DE102006051721A1 - Polymerizing olefins in the presence of catalyst comprising organic transition metal complex, where the comonomer incorporation behavior of the catalyst is controlled by addition of auxiliaries - Google Patents

Abstract

Polymerizing olefins in the presence of at least one catalyst comprising an organic transition metal complex, where the comonomer incorporation behavior of the catalyst is controlled by addition of auxiliaries.

Description

The The present invention relates to a method of polymerization of olefins in the presence of at least one catalyst an organo-transition metal complex.

to Improving the property profile of polyolefins proves it increasingly required to have close control over the obtain molecular composition of polyolefins. A clear one Progress in this direction resulted in the development of the so-called Single-site catalysts in which only one kind is catalytic active centers. The obtained with such catalysts Polymers have a relatively uniform distribution of polymer chains in terms of molecular weight, the comonomer distribution and optionally the stereoregularity on.

A Class of these catalysts are the chromium single-site catalysts, based on Monocyclopentadienylkomplexen. These can be alone or in combination with other catalysts as so-called Hybrid catalysts are used.

One essential factor for the properties of the polymerization catalysts or catalyst mixtures is their comonomer incorporation behavior. For a catalyst species is the comonomer incorporation behavior is essentially a predetermined size. To one To be able to produce polymer with different Comonomergehalt, was for chromium single-site catalysts as with other single-site catalysts so far the substitution pattern of the cyclopentadienyl ligand, which is a relatively large one Effort means, since in each case a new catalyst arises.

Furthermore, it is known that in the polymerization of olefins by the addition of auxiliaries, which are often referred to as modifiers, the properties of the polymers formed can be influenced. Called here are chain transfer agents such as hydrogen, which is generally used to control the average molecular weight of the polymer chains formed. Furthermore, it is known that other compounds for controlling the molecular weight of polyolefins can be used. For example, in the WO 95/13305 described that in the olefin polymerization with supported metallocene catalysts by addition of electron donor compounds, the molecular weight of the polyolefins formed can be increased, while using water or electron-withdrawing compounds, the molecular weight is lowered.

From the EP-A 435 250 It is known that dialkylzinc compounds act as molecular weight regulators in Ziegler catalysts and increase the activity of the catalysts. EP-A 1 092 730 describes such, reducing the molecular weight and increasing the activity of the catalysts effect of dialkylzinc compounds for metallocene catalysts. Continue to teach EP-A 1 092 730 . WO 98/56835 and US Pat. No. 6,642,326 in that also silanes which are substituted by a maximum of three radicals other than hydrogen act as molecular weight regulators which lower the molecular weight and at the same time increase the activity of the catalysts. Substituted silanes in which at least one radical is an alkoxy or aryloxy group are, for example, from EP-A 447 959 known as cocatalysts for Ziegler-Natta catalysts. WO 03/104290 discloses that corresponding substituted silanes in cyclopentadienyl ligand-containing single-site catalysts result in an increase in the molecular weight of the polyolefins formed without reducing the activity of the catalysts.

In connection with hybrid catalysts describes WO 02/090398 a process for the preparation of polyolefins in a polymerization step employing a hybrid catalyst and an adjuvant selected from the group consisting of phosphines, phosphites, acetylenes, dienes, thiophenes and aluminum alkyls. These adjuvants influence the molecular weight of the polymer components formed by the individual active sites, whereby the different active sites are influenced differently and thus a change in the ratio of high molecular weight component to low molecular weight component is made possible. The auxiliaries can be used instead of or together with hydrogen. In this process, however, variants in the polymers produced are only accessible to a very limited extent since, although a variation in the molecular weight of the polymer components is achieved, their properties otherwise remain unchanged.

at Olefinpolymerisationsverfahren in a cascade of several reactors carried out it will be possible produce several polymer components, in addition to a different Molecular weight also have a different content of comonomer. To such products with the help of hybrid catalysts in only one To produce reactor, the respective catalyst component in structurally adapted to their comonomer incorporation behavior, as far as this at all possible is.

task Therefore, it was the object of the present invention with a catalyst species Produce polymers with different comonomer content or be able to change the comonomer incorporation behavior targeted.

It has now been found to be based on using catalysts of organo-transition metal complexes, by using suitable auxiliaries, the comonomer incorporation behavior succeeds to control.

Accordingly, the subject the present invention, a method for the polymerization of Olefins in the presence of at least one catalyst comprising an organo-transition metal complex, wherein the comonomer incorporation behavior of the catalyst by adding one or more auxiliaries is controlled.

In order to it is possible by adding such compounds, the comonomer content that with the help of the organo-transition metal complex targeted to change based catalysts produced polymers to with a catalyst species polymers with different comonomer content manufacture.

Suitable organo-transition metal complexes are in principle all compounds of the transition metals of groups 3 to 12 of the Periodic Table or of the lanthanides containing organic groups, which usually form active catalysts for the polymerization of olefins after reaction with a cocatalyst and optionally organometallic compounds. These are usually compounds in which at least one mono- or polydentate ligand is bound to the central atom via sigma or pi bonding. Suitable ligands are both those which contain cyclopentadienyl radicals and those which are free of cyclopentadienyl radicals. In Chem. Rev. 2000, Vol. 100, No. 4 For example, a variety of such compounds suitable for olefin polymerization are described. Furthermore, polynuclear cyclopentadienyl complexes are also suitable for the polymerization of olefins.

Under Comonomereinereinverhalten according to the invention is the property of the respective Catalyst or the respective catalyst component understood Comonomer in proportion to install the monomer. Quantitatively, this is due to the copolymerization constant to capture.

• a) Silanen der allgemeinen Formel R_aSiR'_b oder R_aSi(OR')_b,
• b) Zinkdialkylen der allgemeinen Formel ZnR'₂,
• c) Ethern der allgemeinen Formel R'-O-R' und
• d) Bortrialkylen der allgemeinen Formel BR'₃,

wobei
R jeweils gleich oder verschieden ist und für einen C₁-C₂₀-Alkyl-, C₆-C₂₀-Aryl-, C₆-C₂₀-Arylalkyl- oder C₆-C₂₀-Alkylarylrest steht, der mit mindestens einer polaren Gruppe der allgemeinen Formeln -NR''₂, -OR'', -COR'' oder -COOR'' substituiert ist,
R' jeweils gleich oder verschieden ist und einen C₁-C₂₀-Alkyl-, C₆-C₂₀-Aryl-, C₆-C₂₀-Arylalkyl- oder C₆-C₂₀-Alkylarylrest bedeutet,
R'' jeweils gleich oder verschieden ist und Wasserstoff oder einen C₁-C₂₀-Alkyl-, C₆-C₂₀-Aryl-, C₆-C₂₀-Arylalkyl- oder C₆-C₂₀-Alkylarylrest bedeutet,
a 1, 2, 3 oder 4 ist und
b so gewählt ist, dass a + b = 4 ist.A preferred embodiment of the present invention comprises a process for the polymerization of olefins in the presence of at least one catalyst comprising a monocyclopentadienyl complex of the formula Cp-Y _m M ^A (I), in which the variables have the following meanings:
Cp is a cyclopentadienyl system,
Y is a Cp-bonded substituent containing at least one neutral donor D which contains at least one atom of groups 15 or 16 of the periodic table,
M ^A titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, in particular chromium and
m 1, 2 or 3,
It is further preferred if the one or more auxiliaries are selected from the group consisting of

• a) silanes of the general formula R _a SiR _'b or R _a Si (OR') _b,
• b) zinc dialylene of the general formula ZnR ' ₂ ,
• c) ethers of the general formula R'-OR 'and
• d) boron trialkyls of the general formula BR ' ₃ ,

in which
R is in each case identical or different and is a C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -arylalkyl or C ₆ -C ₂₀ -alkylaryl radical which reacts with at least one polar Group of the general formulas -NR '' ₂ , -OR '', -COR '' or -COOR '' is substituted,
R 'is in each case identical or different and is a C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -arylalkyl or C ₆ -C ₂₀ -alkylaryl radical,
R '' is in each case identical or different and is hydrogen or a C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -arylalkyl or C ₆ -C ₂₀ -alkylaryl radical,
a is 1, 2, 3 or 4 and
b is chosen such that a + b = 4.

This is particularly interesting when using hybrid catalysts, since it was found that the monocyclopentadienyl based catalysts particularly pronounced respond to the modifier while other types of catalysts such as classical metallocene catalysts or especially late transition metal catalysts be less strongly influenced in their Comonomereinereinverhaltenverhalten.

The Adjuvants are preferably used singly but may be also be used together. The mentioned auxiliaries are hereinafter referred to collectively or alone as a modifier.

The added amounts of modifier serve in particular to the Changing comonomer installation behavior of the catalyst. Depending on the used Modifier can simultaneously also the average molecular weight of the catalyst suitably influenced up or down and so on Polymer or a polymer component with tailored properties to be obtained. It should be emphasized that, in addition, additional additional and adjuvants such as antistatic agents or scavengers in the method of the invention can be used.

Usually The modifiers are in an amount of 2 to 100 mol ppm, respectively based on the total reaction mixture used. The exact The amount of modifier used is dependent in particular on the sensitivity of the catalyst to the modifier and the Type and amount of added scavengers such as metal alkyls. It is therefore to be adapted empirically to the respective reaction conditions. The amount should not be chosen so high that one or several catalyst components are completely killed, as for example usual before the shutdown of the reactor is.

The mentioned modifier are preferred in an amount of at least 3 mol ppm, more preferably at least 5 mol ppm, further preferably used of at least 8 mol ppm. It is preferred in a crowd of at most 90 mol ppm, further preferably at most 75 mol ppm, further preferably of at most 50 mol ppm used. A preferred concentration range extends from 3 to 80 mol ppm, more preferably from 3 to 60 mol ppm, more preferably from 5 to 40 mol ppm.

Next the said modifiers can still further auxiliaries, in particular modifiers, be present preferably a different selectivity to the catalyst components exhibit. The addition of further modifiers may be particularly useful although the hybrid catalyst contains more than two components.

• a) Silanen der allgemeinen Formel R_aSiR'_b oder R_aSi(OR')_b,
• b) Zinkdialkylen der allgemeinen Formel ZnR'₂,
• c) Ethern der allgemeinen Formel R'-O-R' und
• d) Bortrialkylen der allgemeinen Formel BR'₃,

bei denen die Reste R, R' und R'' die oben genannte Bedeutung haben.Preferably, modifiers are selected from the group consisting of

• a) silanes of the general formula R _a SiR _'b or R _a Si (OR') _b,
• b) zinc dialylene of the general formula ZnR ' ₂ ,
• c) ethers of the general formula R'-OR 'and
• d) boron trialkyls of the general formula BR ' ₃ ,

in which the radicals R, R 'and R "have the abovementioned meaning.

Preferred silanes R _a SiR ' _b or R _a Si (OR') _b are those in which
R is in each case identical or different and is a C ₁ -C ₂₀ -alkyl radical which is substituted by at least one polar group of the general formulas -NR " ₂ , -OR", -COR "or -COOR",
Each R 'is the same or different and is a C ₁ -C ₂₀ alkyl radical, and
R "is in each case identical or different and is hydrogen or a C ₁ -C ₂₀ -alkyl radical.

preferred Substituents R are methylamino, ethylamino, n-propylamino, isopropylamino, Buylamino, and Hexylaminoreste. Particular preference is given to N, N- (diethylamino) -trimethylsilane, 3-Aminopropyltrimethylsilan, Bis- (dimethylamino) -dimethylsilane, anilinotrimethylsilane.

Preferred zinc dialkyls ZnR ₂ 'are those wherein R' is independently methyl, ethyl, n-propyl, isopropyl, butyl, hexyl and / or cyclohexyl. Particularly preferred is diethylzinc.

preferred Ether R'-O-R 'are in particular those in which R 'are independent of each other equal to methyl, ethyl, propyl, butyl, pentyl, hexyl. Especially preferred are butyl methyl ether and diethyl ether.

Preferred boron trialkyl BR ' ₃ are those in which R' independently of one another are methyl, ethyl, propy, isopropyl or butyl. Particularly preferred is triethylboron.

When Catalysts according to the invention are those based on organo transition metal complexes for use. These become common also as single-site catalysts referred to as being on a chemically unified complex compound based.

