in a solution tel mixed. As a solvent, the reaction conditions inert solvents such as toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene or mixtures thereof as suitable proven. In addition, alkanes such as n-heptane or Isododecane is suitable as a solvent, furthermore mixtures of Al can with toluene, ortho-xylene, meta-xylene, para-xylene or Ethyh benzene. After all, halogenated hydrocarbons such as methylene chloride, chloroform, chloromethane or chlorobenzene as proven suitable. Ethers such as diethyl ether or THF are general solvents when using activators Formulas IIa or b also possible; in the event that an asset Tor of the general formula IIc to be used are ethers not suitable as a solvent.

The molar ratios of complex Ia or Ib to activator IIa to c can be varied within certain limits. So Mol ratios Ia (or Ib) to IIa or IIb or IIc of 10: 1 up to 1:10, the ratios are preferably 2: 1 to 1: 2 and particularly preferably 1: 1. The order is the addition of the components is not critical.

Pressure and temperature conditions of the implementation described can be varied within wide limits. Working is preferred at normal pressure. As temperatures are -20 ° C to + 120 ° C mentioned as suitable, 0 to 100 ° C are preferred and 20 to 80 ° C are particularly preferred. The hiring of a Temperature profile has proven particularly useful; so the implementation formation of the complex of the late transition metal with the molecular defined activator preferably carried out at 60 to 100 °, ins especially if the activator is a salt delt.  

The solid carrier material is mixed with the mixture described above impregnated, it being possible to be the solid support material admit at the beginning of the implementation.

As support materials such. B. porous metal oxides of metals from groups 2 to 14 or mixtures thereof, furthermore sheet silicates or amorphous silica gels such as diatomite, but also solid halides of metals from groups 1, 2 and 13. Preferred examples of metal oxides from groups 2 to 14 are SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , MgO, CaO and ZnO. Preferred layered silicates are Montmor rilonite or Bentonite; preferred halides are MgCl ₂ or amorphous AlF ₃ .

Particularly preferred carrier materials are spherical silica gels and aluminosilicate gels of the general formula SiO ₂ .a Al ₂ O ₃ , where a generally stands for a number in the range from 0 to 2, preferably 0 to 0.5. Such silica gels are commercially available, e.g. B. Silica Gel SG 332, Sylopol® 948 or Sylopol 952 or S 2101 from WR Grace or ES 70X from Crosfield.

As the particle size of the carrier material, average particle diameters of 1-300 μm have proven useful, preferably from 20 to 80 μm, the particle diameter being determined by known methods such as sieving methods. The pore volume of these carriers is 1.0 to 3.0 ml / g, preferably 1.6 to 2.2 ml / g and particularly preferably 1.7 to 1.9 ml / g. The BET surface area is 200 to 750 m ² / g, preferably 250 to 400 m ² / g.

It is essential that none for the method according to the invention Pretreatment of the substrate is required. Commercially Available silica gels and aluminosilicate gels, but also layered silicas Likate or alumina gels usually contain water that can be physisorbed or chemisorbed and for the manufacturer treatment of a supported catalyst according to WO 99/46304 initially dry must be net. The water content of commercially available kie selgele is usually in the range of 2 to 10 wt .-%, be preferably 3.5 to 10% by weight, determined by differential thermography vimetry. The commercially available carrier materials can depending on the manufacturing process also other volatile inventory adsorb parts, for example alcohols such as methanol, ethanol or propanol. All of these ingredients can be found during the inventions process according to the invention remain in the silica gel.

The conditions for impregnation can vary within wide limits can be varied. Working at normal pressure is preferred. As Temperatures may be mentioned as suitable before -20 ° C to + 120 ° C are 0 to 100 ° C and a reaction is particularly preferred  at room temperature. During the impregnation, further sol be added or fixation of the active components on the carrier material by a solvent, in the complex and Activator are poorly soluble, such as n-pentane, n- Heptane or iso-dodecane.

