DE10323276A1 - Transition metal complex for olefin polymerization catalyst system, consists of Group 3-6 transition metal and specific tridentate nitrogen-containing ligand - Google Patents

Abstract

A transition metal complex consists of transition metal of group 3-6 of periodic table, and specific tridentate nitrogen-containing ligand (II). A transition metal complex is of formula (Z)M. M : transition metal of group 3-6 of periodic table; Z : ligand of formula (II); A : CR 1>, SiR 1>or P; R 1>hydrogen, 1-20C alkyl, 2-20C alkenyl, 6-20C aryl, alkylaryl having 1-10C alkyl portion and 6-20C aryl portion, NR 9>2, N(SiR 9>3) 2, OH, OSiR 9>3, SiR 9>3or halogen; L 1>-L 3>group of formulae (IIa or IIb); E 1>-E 6>carbon or nitrogen; R 2>-R 8>H, 1-20C alkyl, 2-20C alkenyl, 6-20C aryl, alkylaryl having 1-10C alkyl portion and 6-20C aryl portion, NR 9>2, N(SiR 9>3) 2, OH, OSiR 9>3, SiR 9>3or halogen, where R 2>-R 8>may be substituted by halogen, and two vicinal radicals R 2>-R 8>joins to form 5 or 6 membered ring, and/or two vicinal radicals R 2>-R 8>joins to form heterocyclic containing at least one atom chosen from nitrogen, phosphorus, oxygen and sulfur;and R 9>H, 1-20C alkyl, 2-20C alkenyl, 6-20C aryl, alkylaryl having 1-10C alkyl portion and 6-20C aryl portion, where two geminal radicals R 9>joins to form 5 or 6 membered rings. When E 1>-E 6>is nitrogen then p=0, and when E 1>-E 6>is carbon then p=1. [Image] [Image] Independent claims are included for the following: (1) catalyst system for olefin polymerization comprising at least one transition metal complex, and optionally an organic or inorganic support, one or more activating compounds, olefin polymerization catalyst and one or more metal compounds of group 1, 2 or 13 of periodic table; (2) a prepolymerized catalyst system comprising the catalyst system and one or more linear 2-10C 1-alkene polymerized on to it in a mass ratio of 1:0.1-1:1000; (3) use of catalyst system for polymerization or copolymerization of olefins; and (4) process for preparing polyolefin by (co)polymerization of olefin in presence of catalyst system.

Description

The The present invention relates to transition metal complexes with tridentate, nitrogen-containing, neutral ligand systems and a catalyst system containing at least one of the transition metal complexes.

Also concerns the invention the use of the catalyst system for polymerization or copolymerization of olefins and a process for their preparation of polyolefins by polymerization or copolymerization of Olefins in the presence of the catalyst system.

catalyst systems win with a uniformly defined, active center, so-called single-site catalysts is becoming increasingly important in the polymerization of olefins. This Catalyst system driving to polymers with narrow molecular weight distributions, what in particularly cheap mechanical properties results. Among these single site catalysts Metallocene catalysts in particular have so far been of technical importance obtained. With these you can the polymer properties by suitable substitution on the cyclopentadienyl ligand affected become. However, many metallocene catalysts are only through multi-stage Obtain syntheses and therefore represent a considerable Cost factor in olefin polymerization.

Especially mostly heterocycles and their various ones are easy to represent substituted derivatives and are therefore as starting materials for ligand synthesis especially interesting. Substituted and unsubstituted tridentate Ligand systems based on pyrazoles are often considered to be one Type cyclopentadienyl replacement used. A lot of complexes were made with various types of trispyrazolylborates, these ligands additionally have a negative charge. For example, (cyclopentadienyl) (trispyrazolyl) are complex of Ti and Zr suitable catalysts for the polymerization of olefins.

Other Complexes based on neutral tridentate ligands, which built up from heterocycles are less well studied. Many ligand systems are known and can also be represented quite simply and inexpensively, however, only late transition metal complexes have so far been synthesized with it. Many of these late transition metal complexes serve much more as model substances for enzymes and the suitability of corresponding complexes of the earlier transition metals little is known.

Tridentate imidazole complexes of chromium, with three (N-methylimidazole) in the 2-position linked via a COCH ₃ bridge, have been described by Ruether, Thomas; Braussaud, Nathalie; Cavell, Kingsley J. in Organometallics (2001), 20 (6), 1247-1250. In the presence of methylaluminoxane, however, only oligomers of ethylene can be obtained with this complex.

The The invention was based on the object of further transition metal complexes the base of cyclopentadienyl ligands with a bridged donor to find that for the polymerization of olefins are suitable.

wobei
A CR¹, SiR¹ oder P ist,
R¹ Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, NR⁹ ₂, N(SiR⁹ ₃)₂, OH, OSiR⁹ ₃, SiR⁹ ₃ oder Halogen bedeutet,
L¹–L³ unabhängig vonainander

bedeutet und worin
E¹–E⁶ Kohlenstoff oder Stickstoff ist,
p 0 ist, wenn E¹–E⁶ gleich Stickstoff bedeutet und 1 ist, wenn E¹–E⁶ gleich Kohlenstoff bedeutet,
R²–R⁸ unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Aryl rest, NR⁹ ₂, N(SiR⁹ ₃)₂, OR⁹, OSiR⁹ ₃, SiR⁹ ₃ oder Halogen bedeuten, wobei die organischen Reste R²-R⁸ auch durch Halogene substituiert sein können und je zwei vicinale Reste R²-R⁸ auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R²-R⁸ zu einem Heterocyclus verbunden sind, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält und
R⁹ unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest beutet und je zwei geminale Reste R⁹ auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können.Accordingly, transition metal complexes have been found which contain the following structural feature of the general formula (Z) M (I), in which the variables have the following meaning:
M is a transition metal of group 3, 4, 5 or 6 of the periodic system of the elements and
Z is a ligand of the formula (II)

in which
A is CR ¹ , SiR ¹ or P,
R ^{1 is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OH, OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen,
L ¹ -L ³ independently of each other

means and in what
E ¹ -E ^{6 is} carbon or nitrogen,
p is 0 if E ¹ -E ⁶ is nitrogen and 1 if E ¹ -E ⁶ is carbon,
R ² -R ⁸ independently of one another are hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OR ⁹ , OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen, where the organic radicals R ² -R ^{8 can} also be substituted by halogens and two vicinal radicals R ² -R ^{8 can} also be connected to a five- or six-membered ring, and / or that two vicinal radicals R ² -R ^{8 are connected} to a heterocycle which contains at least one atom from the group N, P, O or S. and
R ⁹ independently of one another is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical and two geminal radicals R ^{9 can} also be connected to form a five- or six-membered ring.

Farther a catalyst system containing the transition metal complexes according to the invention, the use of the transition metal complexes or the catalyst system for polymerization or copolymerization of olefins and a process for producing polyolefins by polymerization or copolymerization of olefins in the presence of the transition metal complex or the catalyst system and polymers obtainable therefrom.

The transition metal complexes according to the invention contain the structural element of the general formula (Z) M (I), where the variables have the above meaning. To the metal atom M can therefore further ligands are bound. The number of others Ligand hangs for example on the oxidation level of the metal atom. As a ligand cyclopentadienyl systems are out of the question. Mono and dianionic ligands as described for example for X. are. additionally can also Lewis bases such as amines, ethers, ketones, aldehydes, Esters, sulfides or phosphines can be bound to the metal center M.

M is a transition metal selected from the group scandium, yttrium, lanthanum, titanium, zircon, hafnium, Vanadium, niobium, tantalum, chromium, molybdenum and tungsten. Are preferred Titanium, zirconium, hafnium, vanadium and chromium, especially vanadium and chrome. The transition metals are preferably located in oxidation states 2, 3 and 4, especially 3 and 4.

Z is a tridentate, neutral ligand system, which can be substituted and / or with one or more aromatic, aliphatic, heterocyclic or heteroaromatic rings can be condensed. there can have 1, 2 or 3 nitrogen atoms of the C = N-L groups at the transition metal center be bound. All three C = N groups are preferred over the Nitrogen to a transition metal center bound. The transition metal complexes according to the invention can monomeric, dimer, trimer or oligomer present. Monomeric transition metal complexes are preferred.

The groups -C = NL ¹ , -C = NL ² and -C = NL ³ are five- or six-membered heteroaromatics. In the case of the five-ring heteroaromatics, these contain at least two nitrogen atoms and can contain three, four or five nitrogen atoms and preferably contain two nitrogen atoms. In the case of six-ring heteroaromatics, these contain at least one nitrogen atom and can contain two, three, four, five or six nitrogen atoms and preferably contain one or two nitrogen atoms. Examples of five-ring heteroaromatics are imidazole, 1,2,3-triazole or 1,2,4-triazole. Examples of six-ring heteroaromatics are pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine or 1,2,3-triazine.

The five- and six-ring heteroaromatics are each linked to A in accordance with the formula (I). Examples of five-ring heteroaromatics, stating the point of attachment, are 2-imidazolyl, 4-imidazolyl, 4-1,2,3-triazolyl, 3-1,2,4-triazolyl or 5-1,2,4-triazolyl. Examples of six-ring heteroaromatics are given the linkage point is 2-pyridinyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, 1,2 , 4-triazin-5-yl or 1,2,4-triazin-6-yl.

By varying the substituents R ² -R ⁸ , the polymerization behavior of the transition metal complexes according to the invention can be influenced. The accessibility of the transition metal atom M for the olefins to be polymerized can be influenced or the bond angle of the ligand Z can be modified by the number and type of the substituents. It is thus possible to modify the activity and selectivity of the catalyst with regard to various monomers, in particular sterically demanding monomers. Since the substituents can also influence the rate of termination reactions of the growing polymer chain, the molecular weight of the resulting polymers can also be changed as a result. The chemical structure of the substituents R ² to R ⁸ can therefore be varied within wide ranges in order to achieve the desired results and to obtain a tailor-made catalyst system. The five- and six-ring heteroaromatics here can be, for example, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-10 C atoms in the aryl radical, trialkylsilyl or halogens, such as Fluorine, chlorine or bromine, dialkylamide, alkylarylamide, diarylamide, alkoxy or aryloxy substituted or condensed with one or more aromatics or heteroaromatics. Examples of suitable C-organic substituents R ² -R ⁸ are: C ₁ -C ₂₀ -alkyl, where the alkyl can be linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl , iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn is a C ₆ -C ₁₀ aryl group can carry as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the double bond can be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, the aryl radical being substituted by further alkyl groups may be substituted, such as, for example, phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, 2,3, 4-, 2,3, 5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl, it being possible for the arylalkyl to be substituted by further alkyl groups, such as, for example, benzyl, o -, m-, p-Methylbenzyl, 1- or 2-ethylphenyl, where optionally two R ² to R ⁸ can also be connected to form a 5- or 6-membered ring and the organic radicals R ² -R ⁸ also by halogens, such as fluorine, chlorine or bromine can be substituted. Furthermore, R ² -R ^{8 can be} amino or alkoxy, such as dimethylamio, N-pyrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy. Suitable Si-organic substituents SiR ⁹ ₃ for R ^{9 are} the same C-organic radicals as explained in more detail above for R ² -R ⁸ , with two R ⁹ possibly also being connected to form a 5- or 6-membered ring can, such as trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tritert.butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These SiR ⁹ ₃ residues can also be bound via an oxygen or nitrogen, such as trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or Tritert.butylsilyloxy. R ² -R ⁸ are preferably hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , Vinyl, allyl, benzyl, phenyl, ortho dialkyl or dichloro substituted phenyls, trialkyl or trichloro substituted phenyls, naphthyl, biphenyl and anthranyl. Particularly suitable Si-organic substituents are trialkylsilyl groups with 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl groups.

Furthermore, those compounds are preferred in which two vicinal radicals R ² -R ^{8 form} a cyclic condensed ring system, ie together with E ² -E ^{6 form} an unsubstituted or substituted benzo or heteroaromatic system. The two vicinal residues R ² -R ⁸ together with -C = NL ¹ , -C = NL ² or -C = NL ³ thus form a heteroaromatic system which is condensed to a heteroaromatic or benzene. An example of a suitable benzo-fused five-ring heteroaromatic is benzimidazole. Examples of suitable benzo-fused six-ring heteroaromatics are quinoline, isoquinoline, phenantridine, cinnoline, phthalazine, quinazoline or quinoxaline. Purine is an example of suitable heteroaromatic-condensed five-ring heteroaromatics. Examples of suitable heteroaromatic-fused six-ring heteroaromatics are 1,8-naphthyridine, 1,5-naphthyridine, pteridine or 1,10-phenanthroline. The name and numbering of the heterocycles was taken from Lettau, Chemistry of Heterocycles, 1st edition, VEB, Weinheim 1979. The heteroaromatics are preferably condensed with the five- or six-ring heteroaromatics via a CC double bond (E ² -E ⁶ is C). An example of a benzo-fused five-membered heteroaromatic compound, stating the point of attachment, is 2-benzimidazolyl. Examples of benzo-fused six-ring heteroaromatics, stating the point of attachment, are 2-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 3-cinnolyl, 1-phthalazyl, 2-quinazolyl, 4-quinazolyl, 2-quinoxalyl, 1-phenanthridyl or 4-1.2 , 3-benzotriazinyl. The condensed aromatic or heteroaromatic ring system can be further C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OR ⁹ , OSiR ⁹ ₃ or SiR ⁹ ₃ .

L ¹ to L ³ can be the same or different. Five and six-membered heteroaromatics can be contained in Z with different L ¹ to L ³ . On the other hand, Z can also contain two or three different five-membered heteroaromatics or two or three different six-membered heteroaromatics. All three L ¹ to L ³ are preferably the same. L ¹ to L ³ are particularly preferably the same and each form a five-ring heteroaromatic system with C = N.

The groups -C = NL ¹ , -C = NL ² and -C = NL ³ are linked together via A. A is CR ¹ , SiR ¹ or P, where R ^{1 is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OH, OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen. By varying the substituent R ¹ , the polymerization behavior of the transition metal complexes according to the invention can be influenced. For example, the nature of the substituent can influence the arrangement of other substituents parallel to R ¹ , which means that the bond angle of the ligand Z can be modified. The chemical structure of the substituent R ¹ can be varied within a wide range. R ¹ can be, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-10 C atoms in the aryl radical, trialkylsilyl or halogens, such as fluorine, chlorine or bromine, dialkylamide, alkylarylamide, diarylamide, hydroxy, siloxy or silyl. Examples of suitable C-organic substituents R ¹ are: C ₁ -C ₂₀ -alkyl, where the alkyl can be linear or branched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn is a C ₆ -C Can carry ₁₀ aryl group as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the double bond internally or terminally can be, for example vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, where the aryl radical can be substituted by further alkyl groups such as phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3, 6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl, where the arylalkyl can be substituted by further alkyl groups, such as benzyl, o-, m-, p- Methylbenzyl, 1- or 2-ethylphenyl, where appropriate the organic radical R ^{1 can} also be substituted by halogens, such as fluorine, chlorine or bromine. Furthermore, R ¹ can be amino or siloxy, such as, for example, dimethylamio, N-pyrolidinyl, picolinyl, trimethylsiloxy, triethylsiloxy or triisopropylsiloxy. Suitable Si-organic substituents SiR ⁹ ₃ for R ^{9 are} the same C-organic radicals as explained in more detail above for R ² -R ⁸ , with two R ⁹ possibly also being connected to form a 5- or 6-membered ring can, such as trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tritert.butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These SiR ⁹ ₃ residues can also be bound via an oxygen or nitrogen, such as trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or Tritert.butylsilyloxy. Preferred R ¹ radicals are somewhat more demanding sterically, since this favors polymerization vs oligomerization and are C ₂ -C ₂₀ alkyl, in particular branched C ₂ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ - C ₂₀ Aryl, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, and in particular ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n - Pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho dialkyl or dichloro substituted phenyls, trialkyl or trichloro substituted phenyls, naphthyl, biphenyl and anthranyl. A is particularly preferred phosphorus.