The catalysts comprising monocyclopentadienyl complexes preferably contain the structural element having the general formula Cp-Y _m M ^A (I), in which the variables have the following meanings:
Cp is a cyclopentadienyl system,
Y is a Cp-bonded substituent containing at least one neutral donor D which contains at least one atom of groups 15 or 16 of the periodic table,
M ^A titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, in particular chromium and
m 1, 2 or 3.

To the metal atom M ^A further ligands may be bound. The number of further ligands depends, for example, on the oxidation state of the metal atom. As ligands no further cyclopentadienyl systems are suitable. Suitable are mono- and dianionic ligands as described, for example, for X. In addition, Lewis bases such as amines, ethers, ketones, aldehydes, esters, sulfides or phosphines may be bound to the metal center M. The monocyclopentadienyl complexes may be monomeric, dimeric or oligomeric. Preferred are the Monocyclopentadienylkomplexe in monomeric form.

M ^A is a metal selected from the group titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten. The oxidation states of the transition metals M ^A in catalytically active complexes are generally known to the person skilled in the art. Chromium, molybdenum and tungsten are most likely present in the oxidation state +3, zirconium and hafnium in the oxidation state +4 and titanium in the oxidation state +3 or +4. However, it is also possible to use complexes whose oxidation state does not correspond to that of the active catalyst. Such complexes can then be appropriately reduced or oxidized by suitable activators. Preferably, M ^{A is} titanium in the oxidation state +3, vanadium, chromium, molybdenum and tungsten. Particularly preferred is chromium in the oxidation states +2, +3 and +4, in particular +3.

m may be 1, 2 or 3, i. 1, 2 or 3 containing a donor Substituents Y can be bound to Cp, wherein in the presence of 2 or 3 substituents Y, these may be the same or different. Preferred is only one Substituent Y bound to Cp (m = 1).

The C-attached substituent Y contains at least one neutral donor A. A is a member of the 15th or 16th group of the periodic table containing neutral functional group, eg, amine, imine, carboxamide, carboxylic ester, ketone (oxo), ether, thioketone, phosphine , Phosphite, phosphine oxide, sulfonyl, sulfonamide, or unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring systems. The donor A can be bound to the transition metal M ^A inter- or intramolecularly or not bound. Preferably, donor ^{A is} bound intramolecularly to the metal center M ^A. In particular, monocyclopentadienyl complexes which contain the structural element of the general formula Cp-YM ^A are preferred.

Cp is a cyclopentadienyl system which may be arbitrarily substituted and / or condensed with one or more aromatic, aliphatic, heterocyclic or even heteroaromatic rings, wherein 1, 2 or 3 substituents, preferably 1 substituent of the group Y is formed and / or 1, 2 or 3 substituents, preferably 1 substituent from the group Y is substituted and / or the aromatic, aliphatic, heterocyclic or heteroaromatic condensed ring 1, 2 or 3 substituents, preferably 1 substituent Y carries. The cyclopentadienyl backbone itself is a C ₅ ring system with 6 π-electrons, wherein one of the carbon atoms may also be replaced by nitrogen or phosphorus, preferably phosphorus. Preferably, C ₅ ring systems are used without replacement by a heteroatom. To this cyclopentadienyl skeleton, for example, a heteroaromatic, which contains at least one atom of the group N, P, O or S or an aromatic be angeckesesiert. Condensed herein means that the heterocycle and the cyclopentadienyl backbone have two atoms in common, preferably carbon atoms. The cyclopentadienyl system is bound to M ^A.

wobei die Variablen folgende Bedeutung besitzen:
E^1A–E^5A Kohlenstoff oder maximal ein E^1A bis E^5A Phosphor,
R^1A–R^4A unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, C₂-C₂₂-Alkenyl, C₆-C₂₂-Aryl, Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, NR^5A ₂, N(SiR^5A ₃)₂, OR^5A, OSiR^5A ₃, SiR^5A ₃, BR^5A ₂, wobei die organischen Reste R^1A–R^4A auch durch Halogene substituiert sein können und je zwei vicinale Reste R^1A–R^4A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^1A–R^4A zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sind, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält,
R^5A 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 und je zwei geminale Reste R^5A auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können,
Z eine divalente Brücke zwischen A und Cp ist, ausgewählt aus der folgenden Gruppe

wobei
L^1A–L^3A unahängig voneinander Silizium oder Germanium bedeutet,
R^6A–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 Arylrest oder SiR^12A ₃ bedeutet, wobei die organischen Reste R^6A–R^11A auch durch Halogene substituiert sein können und je zwei geminale oder vicinale Reste R^6A–R^11A auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können und, wobei
R^12A unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl oder Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest C₁-C₁₀-Alkoxy oder C₆-C₁₀-Aryloxy bedeutet und je zwei Reste R^12A auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können,
A eine neutrale Donorgruppe enthaltend ein oder mehrere Atome der Gruppe 15 und/oder 16 des Periodensystems der Elemente, bevorzugt ein unsubstituiertes, substituiertes oder kondensiertes, heteroaromatisches Ringsystem,
M^A ein Metall ausgewählt aus der Gruppe Titan in der Oxidationsstufe 3, Vanadium, Chrom, Molybdän und Wolfram, insbesondere Chrom und
k 0 oder 1 ist.Particularly suitable are monocyclopentadienyl complexes in which Y is formed by the group -Zk-A- and with the cyclopentadienyl system Cp and M ^A forms a monocyclopentadienyl complex containing the structural element of the general formula Cp-Zk-AM ^A (II), in which the variables have the following meaning to have:

where the variables have the following meaning:
E ^1A -E ^5A carbon or at most one E ^1A to E ^5A phosphor,
R ^1A -R ^4A are each independently hydrogen, C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₂₂ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR ^5A ₂ , N (SiR ^5A ₃ ) ₂ , OR ^5A , OSiR ^5A ₃ , SiR ^5A ₃ , BR ^5A ₂ , where the organic radicals R ^1A -R ^{4A may} also be substituted by halogens and each represent two vicinal radicals R ^1A -R ^{4A may} also be connected to a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^1A -R ^{4A are connected} to a five-, six- or seven-membered heterocycle which comprises at least one atom contains the group N, P, O or S,
R ^5A independently of one another are 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 geminal radicals R ^{5A can} also be linked to form a five- or six-membered ring,
Z is a divalent bridge between A and Cp selected from the following group

in which
L ^1A -L ^3A independently of one another means silicon or germanium,
R ^6A- R ^11A independently of one another are 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 or SiR ^12A ₃ , where the organic radicals R ^6A -R ^{11A may} also be substituted by halogens and any two geminal or vicinal radicals R ^6A -R ^{11A may} also be connected to a five- or six-membered ring and, wherein
R ^12A independently of one another are 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 C C ₁ -C ₁₀ -alkoxy or C ₆ -C ₁₀ -aryloxy and in each case two radicals R ^{12A may} also be linked to form a five- or six-membered ring,
A is a neutral donor group containing one or more atoms of group 15 and / or 16 of the Periodic Table of the Elements, preferably an unsubstituted, substituted or fused, heteroaromatic ring system,
M ^{A is} a metal selected from the group titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten, in particular chromium and
k is 0 or 1.

In preferred cyclopentadienyl systems Cp, all E ^1A to E ^{5A are} carbon.

By varying the substituents R ^1A -R ^4A , it is possible to influence the polymerization behavior of the metal complexes. The number and type of substituents can influence the accessibility of the metal atom M ^A for the olefins to be polymerized. Thus, it is possible to modify the activity and selectivity of the catalyst with respect to various monomers, in particular sterically demanding monomers. Since the substituents can also influence the rate of termination reactions of the growing polymer chain, this can also change the molecular weight of the resulting polymers. The chemical structure of the substituents R ^1A to R ^4A can therefore be varied within wide limits in order to achieve the desired results and to obtain a tailor-made catalyst system. Examples of suitable C-organic substituents R ^1A -R ^4A are: hydrogen, C ₁ -C ₂₂ -alkyl, where the alkyl may be linear or branched, such as, for example, 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 a C ₁ -C ₁₀ alkyl group and / or C ₆ -C ₁₀ aryl group may bear as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₂ alkenyl, wherein the alkenyl may be linear, cyclic or branched and the double bond may be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ C ₂₂ -aryl, where the aryl radical may 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, wherein the arylalkyl may be substituted by further alkyl groups, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, optionally also two R ^1A to R ^4A may be connected to a 5-, 6- or 7-membered ring and / or two of the vicinal radicals R ^1A -R ^{4A may be connected} to a five-, six- or seven-membered heterocycle which contains at least one atom from the group N, P, O or S contains and / or the organic radicals R ^1A -R ^{4A may} also be substituted by halogens, such as fluorine, chlorine or bromine. Furthermore, R ^1A -R ^{4A can be} amino NR ^5A ₂ , or N (SiR ^5A ₃ ) ₂ , alkoxy or aryloxy OR ^5A , for example dimethylamino, N-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy. As Si-organic substituents SiR ^5A ₃ , the same C-organic radicals for R ^5A , as detailed above for R ^1A -R ^4A , where appropriate, two R ^{5A may be connected} to a 5- or 6-membered ring, in Consider such as trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These SiR ^5A ₃ radicals can also be bonded to the cyclopentadienyl skeleton via an oxygen or nitrogen, for example trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or tri-tert-butylsilyloxy. Preferred radicals R ^1A -R ^4A are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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. Suitable Si-organic substituents are in particular trialkylsilyl groups having 1 to 10 C atoms in the alkyl radical, in particular trimethylsilyl groups.

Two vicinal radicals R ^1A -R ^4A can each form with the E ^1A -E ^5A carrying them, a heterocycle, preferably heteroaromatics, which is at least one atom from the group nitrogen, phosphorus, oxygen and / or sulfur, particularly preferably nitrogen and / or Contains sulfur, wherein the heterocycle or heteroaromatic E ^1A -E ^{5A contained are} preferably carbons. Preference is given to heterocycles and heteroaromatics having a ring size of 5 or 6 ring atoms. Examples of 5-membered ring heterocycles which besides carbon atoms can contain one to four nitrogen atoms and / or one sulfur or oxygen atom as ring members are 1,2-dihydrofuran, furan, thiophene, pyrrole, isoxazole, 3-isothiazole, pyrazole, oxazole, Thiazole, imidazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-triazole or 1,2,4-triazole. Examples of 6-membered heteroaryl groups which may contain one to four nitrogen atoms and / or one phosphorus atom are pyridine, phosphabenzene, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine or 1,2 , 3-triazine. The 5-membered ring and 6-membered ring heterocycles can also be replaced by C ₁ -C ₁₀ -alkyl, C ₆ -C ₁₀ -aryl, alkylaryl having 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 or may be condensed with one or more aromatics or heteroaromatics. Examples of benzo-fused 5-membered heteroaryl groups are indole, indazole, benzofuran, benzothiophene, benzothiazole, benzoxazole or benzimidazole. Examples of benzo-fused 6-membered heteroaryl groups are chroman, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, 1,10-phenanthroline or quinolizine. The name and numbering of the heterocycles was determined Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979 taken. The heterocycles / heteroaromatics are preferably condensed with the cyclopentadienyl skeleton via a C-C double bond of the heterocycle / heteroaromatic. Heterocycles / heteroaromatics having one heteroatom are preferably 2,3- or b-fused.

cyclopentadienyl systems Cp with a condensed heterocycle are, for example, thiapentals, 2-methylthiapentals, 2-ethylthiapentals, 2-isopropylthiapentals, 2-n-Butylthiapentalen, 2-tert-butylthiapentals, 2-trimethylsilylthiapentals, 2-phenylthiapentals, 2-Naphthylthiapentalen, 3-methylthiopentals, 4-phenyl-2,6-dimethyl-1-thiopentals, 4-phenyl-2,6-diethyl-1-thiopentals, 4-phenyl-2,6-diisopropyl-1-thiopentals, 4-phenyl-2,6-di-n-butyl-1-thiopentals, 4-phenyl-2,6-di-trimethylsilyl-1-thiopentals, Azapentals, 2-methylazapentals, 2-ethylazapentals, 2-isopropylazapentals, 2-n-butylazapentals, 2-trimethylsilylazapentals, 2-phenylazapentals, 2-naphthylazapentals, 1-phenyl-2,5-dimethyl-1-azapentals, 1-phenyl-2,5-diethyl-1-azapentals, 1-phenyl-2,5-di-n-butyl-1-azapentals, 1-phenyl-2,5-di-tert-butyl-1-azapentals, 1-phenyl-2,5-di-trimethylsilyl-1-azapentalene, 1-tert-butyl-2,5-dimethyl-1-azapentalene, Oxapentals, phosphapentalene, 1-phenyl-2,5-dimethyl-1-phosphapentalene, 1-phenyl-2,5-diethyl-1-phosphapentalen, 1-phenyl-2,5-di-n-butyl-1-phosphapentals, 1-phenyl-2,5-di-tert-butyl-1-phosphapentals, 1-phenyl-2,5-di-trimethylsilyl-1-phosphapentalene, 1-methyl-2,5-dimethyl-1-phosphapentalene, 1-tert-butyl-2,5-dimethyl-1-phosphapentals, 7-cyclopenta [1,2] thiophene [3,4] cyclopentadiene or 7-cyclopenta [1,2] pyrrole [3,4] cyclopentadiene.