The amount of the carrier added can vary within wide limits become. Usually one works in such a way that about 5 to 200 µmol Complex of the general formulas Ia or b, based on 1 g Carrier material on which the carrier material deposits. You can deposit higher amounts of complex, but this becomes the kata lysator very expensive, because usually the complex is clearly expensive rer than the carrier material. When choosing the amount of ab outgoing complex of general formulas Ia or b is excluded to take into account that at high concentration of complex the resulting heat of polymerization is worse on the carrier can be dissipated.

After the impregnation, the solvent or solvents usually removed to the catalyst of the invention isolate. The removal of the solvent can be done by common Techniques are used, such as evaporation or filtration or a combination of several steps. For removal poorly fixed active components (complex of formulas Ia or b or activator of the general formulas IIa to c) can Ka be washed with an inert solvent.

Another object of the present invention is a kata analyzer, obtainable by the method described above. This The catalyst stands out from those of the prior art known catalysts with late transition metals, that it has no air or moisture sensitive metal alkyl Compounds such as aluminum alkyl compounds ent holds and therefore stored without special precautions and can be transported.

The manufactured according to the inventive method appropriate catalyst is suitable for polymerization and copolyme rization of olefins. A process for polymerization and copo polymerization of olefins using the invention Catalyst is another subject of the present invention dung.

The following olefins are suitable as monomers: ethylene, propy len, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-undecene, ethylene being particularly preferred.  

Α-olefins are suitable as comonomers, for example 0.1 up to 20 mol% 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-oc ten, 1-decene or 1-undecene. But isobutene and styrene are also suitable comonomers, furthermore cycloolefins such as, for example Cyclopentane, norbornene or norbornadiene and substituted nor bornene.

Pressure and temperature conditions during the polymerization can can be chosen within wide limits. Be a pressure proven to be suitable from 0.5 bar to 4000 bar, preferred are 10 to 75 bar or high pressure conditions from 500 to 2500 bar. The temperature range from 0 to 120 ° C is suitable gnet proven, 40 to 100 ° C are preferred and particularly preferred 50 to 85 ° C.

To use the catalyst according to the invention, it must be brief before polymerization with a metal alkyl compound, which as Alkylating agent is used to be treated. This can either be in in a separate vessel or by using the Catalyst in the Po simultaneously with an alkylating agent dosing vessel. It is advantageous to use a catalyst and dosing alkylating agents with separate dosing systems, so the reaction of the catalyst with the alkylating agent takes place in situ in the polymerization reactor.

The alkylating agent is selected from LiR ¹¹ , MgR ¹¹ R ¹² or AlR ¹² R ¹³ R ¹⁴ , where the radicals have the following meaning:
R ¹¹ to R ¹⁴ are independently selected from

• - C ₁ -C ₁₂ alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n- Dode cyl; preferably C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• - C ₇ -C ₁₃ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Me thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, especially preferred benzyl;
• - C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.

Particularly preferred alkylating agents are n-butyllithium, tri methyl aluminum, triethyl aluminum, triisobutyl aluminum, tri- n-hexyl aluminum and butyl octyl magnesium ("BOMag").

In a particular embodiment of the present invention mixtures of several alkylating agents can also be added.

The polymerization process according to the invention can be found in ver perform different embodiments, the modern Po Polymerization processes such as suspension processes, bulk polymerisation tion process or gas phase process can be used. As plants are stirred tanks, tubular reactors, loop reactors and stirred kettle cascades, whereby also stirred kettle and Loop reactors can be cascaded. It will no polymer morphology problems (chunks, wall coverings, ver blockages in lines or heat exchangers) observed.

In a further embodiment of the present invention, a compound of the general formulas Ia or b with a mo lularly defined activator of the general formulas IIa to c and a further transition metal complex, which can be used for the polymerization of olefins as a catalytically active catalyst component, on a like available above described se se r free carrier material deposited. Examples include metal locenes of the general formulas IIIa to e, Ni or Pd complexes, as described in WO 96/23010.