A^A CR^1A, SiR^1A oder P ist,
R^1A Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, NR^11A ₂, N(SiR^11A ₃)₂, OH, OSiR^11A ₃, SiR^11A ₃ oder Halogen bedeutet,
R^2A–R^10A unabhängig voneinander Wasserstoff C₁-C₂₀-Alkyl C₂-C₂₀-Alkenyl C₆-C₂₀-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, NR^11A ₂, N(SiR^11A ₃)₂, OR^11A, OSiR^11A ₃, SiR^11A ₃ oder Halogen bedeuten, wobei die organischen Reste R^2A–R^10A auch durch Halogene substituiert sein können und je zwei vicinale Reste R^2A–R^10A auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^2A–R^10A zu einem Heterocyclus verbunden sind, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält und
R^11A unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Aryl rest beutet und je zwei geminale Reste R^11A auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können.Preferred transition metal complexes are those in which M is M ^A and Z is Z ^A which contain the following structural feature of the general formula (Z ^A ) M ^A (III), in which the variables have the following meaning:
M ^{A is} a transition metal of group 3, 4, 5 or 6 of the periodic system of the elements and
Z ^{A is} a ligand of the formula (IV)

A ^{A is} CR ^1A , SiR ^1A or P,
R ^{1A is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ^11A ₂ , N denotes (SiR ^11A ₃ ) ₂ , OH, OSiR ^11A ₃ , SiR ^11A ₃ or halogen,
R ^2A -R ^10A independently of one another are hydrogen C ₁ -C ₂₀ alkyl C ₂ -C ₂₀ alkenyl C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ^11A ₂ , N (SiR ^11A ₃ ) ₂ , OR ^11A , OSiR ^11A ₃ , SiR ^11A ₃ or halogen, where the organic radicals R ^2A -R ^{10A can} also be substituted by halogens and two vicinal radicals R ^2A -R ^{10A can} also be connected to form a five- or six-membered ring, and / or that two vicinal radicals R ^2A -R ^{10A are connected} to form a heterocycle which contains at least one atom from the group N, P, O or S and
R ^11A independently of one another hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical looted and two geminal R ^11A residues can also be connected to form a five- or six-membered ring.

The preferred transition metal complexes contain the structural element of the general formula (Z ^A ) M ^A (III), the variables having the meaning given above. Further ligands can therefore also be bound to the metal atom M ^a . The number of other ligands depends, for example, on the oxidation state of the metal atom. Cyclopentadienyl systems are not suitable as ligands. Mono- and dianionic ligands such as those described for X are suitable. In addition, Lewis bases such as amines, ethers, ketones, aldehydes, esters, sulfides or phosphines may be bound to the metal center M ^A.

M ^A is a transition metal selected from the group scandium, yttrium, lanthanum, titanium, zircon, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten. Titanium, zirconium, hafnium, vanadium and chromium are preferred, in particular titanium, vanadium and chromium. The transition metals are preferably in oxidation states 2, 3 and 4, in particular 3 and 4. Chromium in oxidation state 3 is particularly preferred.

Z ^A is a tridentate, neutral ligand system with three imidazole systems linked by A ^A in the 2-position, which can be substituted as desired and / or can be fused with one or more aromatic, aliphatic, heterocyclic or also heteroaromatic rings. Z can be bonded to the transition metal center with 1, 2 or 3 nitrogen atoms of the three imidazole groups (with one C = N group per imidazole). All three C = N groups are preferably bonded to the transition metal center M ^A via the nitrogen. The transition metal complexes according to the invention can be monomeric, dimeric, trimeric or oligomeric. Monomeric transition metal complexes are preferred.

By varying the substituents R ^2A -R ^10A , it is also possible to influence the polymerization behavior of the metal complexes. The accessibility of the metal atom M for the olefins to be polymerized can be influenced by the number and type of the substituents. It is thus possible to modify the activity and selectivity of the catalyst with regard to various monomers, in particular sterically demanding monomers. Since the substituents can also influence the rate of termination reactions of the growing polymer chain, the molecular weight of the resulting polymers can also be changed as a result. The chemical structure of the substituents R ^2A to R ^10A can therefore be varied within a wide range in order to achieve the desired results and to obtain a tailor-made catalyst system. Examples of suitable C-organic substituents R ^2A- R ^10A are as follows: C ₁ -C ₂₀ -alkyl, where the alkyl can be linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl , iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn is a C Can carry ₆ -C ₁₀ aryl group as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclo hexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the Double bond can be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, the aryl radical being further Alkyl groups can be substituted, such as phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, 2,3 , 4-, 2,3 , 5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl, where the arylalkyl can be substituted by further alkyl groups, such as benzyl, o-, m-, p-Methylbenzyl, 1- or 2-ethylphenyl, where optionally two R ^2A to R ^10A can also be connected to form a 5- or 6-membered ring and the organic radicals R ^2A -R ^10A also by halogens , such as fluorine, chlorine or bromine can be substituted. Furthermore, R ^2A -R ^{10A can be} amino or alkoxyl, such as, for example, dimethylamio, N-pyrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy. Suitable Si-organic substituents SiR ^11A ₃ for R ^{11A are} the same radicals as detailed above for R ^2A -R ^10A , it also being possible for two R ^11A to be joined to form a 5- or 6-membered ring, such as e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, Tritert.butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These SiR ^11A ₃ radicals can also be bonded to the cyclopentadienyl backbone via an oxygen or nitrogen, such as, for example, trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or Tritert.butylsilyloxy.

The radicals R ^2A , R ^5A and R ^8A can be the same or different. R ^2A , R ^5A and R ^8A are preferably the same. The radicals R ^2A , R ^5A and R ^8A are preferably a C ₁ -C ₂₀ linear or branched alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl or an arylalkyl with 1-10 C-atoms in the alkyl and 6-20 C-atoms in the aryl, such as benzyl or ethylphenyl. The radicals R ^3A , R ^6A and R ^9A can be the same or different. R ^3A , R ^6A and R ^9A are preferably the same. The radicals R ^3A , R ^6A and R ^9A are preferably a C ₁ -C ₂₀ -alkyl, where the alkyl can be linear or branched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn is a C ₆ -C Can carry ₁₀ aryl group as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the double bond internally or terminally can be, for example vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, where the aryl radical can be substituted by further alkyl groups such as phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5 -Trimethylphenyl, or arylalkyl, where the arylalkyl can be substituted by further alkyl groups, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where appropriate also the organic radicals R ^3A , R ^6A and R ^{9A can} also be substituted by halogens such as fluorine, chlorine or bromine and in particular R ^3A , R ^6A and R ^{9A are} hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho dialkyl or dichloro substituted phenyls, trialkyl or trichloro substituted phenyls, naphthyl, biphenyl and anthranyl. The radicals R ^4A , R ^7A and R ^10A can be the same or different. R ^4A , R ^7A and R ^10A are preferably the same. The preferred embodiments for R ^4A , R ^7A and R ^10A are the same as for R ^3A , R ^6A and R ^9A described above. In a preferred embodiment, the group of the substituents R ^2A , R ^5A and R ^8A and the group of the substituents R ^3A , R ^6A and R ^9A and the group of the substituents R ^4A , R ^7A and R ^10A are each identical within a group , The individual groups can be the same or different from one another.

In a further preferred embodiment, two vicinal radicals R ^3A and R ^4A , R ^6A and R ^7A and R ^9A and R ^10A together with the carbon atoms carrying them form an unsaturated or partially unsaturated 5- or 6-membered carbon or heterocycle ring. This heterocycle, preferably heteroaromatic, contains at least one atom from the group nitrogen, phosphorus, oxygen and / or sulfur, particularly preferably nitrogen and / or sulfur. These pairs of substituents particularly preferably form a substituted or unsubstituted 6-ring aromatic.

A ^A is CR ^1A , SiR ^1A or P, where R ^{1A is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₉ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ^11A ₂ , N (SiR ^11A ₃ ) ₂ , OH, OSiR ^11A ₃ , SiR ^11A ₃ or halogen. R ^1A can be, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-10 C atoms in the aryl radical, trialkylsilyl or halogens, such as fluorine, chlorine or bromine, dialkylamide, alkylarylamide, diarylamide, hydroxy, siloxy or silyl. Examples of suitable C-organic substituents R ^1A are: C ₁ -C ₂₀ -alkyl, where the alkyl can be linear or branched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn is a C ₆ -C Can carry ₁₀ aryl group as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the double bond internally or terminally can be, for example vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, where the aryl radical can be substituted by further alkyl groups such as phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3 , 6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl, where the arylalkyl can be substituted by further alkyl groups, such as benzyl, o-, m-, p -Methylbenzyl, 1- or 2-ethylphenyl, where the organic radical R ^{1A may} also be substituted by halogens such as fluorine, chlorine or bromine. Furthermore, R ^1A can be amino or siloxy, such as, for example, dimethylamio, N-pyrolidinyl, picolinyl, trimethylsiloxy, triethylsiloxy or triisopropylsiloxy. Suitable Si-organic substituents SiR ^11A ₃ for R ^{11A are} the same C-organic radicals as ^{explained in} more detail above for R ^2A -R ^10A , with two R ^11A possibly also being connected to form a 5- or 6-membered ring can, such as trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tritert.butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These SiR ^11A ₃ radicals can also be bonded via an oxygen or nitrogen, such as, for example, trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or Tritert.butylsilyloxy. R ^1A radicals are preferably hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, Allyl, benzyl, phenyl, ortho dialkyl or dichloro substituted phenyls, triallryl or trichloro substituted phenyls, naphthyl, biphenyl and anthranyl. A ^A is particularly preferably phosphorus.

Of the transition metal complexes according to the invention, preference is given to those of the general formulas (Z) MX _k (V) and (Z ^A ) M ^A X _k (VI), in which the variables Z, M, Z ^A and M ^{A have} the above meanings and also their meanings preferred embodiments are preferred herein and:
X independently of one another fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1–10 C atoms in the alkyl radical and 6– 20 carbon atoms in the aryl radical, NR ^1X R ^2X , OR ^1X , SR ^1X , SO ₃ R ^1X , OC (O) R ^1X , CN, SCN, β-diketonate, CO, BF ₄ ^- , PF ₆ ^- , or bulky is non-coordinating anions,
R ^1X -R ^2X independently of one another hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical or SiR ^3X ₃ , where the organic radicals R ^1X -R ^{2X can} also be substituted by halogens or nitrogen and oxygen-containing groups and two radicals R ^1X -R ^{2X can} also be connected to form a five- or six-membered ring,
R ^{3X is} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical and two radicals R ^{3X can} also be connected to form a five- or six-membered ring and
k is 1, 2, or 3.

The above-mentioned embodiments and preferred embodiments for Z, M, Z ^A and M ^{A also} apply individually and in combination for these preferred transition metal complexes.

The ligands X result, for example, from the selection of the corresponding metal starting compounds which are used for the synthesis of the monocyclopentadienyl complexes, but can also be varied subsequently. Halogens such as fluorine, chlorine, bromine or iodine and in particular chlorine are particularly suitable as ligands X. Alkyl residues, such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl, are also advantageous ligands X. Trifluoroacetate, BF ₄ ^- , PF ₆ ^- and weakly or non-coordinating ligands are only intended as examples and in no way conclusive Anions (see, for example, S. Strauss in Chem. Rev. 1993, 93, 927-942) such as B (C ₆ F ₅ ) ₄ ^- can be mentioned.

Amides, alcoholates, sulfonates, carboxylates and β-diketonates are also particularly suitable ligands X. By varying the radicals R ^1X and R ^2X , for example, physical properties such as solubility can be finely adjusted. Examples of suitable C-organic substituents R ^1X -R ^2X are as follows: C ₁ -C ₂₀ -alkyl, where the alkyl can be linear or branched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl , iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn is a C ₆ -C ₁₀ aryl group can carry as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the double bond can be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, the aryl radical being substituted by further alkyl groups and / or radicals containing N or O can be substituted, such as, for example, phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or r 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, 2-methoxyphenyl, 2-N, N-dimethylaminophenyl or arylalkyl, where the arylalkyl can be substituted by further alkyl groups, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where appropriate also R ^1X can be linked with R ^2X to form a 5- or 6-membered ring and the organic radicals R ^1X -R ^{2X can} also be substituted by halogens, such as fluorine, chlorine or bromine. Suitable Si-organic substituents SiR ^3X ₃ for R ^{3X are} the same radicals as detailed above for R ^1X -R ^2X , where two R ^3X can optionally also be linked to form a 5- or 6-membered ring, such as eg trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. C ₁ -C ₁₀ -Alkyl, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and vinyl, allyl, benzyl and Phenyl used as radicals R ^1X and R ^2X . Some of these substituted ligands X are used with particular preference since they can be obtained from cheap and easily accessible starting materials. A particularly preferred embodiment is when X is dimethylamide, methanolate, ethanolate, isopropanolate, phenolate, naphtholate, triflate, p-toluenesulfonate, acetate or acetylacetonate.

The number k of ligands X depends on the oxidation state of the transition metal M or M ^A. The number k cannot therefore be specified in general. The oxidation state of the transition metals M or M ^A in catalytically active complexes is mostly known to the person skilled in the art. Chromium, molybdenum and tungsten are most likely in the +3 oxidation state, vanadium in the +3 or +4 oxidation state. However, complexes can also be used whose oxidation level does not correspond to that of the active catalyst. Such complexes can then be reduced or oxidized accordingly by suitable activators. Chromium complexes in oxidation state +3 and titanium complexes in oxidation state 3 are preferably used.

The synthesis of such ligand systems Z or Z ^A is described, for example, by NJ Curtis and RS Brown in J. Org. Chem. 1980, 45, 4038-4040 and by AA Tolmachev, AA Yurchenko, AS Merculov, MG Semenova, EV Zarudnitskii, VV Ivanov and AM Pinchuk in heteroatom. Chem. 1999, 10 (7), 585-597.

The Metal complexes, especially the chrome complexes, can be opened up easily obtained if the corresponding ligands Z or ZA with metal salts such as metal chlorides e.g. with chrome trichloride tris (tetrahydrofuranj, Titanium trichloride tris (tetrahydrofuran) or vanadium trichloride tris (tetrahydrofuran).

• A) mindestens einen erfindungsgemässen Übergangsmetallkomplex
• B) optional einen organischen oder anorganischen Träger,
• C) optional eine oder mehrere aktivierende Verbindungen,
• D) optional ein oder mehrere zur Olefinpolymerisation geeignete Katalysatoren und
• E) optional eine oder mehrere Metallverbindungen mit einem Metall der Gruppe 1, 2 oder 13 des Periodensystems.

The transition metal complexes according to the invention can be used alone or with other components as a catalyst system for olefin polymerization. Catalyst systems for olefin polymerization were also found to contain

• A) at least one transition metal complex according to the invention
• B) optionally an organic or inorganic carrier,
• C) optionally one or more activating connections,
• D) optionally one or more catalysts and suitable for olefin polymerization
• E) optionally one or more metal compounds with a metal from group 1, 2 or 13 of the periodic table.

So can more than one of the monocyclopentadienyl complexes according to the invention in contact with the olefin (s) to be polymerized simultaneously to be brought. This has the advantage that such a wide range Polymers can be generated. In this way e.g. bimodal products getting produced.

In order to the transition metal complexes according to the invention in polymerization processes in the gas phase or in suspension can be used it is often an advantage that the Metallocenes are used in the form of a solid, i.e. that they're on a solid support B) are applied. The supported transition metal complexes also have a high productivity on. The transition metal complexes according to the invention can therefore optionally also immobilized on an organic or inorganic carrier B) and in supported Form used in the polymerization. This can cause reactor deposits, for example be avoided and the polymer morphology controlled. As support materials preference is given to silica gel, magnesium chloride, aluminum oxide, mesoporous materials, Aluminosilicates, hydrotalcites and organic polymers such as polyethylene, Polypropylene, polystyrene, polytetrafluoroethylene or polar functionalized Polymers, such as copolymers of ethene and acrylic esters, Acrolein or vinyl acetate are used.

Especially a catalyst system containing a transition metal complex according to the invention is preferred and at least one activating compound C), which additionally an support component B) contains.