In further preferred cyclopentadienyl systems Cp, the four radicals R ^1A -R ^4A , ie two vicinal radicals together, form two heterocycles, in particular heteroaromatics. The heterocyclic systems are the same as explained above. Cyclopentadienyl systems Cp having two fused heterocycles are, for example, 7-cyclopentadithiophene, 7-cyclopentadipyrrole or 7-cyclopentadiphosphole.

The synthesis of such cyclopentadienyl systems with fused-on heterocycle is mentioned, for example, in the introduction WO 98/22486 described. In "metal organic catalysts for synthesis and polymerization", Springer Verlag 1999, are by Ewen et al., p.150 ff further syntheses of these Cyclopentadienylsyteme described.

Particularly preferred substituents R ^1A -R ^4A are the C-organic substituents described above and the C-organic substituents which form a cyclic fused ring system, ie together with the E ^1A -E ^5A -, preferably a C ₅ -cyclopentadienyl skeleton for example, form an unsubstituted or substituted indenyl, benzindenyl, phenantrenyl, fluorenyl or tetrahydroindenyl system. and in particular their preferred embodiments.

Examples of such cyclopentadienyl systems (without the group -ZA-, this preferably being in the 1-position) are 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3-isopropylcyclopentadienyl, 3-tert-butylcyclopentadienyl, di-, for example tetrahydroindenyl, 2, 4-dimethylcyclopentadienyl or 3-methyl-5-tert-butylcyclopentadienyl, tri-, such as, for example, 2,3,5-trimethylcyclopentadienyl or tetraalkylcyclopentadienyl, for example 2,3,4,5-tetramethylcyclopentadienyl, and also indenyl, 2-methylindenyl, 2- Ethylindenyl, 2-isopropylindenyl, 3-methylindenyl, benzindenyl or 2-methylbenzindenyl. The fused ring system may be further 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 ^5A ₂ , N (SiR ^5A ₃ ) ₂ , OR ^5A , OSiR ^5A ₃ or SiR ^5A ₃ such as 4-methylindenyl, 4-ethylindenyl, 4-isopropylindenyl, 5-methylindenyl, 4-phenylindenyl, 5-methyl 4-phenylindenyl, 2-methyl-4-phenylindenyl or 4-naphthylindenyl.

In a particularly preferred embodiment, one of the substituents R ^1A -R ^4A , preferably R ^2A , a C ₆ -C ₂₂ -aryl or an alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, is preferred C ₆ -C ₂₂ -aryl, for example phenyl, naphthyl, biphenyl, anthracenyl or phenantrenyl, in which the aryl is also substituted by N, P, O or S-containing substituents, C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ alkenyl, halogens or haloalkyls or haloaryls having 1-10 C atoms may be substituted, such as 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, o-, m -, p-dimethylaminophenyl, o-, m-, p-methoxyphenyl, o-, m-, p-fluorophenyl, o-, m-, p-chlorophenyl, o-, m-, p-trifluoromethylphenyl, 2,3- , 2,4-, 2,5- or 2,6-difluorophenyl, 2,3-, 2,4-, 2,5- or 2,6-dichlorophenyl or 2,3-, 2,4-, 2 , 5-, or 2,6-di (trifluoromethyl) phenyl. The N-, P-, O- or S-containing substituents, C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl, halogens or haloalkyls or halogenoaryls having 1-10 C atoms as substituents of the aryl radical are preferably present in para position, relative to the bond to the cyclopentadienyl ring. The aryl substituent may be bonded in the vicinal position to the substituent -ZA or the two substituents are located in the 1,3-position on the cyclopentadienyl ring relative to each other. Preferably, -ZA and the aryl substituent are in the 1,3-position relative to each other on the cyclopentadienyl ring.

The monocyclopentadienyl complexes can be chiral. Thus, on the one hand, one of the substituents R ^1A -R ^{4A of} the cyclopentadienyl skeleton may possess one or more chiral centers, or else the cyclopentadienyl system Cp itself may be enantiotopic, so that chirality is induced by its binding to the transition metal M (to the formalism of chirality for cyclopentadienyl compounds see R. Halterman, Chem. Rev. 92, (1992), 965-994) ,

The bridging Z between the cyclopentadienyl system Cp and the neutral donor A, if present (k = 1), an organic divalent bridging, is preferred consisting of carbon and / or silicon and / or boron-containing Bridge members. By a change the join length between the Cyclopentadienyl system and A can affect the activity of the catalyst. Preferably, Z is adjacent to the fused heterocycle or fused Aromatic bound to the cyclopentadienyl skeleton. So it is the heterocycle or aromatics condensed in the 2,3-position of the cyclopentadienyl backbone, thus, Z preferably sits in the 1- or 4-position of the cyclopentadienyl skeleton.

Examples of suitable C-organic substituents R ^6A- R ^{11A of} the linkage Z include the following: hydrogen, C ₁ -C ₂₀ -alkyl, where the alkyl may be linear or branched, such as, for example, 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 may carry a C ₆ -C ₁₀ aryl group as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, wherein the alkenyl is 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, where the aryl radical may be substituted by further alkyl groups, such as phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, ode r is 2,6-dimethylphen-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4, 5-trimethylphen-1-yl, or arylalkyl, wherein the arylalkyl may be substituted by further alkyl groups, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, optionally also two R ^6A to R ^{11A may be connected} to a 5- or 6-membered ring, such as cyclohexane, and the organic radicals R ^6A -R ^11A also by halogens, such as fluorine, chlorine or bromine, such as pentafluorophenyl or bis-3,5-trifluoromethylphen 1-yl and alkyl or aryl may be substituted.

Suitable Si-organic substituents SiR ^12A ₃ are the same radicals for R ^12A as described in more detail above for R ^6A- R ^11A , it also being possible for two R ^12A to be joined to form a 5- or 6-membered ring for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tritert.butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. Preferred radicals R ^6A- R ^11A are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , Benzyl, phenyl, ortho-dialkyl- or dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl.

Particular preference is given to substituents R ^6A to R ^11A being hydrogen, C ₁ -C ₂₀ -alkyl, where the alkyl may be linear or branched, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl C ₆ -C ₂₀ -aryl, where the aryl radical may 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-dimethylphen-1-yl, 2,3, 4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphen-1-yl, or arylalkyl, wherein the arylalkyl by other alkyl groups may be substituted, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, wherein optionally also two R ^6A to R ^{11A may be connected} to a 5- or 6-membered ring, as for example, cyclohexane, and the organic radicals R ^6A- R ^2B also by halogens, such as fluorine, chlorine or bromine, in particular fluorine such as pentafluorophenyl or bis-3,5-T Rifluormethylphen-1-yl and alkyl or aryl may be substituted. Particularly preferred are methyl, ethyl, 1-propyl, 2-iso-propyl, 1-butyl, 2-tert-butyl, phenyl and pentafluorophenyl.

Z is preferably a group -CR ^6A R ^7A -, -SiR ^6A R ^7A -, in particular -Si (CH _{3) 2,} -CR ^6A R ^7A CR ^8A R ^9A -, -SiR ^6A R ^7A CR ^8A R ^9A - or substituted or unsubstituted 1,2-phenylene and especially -CR ^6A R ^7A -. The preferred embodiments of the substituents R ^6A to R ^11A described above are also preferred embodiments herein. , -CH ₂ - - preferably -CR ^6A R ^{7A is} a group -CHR ^6A is or -C (CH _{3) 2} -. The group -SiR ^6A R ^7A - in -L ^1A R ^6A R ^7A CR ^8A R ^9A - may be attached to the cyclopentadienyl system or to A. Preferably, this group -SiR ^6A R ^7A - or its preferred embodiments is bound to Cp.

k is 0 or 1, in particular k is 1 or, if A is an unsubstituted, substituted or fused heterocyclic ring system, also 0. Preferably k is equal to 1.

A is a neutral donor containing one atom of Groups 15 or 16 of the Periodic Table, preferably one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen or phosphorus, preferably nitrogen or phosphorus. The donor function in A can bind to the metal M ^A inter- or intramolecularly. Preferably, the donor in A is bound intramolecularly to M. Suitable donors are neutral functional groups which contain an element of the 15th or 16th group of the periodic table, for example amine, imine, carboxamide, carboxylic esters, ketone (oxo), ethers, thioketone, phosphine, phosphite, phosphine oxide, sulfonyl, sulfonamide, or unsubstituted, substituted or fused, heterocyclic ring systems into consideration. The synthetic attachment of A to the cyclopentadienyl radical and Z can, for example, in analogy to WO 00/35928 be performed.

A is preferably a group selected from -OR ^13A -, -SR ^13A -, -NR ^13A R ^14A -, -PR ^13A R ^14A -, -C = NR ^13A - and unsubstituted, substituted or fused heteroaromatic ring systems, in particular -NR ^13A R ^14A -, -C = NR ^13A - and unsubstituted, substituted or fused heteroaromatic ring systems.

R ^13A and R ^14A independently of one another represent hydrogen, C ₁ -C ₂₀ -alkyl, where the alkyl may be linear or branched, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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 may carry as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, wherein the alkenyl may be linear, cyclic or branched and the double bond may 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, where the aryl radical may be substituted by further alkyl groups, such as for example, phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphen-1-yl, 2,3,4 , 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphen-1-yl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical wherein the arylalkyl may be substituted by further alkyl groups, such as Benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl or SiR ^15A ₃ , where the organic radicals R ^13A -R ^14A also by halogens, for example fluorine, chlorine or bromine or nitrogen-containing groups and others C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₆ -C ₂₀ -aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR ^15A ₃ may be substituted and any two vicinal radicals R ^13A -R ^{14A may} also be linked to form a five- or six-membered ring and R ^15A independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₆ -C ₂₀ - Aryl, or alkylaryl having 1 to 10 carbon atoms in the alkyl radical and 6-20 C atoms in the aryl radical and each two radicals R ^{15A may} also be connected to a five- or six-membered ring.

NR ^13A R ^14A represents an amide substituent. These are preferably secondary amides such as dimethylamide, N-ethyl-methylamide, diethylamide, N-methyl-propylamide, N-methyl-isopropylamide, N-ethylisopropylamide, dipropylamide, diisopropylamide, N-methyl-butylamide, N-ethyl-butylamide, N- methyl-tert. Butylamide, N-tert-butyl-isopropylamide, dibutylamide, diisobutylamide, diisobutylamide, tert.-amyl-tert-butyl-amide, dipentylamide, N-methyl-hexyl-amide, dihexylamide, tert-amyl-tert.-octylamide, dioctylamide, bis (2-) Ethylhexyl) amide, didecylamide, N-methyl-octadecylamide, N-methyl-cyclohexylamide, N-ethyl-cyclohexylamide, N-isopropylcyclohexylamide, N-tert-butyl-cyclohexylamide, dicyclohexylamide, pyrrolidine, piperidine, hexamethyleneimine, decahydroquinoline, diphenylamine, N- Methylanilide or N-ethylanilide.

In the imino group -C = NR ^13A , R ^{13A is} preferably a C ₆ -C ₂₀ -aryl, where the aryl radical may be substituted by further alkyl groups, such as, for example, phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p Methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphen-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphen-1-yl.