Metallocenes of the general formulas IIIa to e are preferred. In Formula IIIa

• - M "is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and be particularly preferably Zr or Hf;
• - X ³ and X ^{4 are} independent of each other
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-hep tyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• - C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n- Pentoxy, iso-pen toxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy or
• - E is selected from C, Si, Ge or Sn; preferred are C and Si;
• - n is selected from the numbers 1, 2 or 3; n is preferred is 1 or 2 and particularly preferably 1;
• - R and R 'are independent of each other
• - hydrogen,
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso -Pro pyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
• - C ₂ -C ₁₂ alkenyl, preferably C ₂ - to ω-C ₈ alkenyl such as vinyl, allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω -Octenyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• - or C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n -Pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy

where R and R 'together with E together are saturated or can form unsaturated 4- to 9-membered ring;

• - R ¹⁵ to R ^{22 are} independent of one another
• - hydrogen,
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-hep tyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec.-butyl and tert.-butyl,
• - One or more halogenated C ₁ -C ₁₂ alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl and periforbyl ;
• - C ₂ -C ₁₂ alkenyl, preferably C ₂ - to ω-C ₈ alkenyl such as vinyl, allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω -Octenyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• - Siloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ¹⁰ independently of one another from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, substituted C ₆ - C ₁₄ aryl groups, C ₁ -C ₁₂ alkoxy groups, benzyl groups and C ₆ -C ₁₄ aryl groups are selected; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxyxylysilyloxyxylysilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyx; the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• - Silyl groups SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; be preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl, and tri-para-silyl groups; the trimethyl silyl group and the tert-butyldimethylsilyl group are particularly preferred;
• - C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n- Pentoxy, iso-pen toxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• C ₆ -C ₁₄ aryl groups, which in turn are substituted by one or more C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkenyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, Si loxy groups OSiR ⁸ R ⁹ R ¹⁰ or C ₁ -C ₁₂ alkoxy groups, these groups being as specified above;

where two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring,
for example, two residues can be together; - (CH ₂

) ₃

- (trimethylene), - (CH ₂

) ₄

- (tetramethylene), - (CH ₂

) ₅

- (pentamethylene), - (CH ₂

) ₆

- (hexamethylene), -CH ₂

-CH = CH-, -CH ₂

-CH = CH-CH ₂

-, -CH = CH-CH = CH-, -O-CH ₂

-O-, -O-CH (CH ₃

) -O-, -CH- (C ₆

H ₅

) -O-, -O-CH ₂

-CH ₂

-O-, -OC (CH ₃

) ₂

-O-, -N (CH ₃

) -CH ₂

-CH ₂

-N (CH ₃

) -, -N (CH ₃

) -CH ₂

-N (CH ₃

) - or -O-Si (CH ₃

) ₂

-O-.

A special embodiment are metallocenes according to the formula IIIb.

In formula IIIb

• - R ¹¹ , R ¹⁶ , R ¹⁹ , R ²⁰ and R ²³ to R ^{30 are} independent of one another
• - hydrogen,
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;  
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
• - One or more halogenated C ₁ -C ₁₂ alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl and periforbyl ;
• C ₂ -C ₁₂ alkenyl, preferably C ₂ to ω-C ₈ alkenyl such as vinyl, allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω- Octenyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• - Siloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ¹⁰ independently of one another from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, substituted C ₆ - C ₁₄ aryl groups, C ₁ -C ₁₂ alkoxy groups, benzyl groups and C ₆ -C ₁₄ aryl groups are selected; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxyxylysilyloxyxylysilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyx; the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• - Silyl groups SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; be preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl, and tri-para-silyl groups; the trimethyl silyl group and the tert-butyldimethylsilyl group are particularly preferred;
• - C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n- Pentoxy, iso-pen toxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• C ₆ -C ₁₄ aryl groups, which in turn are substituted by one or more C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkenyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, Si loxy groups OSiR ⁸ R ⁹ R ¹⁰ or C ₁ -C ₁₂ alkoxy groups, these groups being as specified above;

where two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring,
for example, two residues can be together: - (CH ₂