Around such a supported one To get the catalyst system, the unsupported catalyst system with a support component B) be implemented. In principle, the order of assembly is of carrier component B), transition metal complex according to the invention A) and the activating compound C) any. The transition metal complex according to the invention A) and the activating compound C) can be independent of one another or simultaneously be fixed. After the individual process steps, the Solid with suitable inert solvents such as. B. aliphatic or aromatic hydrocarbons.

In a preferred form of representation of the supported catalyst system at least one of the transition metal complexes according to the invention in one suitable solvent brought into contact with at least one activating compound C), preferably a soluble Reaction product, an adduct or a mixture is obtained. The preparation thus obtained is then dehydrated or inertized carrier material mixed, the solvent removed and the resulting supported transition metal complex catalyst system dried to ensure that the solvent is complete or mostly from the pores of the carrier material Will get removed. The worn one Catalyst is considered to be free flowing Get powder. examples for the technical implementation of the above method are in WO 96/00243, WO 98/40419 or WO 00/05277. Another preferred embodiment is, initially to generate the activating compound C) on the carrier component B) and then this supported one Connection with the transition metal complex according to the invention A) contact.

As support component B) finely divided carriers are preferably used, any one can be organic or inorganic solid. In particular, the support component B) a porous support such as Talc, a layered silicate such as Montmorillonot, Mica or mica, an inorganic oxide or a finely divided polymer powder (e.g. Polyolefin or polar functionalized polymer).

The carrier materials used preferably have a specific surface area in the range from 10 to 1000 m ² / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size of 1 to 500 μm. Carriers with a specific surface area in the range from 50 to 700 m ² / g, a pore volume in the range between 0.4 and 3.5 ml / g and an average particle size in the range from 5 to 350 μm are preferred. Carriers with a specific surface area in the range from 200 to 550 m ² / g, a pore volume in the range between 0.5 to 3.0 ml / g and an average particle size of 10 to 150 μm are particularly preferred.

The inorganic carrier can be subjected to a thermal treatment, for example to remove adsorbed water. Such a drying treatment is generally carried out at temperatures in the range from 80 to 300.degree. C., preferably from 100 to 200.degree. C., the drying at 100 to 200.degree. C. preferably under vacuum and / or an inert gas blanket (e.g. nitrogen) takes place, or the inorganic carrier can be calcined at temperatures of 200 to 1000 ° C to adjust the desired structure of the solid and / or the desired OH concentration on the surface if necessary. The carrier can also be treated chemically, it being possible to use customary drying agents such as metal alkyls, preferably aluminum alkyls, chlorosilanes or SiCl ₄ , but also methylalumoxane. Appropriate treatment methods are described, for example, in WO 00/31090.

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

organic support materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) are also used and should preferably also be used before Use of adhering moisture, solvent residues or others Contamination from appropriate cleaning and drying operations be freed. It can also functionalized polymer carriers, z. B. based on polystyrene, polyethylene or polypropylene be about their functional groups, for example ammonium or hydroxy groups, at least one of the catalyst components can be fixed.

Suitable inorganic oxides as carrier component B) can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the periodic table of the elements. Examples of preferred oxides as carriers include silicon dioxide, aluminum oxide and mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for example, MgO, CaO, AlPO ₄ , ZrO ₂ , TiO ₂ , B ₂ O ₃ or mixtures thereof.

As solid substrates B) for Catalysts for the olefin polymerization is preferably carried out using silica gels, because particles can be produced from this material, which in their Size and structure as a carrier for the Olefin polymerization are suitable. Have proven particularly successful spray dried itself Silica gels, which are spherical agglomerates from smaller ones granular Particles, the so-called primary particles, is. The silica gels can be dried and / or calcined before use.

Likewise preferred carriers B) are hydrotalcites and calcined hydrotalcites. In mineralogy, hydrotalcite is a natural mineral with the ideal formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O referred to, whose structure is derived from that of the brucite Mg (OH) ₂ . Brucite crystallizes in a layer structure with the metal ions in octahedral gaps between two layers of densely packed hydroxyl ions, with only every second layer of the octahedral gaps being occupied. In the hydrotalcite, some magnesium ions are replaced by aluminum ions, which gives the layer package a positive charge. This is compensated for by the anions, which are located in the intermediate layers together with crystal water.

Corresponding layer structures can be found not only in the case of magnesium-aluminum hydroxides, but generally in the case of mixed metal hydroxides of the general formula which have a layered structure M (II) _2x ²⁺ M (III) ₂ ³⁺ (OFi) _{4x + 4} · A _{2 / n} ⁿ - · zH ₂ O in which M (II) is a divalent metal such as Mg, Zn, Cu, Ni, Co, Mn, Ca and / or Fe and M (III) is a trivalent metal such as Al, Fe, Co, Mn, La, Ce and / or Cr is, x stands for numbers from 0.5 to 10 in 0.5 steps, A stands for an interstitial anion and n for the charge of the interstitial anion, which can be from 1 to 8, usually from 1 to 4, and z is a whole Number from 1 to 6, in particular from 2 to 4 means. Interstitial anions are organic anions such as alcoholate anions, alkyl ether sulfates, aryl ether sulfates or glycol ether sulfates, inorganic anions such as especially carbonate, hydrogen carbonate, nitrate, chloride, sulfate or B (OH) ₄ ^- or polyoxometal anions such as Mo ₇ O ₂₄ ^6- or V ₁₀ O ₂₈ ^{6 -} into consideration. However, it can also be a mixture of several such anions.

Accordingly all such should be layered constructed, mixed metal hydroxides as hydrotalcites in the sense of the present invention.

Out Hydrotalcites can be obtained by calcination, i.e. Warm that produce so-called calcined hydrotalcites, which among other things the desired Content of hydroxyl groups can be adjusted. Still changing also the structure of the crystal structure. The production of the used according to the invention Calcined hydrotalcites usually take place at temperatures above of 180 ° C. Calcination for a period of 3 to is preferred 24 hours at temperatures from 250 ° C to 1000 ° C and especially from 400 ° C to 700 ° C. Simultaneous transfer of air or inert gas or applying vacuum is possible.

At the Heating give the natural or synthetic hydrotalcites first water, i.e. it takes place a drying. With further heating, the actual calcination, the metal hydroxides change with elimination of hydroxyl groups and interstitial anions into the metal oxides, also in the calcined hydrotalcites also OH groups or interstitial Anions such as carbonate can be included. One measure of this is Loss on ignition. This is the weight loss that a sample suffers from two steps first for 30 min at 200 ° C in a drying cabinet and then for 1 hour at 950 C in one Muffle furnace is heated.

at the calcined hydrotalcites used as component B) mixed oxides of the divalent and trivalent metals M (II) and M (III), the molar ratio of M (II) to M (III) in generally in the range from 0.5 to 10, preferably from 0.75 to 8 and in particular from 1 to 4. Furthermore, usual amounts of impurities, for example on Si, Fe, Na, Ca or Ti and also chlorides and sulfates be included.

preferred calcined hydrotalcites B) are mixed oxides in which M (II) magnesium and M (III) is aluminum. Corresponding aluminum-magnesium mixed oxides are from Condea Chemie GmbH (now Sasol Chemie), Hamburg available under the trade name Puralox Mg.

Prefers are also calcined hydrotalcites, in which the structural Conversion almost or completely is completed. Calcination, i.e. a transformation of the structure let yourself for example using X-ray diffractograms determine.

The hydrotalcites, calcined hydrotalcites or silica gels used are generally used as fine-particle powders with an average particle diameter D50 of 5 to 200 μm, preferably 10 to 150 μm, particularly preferably 15 to 100 μm and in particular 20 to 70 μm Usually pore volumes from 0.1 to 10 cm ³ / g, preferably from 0.2 to 5 cm ³ / g, and specific surfaces from 30 to 1000 m ² / g, preferably from 50 to 800 m ² / g and in particular from 100 up to 600 m ² / g. The transition metal complexes according to the invention are preferably applied in an amount such that the concentration of the transition metal complex in the finished catalyst system is 5 to 200 μmol, preferably 20 to 100 μmol and particularly preferably 25 to 70 μmol per g of support B).

The transition metal complexes according to the invention are for are only partially active in polymerization and then become with an activator, component C), brought into contact for good polymerization to be able to develop. Furthermore contains the catalyst system therefore optionally as component C) one or several activating compounds, preferably at least one cation-forming Compound C).

suitable Compounds C) capable of reacting with the transition metal complex A) convert it into a catalytically active or more active compound e.g. Compounds of the aluminoxane type, a strong neutral Lewis acid an ionic compound with a Lewis acidic cation or an ionic Compound with Bronsted acid as Cation.

wobei R^1C–R^4C unabhängig voneinander eine C₁-C₆-Alkylgruppe bedeutet, bevorzugt eine Methyl-, Ethyl-, Butyl- oder Isobutylgruppe und I für eine ganze Zahl von 1 bis 30, bevorzugt 5 bis 25 steht.The compounds described in WO 00/31090, for example, can be used as aluminoxanes. Open-chain or cyclic aluminoxane compounds of the general formulas (X) or (XI) are particularly suitable.

where R ^1C -R ^4C independently of one another denotes a C ₁ -C ₆ alkyl group, preferably a methyl, ethyl, butyl or isobutyl group and I represents an integer from 1 to 30, preferably 5 to 25.

A particularly suitable aluminoxane compound is methylaluminoxane.

The These oligomeric aluminoxane compounds are usually prepared by controlled implementation of a solution of trialkyl aluminum with water. As a rule, the oligomers obtained in this way lie Aluminoxane compounds as mixtures of different lengths, both linear as well as cyclic chain molecules, so that I as Mean is to be seen. The aluminoxane compounds can also in a mixture with other metal alkyls, usually with aluminum alkyls available. Suitable aluminoxane preparations as component C) are commercially available.

Farther can as component C) instead of the aluminoxane compounds of the general Formulas (X) or (XI), modified aluminoxanes can also be used, where some of the hydrocarbon residues or hydrogen atoms, Alkoxy, aryloxy, siloxy, or amide residues are replaced.

It has proven to be advantageous, the monocyclopentadienyl complexes A) and to use the aluminoxane compounds in such amounts that this atomic ratio between aluminum from the aluminoxane compounds including still contained aluminum alkyl, and the transition metal from the transition metal complex A) in the range from 1: 1 to 1000: 1, preferably from 10: 1 to 500: 1 and in particular in the range from 20: 1 to 400: 1.

A Another type of suitable activating component C) are so-called hydroxyaluminoxanes. These can be added, for example from 0.5 to 1.2 equivalents Water, preferably 0.8 to 1.2 equivalents Water per equivalent Aluminum of an alkyl aluminum compound, in particular triisobutyl aluminum, at low temperatures, usually below 0 ° C getting produced. Such compounds and their use in olefin polymerization are described, for example, in WO 00/24787 described. The atomic ratio between aluminum from the hydroxyaluminoxane compound and the transition metal from the transition metal complex A) usually lies in the range from 1: 1 to 100: 1, preferably from 10: 1 to 50: 1 and in particular in the range from 20: 1 to 40: 1. A transition metal metal is preferred Dialkyl compound A) used.

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

Further examples for strong, neutral Lewis acids are mentioned in WO 00/31090.

In particular, as component C) boranes and boroxines are suitable, such as. B. trialkylborane, triarylborane or trimethylboroxine. Boranes which carry at least two perfluorinated aryl radicals are particularly preferably used. Particularly preferred are compounds of the general formula (XII) in which X ^1C , X ^2C and X ^{3C are the} same, preferably tris (pentafluorophenyl) borane.

suitable Compounds C) are preferred from the reaction of aluminum or boron compounds of the formula (XII) with water, alcohols, phenol derivatives, Thiophenol derivatives or aniline derivatives shown, being particularly the halogenated and in particular the perfluorinated alcohols and Phenols are important. Examples of particularly suitable compounds are pentafluorophenol, 1,1-bis (pentafluorophenyl) methanol or 4-hydroxy-2,2 ', 3,3', 4,4 ', 5,5', 6,6'-nonafluorobiphenyl. examples for are the combination of compounds of formula (XII) with Broensted acids in particular trimethyl aluminum / pentafluorophenol, trimethyl aluminum / 1-bis (pentafluorophenyl) methanol, Trimethylaluminum / 4-hydroxy-2,2 ', 3,3', 4,4 ', 5,5', 6,6'-nonafluorobiphenyl, Triethyl aluminum / pentafluorophenol or triisobutyl aluminum / pentafluorophenol or triethyl aluminum / 4,4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl Hydrate.

In other suitable aluminum and boron compounds of the formula (XII), X ^{1C is} an OH group, such as, for example, in boronic acids and boric acids, boric acids with perfluorinated aryl radicals, such as (C ₆ F ₅ ) ₂ BOH, being mentioned in particular.

Strength neutral Lewis acids, which are suitable as activating compounds C) are also Reaction products from the reaction of a boronic acid with two equivalents of an aluminum trialkyl or the reaction products from the reaction an aluminum trialkyl with two equivalents of an acidic fluorinated one, in particular perfluorinated carbon compound such as pentafluorophenol or bis (pentafluorophenyl) boric acid.

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

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

salts with non-coordinating anions can also be combined a boron or aluminum compound, e.g. an aluminum alkyl, with a second compound by reaction two or more Link boron or aluminum atoms can, e.g. Water, and a third compound associated with the boron or Aluminum compound forms an ionizing ionic compound, e.g. Triphenylchloromethane, or optionally a base, preferably one organic nitrogenous base, such as an amine, an aniline derivative or a nitrogen heterocycle become. additionally can be a fourth compound, also with the boron or aluminum compound responds, e.g. Pentafluorophenol, can be added.

Ionic compounds with Bronsted acids as cations preferably also have non-coordinating counterions. Protonated amine or aniline derivatives are particularly preferred as Bronsted acid Trains t. Preferred cations are N, N-dimethylanilinium, N, N-dimethylcylohexylammonium and N, N-dimethylbenzylammonium and derivatives of the latter two.

Also Compounds with anionic boron heterocycles, as described in WO 9736937 are suitable as component C), in particular Dimethylanilinium boratabenzenes or tritylboratabenzenes.

preferred Ionic compounds C) contain borates which have at least two wear perfluorinated aryl residues. N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate and in particular are particularly preferred N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate or Trityl.

Two or more borate anions and or boranes can also be linked to one another or a borate anion to a borane, as in the dianion ((C ₆ F ₅ ) ₃ BC ₆ F ₄ -B (C ₆ F ₅ ) ₃ ] ^2- , the anion [(C ₆ F ₅ ) ₃ B-CN-B (C ₆ F ₅ ) ₃ ] ^- or the borate anion can be bonded to the support surface via a bridge with a suitable functional group.

Further suitable activating compounds C) are listed in WO 00/31090.

The Amount of strong, neutral Lewis acids, ionic compounds with Lewis acid cations or ionic compounds with Brönsted acids as Cations preferably 0.1 to 20 equivalents, preferably 1 to 10 equivalents, based on the transition metal complex A).

suitable activating compounds C) are also boron-aluminum compounds such as di- [bis (pentafluorophenylboroxy)] methylalane. Corresponding boron-aluminum compounds are, for example, those disclosed in WO 99/06414.

It can also mixtures of all the activating compounds C) mentioned above be used. Preferred mixtures contain aluminoxanes, especially methylaluminoxane, and an ionic compound, especially one containing the tetrakis (pentafluorophenyl) borate anion and / or a strong neutral Lewis acid, especially tris (pentafluorophenyl) borane.

Preferably become both the transition metal complexes A) and the activating compounds C) in a solvent used, with aromatic hydrocarbons having 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or mixtures of these are preferred.

Of there is another possibility to use an activating compound C), which simultaneously as carrier B) can be used. Such systems are, for example from an inorganic oxide treated with zirconium alkoxide and subsequent chlorination e.g. obtained with carbon tetrachloride. The representation of such systems is for example in WO 01/41920.

On a wide range of products can also be obtained by using the transition metal complexes according to the invention A) in combination with at least one other for the polymerization catalyst D) suitable for olefins. Therefore, as optional component D) one or more for olefin polymerization suitable catalysts can be used in the catalyst system. As Catalysts D) are particularly classic Ziegler Natta Titanium-based catalysts and classic Phillips catalysts based on chromium oxides.