A is preferably an unsubstituted, substituted or fused heteroaromatic ring system which, in addition to carbon ring members, may contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus. Examples of 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and / or one 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 may contain one to four nitrogen atoms and / or one 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-membered ring and 6-membered ring heteroaryl groups can also be substituted by C ₁ -C ₁₀ -alkyl, C ₆ -C ₁₀ -aryl, alkylaryl having 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 condensed with one or more aromatics or heteroaromatics. Examples of benzo-fused 5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumaronyl, 7-coumaro nyl, 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. The name and numbering of the heterocycles was determined L. Fieser and M. Fieser, Textbook of Organic Chemistry, 3rd revised edition, Verlag Chemie, Weinheim 1957 taken.

wobei
E^6A–E^9A unabhängig voneinander Kohlenstoff oder Stickstoff,
R^16A–R^19A 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 oder SiR^20A ₃ bedeutet, wobei die organischen Reste R^16A–R^19A auch durch Halogene oder Stickstoff und weitere 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 oder SiR^20A ₃ substituiert sein können und je zwei vicinale Reste R^16A–R^19A oder R^16A und Z auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können und
R^20A unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₀-Aryl oder Alkylaryl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest bedeutet und je zwei Reste R^20A auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können und
p unabhangig voneinander 0 für E^6A–E^9A gleich Stickstoff und 1 für E^6A–E^9A gleich Kohlenstoff ist.Of these heteroaromatic systems A are particularly unsubstituted, substituted and / or condensed six-membered heteroaromatic having 1, 2, 3, 4 or 5 nitrogen atoms in the heteroaromatic moiety, in particular substituted and unsubstituted 2-pyridyl or 2-quinolyl preferred. A is therefore preferably a group of the formula (IV)

in which
E ^6A -E ^9A independently of one another carbon or nitrogen,
R ^16A- R ^19A are each 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 or SiR ^20A ₃ , where the organic radicals R ^16A- R ^{19A are} also substituted by halogens or nitrogen and further C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₆ -C ₂₀ -aryl, alkylaryl 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical or SiR ^20A ₃ may be substituted and each two vicinal radicals R ^16A- R ^19A or R ^16A and Z may also be connected to a five- or six-membered ring and
R ^20A independently of one another are 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 each two radicals R ^{20A can} also be connected to a five- or six-membered ring and
p is independently of each other 0 for E ^6A -E ^9A equal to nitrogen and 1 for E ^6A -E ^9A equal to carbon.

In particular, 0 or 1 E ^6A -E ^9A is nitrogen and the remainder carbon. More preferably, A is 2-pyridyl, 6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl , 3-pyridazyl, 4-pyrimidyl, 6-methyl-4-pyrimidyl, 2-pyrazinyl, 6-methyl-2-pyrazinyl, 5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethylpyrazinyl, 3 , 5,6-trimethyl-2-pyrazinyl, 2-quinolyl, 4-methyl-2-quinolyl, 6-methyl-2-quinolyl, 7-methyl-2-quinolyl, 2-quinoxalyl or 3-methyl-2-quinoxalyl ,

A preferred combination of Z and A is, for ease of presentation, Z is unsubstituted or substituted 1,2-phenylene with A equal to NR ^16A R ^17A , and the combination Z is -CHR ^6A -, -CH ₂ -, -C (CH ₃ ) ₂ or -Si (CH ₃ ) ₂ - and A is unsubstituted or substituted 2-quinolyl or unsubstituted or substituted 2-pyridyl. Systems without bridge Z, where k is 0, are also very easily accessible. Preferred A in this case is unsubstituted or substituted 8-quinolyl. In the case of k, equal to 0, R ^{2A is} also preferably a C ₆ -C ₂₂ -aryl or an alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C-atoms in the aryl radical, preferably C ₆ -C ₂₂ -aryl, such as for example, phenyl, naphthyl, biphenyl, anthracenyl or phenantrenyl, wherein the aryl also by N, P, O or S-containing substituents, C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl, halogens or haloalkyls or Halogenaryle can be substituted by 1-10 C atoms.

The are the preferred embodiments of the variables described above also preferred in these preferred combinations.

M ^A is a metal selected from the group titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten, preferably titanium in the oxidation state 3 and chromium. Particularly preferred is chromium in the oxidation states 2, 3 and 4, in particular 3. The metal complexes, in particular the chromium complexes, can be obtained in a simple manner by reacting the corresponding metal salts such as metal chlorides with the ligand anion (eg analogously to the examples in DE 197 10 615 ).

Of the suitable monocyclopentadienyl complexes, preference is given to those of the general formula Cp-Y _m M ^A X ^A _n (V), in which the variables Cp, Y, A, m and M ^{A have} the above meaning and also preferred embodiments thereof are preferred herein, and
X ^A 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 having 1-10 C atoms in the alkyl radical and 6 -20 C atoms in the aryl radical, NR ^21A R ^22A , OR ^21A , SR ^21A , SO ₃ R ^21A , OC (O) R ^21A , CN, SCN, β-diketonate, CO, BF ₄ ^- , PF ₆ ^- , or are bulky non-coordinating anions or two radicals X ^{A is} a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals X ^{A are} optionally bonded together,
R ^21A- R ^22A independently of one another are 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, SiR ^23A ₃ , where the organic radicals R ^21A- R ^{22A may} also be substituted by halogens or nitrogen- and oxygen-containing groups and in each case two radicals R ^21A- R ^{22A may} also be linked to form a five- or six-membered ring,
R ^23A independently of one another are 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 each two radicals R ^{23A can} also be connected to a five- or six-membered ring and
n is 1, 2, or 3.

The above-mentioned embodiments and preferred embodiments for Cp, Y, Z, A, m and M ^{A also} apply individually and in combination for these preferred monocyclopentadienyl complexes.

The ligands X ^A arise, for example, by the choice of the corresponding metal starting compounds which are used for the synthesis of monocyclopentadienyl complexes, but can also be subsequently varied. Suitable ligands X ^A are in particular the halogens such as fluorine, chlorine, bromine or iodine and, in particular, chlorine. Also, alkyl radicals, such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl are advantageous ligands X ^A. As further ligands X ^A are only exemplary and by no means exhaustive trifluoroacetate, BF ₄ ^- , PF ₆ ^- and weak or non-coordinating anions (see, eg S. Strauss in Chem. Rev. 1993, 93, 927-942 ) as B (C ₆ F ₅ ) ₄ ^{- are} called.

Amides, alcoholates, sulfonates, carboxylates and β-diketonates are also particularly suitable ligands X ^A. By varying the radicals R ^21A and R ^22A , for example, physical properties such as solubility can be finely adjusted. Suitable C-organic substituents R ^21A- R ^22A are, for example, the following: C ₁ -C ₂₀ -alkyl, where the alkyl may be linear or branched, such as, for example, 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 may bear as a substituent, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl may be linear, cyclic or branched and the double bond may 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, where the aryl radical is further alkyl groups and / or N- or O-containing radicals may be substituted, such as phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, o 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, wherein the arylalkyl may be substituted by further alkyl groups, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, optionally also R ^21A with R ^{22A may be connected} to a 5- or 6-membered ring and the organic radicals R ^21A- R ^{22A may} also be substituted by halogens, such as fluorine, chlorine or bromine. Suitable Si-organic substituents SiR ^23A ₃ are the same radicals for R ^23A , as described in more detail above for R ^21A- R ^22A , it also being possible for two R ^23A to be joined to form a 5- or 6-membered ring for example, trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. Preference is given to 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 ^21A and R ^22A . Some of these substituted ligands X are particularly preferably used because they are obtainable from inexpensive and readily available starting materials. Thus, a particularly preferred embodiment is when x ^{A is} dimethylamide, methanolate, ethanolate, isopropanolate, phenolate, naphtholate, triflate, p-toluenesulfonate, acetate or acetylacetonate.

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

Preferred monocyclopentadienyl complexes of this type are 1- (8-quinolyl) -3-phenylcyclopentadienylchromo (III) dichloride, 1- (8-quinolyl) -3- (1-naphthyl) -cyclopentadienylchromo (III) dichloride, 1- (8-quino lyl) -3- (4-trifluoromethylphenylcyclopentadienylchromo (III) dichloride, 1- (8-quinolyl) -3- (4-chlorophenyl) -cyclopentadienylchromo (III) dichloride, 1- (8-quinolyl) -2-methyl- 3-phenylcyclopentadienyl chromium (III) dichloride, 1- (8-quinolyl) -2-methyl-3- (1-naphthyl) cyclopentadienyl chromium (III) dichloride, 1- (8-quinolyl) -2-methyl-3- (4 trifluoromethylphenyl cyclopentadienyl chromium (III) dichloride, 1- (8-quinolyl) -2-methyl-3- (4-chlorophenyl) -cyclopentadienyl chromium (III) dichloride, 1- (8-quinolyl) -2-phenylindenyl chromium (III) dichloride , 1- (8-Quinolyl) -2-phenylbenzindenylchromo (III) dichloride, 1- (8- (2-methylquinolyl)) - 2-methyl-3-phenylcyclopentadienyl chromium (III) dichloride, 1- (8- (2-methylquinolyl )) - 2-phenylindenylchromo (III) dichloride, 1- (2-pyridylmethyl) -3-phenyl-cyclopentadienylchromo (III) dichloride, 1- (2-pyridylmethyl) -2-methyl-3-phenyl-cyclopentadienylchromo (III) dichloride , 1- (2-Quinolylmethyl) -3-phenylcyclopentadienylchromium dichloride, 1- (2-pyridylethyl)) - 3-phenyl-cyclopentadienylchromium dichloride, 1- (2-pyridyl-1-methylethyl) -3-phenylcyclo pentadienylchromium dichloride, 1- (2-pyridyl-1-phenylmethyl) -3-phenyl-cyclopentadienylchromium dichloride, 1- (2-pyridylmethyl) indenyl-chromium (III) dichloride, 1- (2-quinolylmethyl) indenyl-chromium dichloride, 1- (2-pyridylethyl) indenyl-chromium dichloride , 1- (2-pyridyl-1-methylethyl) indenyl-chromium dichloride, 1- (2-pyridyl-1-phenylmethyl) indenyl-chromium dichloride, 5 - [(2-pyridyl) methyl] -1,2,3,4-tetramethylcyclopentadienylchromium dichloride or 1- (8- (2-methylquinolyl)) - 2-methylbenzindenylchrom (III) dichloride.

The preparation of such functional cyclopentadienyl ligands is known. Different synthesis routes are eg of 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 synthesis can be carried out by methods known per se, wherein the reaction of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, vanadium or chromium is preferred. Examples of corresponding production processes are, inter alia, in Journal of Organometallic Chemistry, 369 (1989), 359-370 and in the EP-A-1212333 described.

The inventive method let yourself advantageous in the use of so-called hybrid catalysts use to target the comonomer content of the polymer component to change. Particularly preferred are hybrid catalysts containing catalyst components based on monocyclopentadienyl complexes of the formula (I). Under Hybrid catalysts are to be understood as catalyst systems, having at least two different types of active sites, consisting of at least two chemically different organo-transition metal compounds derived. The different active centers may be from different transition metal coordination compounds active sites obtained, one of which is a monocyclopentadienyl complex of the formula (I). It can, however also active centers are used, which differ from Ziegler-Natta catalysts or Derive chromium-based catalysts such as Phillips catalysts and not according to the invention to the organo-transition metal complexes belong.

By definition, the Hybrid catalysts suitable, bimodal or multimodal polymer products to produce the at least one higher molecular weight polymer component and a lower molecular weight polymer component. bimodal is a polymer that has two different polymer components Multimodal is a polymer that is more than two different Comprising polymer components. A polymer component is consistent a polymer created by a special type of active component in a multi-component polymerization catalyst was produced.

The in the process according to the invention used hybrid catalysts can mixtures of two or more different particulate Have catalyst solids. Preferably, however, catalyst systems used, containing catalyst solids in which all Types of active sites on each one catalyst particle are located. Particularly preferred is the use of several catalyst components, which together on a support were fixed.

Preferably be in the process of the invention Hybrid catalysts used in which at least two of the from the different transition metal components resulting components of the hybrid catalysts in their comonomer incorporation behavior differ. These lead to polymer products in which the comonomer content of the higher molecular weight Polymer component of that of the lower molecular weight polymer component distinguishes, i. the catalyst components different Comonomer installation behavior show. A different comonomer installation behavior For the purposes of the present application, if the comonomer content the different polymer components differ by at least 30%. The comonomer content of the polymer components preferably differs by at least 50%, more preferably by a factor of 2, continue preferably by a factor of 10, more preferably by a factor 100th

In a preferred variant, the higher molecular weight polymer component is the one with the higher comonomer content. This higher molecular weight polymer component is particularly preferred by the cata- torkomponente containing the Monocyclopentadienylkomplex formed of the formula (I). In one embodiment, the low molecular weight polymer component has a comonomer content of 0-1.5 mol%, preferably 0-0.8 mol%, particularly preferably 0-0.3 mol%. In a further embodiment, the higher molecular weight polymer component has a comonomer content of 0 to 15 mol%, preferably from 0.01 to 10 mol%, particularly preferably 0.3 to 3 mol%.