) ₃

- (tri methylene), - (CH ₂

) <26275 00070 552 001000280000000200012000285912616400040 0002010017663 00004 26156SUB <4- (tetramethylene), - (CH ₂

) ₅

- (pentamethylene), - (CH ₂

) ₆

- (hexamethylene), -CH ₂

-CH = CH-, -CH ₂

-CH = CH-CH ₂

-, -CH = CH-CH = CH-, -O-CH ₂

-O-, -O-CH (CH ₃

) -O-, -CH- (C ₆

H ₅

) -O-, -O-CH ₂

-CH ₂

-O-, -OC (CH ₃

) ₂

-O-, -N (CH ₃

) -CH ₂

-CH ₂

-N (CH ₃

) -, -N (CH ₃

) -CH ₂

-N (CH ₃

) - or -O-Si (CH ₃

) ₂

-O-.

The remaining variables are defined as in Formula IIIa.

In Formula IIIc

• - R ¹⁵ to R ²² and R ³¹ and R ^{32 are} independent of one another
• - hydrogen,
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
• - One or more halogenated C ₁ -C ₁₂ alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl are particularly preferred and perfluorobutyl;
• - C ₂ -C ₁₂ alkenyl, preferably C ₂ - to ω-C ₈ alkenyl such as vinyl, allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω -Octenyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1- Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• - Siloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ¹⁰ independently of one another from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, substituted C ₆ - C ₁₄ aryl groups, C ₁ -C ₁₂ alkoxy groups, benzyl groups and C ₆ -C ₁₄ aryl groups are selected; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenyllyyloxy groups, the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• - SiR ⁸ R ⁹ R ¹⁰ silyl groups, where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xyl group; the trimethylsilyl group and the tert-butyldimethylsiyl group are particularly preferred;
• - C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n Pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• - C ₆ -C ₁₄ aryl groups, which in turn are substituted with one or more C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkenyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, siloxy groups OSiR ⁸ R ⁹ R ¹⁰ or C ₁ -C ₁₂ alkoxy groups, these groups being as specified above;

where two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring. For example, two residues can be together:
- (CH ₂

) ₃

- (trimethylene), - (CH ₂

) ₄

- (tetramethylene), - (CH ₂

) ₅

- (penta methylene), - (CH ₂

) ₆

- (hexamethylene), -CH ₂

-CH = CH-, -CH ₂

-CH = CH-CH ₂

-, -CH = CH-CH = CH-, -O-CH ₂

-O-, -O-CH (CH ₃

) -O-, -CH- (C ₆

H ₅

) -O-, -O-CH ₂

-CH ₂

-O-, -OC (CH ₃

) ₂

-O-, -N (CH ₃

) -CH ₂

-CH ₂

-N (CH ₃

) -, -N (CH ₃

) -CH ₂

-N (CH ₃

) - or -O-Si (CH ₃

) ₂

-O-.

The remaining variables are defined as in Formula IIIa.

A special embodiment are metallocenes according to formula IIId.

In Formula IIId

• - R ¹⁵ to R ¹⁷ , R ¹⁹ to R ²¹ and R ²³ to R ^{30 are} independent of each other
• - hydrogen,
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; before C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso -Pro pyl, n-butyl, iso-butyl, sec.-butyl and tert.-butyl,
• mono- or polyhalogenated C ₁ -C ₁₂ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl and perfluorobutyl are particularly preferred;
• C ₂ -C ₁₂ alkenyl, preferably C ₂ to ω-C ₈ alkenyl such as vinyl, allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω- Octenyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• - Siloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ¹⁰ independently of one another from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, substituted C ₆ - C ₁₆ aryl groups, C ₁ -C ₁₂ alkoxy groups, benzyl groups and C ₆ -C ₁₄ aryl groups are selected; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxyxylysilyloxyxylysilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyx; the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• - Silyl groups SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; be preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl, and tri-para-silyl groups; the trimethyl silyl group and the tert-butyldimethylsilyl group are particularly preferred;
• - C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy , iso-pen toxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• C ₆ -C ₁₄ aryl groups, which in turn are substituted by one or more C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkenyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, Si loxy groups OSiR ⁸ R ⁹ R ¹⁰ or C ₁ -C ₁₂ alkoxy groups, these groups being as specified above;

where two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring. For example, two residues can be together:
- (CH ₂