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

in der die Substituenten und Indizes folgende Bedeutung haben:
M^1D Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdän oder Wolfram, sowie Elemente der 3. Gruppe des Periodensystems und der Lanthaniden,
X^D Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, C₂-C₁₀-Alkenyl, C₆-C₁₅-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, -OR^6D oder -NR^6DR^7D, oder zwei Reste X^D für einen substituierten oder unsubstituierten Dienliganden, insbesondere einen 1,3-Dienliganden, stehen, und die Reste X^D gleich oder verschieden sind und gegebenenfalls miteinander verbunden sind,
E^1D–E^5D Kohlenstoff oder maximal ein E^1D bis E^5D Phosphor oder Stickstoff, bevorzugt Kohlenstoff
t 1, 2 oder 3 ist, wobei t entsprechend der Wertigkeit von M^1D den Wert aufweist, bei dem der Metallocenkomplex der allgemeinen Formel (XIV) ungeladen vorliegt,
wobei
R^6D und R^7D C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl, Alkylaryl, Arylalkyl, Fluoralkyl oder Fluoraryl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest bedeuten und
R^1D bis R^5D unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, die ihrererseits durch C₁-C₁₀-Alkyl substituiert sein können, C₂-C₂₂-Alkenyl, C₆-C₂₂-Aryl, Arylalkyl mit 1 bis 16 C-Atomen im Alkylrest und 6 bis 21 C-Atomen im Arylrest, NR^8D ₂, N(SiR^8D ₃)₂, OR^8D, OSiR^8D ₃, SiR^8D ₃, wobei die organischen Reste R^1D–R^5D auch durch Halogene substituiert sein können und/oder je zwei Reste R^1D–R^5D, insbesondere vicinale Reste, auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^1D-R^5D zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sein können, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält, mit
R^8D gleich oder verschieden C₁-C₁₀-Alkyl, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryloxy sein kann und
Z^1D für X^D oder

steht,
wobei die Reste
R^9D bis R^13D unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, die ihrererseits durch C₁-C₁₀-Alkyl substituiert sein können, C₂-C₂₂-Alkenyl, C₆-C₂₂-Aryl, Arylalkyl mit 1 bis 16 C-Atomen im Alkylrest und 6–21 C-Atomen im Arylrest, NR^14D ₂, N(SiR^14D ₃)₂, OR^14D, OSiR^14D ₃, SiR^14D ₃, wobei die organischen Reste R^9D–R^13D auch durch Halogene substituiert sein können und/oder je zwei Reste R^9D–R^13D, insbesondere vicinale Reste, auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^9D–R^13D zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sein können, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält, mit
R^14D gleich oder verschieden C₁-C₁₀-Alkyl, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryloxy bedeuten,
E^6D-E^10D Kohlenstoff oder maximal ein E^6D bis E^10D Phosphor oder Stickstoff, bevorzugt Kohlenstoff
oder wobei die Reste R^4D und Z^1D gemeinsam eine Gruppierung -R^15D _v -A^1D-bilden, in der

=BR^16D, =BNR^16DR^17D, =AlR^16D, -Ge-, -Sn-, -O-, -S-, =SO, =SO₂, = NR^16D, =CO, =PR^16D oder =P(O)R^16D ist,
wobei
R^66D–R^21D gleich oder verschieden sind und jeweils ein Wasserstoffatom, ein Halogenatom, eine Trimethylsilylgruppe, eine C₁-C₁₀-Alkylgruppe, eine C₁-C₁₀-Fluoralkylgruppe, eine C₆-C₁₀-Fluorarylgruppe, eine C₆-C₁₀-Arylgruppe, eine C₁-C₁₀-Alkoxygruppe, eine C₇-C₁₅-Alkylaryloxygruppe, eine C₂-C₁₀-Alkenylgruppe, eine C₇-C₄₀-Arylalkylgruppe, eine C₈-C₄₀-Arylalkenylgruppe oder eine C₇C₄₀-Alkylarylgruppe bedeuten oder wobei zwei benachbarte Reste jeweils mit den sie verbindenden Atomen einen 4 bis 15 C-Atome aufweisenden gesättigten oder ungesättigten Ring bilden, und
M^2D–M^4D Silicium, Germanium oder Zinn ist, bevorzugt Silicium

-NR^22D ₂, -PR^22D ₂ oder ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem bedeuten, mit
R^22D unabhängig voneinander C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl, C₃-C₁₀-Cycloalkyl, C₇-C₁₈-Alkylaryl oder Si(R^23D)₃,
R^23D Wasserstoff, C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl, das seinerseits mit C₁-C₄-Alkylgruppen substituiert sein kann oder C₃-C₁₀-Cycloalkyl,
v 1 oder im Fall von A^1D gleich ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem auch 0
oder wobei die Reste R^4D und R^12D gemeinsam eine Gruppierung -R^15D- bilden.Particularly suitable components D) are also those with at least one cyclopentadienyl ligand, which are commonly referred to as metallocene complexes. Metallocene complexes of the general formula (XIV) are particularly suitable here

in which the substituents and indices have the following meaning:
M ^1D titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, as well as elements of the 3rd group of the periodic table and the lanthanides,
X ^D fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₁₅ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, -OR ^6D or -NR ^6D R ^7D , or two radicals X ^{D represent} a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals X ^{D are the} same or different and are optionally together are connected,
E ^1D -E ^5D carbon or at most one E ^1D to E ^5D phosphorus or nitrogen, preferably carbon
t is 1, 2 or 3, where t has the value at which the metallocene complex of the general formula (XIV) is uncharged, corresponding to the valency of M ^1D ,
in which
R ^6D and R ^{7D are} C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical and
R ^1D to R ^5D independently of one another are hydrogen, C ₁ -C ₂₂ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn can be substituted by C ₁ -C ₁₀ alkyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₂₂ aryl, arylalkyl with 1 to 16 carbon atoms in the alkyl radical and 6 to 21 carbon atoms in the aryl radical, NR ^8D ₂ , N (SiR ^8D ₃ ) ₂ , OR ^8D , OSiR ^8D ₃ , SiR ^8D ₃ , wherein the organic radicals R ^1D -R ^{5D can} also be substituted by halogens and / or two radicals R ^1D -R ^5D , in particular vicinal radicals, can also be linked to form a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^1D -R ^5D can be linked to form a five-, six- or seven-membered heterocycle which contains at least one atom from the group N, P, O or S.
R ^{8D may be the} same or different C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl, C ₁ -C ₄ alkoxy or C ₆ -C ₁₀ aryloxy and
Z ^1D for X ^D or

stands,
being the leftovers
R ^9D to R ^13D independently of one another are hydrogen, C ₁ -C ₂₂ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn can be substituted by C ₁ -C ₁₀ alkyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₂₂ aryl, arylalkyl with 1 to 16 carbon atoms in the alkyl radical and 6-21 carbon atoms in the aryl radical, NR ^14D ₂ , N (SiR ^14D ₃ ) ₂ , OR ^14D , OSiR ^14D ₃ , SiR ^14D ₃ , wherein the organic radicals R ^9D -R ^{13D can} also be substituted by halogens and / or two radicals R ^9D -R ^13D , in particular vicinal radicals, can also be connected to form a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^9D -R ^13D can be linked to form a five-, six- or seven-membered heterocycle which contains at least one atom from the group N, P, O or S.
R ^{14D are the} same or different C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl, C ₁ -C ₄ alkoxy or C ₆ -C ₁₀ aryloxy,
E ^6D -E ^10D carbon or at most one E ^6D to E ^10D phosphorus or nitrogen, preferably carbon
or wherein the radicals R ^4D and Z ^1D together form a grouping -R ^15D _v -A ^1D -, in which

= BR ^16D , = BNR ^16D R ^17D , = AlR ^16D , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , = NR ^16D , = CO, = PR ^16D or = P (O) R ^16D is
in which
R ^66D -R ^{21D are the} same or different and each represents a hydrogen atom, a halogen atom, a trimethylsilyl group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ fluoroalkyl group, a C ₆ -C ₁₀ fluoroaryl group, a C ₆ -C ₁₀ aryl group, a C ₁ -C ₁₀ alkoxy group, a C ₇ -C ₁₅ alkylaryloxy group, a C ₂ -C ₁₀ alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₈ -C ₄₀ arylalkenyl group or a C ₇ C ₄₀ -alkylaryl group or where two adjacent radicals each form a saturated or unsaturated ring having 4 to 15 C atoms with the atoms connecting them, and
M ^2D- M ^{4D is} silicon, germanium or tin, preferably silicon

-NR ^22D ₂ , -PR ^22D ₂ or an unsubstituted, substituted or fused, heterocyclic ring system mean with
R ^22D independently of one another are C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, C ₃ -C ₁₀ cycloalkyl, C ₇ -C ₁₈ alkylaryl or Si (R ^23D ) ₃ ,
R ^{23D is} hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, which in turn can be substituted by C ₁ -C ₄ alkyl groups or C ₃ -C ₁₀ cycloalkyl,
v 1 or, in the case of A ^1D , an unsubstituted, substituted or fused, heterocyclic ring system also 0
or wherein the radicals R ^4D and R ^12D together form a group -R ^15D -.

A ^1D can, for example, form an amine, ether, thioether or phosphine together with the bridge R ^15D . A ^1D can also represent an unsubstituted, substituted or condensed, heterocyclic aromatic ring system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus. Examples of 5-ring heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms and / or a sulfur or oxygen atom as ring members, are 2-furyl, 2-thienyl, 2-pyrrolyl, 3-isoxazolyl, 5-isoxazolyl, 3- Isothiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl or 1,2,4-triazol-3- yl. Examples of 6-membered heteroaryl groups which can contain one to four nitrogen atoms and / or a phosphorus atom are 2-pyridinyl, 2-phosphabenzolyl 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5- Triazin-2-yl and 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl or 1,2,4-triazin-6-yl. The 5-ring and 6-ring heteroaryl groups can also be substituted by C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-10 C atoms in the aryl radical, trialkylsilyl or halogens, such as fluorine, chlorine or bromine, or be condensed with one or more aromatics or heteroaromatics. Examples of benzo-fused 5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumaronyl, 7-coumaronyl, 2-thionaphthenyl, 7-thionaphthenyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl or 7-benzimidazolyl. Examples of benzo-fused 6-membered heteroaryl groups are 2-quinolyl, 8-quinolyl, 3-cinnolyl, 8-cinnolyl, 1-phthalazyl, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl, 5-quinoxalyl, 4-acridyl, 1- Phenanthridyl or 1-phenazyl. description and numbering of the heterocycles was taken from L. Fieser and M. Fieser, Textbook of Organic Chemistry, 3rd revised edition, Verlag Chemie, Weinheim 1957.

The radicals X ^D in the general formula (XIV) are preferably the same, preferably fluorine, chlorine, bromine, C ₁ to C ₇ alkyl, or aralkyl, in particular chlorine, methyl or benzyl.

The Synthesis of such complex compounds can be done according to known Methods are carried out, the implementation of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, Hafnium or chromium is preferred.

bevorzugt.Of the metallocene complexes of the general formula (XIV) are

prefers.

Of the compounds of the formula (XIVa), those are particularly preferred in which
M ^1D titanium, vanadium or chrome
X ^D chlorine, C ₁ -C ₄ alkyl, phenyl, alkoxy or aryloxy
t the number 1 or 2 and
R ^1D to R ^{5D are} hydrogen, C ₁ -C ₆ alkyl or two adjacent R ^1D to R ^{5D are} a substituted or unsubstituted benzo group.

Preferred compounds of the formula (XIVb) are those in which
M ^{1D stands} for titanium, zirconium, vanadium, hafnium or chromium,
X ^{D is} fluorine, chlorine, C ₁ -C ₄ -alkyl or benzyl, or two radicals X ^{D are} a substituted or unsubstituted butadiene ligand,
t 0 for chromium, otherwise 1 or 2, preferably 2
R ^1D to R ^{5D are} hydrogen, C ₁ -C ₈ alkyl, C ₆ -C ₈ aryl, NR ^8D ₂ , OSiR ^8D ₃ or Si (R ^8D ) ₃ and
R ^9D to R ^{13D are} hydrogen, C ₁ -C ₈ alkyl or C ₆ -C ₈ aryl, NR ^14D ₂ , OSiR ^14D ₃ or Si (R) ^14D ₃
or two radicals R ^1D to R ^5D and / or R ^9D to R ^13D together with the C ₅ ring mean an indenyl or substituted indenyl system.

In particular the compounds of the formula (XIVb) in which the cyclopentadienyl radicals are the same are suitable are.

Examples for special Suitable compounds D) of formula (XIVb) include: bis (cyclopentadienyl) chromium, Bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, Bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, Bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, Bis (tetrahydroindenyl) zirconium dichloride and bis (trimethylsilylcyclopentadienyl) zirconium dichloride, as well as the corresponding dimethyl zirconium compounds.

steht
oder =BR^16D oder =BNR^16DR^17D bedeuten,
M^1D für Titan, Zirkon oder Hafnium, insbesondere Zirkon und
X^D gleich oder verschieden für Chlor, C₁-C₄-Alkyl, Benzyl, Phenyl oder C₇-C₁₅-Alkylaryloxy stehen.Of the compounds of the formula (XIVc), those in which

stands
or = BR ^16D or = BNR ^16D R ^17D ,
M ^1D for titanium, zircon or hafnium, especially zircon and
X ^{D are the} same or different for chlorine, C ₁ -C ₄ alkyl, benzyl, phenyl or C ₇ -C ₁₅ alkyl aryloxy.

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

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

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

As Component D) are also preferably bridged bis-indenyl complexes in the rac or pseudo-rac form used, the pseudo-rac form being such complexes acts in which the two indenyl ligands without consideration all other substituents of the complex relative to each other in the rac arrangement.

Further examples of particularly suitable catalysts D) (XIVc) and (XIVc ') include dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconiumdichloridadyl (ethylene bis) dichloride, ethylene bis (dichloride), ethylene bis (dichloride), ethylene bis (dichloride), ethylene bis (dichloride), ethylene bis (dichloride), ethylene bis (dichloride), ethylene bis (dichloride), ethylene bis (dichloride), (tetrahydroindenyl) zirconium dichloride, tetramethylethylene-9-fluorenylcyclopentadienylzirkoniumdichlorid, dimethylsilanediylbis (3-tert-butyl-5-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-tert-butyl-5-ethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2-methylindenyl) zirconium dichloride, dimethylsilanediylbis ( 2-isopropylindenyl) zirconium dichloride, dimethylsilanediylbis (2-tert.butylindenyl) zirconium dichloride, diethylsilanediylbis (2-methylindenyl) zirconiumdibromide, dimethylsilanediylbis (3-methyl-5-methylcyclopentadienyl) 3-zirconiumdisilylidyldichloridiumdichloridium (3) Dimethylsilanediylbis (2-ethylindenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, dimethylsilanediylbis (2-ethyl-4,5-benzindenyl) zirconium dichloride, methylphenylsilanediylbis (2-methyl-zirconium), 4,5-benzodichloride Methylphenylsilanediylbis (2-ethyl-4,5-benzindenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, diphenylsilanediylbis (2-ethyl-4,5-benzindenyl) zirconium dichloride, diphenylsilaniumdiumdichloridiyldichloride, Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride, dimethylsilanediylbis (2-ethyl-4-phenyl-indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4- (1-naphthyl) -indenyl) -zirconiumdichloride -ethyl-4- (1-naphthyl) -indenyl) zirconium dichloride, dimethylsilanediylbis (2-propyl-4- (1-naphthyl) -indenyl) zirconium dichloride, dimethylsilanediylbis (2-i-butyl-4- (1-naphthyl) -indenyl ) zirconium dichloride, dimethylsilanediylbis (2-propyl-4- (9-phenanthryl) -indenyl) -circ onium dichloride, dimethylsilanediylbis (2-methyl-4-isopropylindenyl) zirconium dichloride, dimethylsilanediylbis (2,7-dimethyl-4-isopropylindenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) (2) methyldilidilyl (zirconium) -4 [p-trifluoromethylphenyl] indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4- [3 ', 5'-dimethylphenyl] indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4- [4'-tert.butylphenyl] indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-4- [4'-tert.butylphenyl] indenyl) zirconium dichloride, dimethylsilanediylbis (2-ethyl-4- [4'-tert.butylphenyl] indenyl) zirconiumdichloride, dimethylsilanid -propyl-4- [4'-tert.butylphenyl] indenyl) zirconium dichloride, dimethylsilanediylbis (2-isopropyl-4- [4'-tert.butylphenyljindenyl) zirconium dichloride, dimethylsilanediylbis (2-n-butyl-4- [4 = tert.butylphenyl] -indenyl) zirconium dichloride, dimethylsilanediylbis (2-hexyl-4- [4'-tert.butylphenyl] indenyl) zirconium dichloride, dimethylsilanediyl (2-isop ropyl-4-phenyl-indenyl) - (2-methyl-4-phenyl-indenyl) zirconium dichloride, dimethylsilanediyl (2-isopropyl-4- (1-naphthyl) -indenyl) - (2-methyl-4- (1-naphthyl ) -indenyl) zirconium dichloride, dimethylsilanediyl (2-isopropyl-4- [4'-tert.butylphenyl] indenyl) - (2-methyl-4- [4'-tert.butylphenyl] indenyl) zirconium dichloride, dimethylsilanediyl (2-isopropyl- 4- [4'tert.-butylphenyl] indenyl) - (2-ethyl-4- [4'-tert.butylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl (2-isopropyl-4- [4'-tert.butylphenyl] indenyl) - (2-methyl-4- [3 ', 5'-biis-tert-butylphenyl] indenyl) zirconium dichloride, dimethylsilanediyl (2-isopropyl-4- [4'-tert.butylphenyl] indenyl) - (2-methyl- 4- [1'-naphthyl] indenyl) zirconium dichloride and ethylene (2-isopropyl-4- [4'-tert.butylphenyl] indenyl) - (2-methyl-4- [4'-tert.butylphenyl] indenyl) zirconium dichloride, and the corresponding dimethyl, monochloromono (alkylaryloxy) - and Di- (Alkylaryloxy) zirconium compounds. The complexes are preferably used in the rac form.