The low molecular weight polymer component preferably has an average molecular weight M _{w of} from 10,000 to 100,000 g / mol, more preferably from 20,000 to 80,000 g / mol, particularly preferably from 30,000 to 70,000 g / mol. The relatively high molecular weight polymer component preferably has an average molar mass M _{w of} from 100,000 to 2,000,000 g / mol, more preferably from 150,000 to 1,000,000 g / mol, particularly preferably from 200,000 to 800,000 g / mol. Depending on the product requirements, different combinations of proportions of the high molecular weight and low molecular weight components and the molecular weights of the components are selected. The ratio of the higher molecular weight to the lower molecular weight component is preferably from 5 to 95 wt .-%, more preferably from 10 to 90 wt .-%, particularly preferably from 20 to 80 wt .-%, each based on the sum of the higher and lower molecular weight Component. It should be emphasized that in addition to a higher molecular weight component and a low molecular weight component further polymer components may be present in the polymer product.

to independent Regulation of comonomer content of higher molecular weight to lower molecular weight Polymer component, the catalyst components preferably different response to the modifier of the invention on. To the independent Control of the molecular weights of the higher molecular weight to the lower molecular weight polymer component, the catalyst components still prefers a different response Molar mass regulators such as hydrogen.

bevorzugt, wobei die Substituenten und Indizes folgende Bedeutung haben:
M^1A Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdän oder Wolfram, sowie Elemente der 3. Gruppe des Periodensystems und der Lanthaniden,
X^A gleich oder verschieden sind und unabhängig voneinander Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₁₀-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, -OR^6A oder -NR^6AR^7A, oder zwei Reste X^A miteinander verbunden sind und beispielsweise für einen substituierten oder unsubstituierten Dienliganden, insbesondere einen 1,3-Dienliganden, oder eine Biaryloxygruppierung stehen oder einen Ligand der folgenden Gruppe

worin
Q^1A und Q^2A O, NR^6A, CR^6AR^7A oder S ist und Q^1A und Q^2A an M^1A gebunden sind,
Y^A C oder S ist und
Z^A OR^6A, SR^6A, NR^6AR^7A, PR^6AR^7A, Wasserstoff, C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₁₀-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest oder -SiR^8A ₃ ist,
E^1A bis E^5A Kohlenstoff oder maximal ein E^1A bis E^5A Phosphor oder Stickstoff, bevorzugt Kohlenstoff ist,
t 1, 2 oder 3 ist, wobei t entsprechend der Wertigkeit von M^1A den Wert aufweist, bei dem der Komplex der allgemeinen Formel (VIa), (VIb), (VIc) oder (Id) ungeladen vorliegt,
R^1A bis R^5A unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, die ihrerseits durch C₁-C₁₀-Alkyl substituiert sein können, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, -NR^8A ₂, -N(SiR^8A ₃)₂, -OR^8A, -OSiR^8A ₃, -SiR^8A ₃, wobei die Reste R^1A bis R^5A auch durch Halogen substituiert sein können und/oder je zwei Reste R^1A bis R^5A, insbesondere benachbarte Reste, mit den sie verbindenden Atomen zu einem bevorzugt fünf-, sechs- oder siebengliedrigen Ring oder einem bevorzugt fünf-, sechs- oder siebengliedrigen Heterocyclus, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält, verbunden sein können,
R^6A und R^7A unabhängig voneinander C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest oder -SiR^8A ₃ bedeuten, wobei die Reste R^6A und R^7A auch durch Halogene substituiert sein können und/oder je zwei Reste R^6A und R^7A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können,
R^8A gleich oder verschieden C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, C₁-C₁₀-Alkoxy oder C₆-C₁₀-Aryloxy sein kann, wobei die Reste R^8A auch durch Halogene substituiert sein können und/oder je zwei Reste R^8A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und
R^9A bis R^13A unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, die ihrerseits durch C₁-C₁₀-Alkyl substituiert sein können, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 16 C-Atomen im Alkylrest und 6–21 C-Atomen im Arylrest, -NR^14A ₂, -N(SiR^14A ₃)₂ -OR^14A, -OSiR^14A ₃, oder -SiR^14A ₃ bedeuten, wobei die Reste R^1A bis R^5A auch durch Halogen substituiert sein können und/oder je zwei Reste R^1A bis R^5A, insbesondere benachbarte Reste, mit den sie verbindenden Atomen zu einem bevorzugt fünf-, sechs- oder siebengliedrigen Ring oder einem bevorzugt fünf-, sechs- oder siebengliedrigen Heterocyclus, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält, verbunden sein können, wobei
R^14A gleich oder verschieden C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, C₁-C₁₀-Alkoxy oder C₆-C₁₀-Aryloxy sein kann, wobei die organischen Reste R^14A auch durch Halogene substituiert sein können und/oder je zwei Reste R^14A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und
E^6A bis E^10A Kohlenstoff oder maximal ein E^6A bis E^10A Phosphor oder Stickstoff, bevorzugt Kohlenstoff
oder wobei die Reste R^4A und Z^1A gemeinsam eine Gruppierung -R^15A _v-A^1A- bilden, in der

wobei
R^16A bis R^21A gleich oder verschieden sind und jeweils ein Wasserstoffatom, ein Halogenatom, eine Trimethylsilylgruppe, C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, C₁-C₁₀-Alkoxy oder C₆-C₁₀-Aryloxy bedeuten, wobei die organischen Reste R^16A–R^21A auch durch Halogene substituiert sein können und/oder je zwei Reste R^16A–R^21A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und
M^2A bis M^4A Silicium, Germanium oder Zinn, bevorzugt Silicium ist
A^1A -O-, -S-, -NR^22A-, -PR^22A-, -OR^22A-, -NR^22A ₂, -PR^22A ₂ oder ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem bedeutet, mit
R^22A unabhängig voneinander C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl, Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl oder Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest oder Si(R^23A)₃ ist, wobei die organischen Reste R^22A auch durch Halogene substituiert sein können und/oder je zwei Reste R^22A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können,
R^23A Wasserstoff, C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl, Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl oder Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest ist, wobei die organischen Reste R^23A auch durch Halogene substituiert sein können und/oder je zwei Reste R^23A auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und
v 1 oder, falls A^1A ein unsubstituiertes, substituiertes oder kondensiertes, heterocyclisches Ringsystem ist, 1 oder 0 bedeutet.Alternatively or preferably together with a catalyst component containing a monocyclopentadienyl complex of the formula (I), further catalysts may be present in the polymerization. In particular, those of the general formulas (VIa) to (VIc)

preferably, wherein the substituents and indices have the following meaning:
M ^1A titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, as well as elements of the third group of the periodic table and the lanthanides,
X ^{A are the} same or different and independently of one another fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₁₀ -alkenyl, C ₆ -C ₄₀ -Aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, -OR ^6A or -NR ^6A R ^7A , or two radicals X ^A are interconnected and, for example, a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, or a Biaryloxygruppierung or a ligand of the following group

wherein
Q ^1A and Q ^{2A is} O, NR ^6A , CR ^{6A is} R ^7A or S, and Q ^1A and Q ^{2A are} attached to M ^1A
Y ^{A is} C or S and
Z ^A OR ^6A , SR ^6A , NR ^6A R ^7A , PR ^6A R ^7A , hydrogen, C ₁ -C ₁₀ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C-atoms in the alkyl radical and 6 to 20 C-atoms in the aryl radical or -SiR ^8A ₃ ,
E ^1A to E ^5A carbon or at most one E ^1A to E ^{5A is} phosphorus or nitrogen, preferably carbon,
t is 1, 2 or 3, wherein t corresponding to the valence of M ^{1A has} the value at which the complex of the general formula (VIa), (VIb), (VIc) or (Id) is uncharged,
R ^1A to R ^5A independently of one another are hydrogen, C ₁ -C ₂₂ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn may be substituted by C ₁ -C ₁₀ -alkyl, C ₂ -C ₂₂ -alkenyl, C _6- C ₄₀ -aryl, -NR ^8A ₂ , -N (SiR ^8A ₃ ) ₂ , -OR ^8A , -OSiR ^8A ₃ , -SiR ^8A ₃ , wherein the radicals R ^1A to R ^{5A may} also be substituted by halogen and or two radicals R ^1A to R ^5A , in particular adjacent radicals, with the atoms connecting them to a preferably five-, six- or seven-membered ring or a preferably five-, six- or seven-membered heterocycle which is at least one atom from the group N, P, O or S contains, can be connected,
R ^6A and R ^7A independently of one another are C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical or -SiR ^8A ₃ , wherein the radicals R ^6A and R ^{7A may} also be substituted by halogens and / or each two radicals R ^6A and R ^7A also to a five, six - or seven-membered ring can be connected
R ^{8A is} identical or different and is C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₁₀ -aryloxy, where the radicals R ^{8A may} also be substituted by halogens and / or two radicals R ^8A also to one five-, six- or seven-membered ring may be connected, and
R ^9A to R ^13A independently of one another are hydrogen, C ₁ -C ₂₂ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn may be substituted by C ₁ -C ₁₀ -alkyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 16 C atoms in the alkyl radical and 6-21 C atoms in the aryl radical, -NR ^14A ₂ , -N (SiR ^14A ₃ ) ₂ -OR ^14A , -OSiR ^14A ₃ , or -SiR ^14A ₃ , wherein the radicals R ^1A to R ^{5A may} also be substituted by halogen and / or each two radicals R ^1A to R ^5A , in particular adjacent radicals, with the atoms connecting them to a preferably five-, six- or seven-membered ring or a preferably five-, six- or seven-membered heterocycle, which contains at least one atom from the group N, P, O or S may be connected, wherein
R ^{14A is the} same or different C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₁₀ -aryloxy may be, wherein the organic radicals R ^{14A may} also be substituted by halogens and / or two radicals R ^14A also to may be connected to a five-, six- or seven-membered ring, and
E ^6A to E ^10A carbon or at most an E ^6A to E ^10A phosphorus or nitrogen, preferably carbon
or wherein the radicals R ^4A and Z ^1A together form a grouping -R ^15A _v -A ^1A -, in which

in which
R ^16A to R ^{21A are the} same or different and each represents a hydrogen atom, a halogen atom, a trimethylsilyl group, C ₁ -C ₁₀ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₄₀ aryl, arylalkyl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, C ₁ -C ₁₀ alkoxy or C ₆ -C ₁₀ aryloxy, wherein the organic radicals R ^16A- R ^{21A may} also be substituted by halogens and / or each two radicals R ^16A -R ^{21A may} also be joined to form a five-, six- or seven-membered ring, and
M ^2A to M ^{4A is} silicon, germanium or tin, preferably silicon
A ^1A is -O-, -S-, -NR ^22A -, -PR ^22A -, -OR ^22A -, -NR ^22A _2, -PR ^22A ₂ or represents an unsubstituted, substituted or fused, heterocyclic ring system, with
R ^22A independently of one another are C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl, cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical or Si (R ^23A ) ₃ , wherein the organic radicals R ^{22A may} also be substituted by halogens and / or each two radicals R ^{22A may} also be connected to a five-, six- or seven-membered ring can,
R ^{23A is} hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl, cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, wherein the organic radicals R ^{23A may} also be substituted by halogens and / or each two radicals R ^{23A may} also be connected to a five-, six- or seven-membered ring, and
v 1 or, if A ^{1A is} an unsubstituted, substituted or fused, heterocyclic ring system, 1 or 0.