) ₃

- (trimethylene), - (CH ₂

) ₄

- (tetramethylene), - (CH ₂

) ₅

- (penta methylene), - (CH ₂

) ₆

- (hexamethylene), -CH ₂

-CH = CH-, -CH ₂

-CH = CH-CH ₂

-, -CH = CH-CH = CH-, -O-CH ₂

-O-, -O-CH (CH ₃

) -O-, -CH- (C ₆

H ₅

) -O-, -O-CH ₂

-CH ₂

-O-, -OC (CH ₃

) ₂

-O-, -N (CH ₃

) -CH ₂

-CH ₂

-N (CH ₃

) -, -N (CH ₃

) -CH ₂

-N (CH ₃

) - or -O-Si (CH ₃

) ₂

-O-.

The remaining variables are defined as in Formula IIIa.

In Formula IIIe

• - R ¹⁵ to R ^{18 are} independent of one another
• - hydrogen,
• - Halogen such as fluorine, chlorine, bromine or iodine, where chlorine and Bromine are preferred;
• - C ₁ -C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-hep tyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec.-butyl and tert.-butyl,
• - One or more halogenated C ₁ -C ₁₂ alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl and perfluorobutyl are particularly preferred ;
• - C ₂ -C ₁₂ alkenyl, preferably C ₂ - to ω-C ₈ alkenyl such as vinyl, allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω -Octenyl;
• - C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C ₇ to C ₂₀ aralkyl, preferably C ₇ to C ₁₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• - C ₆ -C ₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• - Siloxy groups OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ¹⁰ independently of one another from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, substituted C ₆ - C ₁₄ aryl groups, C ₁ -C ₁₂ alkoxy groups, benzyl groups and C ₆ -C ₁₄ aryl groups are selected; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxyxylysilyloxyxylysilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyxylsilyloxyx; the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• - Silyl groups SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ to R ^{10 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₅ aralkyl and C ₆ -C ₁₄ aryl groups; be preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl, and tri-para-silyl groups; the trimethyl silyl group and the tert-butyldimethylsilyl group are particularly preferred;
• - C ₁ -C ₁₂ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n- Pentoxy, iso-pen toxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• C ₆ -C ₁₄ aryl groups, which in turn are substituted by one or more C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkenyl groups, C ₃ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, Si loxy groups OSiR ⁸ R ⁹ R ¹⁰ or C ₁ -C ₁₂ alkoxy groups, these groups being as specified above;

where two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring, preferably 5- to 8-membered. For example, two residues can be together:
- (CH ₂

) ₃

- (trimethylene), - (CH ₂

) ₄

- (tetramethylene), - (CH ₂

) ₅

- (penta methylene), - (CH ₂

) ₆

- (hexamethylene), -CH ₂

-CH = CH-, -CH ₂

-CH = CH-CH ₂

-, -CH = CH-CH = CH-, -O-CH ₂

-O-, -O-CH (CH ₃

) -O-, -CH- (C ₆

H ₅

) -O-, -O-CH ₂

-CH ₂

-O-, -OC (CH ₃

) ₂

-O-, -N (CH ₃

) -CH ₂

-CH ₂

-N (CH ₃

) -, -N (CH ₃

) -CH ₂

-N (CH ₃

) - or -O-Si (CH ₃

) ₂

-O-;

• D is oxygen, sulfur, NR ³¹ or PR ³¹ , where R ^{31 is} selected from halogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, substituted or unsubstituted C ₆ -C ₁₄ - Aryl groups or C ₁ -C ₁₂ alkoxy groups and these groups are as defined above.