The Synthesis of such complex compounds can be done according to known Methods are carried out, the implementation of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, Hafnium, vanadium, niobium, tantalum or chromium is preferred. Examples for corresponding manufacturing processes include in the Journal of Organometallic Chemistry, 369 (1989), 359-370.

oder =BR^16D oder =BNR^16DR^17D bedeuten,
A^1D für -O-, -S- oder

steht,
t für 1 oder 2, bevorzugt 2 steht,
R^1D bis R^3D und R^5D für Wasserstoff, C₁-C₁₀-Alkyl, bevorzugt Methyl, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl NR^8D ₂ oder Si(R^8D)₃ stehen, oder wobei zwei benachbarte Reste für 4 bis 12 C-Atome aufweisende cyclische Gruppen stehen, wobei besonders bevorzugt alle R^1D bis R^3D und R^5D Methyl sind.In the case of the compounds of the general formula (XIVd), those in which
M ^{1D is} titanium or zirconium, in particular titanium, and
X ^{D stands} for chlorine, C ₁ -C ₄ alkyl or phenyl or two radicals X ^D stand for a substituted or unsubstituted butadiene ligand,
R ^15D

or = BR ^16D or = BNR ^16D R ^17D ,
A ^1D for -O-, -S- or

stands,
t represents 1 or 2, preferably 2,
R ^1D to R ^3D and R ^{5D represent} hydrogen, C ₁ -C ₁₀ alkyl, preferably methyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl NR ^8D ₂ or Si (R ^8D ) ₃ , or where two adjacent radicals stand for cyclic groups having 4 to 12 carbon atoms, all R ^1D to R ^3D and R ^5D being particularly preferably methyl.

Especially Suitable complexes D) of the formula (XIVd) are dimethylsilanediyl (tetramethylcyclopentadienyl) (benzylamino) titanium dichloride, Dimethylsilanediyl (tetramethylcyclopentadienyl) (tert-butylamino) titanium dichloride, Dimethylsilanediyl (tetramethylcyclopentadienyl) (adamantyl) titanium dichloride or dimethylsilanediyl (indenyl) (tert.butylamino) titanium dichloride.

bedeuten,
A^1D für -O-R^22D, -NR^22D ₂, -PR^22D ₂ oder ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches, insbesondere heteroaromatisches Ringsystem steht,
v 1 oder im Fall von A^1D gleich ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem 0 oder 1 und
R^1D bis R^3D und R^5D für Wasserstoff, C₁-C₁₀-Alky1, C₃-C₁₀-Cycloalkyl, C₆-C₁₅-Aryl oder Si(R^8D)₃ stehen, oder wobei zwei benachbarte Reste für 4 bis 12 C-Atome aufweisende cyclische Gruppen stehen.Another group of compounds of formula (XIVd) which are particularly suitable are those in the
M ¹⁰ for titanium, vanadium or chromium, preferably in oxidation state III and
X ^{D stands} for chlorine, C ₁ -C ₄ alkyl or phenyl or two radicals X ^D stand for a substituted or unsubstituted butadiene ligand,

mean,
A ^{1D stands} for -OR ^22D , -NR ^22D ₂ , -PR ^22D ₂ or an unsubstituted, substituted or fused, heterocyclic, in particular heteroaromatic ring system,
v 1 or, in the case of A ^1D , an unsubstituted, substituted or fused, heterocyclic ring system 0 or 1 and
R ^1D to R ^3D and R ^{5D represent} hydrogen, C ₁ -C ₁₀ alkyl1, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ aryl or Si (R ^8D ) ₃ , or where two adjacent radicals represent 4 are up to 12 carbon atoms cyclic groups.

In a preferred embodiment, A ^1D herein is an unsubstituted, substituted or fused, heteroaromatic ring system and M ^1D chromium. A ^1D is very particularly preferably an unsubstituted or substituted, for example alkyl-substituted, in particular substituted or unsubstituted quinolyl or pyridyl linked in position 8 or 2 and v is 0, for example 8-quinolyl, 8- (2-methylquinolyl), 8- (2, 3,4-trimethylquinolyl), 8- (2,3,4,5,6,7-hexamethylquinolyl, v is 0 and M ^1D is chromium. Preferred catalysts D) of this type are 1- (8-quinolyl) -2- methyl-4-methylcyclopentadienylchromium (III) dichloride, 1- (8-quinolyl) -3-isopropyl-5-methylcyclopentadienylchromium (III) dichloride, 1- (8-quinolyl) -3-tert.butyl-5-methylcyclopentadienylchromium (III) dichloride, 1- (8-quinolyl) -2,3,4,5-tetramethylcyclopentadienylchrome (III) dichloride, 1- (8-quinolyl) tetrahydroindenylchromium (III) dichloride, 1- (8-quinolyl) indenylchromium (III) dichloride, 1- (8-quinolyl) -2-methylindenylchrome (III) dichloride, 1- (8-quinolyl) -2-isopropylindenylchromium (III) dichloride, 1- (8-quinolyl) -2-ethylindenylchrome (III) dichloride, 1- (8-quinolyl) -2-tert-butylindenylchromium (III) dichloride, 1- (8-chino lyl) -benzindenylchrom (III) dichloride, 1- (8-quinolyl) -2-methylbenzindenylchrom (III) dichloride, 1- (8- (2-methylquinolyl)) - 2-methyl-4-methylcyclopentadienylchrom (III) dichloride, 1 - (8- (2-methylquinolyl)) - 2,3,4,5-tetramethylcyclopentadienyl chromium (III) dichloride, 1- (8- (2-methylquinolyl)) tetrahydroindenyl chromium (III) dichloride, 1- (8- (2- Methylquinolyl)) indenylchrome (III) dichloride, 1- (8- (2-methylquinolyl)) - 2-methylindenylchrome (III) dichloride, 1- (8- (2-methylquinolyl)) - 2-isopropylindenylchrome (III) dichloride, 1 - (8- (2-Methylquinolyl)) - 2-ethylindenylchrome (III) dichloride, 1- (8- (2-methylquinolyl)) - 2-tert.butylindenylchrome (III) dichloride, 1- (8- (2-methylquinolyl) )) - benzindenylchrom (III) dichloride, 1- (2-pyridylmethyl) indenylchromium (III) dichloride or 1- (8- (2-methylquinolyl)) - 2-methylbenzindenylchromium (III) dichloride.

Also preferred because of the simple representability is the combination of R ^15D equal to CH = CH or 1,2-phenylene with A ^1D equal to NR ^22D ₂ , as well as R ^15D equal to CH ₂ , C (CH ₃ ) ₂ or Si (CH ₃ ) ₂ and A ^1D are unsubstituted or substituted 2- or 8-quinolyl or unsubstituted or substituted 2-pyridyl.

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

The metal complexes, in particular the chromium complexes, can be obtained in a simple manner if the corresponding metal salts such as metal chlorides are reacted with the ligand anion (for example: analogously to the examples in DE-A-19710615 ).

Further suitable catalysts D) are metallocenes, with at least one Ligands made from a cyclopentadienyl or heterocyclopentadienyl is formed with a condensed heterocycle, the Heterocycles are preferably aromatic and nitrogen and / or sulfur contain. Such compounds are for example in WO 98/22486. These are in particular dimethylsilanediyl- (2-methyl-4-phenyl-indenyl) - (2,5-dimethyl-N-phenyl-4-azapentalene) zirconium dichloride, Dimethylsilanediylbis (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride, Dimethylsilanediylbis (2-ethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride, Bis (2,5-dimethyl-N-phenyl-4-azapentalene) zirconium dichloride or (indenyl) (2,5-dimethyl-N-phenyl-4-azapentalene) zirconium dichloride.

Of Systems are also suitable as catalysts D), in which one Metallocene compound, for example with an inorganic oxide, which has been treated with zirconium alkoxide and then chlorinated, for example, combined with carbon tetrachloride. The representation Such systems are described for example in WO 01/41920.

Geignete Catalysts D) are also Imidochrome compounds, in which chromium is at least a structural feature carries an imido group. These compounds and their preparation are e.g. in WO 01/09148 described.

Further suitable components D) are transition metal complexes with a tridentate macrocyclic ligands, especially substituted and unsubstituted 1,3,5-triazacyclohexanes and 1,4,7-triazacyclononanes. At this Chromium complexes are also preferred type of catalysts. Preferred catalysts of this type are [1,3,5-tri (methyl) -1,3,5-triazacyclohexane] chromium trichloride, [1,3,5-tri (ethyl) -1,3,5-triazacyclohexane] chromium trichloride, [1,3,5-tri (octyl) -1,3,5-triazacyclohexane] chromium trichloride, [1,3,5-tri (dodecyl) -1,3,5-triazacyclohexane) chromium trichloride and (1,3,5-tri (benzyl) -1,3,5-triazacyclohexane] chromium trichloride.

wobei das Übergangsmetall ausgewählt ist aus den Elementen Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt oder ein Element der Seltenerd-Metalle. Bevorzugt sind hierbei Verbindungen mit Nickel, Eisen, Kobalt und Palladium als Zentralmetall.Suitable catalysts D) are, for example, transition metal complexes with at least one ligand of the general formulas XV to XIX,

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

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

The radicals R ^1F to R ^25F , which can be the same or different within a ligand system XV to XIX, stand for the following groups:
R ^1F and R ^4F are independent of one another, preferably hydrocarbon or substituted hydrocarbon radicals thereby hydrocarbon radicals in which the element E ^F adjacent carbon atom is bound to at least two carbon atoms,
R ^2F and R ^3F independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, where R ^2F and R ^{3F can} also together form a ring system in which one or more heteroatoms can also be present,
R ^6F and R ^8F independently of one another for hydrocarbon or substituted hydrocarbon radicals,
R ^5F and R ^9F independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals,
where R ^6F and R ^5F or R ^8F and R ^9F together can also form a ring system,
R ^7F independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, it being possible for two R ^7Fs to form a ring system together,
R ^{10 F} and R ^14F independently of one another for hydrocarbon or substituted hydrocarbon radicals,
R ^11F , R ^12F , R ^{12F '} and R ^13F independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, it also being possible for two or more geminal or vicinal radicals R ^11A , R ^12A , R ^12A' and R ^13A together to form a ring system,
R ^15F and R ^18F independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R ^16F and R ^17F independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R ^19F and R ^25F independently of one another are C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic radicals R ^19F and R ^{25F can} also be substituted by halogens,
R ^20F -R ^24F independently of one another are hydrogen C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical or SiR ^26F ₃ means, where the organic radicals R ^20F -R ^{24F can} also be substituted by halogens and two vicinal radicals R ^20F -R ^{24F each} also form a five- or six-membered ring can be connected and
R ^{26F is} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl or alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical and two R ^{26F radicals can} also be ^linked to form a five- or six-membered ring.
x for 0 or 1, the complex of the formula (XVI) for x being 0 being negative
is loaded and
y for an integer between 1 and 4, preferably 2 or 3.

Transition metal complexes with Fe, Co, Ni, Pd or Pt as the central metal and ligands of the formula (XV) are particularly suitable. Diimine complexes of Ni or Pd are particularly preferred, for example:
Di (2,6-di-ii-propyl-phenyl) -2,3-dimethyl-diiazabutadiene-palladium dichloride, di (di-i-propyl-phenyl) -2,3-dimethyl-diazabutadiene-nickel-dichloride, di ( 2,6-di-i-propyl-phenyl) -dimethyldiazabutadiene-palladium-dimethyl, di (2,6-di-i-propyl-phenyl) -2,3-dimethyl-diazabutadiene-nickel dimethyl, di (2,6- dimethyl-phenyl) -2,3-dimethyl-diazabutadiene-palladium dichloride, di (2,6-dimethyl-phenyl) -2,3-dimethyl-diazabutadiene-nickel dichloride, di (2,6-dimethyl-phenyl) -2 , 3-dimethyldiazabutadiene-palladium-dimethyl, di (2,6-dimethyl-phenyl) -2,3-dimethyl-diazabutadiene-nickel dimethyl, di (2-methyl-phenyl) -2,3-dimethyl-diazabutadiene-palladium dichloride , Di (2-methylphenyl) -2,3-dimethyl-diazabutadiene-nickel dichloride, di (2-methyl-phenyl) -2,3-dimethyldiazabutadiene-palladium-dimethyl, di (2-methyl-phenyl) -2, 3-dimethyl-diazabutadiene-nickel-dimethyl, diphenyl-2,3-dimethyl-diazabutadiene-palladium-dichloride, diphenyl-2,3-dimethyldiazabutadiene-nickel-dichloride, diphenyl-2,3-dimethyl-diazabutadiene-palladium-dimethyl, diphenyl-2,3 -dimethyl-diazabutadiene-nickel-dimethyl, di (2,6-dimethyl-phenyl) -azanaphthene palladium dichloride, di (2,6-dimethyl-phenyl) -azanaphtene-nickel dichloride, di (2,6-dimethylphenyl) - azanaphten-palladium-dimethyl, di (2,6-dimethyl-phenyl) -azanaphten-nickel-dimethyl, 1,1'-dipyridyl-palladium-dichloride, 1,1'-dipyridyl-nickel-dichloride, 1,1'- Dipyridyl-palladium-dimethyl, 1,1'-dipyridyl-nickel-dimethyl.