Of the complexes of the formula (VIa), preference is given in particular to those in which
M ^{1A is} titanium, zirconium or hafnium
X ^{A are the} same or different and independently chlorine, C ₁ -C ₄ alkyl, phenyl, alkoxy or aryloxy, a carboxylate of the formula -OC (O) -R ^6A or a carbamate of the formula -OC (O) -NR ^6A R ^7A mean
t is the number 1 or 2, preferably 2,
R ^1A to R ^{5A are} hydrogen or C ₁ -C ₆ -alkyl or two adjacent radicals R ^1A R ^5A with the atoms connecting them form a substituted or unsubstituted five-, six- or seven-membered ring and in particular a substituted or unsubstituted benzo group six-membered ring , and
R ^6A and R ^{7A are} C ₁ -C ₁₀ -alkyl, C ₆ -C ₄₀ -aryl or arylalkyl having 1 to 10 C-atoms in the alkyl radical and 6 to 20 C-atoms in the aryl radical.

The preparation of such compounds (VIa) and particularly preferred embodiments of the compounds (VIa) are for example in the US Pat. No. 5,527,752 described.

Of the unbridged metallocene complexes of the formula (VIb), preference is given to those in which
M ^{1A stands} for zirconium, hafnium or chromium,
X ^{A is} fluorine, chlorine, C ₁ -C ₄ -alkyl or benzyl, or two radicals X ^{A are} a substituted or unsubstituted diene ligand,
t is 0 for chromium, otherwise 1 or 2 and preferably 2
R ^1A to R ^{5A are} hydrogen, C ₁ -C ₈ -alkyl, C ₆ -C ₁₀ -aryl, -NR ^8A ₂ , -OSiR ^8A ₃ or -Si (R ^8A ) ₃ ,
R ^9A to R ^{13A are} hydrogen, C ₁ -C ₈ -alk, C ₆ -C ₁₀ -aryl, -NR ^14A ₂ , -OSiR ^14A ₃ or -Si (R ^14A ) ₃ and
R ^8A and R ^{14A are the} same or different and are C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₆ -C ₄₀ -aryl, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₁₀ - Aryloxy, wherein the radicals R ^8A and R ^{14A may} also be substituted by halogens and / or each two radicals R ^8A or R ^{14A may} also be connected to a five-, six- or seven-membered ring,
or in each case two radicals R ^1A to R ^5A _{and / or} R ^9A to R ^13A together with the C ₅ ring signify an indenyl, fluorenyl or substituted indenyl or fluorenyl system.

Especially are the complexes of formula (VIb) are suitable in which the Cyclopentadienylreste are the same, for example bis (cyclopentadienyl) chromium or bis (indenyl) chromium.

Examples of particularly suitable complexes of the formula (VIb) are furthermore those in which
M ^{1A is} hafnium,
X ^{A is} fluorine, chlorine, C ₁ -C ₄ -alkyl or benzyl, or two radicals X ^{A are} a substituted or unsubstituted diene ligand,
t is 2, R ^1A to R ^{5A are} hydrogen, C ₁ -C ₈ -alkyl or C ₆ -C ₁₀ -aryl,
R ^9A to R ^{13A are} hydrogen, C ₁ -C ₈ -alkyl or C ₆ -C ₁₀ -aryl,
R ^8A and R ^{14A, the} same or different, are C ₁ -C ₁₀ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₆ -C ₄₀ aryl, C ₁ -C ₁₀ alkoxy or C ₆ -C ₁₀ aryloxy in which the radicals R ^8A and R ^{14A may} also be substituted by halogens and / or in each case two radicals R ^8A or R ^{14A may} also be joined to form a five-, six- or seven-membered ring,
with the C ₅ ring mean or two radicals R ^1A to R ^5A and / or R ^9A to R ^13A together form an indenyl, fluorenyl or substituted indenyl or fluorenyl system,

Another preferred group of complexes (VIb) are those wherein:
M ^1A stands for zirconium,
x ^{A is} fluorine, chlorine, C ₁ -C ₄ -alkyl or benzyl, or two radicals X ^{A are} a substituted or unsubstituted diene ligand,
t is 1 or 2, preferably 2
R ^1A to R ^{5A are} hydrogen, C ₁ -C ₈ alkyl, C ₆ -C ₁₀ aryl, -OSiR ^8A ₃
R ^9A to R ^{13A are} hydrogen, C ₁ -C ₈ -alkyl or C ₆ -C ₁₀ -aryl or -OSiR ^14A ₃ and
R ^8A and R ^{14A, the} same or different, are C ₁ -C ₁₀ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₆ -C ₁₅ aryl, C ₁ -C ₁₀ alkoxy or C ₆ -C ₁₀ aryloxy in which the organic radicals R ^8A and R ^{14A may} also be substituted by halogens and / or each two radicals R ^8A or R ^{14A may} also be linked to form a five-, six- or seven-membered ring,
or in each case two radicals R ^1A to R ^5A and / or R ^9A to R ^13A together with the C ₅ ring signify an indenyl, fluorenyl or substituted indenyl or fluorenyl system.

The production of such systems and preferred embodiments are for example in the FI-A-960437 disclosed.

catalyst components based on the aforementioned unbridged Metallocenes are particularly suitable for the provision of higher molecular weight Polymer component. They are particularly suitable for the provision the comonomer-rich polymer component. Particularly preferred these catalyst components for the production of a comonomer-rich, higher molecular weight polymer component used.

M^1A Titan, Zirkonium oder Hafnium, insbesondere Zirkonium oder Hafnium bedeutet,
X^A gleich oder verschieden für Chlor, C₁-C₄-Alkyl, Benzyl, Phenyl oder C₇-C₁₅-Alkylaryloxy stehen.Of the complexes of the formula (VIc), those are particularly suitable in which

M ^{1A is} titanium, zirconium or hafnium, in particular zirconium or hafnium,
X ^{A are} identical or different and represent chlorine, C ₁ -C ₄ -alkyl, benzyl, phenyl or C ₇ -C ₁₅ -alkylaryloxy.

When Complexes of formula (VIc) are also preferably bridged bis-indenyl complexes used in the rac or pseudo Rac form, wherein the pseudo-Rac form involves such complexes in which the two Indenyl ligands without consideration all other substituents of the complex relative to each other in the rac-arrangement stand.

The synthesis of such complex compounds can be carried out by methods known per se, wherein the reaction of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium, tantalum or chromium, is preferred. Examples of corresponding production processes are, inter alia, in Journal of Organometallic Chemistry, 369 (1989), 359-370 described.

wobei
M^1B Titan, Zirkonium oder Hafnium ist,
R^1B bis R^6B 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-C₄₀-Aryl, Arylalkyl mit 1 bis 16 C-Atomen im Alkylrest und 6 bis 21 C-Atomen im Arylrest oder -SiR^9B ₃ bedeuten, wobei die Reste R^1B–R^6B auch durch Halogene substituiert sein können und/oder je zwei Reste R^1B–R^6B, insbesondere vicinale Reste, auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^1B–R^6B zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sein können, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält,
X^1B unabhängig voneinander Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, C₂-C₁₀-Alkenyl, C₆-C₁₅-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, -OR^7B, -NR^7BR^8B, -O-C(O)-R^7B oder -O-C(O)-NR^7BR^8B bedeutet, und die Reste X^1B gegebenenfalls miteinander verbunden sind,
A^1B -O-, -OR^7B-, -NR^7B- oder -NR^7BR^8B- ist,
m 1 oder 2 ist,
n 1, 2 oder 3 ist, wobei n entsprechend der Wertigkeit von M^1A den Wert aufweist, bei dem der Metallocenkomplex der allgemeinen Formel (VII) ungeladen vorliegt,
o 1 ist, wenn NR^1B mit dem benachbarten Kohlenstoff ein Imin bildet, oder 2 ist, wenn NR^1B eine negative Ladung trägt,
wobei
R^7B und R^8B C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest oder -SiR^9B sind, wobei die organischen Reste R^7B und R^8B auch durch Halogene substituiert sein können und/oder je zwei Reste R^7B und R^8B auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können und
R^9B gleich oder verschieden C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryloxy sein kann, wobei die organischen Reste R^9B auch durch Halogene substituiert sein können und/oder je zwei Reste R^9B auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können.Other suitable compounds are organo transition metal complex compounds which do not contain a cyclopentadienyl unit, hereinafter referred to as Cp-free complexes. Suitable Cp-free complexes are complexes of the general formula (VII)

in which
M ^{1B is} titanium, zirconium or hafnium,
R ^1B to R ^6B independently of one another are hydrogen, C ₁ -C ₂₂ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, which in turn may be substituted by C ₁ -C ₁₀ -alkyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl radical and 6 to 21 C-atoms in the aryl radical or -SiR ^9B ₃ , wherein the radicals R ^1B -R ^{6B may} also be substituted by halogens and / or in each case two radicals R ^1B -R ^6B , in particular vicinal radicals, may also be linked to form a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^1B -R ^6B may be linked to a five-, six- or seven-membered heterocycle which contains at least one atom from the group N, P, O or S,
X ^1B independently of one another are fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₆ -C ₁₅ -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, -OR ^7B , -NR ^7B R ^8B , -OC (O) -R ^7B or -OC (O) -NR ^7B R ^8B , and the radicals X ^{1B are} optionally linked together,
A ^{1B is} -O-, -OR ^7B -, -NR ^7B - or -NR ^7B R ^8B - is,
m is 1 or 2,
n is 1, 2 or 3, where n corresponding to the valency of M ^{1A has} the value at which the metallocene complex of the general formula (VII) is uncharged,
o is 1 when NR ^1B forms an imine with the adjacent carbon, or 2 when NR ^1B bears a negative charge,
in which
R ^7B and R ^{8B are} C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical or -SiR ^9B , wherein the organic radicals R ^7B and R ^{8B may} also be substituted by halogens and / or each two radicals R ^7B and R ^8B also to a five-, six- or can be connected to a seven-membered ring and
R ^{9B are,} identically or differently, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, C ₁ -C ₄ -alkoxy or C ₆ - C ₁₀ aryloxy may be, wherein the organic radicals R ^{9B may} also be substituted by halogens and / or each two radicals R ^{9B may} also be connected to a five-, six- or seven-membered ring.

Preferred organo-transition metal complex compounds of general formulas (VII) are iminophenolate complexes wherein A ^1B is -O- and o is 1, the ligands being prepared, for example, starting from substituted or unsubstituted salicylaldehydes and primary amines, in particular substituted or unsubstituted arylamines. The representation of such compounds is for example in the EP-A 1013674 described.

worin
M^1C Titan, Zirkonium oder Hafnium ist,
R^1C bis R^5C unabhängig voneinander Wasserstoff, C₁-C₂₂-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 16 C-Atomen im Alkylrest und 6 bis 21 C-Atomen im Arylrest oder -SiR^8C ₃ bedeuteen, wobei die organischen Reste R^1C bis R^5C auch durch Halogene substituiert sein können und/oder je zwei Reste R^1C bis R^5C, insbesondere benachbarte Reste, auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^1C bis R^5C zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sein können, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält,
X^1C unabhängig voneinander Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, -OR^6C, -NR^6CR^7C, -O-C(O)-R^6C oder -O-C(O)-NR^6CR^7C bedeutet, und die Reste X^1C gegebenenfalls miteinander verbunden sind,
A^1C -CR^6CR^7C- oder -CR^6C= ist,
m 1 oder 2 ist,
n 1, 2 oder 3 ist, wobei n entsprechend der Wertigkeit von M^1A den Wert aufweist, bei dem der Metallocenkomplex der allgemeinen Formel (VII) ungeladen vorliegt,
o 0 oder 1 ist,
wobei
R^6C und R^7C C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest oder -SiR^8C ist, wobei die organischen Reste R^6C und R^7C auch durch Halogene substituiert sein können und/oder je zwei Reste R^6C und R^7C auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können und
R^8C gleich oder verschieden C₁-C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, C₁-C₄-Alkoxy oder C₆-C₁₀-Aryloxy sein kann, wobei die organischen Reste R^6C auch durch Halogene substituiert sein können und/oder je zwei Reste R^8C auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können.Also suitable are Cp-free complexes of the general formula (VIII):

wherein
M ^{1C is} titanium, zirconium or hafnium,
R ^1C to R ^5C independently of one another are hydrogen, C ₁ -C ₂₂ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 16 C- Atoms in the alkyl radical and 6 to 21 C atoms in the aryl radical or -SiR ^8C ₃ mean, where the organic radicals R ^1C to R ^{5C may} also be substituted by halogens and / or two radicals R ^1C to R ^5C , in particular adjacent radicals, may also be connected to a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^1C to R ^{5C may be connected} to a five-, six- or seven-membered heterocycle which contains at least one atom from the group N, Contains P, O or S,
X ^1C independently of one another are fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, -OR ^6C , -NR ^6C R ^7C , -OC (O) -R ^6C or -OC (O) -NR ^6C R ^7C , and the radicals X ^{1C are} optionally linked to one another,
A ^1C -CR ^6C R ^7C - or -CR ^6C = is,
m is 1 or 2,
n is 1, 2 or 3, where n corresponding to the valency of M ^{1A has} the value at which the metallocene complex of the general formula (VII) is uncharged,
o is 0 or 1,
in which
R ^6C and R ^{7C are} C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical or -SiR ^8C , wherein the organic radicals R ^6C and R ^{7C may} also be substituted by halogens and / or each two radicals R ^6C and R ^7C also to a five-, six- or can be connected to a seven-membered ring and
R ^{8C are} identical or different C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, C ₁ -C ₄ -alkoxy or C ₆ -C ₁₀ -aryloxy may be, wherein the organic radicals R ^{6C may} also be substituted by halogens and / or each two radicals R ^8C to a five-, six- or seven-membered ring can be connected.