The remaining variables are defined as in Formula IIIa.

Illustrative, very particularly preferred examples of metallocenes of the formulas IIIa-e are:
Rac. Ethylene bis [indenyl] zirconium dichloride,
Rac. Ethylene bis [4,5,6,7-tetrahydroindenyl] zirconium dichloride,
Rac. Dimethylsilyl-bis- [2-methylindenyl] zirconium dichloride,
Rac. Tetramethylene silyl bis [2-methylindenyl] zirconium dichloride,
Rac. Dimethylsilyl-bis- [2-methylbenzo- (4,5) -indenyl] zirconium dichloride,
Rac. Dimethylsilyl-bis- [2-methyl-4-tert-butylcyclopentadienyl] zirconium dichloride,
Rac. Dimethylsilyl-bis- [2,3,5-trimethylcyclopentadienyl] zirconium dichloride,
Rac. Dimethylsilyl-bis- [2-methyl-4-phenylindenyl] zirconium dichloride,
2,2-isopropylidene-cyclopentadienyl-9-fluorenyl-zirconium dichloride,
Diphenylmethyl-cyclopentadienyl-9-fluorenyl-zirconium dichloride;
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis- [2-methyl-4-tert-butylcyclopentadienyl] zirconium dichloride,
Bis- [2,3,5-trimethylcyclopentadienyl] zirconium dichloride,
Bis [indenyl] zirconium dichloride,
Bis- [2-methylindenyl] zirconium dichloride,
Bis- [2-methylbenzo- (4,5) -indenyl] zirconium dichloride,
Bis- [4,5,6,7-tetrahydroindenyl] zirconium dichloride,
Bis [2-methyl-4-phenylindenyl] zirconium dichloride;
Dimethylsilyl-tert-butylamido-tetramethylcyclopentadienyl-titanium dichloride,
Dimethylsilyl-iso-propylamido-tetramethylcyclopentadienyl-titanium dichloride,
2,3,5-trimethylsilyl-tert-butylamido-tetramethylcyclopentadiene nyl titanium dichloride,
Dimethylsilyl-phenylamido-tetramethylcyclopentadienyl titanium dichloride,
Dimethylsilyloxy-tetramethylcyclopentadienyl titanium dichloride,
2,3,5-trimethylsilyloxy-tetramethylcyclopentadienyl titanium dichloride
as well as the corresponding dibromides and dimethyl compounds.

If you cut a metal complex of the general formulas Ia or b together with another transition metal complex which is used for Polymerization of olefins as a catalytically active catalyst  component can be used, preferably a metallocene general formulas IIIa to e, on the same support, so this process is also known as co-transfer. At the Coträ metal complex Ia or b and the other Transition metal complex in a molar ratio of 1:20 to 20: 1 set, preferably 1:10 to 10: 1.

The catalysts of the invention, regardless of whether they contain a further transition metal complex which can be used for the polymerization of olefins as a catalytically active catalyst component or not, can also be used together with one or more other known polymerization catalysts. So you can along with

• - Ziegler-Natta catalysts,
• - supported metallocene catalysts of the transition metals of the Groups 4 to 6 of the Periodic Table of the Elements,
• Catalysts of the late transition metals (WO 96/23010),
• - Or also used chromium oxide catalysts according to Phillips become.

It is possible to combine different catalysts mix and dose together - such a mixture will also known as a catalyst blend - or various catalyzes separately in the same or different places in meter the polymerization vessel. Through this fiction Modern methods can use polymers with a bimodal molecular weight distribution can be obtained.