Particularly suitable compounds (XIX) are also those which are described in J. Am. Chem. Soc. 120, pp. 4049 ff. (1998), J. Chem. Soc., Chem. Commun. 1998, 849 and WO 98/27124. E ^F is preferably nitrogen and R ^19F and R ^25F in (XIX) are preferably phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, -dichlorophenyl, or -dibromophenyl, 2-chloro-6-methylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, especially 2,3- or 2,6-dimethylphenyl, -diisopropylphenyl, -dichlorophenyl, or -dibromophenyl and 2,4,6-trimethylphenyl. At the same time, R ^20F and R ^{24F are} preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl or phenyl , especially hydrogen or methyl. R ^21F and R ^23F are preferably hydrogen and R ^{22F is} preferably hydrogen, methyl, ethyl or phenyl, in particular hydrogen. Complexes of the ligands F-XIX with transition metals Fe, Co or Ni, in particular Fe, are preferred. 2,6-Diacetylpyridinebis (2,4-dimethylphenylimine) iron dichloride, 2,6-diacetylpyridinebis (2,4,6-timethylphenylimine) iron dichloride, 2,6-diacetylpyridinebis (2-chloro-6-methylphenyl) iron dichloride, 2 are particularly preferred , 6-diacetylpyridinebis (2,6-diisopropylphenylimine) iron dichloride, 2,6-diacetylpyridinebis (2,6-dichlorophenylimine) iron dichloride, 2,6-pyridinedicarboxaldehyde bis (2,6-diisopropylphenylimine) iron dichloride, 2,6-diacetylpyridinebis (2.4 -dimethylphenylimine) cobalt dichloride, 2,6-diacetylpyridinbis (2,4,6-trimethylphenylimine) cobalt dichloride, 2,6-diacetylpyridinbis (2-chloro-6-methylphenyl) cobalt dichloride, 2,6-diacetylpyridinbis (2,6-diisopropylphenylimine) cobalt dichloride , 2,6-diacetylpyridinebis (2,6-dichlorophenylimine) cobalt dichloride and 2,6-pyridinedicarboxaldehyde bis (2,6-diisopropylphenylimine) cobalt dichloride.

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

Of further suitable as catalysts D) are complexes the two or tridentate have chelating ligands. With such ligands, for example an ether with an amine or Amide functionality or an amide linked to a heteroaromatic such as pyridine.

Such combinations of components A) and D) can be used, for example, to produce bimodal products or to produce comonomers in situ. At least transition metal complex A) is preferably used in the presence of at least one further catalyst D) customary for the polymerization of olefins and, if desired, one or more activating compounds C). Depending on the cat gate combinations A) and D) one or more activating compounds C) advantageous. The polymerization catalysts D) can also be supported and used simultaneously or in any order with the complex A) according to the invention. The transition metal complex A) and the polymerization catalysts D) can be applied, for example, together on a support B) or different supports B}. Mixtures of different catalysts can also be used as component D). The molar ratio of transition metal complex A) to polymerization catalyst D) is usually in the range from 1: 100 to 100: 1, preferably from 1:10 to 20: 1 and particularly preferably from 1: 1 to 10: 1.

As a further component E), the catalyst system can additionally contain a metal compound of the general formula (XX, M ^G (R ^1G ) _r G (R ^2G ) _s G (R ^3G ) _t G (XX) in the
M ^{G means} Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gallium, indium, thallium, zinc, in particular Li, Na, K, Mg, boron, aluminum or Zn,
R ^{1G is} hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl or arylalkyl, each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
R ^2G and R ^{3G are} hydrogen, halogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl or alkoxy each having 1 to 20 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, or alkoxy with C ₁ -C ₁₀ alkyl or C ₆ -C ₁₅ aryl,
r ^{G is} an integer from 1 to 3 and
s ^G and t ^G are integers from 0 to 2, with the sum r ^G + s ^G + t ^G corresponding to the valence of M ^G,
included, wherein component E) is not identical to component C). Mixtures of different metal compounds of the formula (XX) can also be used.

Of the metal compounds of the general formula (XX), those are preferred in which
M ^{G means} lithium, magnesium, boron or aluminum and
R ^{1G is} C ₁ -C ₂₀ alkyl.

Especially preferred metal compounds of formula (XX) are methyl lithium, Ethyl lithium, n-butyllithium, Methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, Ethylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, Diethylmagnesium, dibutylmagnesium, n-butyl-n-octylmagnesium, n-butyl-n-heptyl-magnesium, in particular n-butyl-n-octyl magnesium, tri-n-hexyl aluminum, tri-iso-butyl aluminum, Tri-n-butyl aluminum, triethyl aluminum, dimethyl aluminum chloride, Dimethyl aluminum fluoride, methyl aluminum dichloride, methyl aluminum sesquichloride, Diethyl aluminum chloride and trimethyl aluminum and mixtures thereof. The partial hydrolysis products of aluminum alkyls with alcohols can also be used become.

If a metal compound E) is used, it is preferably present in the catalyst system in such an amount that the molar ratio of M ^G from formula (XX) to transition metal from transition metal compound A) is from 2000: 1 to 0.1: 1, preferably from 800: 1 to 0.2: 1 and particularly preferably from 100: 1 to 1: 1.

In usually the catalyst solid together with other metal compound E) of the general formula (XX), which differs from that Metal compounds used in the preparation of the catalyst solid E) can differentiate, as part of a catalyst system used for the polymerization or copolymerization of olefins. It is also possible, especially when the catalyst solid is not activating Component C) contains that this Additional catalyst system one or more activating compounds to the catalyst solid C) contains the same or different from possibly in the catalyst solid containing activating compounds C).

Prefers is at least for the preparation of the catalyst systems of the invention one of the components A) and / or C) on the carrier B) by physisorption or by a chemical reaction, that means a covalent Connection of the components, fixed with reactive groups of the carrier surface. The order of combining carrier component B), component A) and optionally component C) is optional. The components A) and C) can independently from each other or also simultaneously or premixed to B) become. After the individual process steps, the solid can suitable inert solvents such as aliphatic or aromatic hydrocarbons.

In a preferred embodiment becomes the transition metal complex A) in a suitable solvent brought into contact with the activating compound C), usually a soluble Reaction product, an adduct or a mixture is obtained. The The preparation obtained in this way is then pretreated with the one, if necessary carrier B) contacted, and the solvent completely or partially removed. A solid is then preferably obtained in the form of a free flowing Powder. examples for the technical implementation of such a method are in WO 96/00243, WO 98/40419 or WO 00/05277. Another one preferred embodiment is, initially to generate the activating compound C) on the carrier B) and then this supported activating compound with the transition metal complex A) contact.

The Component D) can also be in any order with the components A) and optionally B), C) and E) are implemented. D) is preferred first brought into contact with component C) and then with the Components A) and B) and possibly other C) as above method. In another preferred embodiment, a catalyst solid from components A), B) and C) as described above and this while, at the beginning or shortly before the polymerization with component E) in Brought in contact. E) is preferred first with the α-olefin to be polymerized in Brought into contact and then the catalyst solid components A), B) and C) added as described above. The transition metal complex A) can be either before or after contacting those to be polymerized Olefins in contact with the component or components C) and / or D) to be brought. Pre-activation with one or more Components C) before mixing with the olefin and further addition the same or different components C) and / or D) after contacting this mixture with the olefin is possible. A pre-activation usually takes place at temperatures between 10-100 ° C, preferably between 20-80 ° C.

It is also possible to prepolymerize the catalyst system first with α-olefins, preferably linear C ₂ -C ₁₀ -1-alkenes and in particular with ethylene or propylene, and then to use the resulting prepolymerized catalyst solid in the actual polymerization. The mass ratio of the catalyst solid used in the prepolymerization to the copolymerized monomer is usually in the range from 1: 0.1 to 1: 1000, preferably 1: 1 to 1: 200.

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

The catalyst systems according to the invention are suitable for the polymerization of olefins and especially for the polymerization of α-olefins, ie hydrocarbons with terminal double bonds. Suitable monomers can be functionalized olefinically unsaturated compounds such as acrolein, ester or amide derivatives of acrylic or methacrylic acid, for example acrylates, methacrylates or acrylonitrile or vinyl esters, for example vinyl acetate. Nonpolar olefinic compounds are preferred, including aryl-substituted α-olefins. Particularly preferred α-olefins are linear or branched C ₂ -C ₁₂ -1-alkenes, in particular linear C ₂ -C ₁₀ -1-alkenes such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene , 1-octene, 1-decene or branched C ₂ -C ₁₀ -1-alkenes such as 4-methyl-1-pentene, conjugated and non-conjugated dienes such as 1,3-butadiene, 1,5-hexadiene, or 1.7 -Octadiene or vinyl aromatic compounds such as styrene or substituted styrene. Mixtures of different α-olefins can also be polymerized. At least one olefin selected from the group ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene is preferably polymerized.

suitable Olefins are also those in which the double bond is part of a is cyclic structure, which have one or more ring systems can. Examples of this are cyclopentene, cyclohexene, norbornene, tetracyclododecene or Methylnorbornene or dienes such as 5-ethylidene-2-norbornene, norbornadiene or ethyl norbornadiene.

Mixtures of two or more olefins can also be polymerized. In contrast to some known iron and cobalt complexes, the transition metal complexes according to the invention show good polymerization activity even with higher α-olefins, so that their suitability for copolymerization is particularly noteworthy. In particular, the transition metal complexes according to the invention can be used for the polymerization or copolymerization of ethene or propene. Preferred comonomers in the ethene polymerization are C ₃ -C ₈ -α-olefins or norbornene, in particular 1-butene, 1-pentene, 1-hexene and / or 1-octene used. Monomer mixtures with at least 50 mol% of ethene are preferably used. Preferred comonomers in propylene polymerization are ethene and / or butene.

The Polymerization can be carried out in bulk, in suspension, in a known manner the gas phase or in a supercritical Medium in the usual, for the Polymerization of olefins used reactors are carried out. It can be carried out discontinuously or preferably continuously in one or several stages. High-pressure polymerization processes are coming in tubular reactors or autoclaves, solution processes, suspension processes, stirred Gas phase process or gas phase fluidized bed process into consideration.

The polymerizations are usually carried out at temperatures in the range from -60 to 350 ° C. and under pressures from 0.5 to 4000 bar with average residence times from 0.5 to 5 hours, preferably from 0.5 to 3 hours. The advantageous pressure and temperature ranges for carrying out the polymerizations usually depend on the polymerization method. In the high-pressure polymerization processes, which are usually carried out at pressures between 1000 and 4000 bar, in particular between 2000 and 3500 bar, high polymerization temperatures are generally also set. Advantageous temperature ranges for these high pressure polymerization processes are between 200 and 320 ° C, in particular between 220 and 290 ° C. In the case of low-pressure polymerization processes, a temperature is generally set which is at least a few degrees below the softening temperature of the polymer. In particular, temperatures between 50 and 180 ° C., preferably between 70 and 120 ° C., are set in these polymerization processes. In the case of suspension polymerizations, polymerization is usually carried out in a suspending agent, preferably in an inert hydrocarbon, such as, for example, isobutane, or mixtures of hydrocarbons, or else in the monomers themselves. The polymerization temperatures are generally in the range from -20 to 115 ° C, the pressure generally in the range from 1 to 100 bar. The solids content of the suspension is generally in the range from 10 to 80%. It can be carried out batchwise, for example in stirred autoclaves, or continuously, for example in tubular reactors, preferably in loop reactors. In particular, according to the Phillips-PF method, as in the US-A 3,242,150 and US-A 3,248,179 described, worked. The gas phase polymerization is generally carried out in the range from 30 to 125 ° C.

Of the polymerization process mentioned is gas phase polymerization, especially in gas phase fluidized bed reactors, solution polymerization, as well as suspension polymerization, especially in loop and stirred tank reactors, particularly preferred. The gas phase polymerization can also in the so-called condensed or supercondensed driving styles are carried out, where some of the circulating gas is cooled below the dew point and as a two-phase mixture is returned to the reactor. Furthermore, a so-called multi-zone reactor can be used wherein two polymerization zones are linked together and the polymer alternately passed several times through these two zones the two zones also have different polymerization conditions can own. Such a reactor is described, for example, in WO 97/04015. The different or the same polymerization processes can also optionally be connected in series with one another and thus form a polymerization cascade, such as in the hostal process. Also a parallel reactor guide two or several identical or different processes are possible. Farther can in the polymerizations also molecular weight regulators, for example hydrogen, or usual Additives such as antistatic agents can also be used.

The transition metal complexes according to the invention and the catalyst systems containing them can also be combinatorial Methods presented or based on these combinatorial methods their polymerization activity getting tested.

By the inventive method polymers of olefins can be prepared. The term polymerization, as used to describe the invention herein includes both Polymerization as well as oligomerization, i.e. Oligomers and polymers with molecular weights Mw in the range of about 56 to 10000000 can by these processes are generated.

On Because of their good mechanical properties, they are also suitable the catalyst system according to the invention prepared polymers of olefins especially for the production of films, fibers and moldings.

The catalyst systems according to the invention are characterized in that with polymers with high molecular weights are obtained. The catalyst systems according to the invention also show at a relatively low molar ratio of Alumoxane to organo transition metal one good activity.

Examples

All Syntheses and polymerizations were carried out under a nitrogen protective gas atmosphere.

The density [g / cm ³ ] was determined according to ISO 1183.

The Determination of the molecular weight distributions and the derived ones Mn, Mw, and Mw / Mn were averaged by high temperature gel permeation chromatography based on DIN 55672 under the following conditions: Solvent: 1,2,4-trichlorobenzene, river: 1 ml / min, temperature: 140 ° C, Calibration with PE standards.

The DSC melting temperature was determined according to ISO 3146.

The Staudinger index (n) [dl / g] was performed using an automatic Ubbelohde Viscometer (Lauda PVS 1) determined with decalin as solvent at 130 ° C (ISO1628 at 130 ° C, 0.001 g / ml decalin).

The number of methyl branches per 1000 carbon atoms of the polymer chain (CH _3/1000) was also determined by means of IR.

The NMR spectra were measured on a Bruker DRX 200 ( ¹ H: 200.13 MHz; ³¹ P: 81.01 MHz) or Bruker AC 300 ( ¹ H: 300.13 MHz; ³¹ P: 121.49 MHz). The signal of the incompletely deuterated portion of the solvents used served as the internal standard for ¹ H-NMR spectra. 30% H ₃ PO ₄ in D ₂ O was used as the external standard for measuring ³¹ P NMR spectra. All signals were calibrated to the corresponding literature values.

mass spectra were recorded on a Finnigan MAT 8230, high-resolution mass spectra measured on a Micromass CTD ZAB-2F VN spectrometer.

GC / MS coupled Mass spectra were recorded on an HP 5890 II gas chromatograph (column HP-5, methyl silicone with 5% phenyl silicone, 30 m × 0.25 mm × 0.25 μm) with HP 5971 MSD added.

The Imidazole starting compounds are commercially available (Aldrich), or the dialkoxy-protected Derivatives were according to N. J. Curtis, R. S. Brown, J. Org. Chem. 1980, 45, 4038.

Kat.

Katalysator

t(Poly)

Dauer der Polymerisation

Polymer

Menge an gebildetem Polymer

Mw

Gewichtsmittel der Molmasse

Mn

Zahlenmittel der Molmasse

Dichte

Polymerdichte

Prod.

Produktivität des Katalysators in g erhaltenem Polymer pro mmol eingeseztem Katalysator (Übergangsmetallkomplex) pro Stunde

DSC

Schmelzpunkt ermittelt via DSC

Abbreviations in the following table:

Cat.

catalyst

t (poly)

Duration of the polymerization

polymer

Amount of polymer formed

mw

Weight average molecular weight

Mn

Number average molecular weight

density

polymer density

Prod.

Productivity of the catalyst in g of polymer obtained per mmol of catalyst (transition metal complex) used per hour

DSC

Melting point determined via DSC

example 1

1.1. Preparation of tris (1-benzylimidazol-2-yl) phosphine

• MS (EI): m/z (%) = 502 (100) [M]⁺, 411 (11) [M – Benzyl]⁺, 344 (14) [M – Benzylimidazol]⁺, 247 (55) (M – Benzylimidazol – Imidazol – P]⁺, 187 (26) [M – 2 Benzylimidazol]⁺, 91 (66) [Benzyl]⁺.
• ¹H-NMR (300 MHz, CDCl₃): δ = 5,18 (s, 6H, H⁶), 6,87 (m, 9H, 3H⁴, 6H⁸), 7,15 (m, 12H, 6H⁹ + 3H¹⁰ + 3H⁵).
• ³¹P-NMR (121,5 MHz, CDCl₃): δ = –64,7

A solution of 3.16 g (20 mmol) of 1-benzylimidazole in 250 ml of diethyl ether was cooled to -50 ° C. and 8 ml of n-BuLi solution (2.5 M in hexane, 20 mmol) were added dropwise. After stirring at -50 ° C for 1 h, the mixture was warmed to room temperature over an hour. The solution was then cooled to -78 ° C. and a solution of 0.91 g (6.6 mmol) of phosphorus trichloride in 8 ml of diethyl ether was slowly added dropwise. After the addition was complete, the resulting suspension was further stirred at -78 ° C for 2 h, brought to room temperature and then stirred at room temperature for a further 14 h. The reaction mixture thus obtained was filtered and the powdery residue washed with several portions of cold diethyl ether, dried under high vacuum and recrystallized in ethanol. The solid obtained in this way was suspended in 100 ml of dichloromethane and stirred with 50 ml of concentrated ammonia for 1 h. The organic phase was over a thin layer of pebble gel filtered, which was washed with several portions of dichloromethane. The solvent was distilled off and the solid was dried under high vacuum. 1.6 g (3.2 mmol) (48%) of tris (1-benzylimidazol-2-yl) phosphine were obtained.