Preferred organo-transition metal complex compounds of general formulas (VIII) are complexes wherein o is 1, A ^1C is -CR ^6C R ^7C - and R ^{1C is} C ₆ -C ₄₀ -aryl. The representation of such compounds is for example in the WO 02/046249 and the WO 03/040201 described.

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.Also suitable are Cp-free complexes with at least one ligand of the general formulas (IXa) to (IXe),

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 a rare earth element element. Preference is given to compounds with nickel, iron, cobalt and palladium as the central metal.

E ^1D 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 ^1D in a molecule may be the same or different. The elements E ^2D in formula (IXe) are independently of one another carbon, nitrogen or phosphorus and in particular carbon.

The radicals R ^1D to R ^25D , which may be identical or different within a ligand system (IXa) to (IXe), stand for the following groups:
R ^1D and R ^4D independently of one another are C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C- Atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, wherein the organic radicals R ^1D and R ^{4D may} also be substituted by halogens, wherein hydrocarbon radicals in which the element E ^1D adjacent carbon atom is connected to at least two carbon atoms, preferred are,
R ^2D and R ^3D independently of one another are hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, wherein the organic radicals R ^2D and R ^{3D may} also be substituted by halogens and wherein R ^2D and R ^{3D can} also together form a ring system in which also one or multiple heteroatoms may be present
R ^5D to R ^9D independently of one another are hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, wherein the organic radicals R ^5D to R ^{9D may} also be substituted by halogens and wherein R ^6D and R ^5D or R ^6D and R ^9D or two R ^7D together Can form ring system,
R ^10D and R ^14D independently of one another are C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C- Atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, where the organic radicals R ^10D and R ^{14D may} also be substituted by halogens,
R ^11D , R ^12D , R ^{12D '} and R ^13D independently of one another are hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having in each case 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, where the organic radicals R ^11D , R ^12D , R ^{12D '} and R ^{13D may} also be substituted by halogens and where two or more geminal or vicinal radicals R ^11D , R ^12D , R ^{12D '} and R ^{13D may} together form a ring system,
R ^15D to R ^18D and R ^20D to R ^24D independently of one another are hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, Arylalkyl having in each case 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical or -SiR ^26D ₃ , where the organic radicals R ^15D- R ^18D and R ^20D -R ^{24D may} also be substituted by halogens and wherein each two vicinal radicals R ^15D- R ^18D and R ^20D- R ^{24D can} also be linked to form a five- or six-membered ring,
R ^19D and R ^25D independently of one another are C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C-atoms in the aryl radical or -NR ^26D ₂ , where the organic radicals R ^19D and R ^25D may also be substituted by halogens or a group containing Si, N, P, O or S,
R ^20D to R ^24D independently of one another are hydrogen, C ₁ -C ₁₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C- Atoms in the alkyl radical and 6-20 C atoms in the aryl radical, -NR ^26D ₂ , -SiR ^26D ₃ , where the organic radicals R ^20D to R ^{25D may} also be substituted by halogens and / or two geminal or vicinal radicals R ^20D to R ^{25D may} also be connected to a five-, six- or seven-membered ring, and / or that two geminal or vicinal radicals R ^20D to R ^{25D are connected} to a five-, six- or seven-membered heterocycle which contains at least one atom from the Contains group N, P, O or S,
R ^26D independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₀ -alkenyl, C ₆ -C ₄₀ -aryl or arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical and in each case two radicals R ^{26D can} also be ^linked to form a five- or six-membered ring,
u is independently 0 for E ^2D is nitrogen or phosphorus and 1 for E ^2D is carbon,
v is independently 1 or 2, where for v equal to 1 the bond between the then one carbon carrying the residue and the adjacent element E ^{1D is} a double bond and for v is equal to 2 the bond between the carbon then carrying two radicals and the adjacent element E ^{1D is} a single bond,
x is 0 or 1, where the complex of formula (IXc) is negatively charged for x = 0 and
y is an integer between 1 and 4, preferably 2 or 3.

Especially suitable are Cp-free complexes with Fe, Co, Ni, Pd or Pt as Central metal and ligands of the formula (IXa).

catalyst components based on said late transition metal complexes are particularly suitable for the provision of the lower molecular weight polymer component. she especially suitable for the provision of the comonomer-poorer, in particular the substantially comonomer-free polymer component. Particularly preferred are these catalyst components for production a comonomer-poor, lower molecular weight polymer component used.

worin

E^2D unabhängig voneinander Kohlenstoff, Stickstoff oder Phosphor, insbesondere Kohlenstoff, bedeuten,
R^20D und R^24D unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, -NR^26D ₂ oder -SiR^26D ₃ ist, wobei die organischen Reste R^20D und R^24D auch durch Halogene substituiert sein können,
R^21D bis R^23D unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, Halogen, -NR^26D ₂ oder -SiR^26D ₃ ist, wobei die organischen Reste R^21D bis R^23D auch durch Halogene substituiert sein können und/oder je zwei vicinale Reste R^21D bis R^23D auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder zwei vicinale Reste R^21D bis R^23D zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sind, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält,
u unabhängig voneinander 0 für E^2D gleich Stickstoff oder Phosphor und 1 für E^2D gleich Kohlenstoff ist,
R^27D bis R^30D unabhängig voneinander C₁-C₂₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, Halogen, -NR^26D ₂, -OR^26D oder -SiR^26D ₃ ist, wobei die organischen Reste R^27D bis R^30D auch durch Halogene substituiert sein können und/oder je zwei vicinale Reste R^27D bis R^30D auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^27D bis R^30D zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sind, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält,
R^31D bis R^36D unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl oder Cycloalkenyl, C₂-C₂₂-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1 bis 10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, Halogen, -NR^26D ₂, -OR^26D oder -SiR^26D ₃, wobei die organischen Reste R^31D bis R^36D auch durch Halogene substituiert sein können und/oder je zwei vicinale Reste R^31D bis R^36D auch zu einem fünf-, sechs- oder siebengliedrigen Ring verbunden sein können, und/oder dass zwei vicinale Reste R^31D bis R^36D zu einem fünf-, sechs- oder siebengliedrigen Heterocyclus verbunden sind, welcher mindestens ein Atom aus der Gruppe N, P, O oder S enthält,
v unabhängig voneinander 0 oder 1,
X^D unabhängig voneinander Fluor, Chlor, Brom, Jod, Wasserstoff, C₁-C₁₀-Alkyl, C₂-C₁₀-Alkenyl, C₆-C₄₀-Aryl, Arylalkyl mit 1–10 C-Atomen im Alkylrest und 6–20 C-Atomen im Arylrest, -NR^26D ₂, -OR^26D, -SR^26D, -SO₃R^26D, -O-C(O)-R^26D, -CN, -SCN, β-Diketonat, CO, BF₄ ^–, PF₆ ^–, oder sperrige nichtkoordinierende Anionen und die Reste X^D gegebenenfalls miteinander verbunden sind,
R^26D 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, wobei die organischen Reste R^26D auch durch Halogene oder Stickstoff- und Sauerstoffhaltige Gruppen substituiert sein können und je zwei Reste R^26D auch zu einem fünf- oder sechsgliedrigen Ring verbunden sein können,
s 1, 2, 3 oder 4, insbesondere 2 oder 3,
D ein neutraler Donor und
t 0 bis 4, insbesondere 0, 1 oder 2.Preferred organo-transition metal complex compounds for the preparation of hybrid catalyst systems are complexes of the ligands (IXe) with transition metals Fe, Co or Ni and in particular those of the general formula (X)

wherein

E ^2D independently of one another denote carbon, nitrogen or phosphorus, in particular carbon,
R ^20D and R ^24D independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C- Atoms in the alkyl radical and 6-20 C atoms in the aryl radical, -NR ^26D ₂ or -SiR ^26D ₃ , where the organic radicals R ^20D and R ^{24D may} also be substituted by halogens,
R ^21D to R ^23D independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl , Arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, halogen, -NR ^26D ₂ or -SiR ^26D ₃ , wherein the organic radicals R ^21D to R ^{23D may} also be substituted by halogens, and or each two vicinal radicals R ^21D to R ^{23D can} also be connected to a five, six or seven-membered ring, and / or two vicinal radicals R ^21D to R ^{23D are bonded} to a five-, six- or seven-membered heterocycle, which contains at least one atom from the group N, P, O or S,
u is independently 0 for E ^2D is nitrogen or phosphorus and 1 for E ^2D is carbon,
R ^27D to R ^30D independently of one another C ₁ -C ₂₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 carbon atoms in the Alkyl radical and 6-20 C atoms in the aryl radical, halogen, -NR ^26D ₂ , -OR ^26D or -SiR ^26D ₃ , where the organic radicals R ^27D to R ^{30D may} also be substituted by halogens and / or two vicinal radicals R ^27D to R ^{30D may} also be connected to a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^27D to R ^{30D are connected} to a five-, six- or seven-membered heterocycle which comprises at least one atom contains the group N, P, O or S,
R ^31D to R ^36D independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C- Atoms in the alkyl radical and 6-20 C atoms in the aryl radical, halogen, -NR ^26D ₂ , -OR ^26D or -SiR ^26D ₃ , where the organic radicals R ^31D to R ^{36D may} also be substituted by halogens and / or two vicinal ^Radicals R ^31D to R ^{36D may} also be ^linked to form a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^31D to R ^{36D are bonded} to a five-, six- or seven-membered heterocycle which contains at least one atom contains from the group N, P, O or S,
v are independently 0 or 1,
X ^D independently of one another fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1-10 C atoms in the alkyl radical and 6 -20 C atoms in the aryl radical, -NR ^26D ₂ , -OR ^26D , -SR ^26D , -SO ₃ R ^26D , -OC (O) -R ^26D , -CN, -SCN, β-diketonate, CO, BF ₄ ^- , PF ₆ ^- , or bulky noncoordinating anions and the radicals X ^{D are} optionally joined together,
R ^26D independently of one another are 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, where the organic radicals R ^{26D can} also be substituted by halogens or nitrogen- and oxygen-containing groups and in each case two radicals R ^{26D can} also be ^linked to form a five- or six-membered ring,
s 1, 2, 3 or 4, in particular 2 or 3,
D is a neutral donor and
t is 0 to 4, in particular 0, 1 or 2.

The mentioned organo transition metal complex compounds are in themselves only partially polymerization-active and are therefore brought into contact with an activating compound in order to develop good polymerization activity. For this reason, the catalyst preferably contains as further component one or more activating compounds, hereinafter also as activators or cocatalysts designated. Depending on the nature of the catalyst components, one or more activators are advantageous. For example, for activation, the same activator or activator mixture, or different cocatalysts can be used. It is advantageous if the same activator is used for at least two, particularly advantageously for all catalyst components.

suitable Activators are e.g. Compounds of the aluminoxane type, a strong neutral Lewis acid, an ionic compound having a Lewis acid cation or an ionic one Compound with Brönsted acid as Cation. Suitable activators for The types of catalysts mentioned are well known.

The Amount of activating connections to use depends on the type of activator. In general, the molar ratio of metal complex A) to be activated compound C) of 1: 0.1 to 1: 10,000, 1: 1 to 1: 2000 are preferred.

To carry out the process according to the invention, it is preferred to use at least one aluminoxane as the activating compound. As aluminoxanes, for example, in the WO 00/31090 be used described compounds. A particularly suitable aluminoxane is methylaluminoxane (MAO).