The catalysts and catalyst blends according to the invention have regardless of whether they have another transition metal com plex, which is used for the polymerization of olefins as catalytically active Catalyst component can be used, contain or not, further proven to be hydrogen controllable, d. H. by encore of hydrogen can be the molecular weight by which he Lower the available catalyst system polymers available. With sufficient hydrogen addition waxes are obtained, the required hydrogen concentration also on the type of ver used polymerization plant depends. A process for polyme risation of olefins with the catalyst according to the invention in The presence of hydrogen as a regulator is also the subject of present invention.  

Working example

If not specifically noted, all work has been done under closure of air and moisture using standard Schlenk techniques performed. Devices and chemicals were gone prepared for speaking. The Fe complexes used can e.g. B. as in J. Chem. Soc., Chem. Commun. 1998, 849 and J. Am. Chem. Soc. 1998, 320, 4049.

The polymer viscosity was determined according to ISO 1628-3. The witch content in the polymer was determined by IR spectroscopy. The The water content of the carrier materials was determined using differential Thermogravimetry determined.

Representation of a supported catalyst a) Carrier loading (general regulation)

50 ml of toluene, the metal complex, were placed in a 100 ml flask (see Table 1), 1.1 equivalents of N, N-dimethylanilinium tetrakis pentafluorophenyl borate (based on metal complex) and 5.0 g of Kie selgel ES 70X (Crosfield). The reaction gene obtained Mix was heated to 80 ° C and for 30 min at this temperature touched. The solvent was then removed in vacuo. Details are given in Table 1.

Table 1

Catalyst production

Chemical pretreatment (comparative example): 5 g of silica gel ES 70X from Crosfield was initially 16 hours at 120 ° C in Va vacuum (1 mbar) and then at room temperature in 50 ml of toluene suspended and 7.5 ml with triisobutyl aluminum added (2M solution in heptane). The carrier was vacuumed dries and then implemented as described above.  

b) Special treatment of catalyst 2

In order to demonstrate the robustness of the catalysts according to the invention, three samples of catalyst 2 (Table 1) were exposed to moisture and optionally atmospheric oxygen. The samples treated with moisture and optional atmospheric oxygen proved to be suitable for catalysis.

c) ethylene homopolymerization (general rule)

In a stirred 1 liter steel autoclave, after careful Purge with nitrogen and temper to the polymerization temperature temperature of 70 ° C 400 ml isobutane and 200 mg triethyl aluminum (as 2M solution in heptane) submitted. Then the according to a) or b) supported catalyst washed in with a further 6 ml of isobutane and Ethylene pressed to a total pressure of 40 bar. The pressure in the autoclave was constant ge by adding ethylene hold. After 90 min the polymerization was started by releasing the pressure Autoclave broken off. Polyethylene was obtained in the form of a good pourable semolina. See Table 2 for details.

Table 2

Ethylene homopolymerization

The catalyst mixture (3 + 4) was mixed in the autoclave before the addition;
nb: not determined

d) ethylene-1-hexene copolymerization (general procedure)

In a stirred 1 liter steel autoclave, after careful Purge with nitrogen and temper to the polymerization temperature temperature of 70 ° C 400 ml isobutane, 40 ml 1-hexene and 200 mg trie presented aluminum (as a 2M solution in heptane). Then the after a) supported catalyst with a further 6 ml of isobutane rinses and ethylene pressed to a total pressure of 40 bar. The pressure in the autoclave was adjusted by adding ethylene kept constant. After 90 min the polymerization was complete Relaxed the autoclave canceled. Polyethylene was obtained in Form of a free-flowing semolina. Details are in Table 3 refer to.

Table 3

Polymerization and polymer data copolymerization

The catalyst mixture (3 + 4) was added to the car mixed slave.