• MS (EI): m / z (%) = 502 (100) [M] ⁺ , 411 (11) [M - benzyl] ⁺ , 344 (14) [M - benzylimidazole] ⁺ , 247 (55) (M - Benzylimidazole - Imidazole - P] ⁺ , 187 (26) [M - 2 Benzylimidazole] ⁺ , 91 (66) [Benzyl] ⁺ .
• ¹ H NMR (300 MHz, CDCl ₃ ): δ = 5.18 (s, 6H, H ⁶ ), 6.87 (m, 9H, 3H ⁴ , 6H ⁸ ), 7.15 (m, 12H, 6H) ⁹ + 3H ¹⁰ + 3H ⁵ ).
• ³¹ P NMR (121.5 MHz, CDCl ₃ ): δ = -64.7

1.2. Preparation of trichloro-tris (1-benzylimidazol-2-ylphosphine) titanium (III)

• MS (FAB): m/z (%) = 772 (100), 620 (18) [M-Cl]⁺, 601 (38), 503 (20) [M-TiCl₃ + H]⁺.
• MS (HR-FAB): C₃₀H₂₇N₆PTi³⁵Cl₂ ber.: 620,0891 gef.: 620,0873

A solution of 0.06 g (0.4 mmol) of titanium (III) was added to a solution of 0.3 g (0.6 mmol) of tris (1-benzylimidazol-2-yl) phosphine in 5 ml of dichloromethane with stirring at room temperature. trichloride in 20 ml dichloromethane slowly added. The solution thus obtained was stirred at room temperature for 12 h, during which time an olive-green precipitate formed, which was filtered off, then washed with hexane and dried under high vacuum. 0.24 g (90%) of trichlorotris (1-benzylimidazol-2y-l) phosphine titanium (III) was obtained as an olive-green solid.

• MS (FAB): m / z (%) = 772 (100), 620 (18) [M-Cl] ⁺ , 601 (38), 503 (20) [M-TiCl ₃ + H] ⁺ .
• MS (HR-FAB): C ₃₀ H ₂₇ N ₆ PTi ³⁵ Cl ₂ calc .: 620.0891 found: 620.0873

Example 2

2.1. Preparation of tris (1-ethylhexylimidazol-2-yl) phosphine

• ¹H-NMR (300 MHz, CDCl₃): δ = 0,76 (m, 6H, CH₃), 1,10 (m, 8H, CH₂), 1,50 (m, 1H, H⁷), 3,88 (d, J = 7,3 Hz, 2H, N-CH₂), ,.02 (1H, H⁴⁽⁵⁾), 7,15 (1H, H⁴⁽⁵⁾).
• ³¹P-NMR (121,5 MHz, CDCl3): δ = –61,6
• MS (FAB): m/z(%) = 568 (100), 539 (11), 511 (11), 390 (15), 291 (11), 179 (29), 161 (13), 150 (12), 113 (12).

A solution of 10 mmol of ethylhexylimidazole in 100 ml of diethyl ether was cooled to -40 ° C. and 4 ml of n-BuLi solution (2.5 M in hexane, 10 mmol) were added dropwise. After stirring at -40 ° C for 1 h, the solution was cooled to -78 ° C and a solution of 3.33 mmol phosphorus trichloride in 10 ml diethyl ether was slowly added dropwise. After the addition was complete, the resulting suspension was further stirred at -78 ° C for 2 h, brought to room temperature and then stirred at room temperature for a further 14 h. The reaction mixture thus obtained was filtered and the powdery residue washed with several portions of cold diethyl ether, dried under high vacuum and recrystallized in ethanol. The solid obtained in this way was suspended in 100 ml of dichloromethane and stirred with 50 ml of concentrated ammonia for 1 h. The organic phase was filtered off through a thin layer of silica gel, which was washed with several portions of dichloromethane. The solvent was distilled off and the solid was dried under high vacuum. Tris (1-ethylhexylimidazol-2-yl) phosphine was obtained in 12% yield.

• ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.76 (m, 6H, CH ₃ ), 1.10 (m, 8H, CH ₂ ), 1.50 (m, 1H, H ⁷ ), 3.88 (d, J = 7.3 Hz, 2H, N-CH ₂ ), .02 (1H, H ^{4 (5)} ), 7.15 (1H, H ^{4 (5)} ).
• ³¹ P NMR (121.5 MHz, CDCl3): δ = -61.6
• MS (FAB): m / z (%) = 568 (100), 539 (11), 511 (11), 390 (15), 291 (11), 179 (29), 161 (13), 150 (12 ), 113 (12).

2.2. Preparation of trichloro-tris (1-ethylhexylimidazol-2yl) phosphine titanium (III)

• MS (FAB): m/z (%) = 723 (63) [M]⁺, 686 (100) [M-Cl₂]⁺, 667 (67).
• MS (HR-FAB): C₃₃H₅₇N₆PTi³⁵Cl₂ ber. 686,3239 gef. 686,3231

To a mixture of 0.158 g (1.02 mmol) of titanium (III) trichloride and of 0.682 g (1.2 mmol) of tris (1-ethylhexylimidazol-2-yl) phosphine, 25 ml of dichloromethane were added at room temperature. The reaction mixture was stirred at room temperature for 12 h, filtered, the solution thus obtained concentrated to 1 ml volume and then mixed with hexane. An olive-green precipitate formed, which was filtered off, then washed with a mixture of tetrahydrofuran and hexane and dried in a high vacuum. 0.72 g (0.99 mmol, 97%) of trichloro-tris (1-ethylhexylimidazol-2y-l) phosphine titanium (III) was obtained as an olive-green solid.

• MS (FAB): m / z (%) = 723 (63) [M] ⁺ , 686 (100) [M-Cl ₂ ] ⁺ , 667 (67).
• MS (HR-FAB): C ₃₃ H ₅₇ N ₆ PTi ³⁵ Cl ₂ calcd. 686.3239 found. 686.3231

Example 3

Preparation of trichloro-tris (1-benzylimidazol-2-ylphosphine) vanadium (III)

To a solution of 0.19 g (0.38 mmol) of tris (1-benzylimidazol-2-yl) phosphine (Example 1.1.) In 5 ml of dichloromethane was added a solution of 0.11 g (0.05 3 mmol) of vanadium (III) trichloride-tris (tetrahydrofuran) in 5 ml of dichloromethane are slowly added. The solution thus obtained was stirred for 4 h at room temperature, the dichloromethane was distilled off and the residue was washed with tetrahydrofuran and dried under high vacuum. 0.16 g (0.24 mmol, 80%) of trichloro-tris (1-benzylinüdazol-2-ylphos phin) vanadium (III) obtained as a purple solid.

• MS (FAB): 623 (28) [M-Cl] ⁺ , 604 (50) [M-2C1 + O] ⁺ , 588 (6) [M-2Cl] ⁺ , 503 (14) (PBzIm ₃ + H) ,
• MS (HR-FAB): C ₃₀ H ₂₇ N ₆ PV ³⁵ Cl ₂ calc .: 623.0851 found: 623.0812 C ₃₀ H ₂₇ N ₆ PV ³⁷ Cl ³⁵ Cl calc .: 625.0822 found: 625 , 0819

Example 4

Preparation of trichloro-tris (1-benzylimidazol-2-ylphosphine) chromium (III)

• ¹H-NMR (200 MHz, CD₂Cl₂): δ = 1,25 (d, J (P, H) = 6,7 Hz, 6H, CH2), 2,01 (s(br), 3H, H4), 4,09 (d, J (P, H) = 5,7 Hz, = 3H, H5), 6,7-8,4 (s(br), 15H, HAryl).
• ³¹P-NMR (81,01 MHz, CD₂Cl₂): δ = 6,1.
• MS (FAB): m/z (%) = 624 (100) [M-Cl]⁺, 589 (37) [M-2C1]⁺, 498 (12) [M-2Cl-Benzyl]⁺.

To a solution of 0.18 g (0.48 mmol) of chromium (III) trichloride-tris (tetrahydrofuran) in 25 ml of dichloromethane was added a solution of 0.31 g (0.62 mmol) of tris (1- Benzylimidazol-2-yl) phosphine (see Ex.1.1.) in 1.5 ml dichloromethane slowly added. The solution thus obtained was stirred at room temperature for 14 h, the dichloromethane was distilled off, the residue was washed with tetrahydrofuran and dried in a high vacuum. 0.25 g (0.38 mmol, 79%) of trchlorotri (1-benzylimidazol-2-ylphosphine) chromium (III) was obtained as a green solid.

• ¹ H-NMR (200 MHz, CD ₂ Cl ₂ ): δ = 1.25 (d, J (P, H) = 6.7 Hz, 6H, CH2), 2.01 (s (br), 3H, H4), 4.09 (d, J (P, H) = 5.7 Hz, = 3H, H5), 6.7-8.4 (s (br), 15H, HAryl).
• ³¹ P NMR (81.01 MHz, CD ₂ Cl ₂ ): δ = 6.1.
• MS (FAB): m / z (%) = 624 (100) [M-Cl] ⁺ , 589 (37) [M-2C1] ⁺ , 498 (12) [M-2Cl-Benzyl] ⁺ .

Example 5

Preparation of trichloro-tris (1-ethylhexylimidazol-2y-l) phosphine chromium (III)

• MS (FAB): m/z (%) = 779 (23) [M + Na]⁺, 690 (44) [M-Cl]⁺, 655 (28) [M-2Cl]+, 591 (44), 569 (100), 390 (40), 179 (50), 165 (30).
• MS (HR-FAB): ber. 690,3164 gef. 690,3118

To a mixture of 0.038 g (0.1 mmol) chromium (III) trichloride-tris (tetrahydrofuran) and 0.2 g (0.35 mmol) tris (1-ethylhexylimidazol-2-yl) phosphine (see Example 2.1 .) 10 ml of tetrahydrofuran were added at room temperature. The reaction mixture was stirred at room temperature for 12 h, filtered, the solution thus obtained concentrated to 1 ml volume and then mixed with 5 ml of hexane. A light green precipitate formed, which was filtered off, then washed with hexane and dried under high vacuum. 0.069 g (95%) of trichlorotris (1-ethylhexylimidazol-2y-l) phosphine chromium (III) was obtained as a green solid.

• MS (FAB): m / z (%) = 779 (23) [M + Na] ⁺ , 690 (44) [M-Cl] ⁺ , 655 (28) [M-2Cl] +, 591 (44), 569 (100), 390 (40), 179 (50), 165 (30).
• MS (HR-FAB): calcd. 690.3164 found. 690.3118

Example 6

6.1. Preparation of tris (1-n-butylimidazol-2-yl) phosphine

• ¹H-NMR (200 MHz, CDCl₃): δ = 0,68 (t, ³J (H, H) = 7,2 Hz, 3H, H⁹), 1,06 (sext, ³J (H, H) = 7,2 Hz, 2H, H⁸), 1,25 (quint, ³J (H, H) = 7,4 Hz, 2H, H⁷), 3,94 (dt, ³J (H, H) = 7,3 Hz, ⁴J (P, H) = 1,1 Hz, 2H, H⁶), 6,99 (s(br), 1H, H⁵), 7,07 (s(br), 1H, H⁴).
• ³¹P-NMR (81,01 MHz, CDCl₃): δ = –63,1.
• MS (EI): m/z (%) = 400 (47) [M]⁺, 371 (5) [M-Ethyl]⁺, 277 (11) [M-Butylimidazol]⁺, 179 (9) [C₁₁H₁₉N₂]⁺, 124(97) [Butylimidazol]⁺, 97 (98) [C₆H₁₁N]⁺, 82 (100) [C₄H₆N₂]⁺, 68 (32) [Imidazol]⁺.

A solution of 4.97 g (40 mmol) of 1-n-butylimidazole in a mixture of 4.05 g (40 mmol) of triethylamine and 20 ml of pyridine was cooled to −0 ° C. and a solution of 1.83 g (13 , 3 mmol) of phosphorus trichloride in 5 ml of pyridine are slowly added dropwise. After the addition has ended brought to room temperature and then stirred for a further 14 h at room temperature. The solvent was distilled off and the solid thus obtained was extracted with warm benzene, filtered through silica gel and then the extractant was distilled off. The viscous oil thus obtained was distilled at 50 ° C in a water bath and 3 · 10 ^-2 mbar. The oily residue thus obtained was taken up in 20 ml of THF, and 0.6 g (14.1 mmol) of lithium chloride were added and the mixture was stirred for several hours. The LiCl complex formed was filtered off on a frit, washed with cold tetrahydrofuran, dried under high vacuum, suspended in CH ₂ Cl ₂ and concentrated with. Ammonia decomplexed with stirring for one hour. The organic phase was filtered through a little silica gel, the solvent was distilled off and the solid was dried under high vacuum. 3.99 g (9.9 mmol) (74%) of tris (1-n-butylimidazol-2-yl) phosphine were obtained in the form of a colorless oil.

• ¹ H-NMR (200 MHz, CDCl ₃ ): δ = 0.68 (t, ³ J (H, H) = 7.2 Hz, 3H, H ⁹ ), 1.06 (sext, ³ J (H, H) = 7.2 Hz, 2H, H ⁸ ), 1.25 (quint, ³ J (H, H) = 7.4 Hz, 2H, H ⁷ ), 3.94 (dt, ³ J (H, H) = 7.3 Hz, ⁴ J (P, H) = 1.1 Hz, 2H, H ⁶ ), 6.99 (s (br), 1H, H ⁵ ), 7.07 (s (br) , 1H, H ⁴ ).
• ³¹ P NMR (81.01 MHz, CDCl ₃ ): δ = -63.1.
• MS (EI): m / z (%) = 400 (47) [M] ⁺ , 371 (5) [M-ethyl] ⁺ , 277 (11) [M-butylimidazole] ⁺ , 179 (9) [C ₁₁ H ₁₉ N ₂ ] ⁺ , 124 (97) [butylimidazole] ⁺ , 97 (98) [C ₆ H ₁₁ N] ⁺ , 82 (100) [C ₄ H ₆ N ₂ ] ⁺ , 68 (32) [imidazole] ⁺ .

6.2. Preparation of trichloro-tris (1-n-butylimidazol-2y-l) phosphine chromium (III)

• ¹H-NMR (200 MHz, CD₂Cl₂): δ = 1,1 (m(br), –2,0 – + 3,5 ppm, 9H, CH₂CH₂CH₂CH₃), 7,2 (m(br), 6,5 – 10 ppm, 1H, H4), 13,9 (s(br), 10,5 – 20,5 ppm, 1H, H5).
• ³¹P-NMR (81,01 MHz, CD₂Cl₂): δ = 6,3.
• MS (FAB): m/z (%) = 522 (100) [M-Cl]⁺, 487 (42) [M-2Cl]⁺.
• MS (HR-FAB): C₂₁H₃₃NgPCr³⁵Cl³⁷Cl ber.: 524,1257 gef.: 524,1334 C₂₁H₃₃N₆PCr³⁵Cl₂ ber.: 522,1286 gef.: 522,1353

To a solution of 0.46 g (1.22 mmol) of chromium (III) trichloride-tris (tetrahydrofuran) in 10 ml of dichloromethane was added a solution of 0.62 g (1.55 mmol) of tris (1- Slowly added n-butylimidazol-2-yl) phosphine in 5 ml dichloromethane. The solution thus obtained was stirred at room temperature for 14 h, the dichloromethane was distilled off and the residue was washed with tetrahydrofuran. The residue was recrystallized from dichloromethane / hexane. 0.52 g (0.93 mmol, 76%) of trichloro-tris (1-n-butylimidazol-2y-l) phosphine chromium (III) was obtained as a green solid.