Claims (17)

1. A process for the preparation of a supported catalyst for the polymerization of olefins, characterized in that one or more compounds of the general formulas Ia or b,
where the variables are defined as follows:
M is a transition metal of groups 5 to 10 of the periodic table of the elements,
A is selected from N, P or As,
A 'is selected from O or S,
Nu ¹ , Nu ² N or P,
X ¹ , X ² halogen or C ₁ -C ₄ alkoxy;
R ¹ , R ² unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-containing heteroaryl,
R ³ , R ^{4 are} hydrogen, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-halti Heteroaryl,
R ⁵ to R ⁷ are independently selected from hydrogen, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or five- or six-membered N-containing heteroaryl, halogen, C ₁ -C ₆ alkoxy, NO ₂ , SiR ⁸ R ⁹ R ¹⁰ or OSiR ⁸ R ⁹ R ¹⁰ , adjacent residues forming a 5- to 10-membered compound with the inclusion of the parent body Ring can be connected
R ⁸ to R ¹⁰ are, independently of one another, independently of one another selected from hydrogen or unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl ;
together with a molecularly defined activator of the general formulas IIa to c
[(LH)] ⁺ [(M ') Q ¹ Q ² Q ³ Q ⁴ ] ^- IIa
[(CAr ₃ )] ⁺ [(M ') Q ¹ Q ² Q ³ Q ⁴ ] ^- IIb
[(M ') Q ¹ Q ² Q ³ ] IIc
where the variables have the following meaning:
[LH] ⁺ is a Brønsted acid, where L is an electroneutral Lewis base,
M 'is an element of group 13 of the Periodic Table of the Elements,
Q ¹ to Q ⁴ are independently selected from hydride, unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl or halide the restriction that at most two radicals Q ¹ and Q ² can be halide;
Ar is the same or different and is selected from unsubstituted or substituted C ₆ -C ₁₄ aryl,
deposits on a porous carrier material which contains 2 to 10% by weight of water and optionally further volatile constituents. 2. The method according to claim 1, characterized in that M in the general formulas Ia and Ib Fe.   3. The method according to claims 1 and 2, characterized in that A, Nu ¹ and Nu ² in the general formula Ia is N. 4. The method according to claims 1 and 2, characterized in that Nu ¹ and Nu ² in the general formula Ib is in each case N and A 'S. 5. The method according to claims 1 to 4, characterized in net that M 'in the formulas IIa to IIc means B or Al. 6. The method according to claims 1 to 5, characterized in net that L in formula IIa is a tertiary amine. 7. The method according to claims 1 to 6, characterized in net that L is selected from tri-n-butylamine, N, N-Dimethy laniline or N, N-dimethylbenzylamine. 8. The method according to claims 1 to 7, characterized in net that all residues Ar in formula IIb are phenyl. 9. The method according to claims 1 to 8, characterized in that one uses a molecularly defined activator of the general formulas IIa to c, in which Q ¹ to Q ^{4 are the} same and are selected from pentafluorophenyl or 3,5-bis- (Trifluoromethyl) phenyl or ortho-perfluorobiphenyl. 10. The method according to claims 1 to 9, characterized in net that the porous carrier material is silica gel acts. 11. The method according to claims 1 to 10, characterized in net that the silica gel has a spherical particle shape. 12. The method according to claims 1 to 11, characterized in net that the silica gel contains 3.5 to 10 wt .-% water. 13. Catalyst produced by the method according to the claims Chen 1 to 12. 14. A catalyst according to claim 13, characterized in that one another transition metal complex that polymeri sation of olefins as a catalytically active catalyst compo nente can be used on the carrier deposits. 15. A process for the polymerization or copolymerization of olefins using a catalyst according to claim 13 or 14, which is activated immediately before the polymerization or in situ in the polymerization reactor with an alkylating agent, selected from LiR ¹¹ , MgR ¹¹ R ¹² or AlR ¹² R ¹³ R ¹⁴ , in which R ¹¹ to R ^{14 are} independently selected from unsubstituted or substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl or C ₆ -C ₁₄ -Aryl. 16. Process for the polymerisation or copolymerisation of olefi nen, characterized in that one after a catalyst Claim 13 together with a further polymerization catalog uses the analyzer. 17. The method according to claim 15 or 16, characterized in that in the presence of hydrogen as a molecular weight regulator po lymerized.