• ¹ H-NMR (200 MHz, CD ₂ Cl ₂ ): δ = 1.1 (m (br), -2.0 - + 3.5 ppm, 9H, CH ₂ CH ₂ CH ₂ CH ₃ ), 7, 2 (m (br), 6.5-10 ppm, 1H, H4), 13.9 (s (br), 10.5-20.5 ppm, 1H, H5).
• ³¹ P NMR (81.01 MHz, CD ₂ Cl ₂ ): δ = 6.3.
• MS (FAB): m / z (%) = 522 (100) [M-Cl] ⁺ , 487 (42) [M-2Cl] ⁺ .
• MS (HR-FAB): C ₂₁ H ₃₃ NgPCr ³⁵ Cl ³⁷ Cl calc .: 524.1257 found: 524.1334 C ₂₁ H ₃₃ N ₆ PCr ³⁵ Cl ₂ calc .: 522.1286 found: 522.1353

Example 7

7.1. Preparation of tris (1-n-butyl-4-phenylimidazol-2-yl) phosphine

• ¹H-NMR (200 MHz, CDCl₃): δ = 0,76 (m, 3H, H⁹), 1,24 (m, 2H, H⁸), 1,54 (m, 2H, H⁷, 4,18 (t, ³J (H, H) = 7,5 Hz, 2H, H⁶), 7,2-7,5 (m, 4H, H⁵ + H^Aryl), 7,8 (m, 2H, H^Aryl).
• ³¹P-NMR (81,01 MHz, CDCl₃): δ = –60,4
• MS (HR-FAB): m/z (%) = 635 (100) [M+Li]⁺;

A solution of 10 mmol of ethylhexylimidazole in 100 ml of diethyl ether was cooled to -40 ° C. and 4 ml of n-BuLi solution (2.5 M in hexane, 10 mmol) were added dropwise. After stirring for 1 h at -40 ° C, the solution was cooled to -78 ° C and a solution of 3.33 mmol of phosphorus trichloride in 10 ml of diethyl ether was slowly added dropwise. After the addition was complete, the resulting suspension was further stirred at -78 ° C for 2 h, brought to room temperature and then stirred at room temperature for a further 14 h. The reaction mixture thus obtained was filtered and the powdery residue washed with several portions of cold diethyl ether, dried under high vacuum and recrystallized in ethanol. The solid obtained in this way was suspended in 100 ml of dichloromethane and stirred with 50 ml of concentrated ammonia for 1 h. The organic phase was filtered off through a thin layer of silica gel, which was washed with several portions of dichloromethane. The solvent was distilled off and the solid was dried under high vacuum. Tris (1-n-butyl-4-phenylimidazol-2-yl) phosphine was obtained in 72% yield.

• ¹ H-NMR (200 MHz, CDCl ₃ ): δ = 0.76 (m, 3H, H ⁹ ), 1.24 (m, 2H, H ⁸ ), 1.54 (m, 2H, H ⁷ , 4 , 18 (t, ³ J (H, H) = 7.5 Hz, 2H, H ⁶ ), 7.2-7.5 (m, 4H, H ⁵ + H ^aryl ), 7.8 (m, 2H , H ^aryl ).
• ³¹ P NMR (81.01 MHz, CDCl ₃ ): δ = -60.4
• MS (HR-FAB): m / z (%) = 635 (100) [M + Li] ⁺ ;

7.2. Preparation of trichloro-tris (1-n-butyl-4-phenylimidazol-2-yl) phosphine chromium (III)

• MS (FAB): m/z (%) = 752 (9) [M-Cl]⁺, 715 (28) [M-2Cl]⁺.
• MS (HR-FAB): C₃₉H₄₅N₆PCr³⁵Cl ber. 715,2537 gef. 715,2521

0.088 g (0.14 mmol) of tris (1-n-butyl-4-phenylimidazole) was added to a solution of 0.053 g (0.14 mmol) of chromium (III) trichloride-tris (tetrahydrofuran) in 25 ml of dichloromethane with stirring at room temperature ) added phosphine. The solution thus obtained was stirred at room temperature for 12 h, the dichloromethane was distilled off, the residue was washed with hexane and dried in a high vacuum. Trichloro (1-n-butyl-4-phenylimidazole) phosphine chromium (III) was obtained as a green solid in quantitative yield.

• MS (FAB): m / z (%) = 752 (9) [M-Cl] ⁺ , 715 (28) [M-2Cl] ⁺ .
• MS (HR-FAB): C ₃₉ H ₄₅ N ₆ PCr ³⁵ Cl calc. 715.2537 found. 715.2521

Example 8

8.1. Preparation of tris (4 (5) -tert-butylimidazol-2-yl) phosphine

• ¹H-NMR (300 MHz, MeOH-d4): δ = 1,20 (bs, 9H, CH₃), 6,82 (bs, 1H, H4(5)).
• ³¹P-NMR (121,5 MHz, MeOH-d4): δ = –70,4.
• MS (EI): m/z (%) = 400 (100) [M-H]⁺, 385 (67) [M-CH₃]⁺, 276 (23), 261 (25), 125 (22), 108 (9).
• MS (HR-EI): ber. 400,2504 gef. 400,2531

A solution of 9.18 g (46.3 mmol) of 1-dimethoxymethyl-4-tert-butylimidazole in 100 ml of tetrahydrofuran was cooled to -40 ° C. and 18.5 ml of n-BuLi solution (2.5 M in hexane , 46.3 mmol) was added dropwise. After stirring at -40 ° C for 1 h, the solution was cooled to -78 ° C and a solution of 2.12 g (15.4 mmol) of phosphorus trichloride in 10 ml of tetrahydrofuran was slowly added dropwise. After the addition was complete, the resulting suspension was further stirred at -78 ° C for 2 h, brought to room temperature and then stirred at room temperature for a further 14 h. The solvent was distilled off from the reaction mixture thus obtained, 100 ml of dichloromethane and 50 ml of concentrated ammonia were added to the residue in succession and the mixture was stirred until phase separation. The organic phase was filtered off through a thin layer of silica gel, which was washed with several portions of dichloromethane. The solvent was distilled off and 100 ml of a 50% water / acetone mixture were added to the residue. After 7 days, the product precipitated out as a fine, white precipitate which was filtered off and dried in vacuo. 2.33 g (5.8 mmol) were obtained (37.8%) tris (4 (5) tert-butylimidazol-2-yl) phosphine.

• ¹ H NMR (300 MHz, MeOH-d4): δ = 1.20 (bs, 9H, CH ₃ ), 6.82 (bs, 1H, H4 (5)).
• ³¹ P NMR (121.5 MHz, MeOH-d4): δ = -70.4.
• MS (EI): m / z (%) = 400 (100) [MH] ⁺ , 385 (67) [M-CH ₃ ] ⁺ , 276 (23), 261 (25), 125 (22), 108 ( 9).
• MS (HR-EI): calc. 400.2504 found 400.2531

8.2. Preparation of trichloro-tris (4 (5) -tert-butylimidazol-2-yl) phosphine chromium (III)

• MS (FAB): m/z (%) = 582 (12) [M + Na]⁺, 522 (100) [M-Cl]⁺, 487 (58) (M-2Cl]⁺, 364 (19), 154 (68).

To a solution of 0.3 g (0.79 mmol) of chromium (III) trichloride-tris (tetrahydrofuran) in 10 ml of tetrahydrofuran was added a solution of 0.36 g (0.8 mmol) of tris (4 ( 5) -tet-Butylimidazol-2-yl) phosphine in 25 ml of tetrahydrofuran added. The solution thus obtained was stirred for 12 hours at room temperature, the solvent was distilled off, the residue was washed with hexane and dried under high vacuum. 0.42 g (94%) of trichloro (1-n-butyl-4-phenylimidazole) phosphine chromium (III) was obtained as a green solid.

• MS (FAB): m / z (%) = 582 (12) [M + Na] ⁺ , 522 (100) [M-Cl] ⁺ , 487 (58) (M-2Cl] ⁺ , 364 (19), 154 (68).

Examples 9-16:

polymerization

In a heated 250 ml Schlenk flask filled with nitrogen the amount (mg) of the catalyst given in Table 1 was weighed out and in 100 ml of toluene with stirring suspended at room temperature. 1.0 ml of a 10% solution of Methylaluminoxane in toluene (about 1.4 mmol Al) added and some Minutes stirred. Then was for the time period given in Table 1 ethene passed over the solution. After completion the gas inlet, the Schlenk flask was briefly flushed with nitrogen and that Reaction mixture for hydrolysis with a solution of concentrated hydrochloric acid in methanol in relation to 1: 2 offset. The polymer thus obtained was filtered off with methanolic hydrochloric acid Washed several times and in a drying cabinet at 110 ° C for 12 hours dried and weighed. To characterize the product the melting point, mass and C / H ratio are determined. The organic Phase is dried with sodium sulfate and on a gas chromatograph mass spectrometer examined for low polymer components.

The Polymer filtration filtrate was measured by GCMS measurements on low polymer Proportions examined. The GCMS investigations of the filtrates showed no indication of low polymer products or cyclotrimerizates, such as cyclohexane.

Table 1: Polymerization results

Examples 17-19

polymerization

It was in a 1 liter four-necked flask with a contact thermometer, stirrer with Teflon blade, heating element and Ga his pipe is polymerized at 40 ° C under argon. The corresponding amount of MAO (10% strength solution in toluene, Cr: Al according to Table 2) was added to a solution of the amount of the corresponding complex given in Table 2 in 250 ml of toluene and the mixture was heated to 40 ° C. in a water bath. In the case of the copolymerization in Example 19, 3 ml of hexene were introduced shortly before the ethylene addition. Then ethylene was passed through at a flow rate of about 20 to 40 l / h at atmospheric pressure. After 1 h under constant ethylene flow, the polymerization was terminated by adding methanolic HCl solution (15 ml of concentrated hydrochloric acid in 50 ml of methanol). 250 ml of methanol were then added and the resulting white polymer was filtered off, washed with methanol and dried at 70.degree.

Claims (10)

Transition metal complexes which contain the following structural feature of the general formula (Z) M (I), where the variables have the following meaning: M is a transition metal of group 3, 4, 5 or 6 of the periodic system of the elements and Z is a ligand of the formula (II)

where A is CR ¹ , SiR ¹ or P, R ^{1 is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OH, OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen means L ¹ -L ³ independently of one another

and where E ¹ -E ^{6 is} carbon or nitrogen, p is 0 when E ¹ -E ⁶ is nitrogen and is 1 when E ¹ -E ⁶ is carbon, R ² -R ^{8 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6–20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OR ⁹ , OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen, where the organic radicals R ² -R ^{8 can} also be substituted by halogens and two vicinal radicals R ² -R ^{8 can} also form a five- or six-membered ring can be connected, and / or that two vicinal radicals R ² -R ^{8 are connected} to form a heterocycle which contains at least one atom from the group N, P, O or S and R ⁹ independently of one another is hydrogen, C ₁ - C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, and two geminal radicals R ⁹ each one five or six-membered ring can be connected. Transition metal complexes according to claim 1, of the general formula (Z) MX _k (V), in which the variables have the following meaning: M is a transition metal of group 3, 4, 5 or 6 of the periodic table of the elements and Z is a ligand of the formula (II)

where A is CR ¹ , SiR ¹ or P, R ^{1 is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OH, OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen means L ¹ -L ³ independently of one another

and where E ¹ -E ^{6 is} carbon or nitrogen, p is 0 when E ¹ -E ⁶ is nitrogen and is 1 when E ¹ -E ⁶ is carbon, R ² -R ^{8 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6–20 C atoms in the aryl radical, NR ⁹ ₂ , N (SiR ⁹ ₃ ) ₂ , OR ⁹ , OSiR ⁹ ₃ , SiR ⁹ ₃ or halogen, where the organic radicals R ² -R ^{8 can} also be substituted by halogens and two vicinal radicals R ² -R ^{8 can} also be a five- or six-membered ring can be connected, and / or that two vicinal radicals R ² -R ^{8 are connected} to a heterocycle which contains at least one atom from the group N, P, O or S and R ⁹ independently of one another hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, and two geminal radicals R ⁹ each to one fo n- or six-membered ring can be connected, X independently of one another fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1- 10 C atoms in the alkyl radical and 6–20 C atoms in the aryl radical, NR ^1X R ^2X , OR ^1X , SR ^1X , SO ₃ R ^1X , OC (O) R ^1X , CN, SCN, β-diketonate, CO, BF ₄ ^- , PF ₆ ^- , or bulky non-coordinating anions, R ^1X -R ^2X independently of one another are hydrogen C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical or SiR ^3X ₃ means, where the organic radicals R ^1X -R ^{2X can} also be substituted by halogens or nitrogen and oxygen-containing groups and two radicals R ^1X -R ^2X can also be linked to form a five- or six-membered ring, R ^3X independently of one another hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6–20 C atoms i m is an aryl radical and two radicals R ^{3x can} also be connected to form a five- or six-membered ring and k is 1, 2 or 3. Transition metal complexes according to Claims 1 or 2, in which M is M ^A and Z is Z ^A , which contain the following structural feature of the general formula (Z ^A ) M ^A (III), in which the variables have the following meaning: M ^{A is} a transition metal of the group 3, 4, 5 or 6 of the periodic table of the elements and Z ^{A is} a ligand of the formula (IV)

where A ^{A is} CR ^1A , SiR ^1A or P, R ^{1A is} hydrogen, C ₁ -C ₂ -alky1, C ₂ -C ₂₀ -alkenyl, C ₆ -C ₂₀ -aryl, alkylaryl with 1 to 10 carbon atoms in the Alkyl radical and 6-20 C atoms in the aryl radical, NR ^11A ₂ , N (SiR ^11A ₃ ) ₂ , OH, OSiR ^11A ₃ , SiR ^11A ₃ or halogen, R ^2A -R ^10A independently of one another are hydrogen, C ₁ -C ₂₀ -Alkyl, C2-C20-alkenyl, C ₆ -C ₂₀ -aryl, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR ^11A ₂ , N (SiR ^11A ₃ ) ₂ , OR ^11A , OSiR ^11A ₃ , SiR ^11A ₃ or halogen, where the organic radicals R ^2A -R ^{10A can} also be substituted by halogens and two vicinal radicals R ^2A -R ^{10A can} also be connected to form a five- or six-membered ring, and / or that two vicinal radicals R ^2A -R ^{10A are connected} to form a heterocycle which contains at least one atom from the group N, P, O or S and R ^11A independently of one another is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical and two geminal radicals R ^{11A can} also be connected to form a five- or six-membered ring. Transition metal complexes according to claims 1 to 3, wherein A or A is ^A P. Transition metal complexes according to Claims 1 to 4, in which M or M ^A denotes titanium, zirconium, vanadium or chromium. Transition metal complexes according to claims 3 to 5, wherein in each case the group of substituents R ^2A , R ^5A and R ^8A and the group of substituents R ^3A , R ^6A and R ^9A and the group of substituents R ^4A , R ^7A and R ^{10A are} each within a group are equal to each other. Catalyst system for olefin polymerization containing A) at least one transition metal complex according to the claims 1 to 6, B) optionally an organic or inorganic carrier, C) optionally one or more activating connections, D) optional other catalysts suitable for olefin polymerization and e) optionally one or more group 1, 2 or metal compounds 13 of the periodic table. Prepolymerized catalyst system containing a catalyst system according to claim 7 and polymerized in addition one or more linear C ₂ -C ₁₀ -1 alkenes in a mass ratio of 1: 0.1 to 1: 1000 based on the catalyst system. Use of a catalyst system according to claims 7 or 8 for the polymerization or copolymerization of olefins. Process for the preparation of polyolefins by Polymerization or copolymerization of olefins in the presence of a Catalyst system according to claims 7 or 8.