Strong, neutral Lewis acids are compounds of the general formula (XI) M 2D X 1D X 2D X 3D (XI) preferred in the
M ^{2D is} an element of the 13th group of the Periodic Table of the Elements, in particular B, Al or Ga, preferably B,
X ^1D , X ^2D and X ^{3D represent} hydrogen C ₁ -C ₁₀ -alkyl, C ₆ -C ₁₅ -aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl having in each case 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, in particular halogenoaryls, preferably pentafluorophenyl. Examples of strong, neutral Lewis acids are in the WO 00/31090 called.

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

Particularly suitable are carbonium cations, oxonium cations and sulfonium cations and cationic organo transition metal complexes. In particular, the Triphenylmethylkation, the silver cation and the 1,1'-Dimethylferrocenylkation be mentioned. They preferably have non-coordinating counterions, in particular boron compounds as they are also known in the art WO 91/09882 tetrakis (pentafluorophenyl) borate is preferred.

It can also mixtures of all aforementioned activators can be used. Preferred mixtures contain aluminoxanes, in particular methylaluminoxane, and an ionic compound, especially one containing the tetrakis (pentafluorophenyl) borate anion contains and / or a strong, neutral Lewis acid, especially tris (pentafluorophenyl) borane or a boroxin.

As a common activator for the said preferred catalysts, an aluminoxane is preferably used. Preference is furthermore given to the combination of salt-like compounds of the cation of the general formula (XIII), in particular N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylbenzylammonium tetrakis (pentafluorophe nyl) borate or Trityltetrakispentafluorophenylborat as an activator for hafnocenes, in particular in combination with an aluminoxane as an activator for the iron complex. Also particularly suitable as a common activator are the reaction products of aluminum compounds of the formula (XIII) with perfluorinated alcohols and phenols.

The Catalysts, in particular hybrid catalysts, can be used in supported or unsupported Form are used, wherein the supported form, in particular during Use in gas phase polymerization reactors, is preferred. Especially it is preferred when using a hybrid catalyst the different catalysts cogeträgert be present on only one carrier, since in this case the inventive method is particularly advantageous. Alternatively, the catalysts can also each carried separately and be used.

When carrier are preferably used finely divided carrier, any may be organic or inorganic solids. As inorganic carrier materials silica gel, magnesium chloride, alumina, mesoporous materials, Aluminosilicates and hydrotalcites used. Especially preferred is the use of silica gel because of this material particles in size and structure as a carrier for olefin polymerization are suitable. Especially proven have spray-dried Silica gels, which are spherical agglomerates of smaller ones granular Particles, the so-called primary particles, is.

The carriers 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 diameter of from 1 to 500 μm. Preference is given to supports having a specific surface area in the range from 50 to 700 m ² / g, a pore volume in the range from 0.4 to 3.5 ml / g and an average particle diameter in the range from 5 to 350 μm. Particular preference is given to supports having a specific surface area in the range from 200 to 550 m ² / g, a pore volume in the range from 0.5 to 3.0 ml / g and an average particle diameter of from 10 to 150, in particular 30-120 μm.

The carrier can before using a thermal treatment e.g. for removal be subjected to adsorbed water. Such a drying treatment is usually at temperatures in the range of 80 to 300 ° C, preferably from 100 to 200 ° C carried out, wherein the drying at 100 to 200 ° C preferably under vacuum and / or inert gas blanketing (e.g., nitrogen). Alternatively, inorganic carriers may be included Temperatures from 200 to 1000 ° C calcined to optionally the desired structure of the solid and / or the desired OH concentration on the surface adjust.

Especially the combinations are the preferred embodiments of the activators with the preferred embodiments for the Catalyst components preferred.

In a preferred form of preparation of a supported catalyst, at least one iron complex is contacted with an activator and then mixed with the dehydrated or inerted carrier. The further transition metal compound, preferably a hafnocene or zirconocene, is also brought into contact with at least one activator in a suitable solvent, preferably a soluble reaction product, an adduct or a mixture being obtained. The preparation thus obtained is then mixed with the immobilized iron complex used directly or after separation of the solvent, and the solvent is completely or partially removed. Preferably, the resulting supported catalyst system is dried to ensure that the solvent is completely or mostly removed from the pores of the support material. The supported catalyst is preferably obtained as a free-flowing powder. Examples of the technical realization of the above method are in WO 96/00243 . WO 98/40419 or WO 00/05277 described. Another preferred embodiment is to first generate the activator on the support and then bring this supported compound into contact with the corresponding transition metal compounds.

The catalyst may additionally contain, as further component, 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 denotes 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 having in each case 1 to 10 C-atom 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 having in each case 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,
contain, wherein the component (E) is usually not identical to the component (C). It is also possible to use mixtures of different metal compounds of the formula (XX).

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

Especially preferred metal compounds of the formula (XX) are methyllithium, 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-octylmagnesium, Tri-n-hexyl-aluminum, triisobutylaluminum, tri-n-butylaluminum, Triethylaluminum, dimethylaluminum chloride, dimethylaluminum fluoride, methylaluminum dichloride, Methylaluminum sesquichloride, diethylaluminum chloride and trimethylaluminum and Mixtures thereof. Also the partial hydrolysis products of aluminum alkyls with alcohols can be used become.

Prefers are as constituents of advantageous usable hybrid catalysts at least one monocyclopentadienyl complex of the formula (I) and a further of said transition metal coordination compounds and in particular, all of the transition metal coordination compounds chemically different. Even if the use of only two transition metal coordination compounds in which hybrid catalyst is particularly preferred, so is the use other transition metal coordination compounds not locked out.

preferred Combinations of Organo-Transition Metal Complex Compounds with a monocyclopentadienyl complex of the formula (I) are those in which at least one Cp-free complex, in particular a complex of the formula (X) is used.

The processes according to the invention are suitable for the polymerization of olefins and especially for the polymerization of 1-olefins, ie hydrocarbons having terminal double bonds, also referred to as α-olefins. Suitable monomers may be functionalized olefinically unsaturated compounds such as ester or amide derivatives of acrylic or methacrylic acid, for example acrylates, methacrylates or acrylonitrile. Preference is given to non-polar olefinic compounds, including aryl-substituted 1-olefins. Particularly preferred α-olefins are linear or branched C ₂ -C ₁₂ -1-alkenes, in particular linear C ₂ -C ₁₀ -1-alkenes such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-Hegten , 1-octene, 1-decene or branched C ₂ -C ₁₀ -1-alkenes such as 4-methyl-1-pentene, conjugated and non-conjugated dienes such as 1,3-butadiene, 1,4-hexadiene, or 1,7 Octadiene or vinyl aromatic compounds such as styrene or substituted styrene. It is also possible to polymerize mixtures of different 1-olefins. Suitable olefins are also those in which the double bond is part of a cyclic structure which may have one or more ring systems. Examples of these are cyclopentene, norbornene, tetracyclododecene or methylnorbornene or dienes such as 5-ethylidene-2-norbornene, norbornadiene or ethylnorbornadiene. It is also possible to polymerize mixtures of two or more olefins.

In particular, the process according to the invention can be used for the polymerization or copolymerization of ethylene or propylene. As comonomers in the ethylene polymerization, preference is given to using C ₃ -C ₈ -1-olefins, in particular 1-butene, 1-pentene, 1-hexene and / or 1-octene. Preferred comonomers in the propylene polymerization are ethylene and / or butene. Particularly preferred is a method in which ethylene is copolymerized with 1-hexene or 1-butene.

The process according to the invention for the polymerization of olefins can be carried out using all industrially known polymerization processes at temperatures in the range from 0 to 200 ° C., preferably from 25 to 150 ° C. and more preferably from 40 to 130 ° C. and under pressures of from 0.05 to 10 MPa and more preferably from 0.3 to 4 MPa perform. The polymerization can be carried out batchwise or, preferably, continuously in one or more stages. Solution methods, suspension methods, stirred gas phase methods or gas phase fluidized bed methods are possible. Methods of this kind are general to the skilled person my known.

The supported or unsupported Hybrid catalysts can be subjected before use to a prepolymerization, wherein the prepolymerization of the supported Catalyst system is preferred. The prepolymerization can hereby in the gas phase, in suspension or in the monomer (bulk), wherein the prepolymerization in a polymerization reactor upstream prepolymerization continuously or in one independent of reactor operation discontinuous prepolymerization can take place.

In the suspension polymerizations is usually polymerized in a suspending agent, preferably in an inert hydrocarbon such as iso-butane, or mixtures of hydrocarbons or in the monomers themselves. The suspension polymerization temperatures are usually in the range of -20 to 115 ° C, the pressure in the range of 0.1 to 10 MPa. The solids content of the suspension is generally in the range of 10 to 80%. It can be carried out both batchwise, for example in stirred autoclaves, and continuously, for example in tubular reactors, preferably in loop reactors. In particular, according to the Phillips PF method, as in US Pat. No. 3,242,150 and US-A 3,248,179 described, worked.

From the mentioned polymerization process are the gas phase polymerization, especially in gas-phase fluidized-bed reactors, the solution polymerization, and the suspension polymerization, in particular in loop and stirred tank reactors, prefers.

Especially preferred is the gas phase polymerization in a gas phase fluidized bed reactor, in which the circulated Reactor gas supplied to the lower end of a reactor and at its upper end is removed again. When used for the polymerization of 1-olefins it is in the run in the circle Reactor gas usually a mixture of the 1-olefin to be polymerized, if desired a molecular weight regulator such as hydrogen and inert gases such as Nitrogen and / or lower alkanes such as ethane, propane, butane, pentane or hexane. Preference is given to the use of propane, if appropriate in combination with other lower alkanes. The speed of the reactor gas must be high enough to be in the pipe, serving as a polymerization zone, mixed bulk bed to stir up of small-particle polymer and on the other hand, the heat of polymerization effectively dissipate (non-condensed mode). The polymerization can also be in the so-called condensed or supercondensed driving style, in which a part of the recycle gas cooled below the dew point and as a two-phase mixture is returned to the reactor, in addition the enthalpy of evaporation for cooling to use the reaction gas.

In Gas phase fluidized bed reactors are recommended when pressing 0.1 to 10, preferably 0.5 to 8 and especially 1.0 to 3 MPa to work. Furthermore the cooling capacity depends on the Temperature at which the (co) polymerization in the fluidized bed carried out becomes. For the process is advantageous to operate at temperatures of 30 to 160 ° C, more preferably between 65 and 125 ° C, wherein for copolymers of higher density preferably temperatures in the upper part of this range, for copolymers lower density preferably temperatures in the lower part of this Range.

Furthermore, a so-called multi-zone reactor can be used in which two polymerization zones are linked together and the polymer is passed alternately, several times through these two zones, wherein the two zones can also have different polymerization conditions. Such a reactor is for example in the WO 97/04015 and the WO 00/02929 described.

The different or even the same polymerization can also optionally be connected in series with each other and so a polymerization cascade form. Also a parallel reactor in two or more same or different methods is possible. The polymerization is preferred however, carried out in only a single reactor.

With the aid of the process according to the invention, it is possible to prepare polymer molding compositions having particularly advantageous properties. The molding compositions preferably have a molecular weight diversity M _w / M _n of more than 4, more preferably from 5 to 50, particularly preferably from 7 to 35. The melt mass flow rate, measured at 190 ° C and a load of 21.6 kg, is preferably from 1 to 300 g / 10 min. If catalysts with different comonomer incorporation behavior are used, the proportion of the respective polymer component can also be used to change the comonomer content of the polymer product, and thus also the density in the polymerization of ethylene.

A important application of bi- or multimodal polyolefins, in particular Polyethylene, is the production of pressure pipes for transportation of gas, drinking water and sewage, without being limited thereto. Polyethylene pressure pipes are increasingly replacing metal pipes. Important for Such an application is as long as possible of the pipe without fear of aging and brittle failure have to. Even small imperfections or nicks on a pressure pipe can be enlarge even at low pressures and too brittle Cause failure, this process being due to temperature increase and / or harsh chemicals can be accelerated. It is therefore extremely important to note the number and size of the defects a pipe, such as specks or "white spots" as far as possible reduce.

Also Films with low specks and very high mechanical strength, and excellent processability can be obtained. The modifier according to the invention Furthermore, they are distinguished by the organoleptic properties of the Do not affect products and therefore also for medical and food applications are particularly suitable.

The Producing the products already in the reactor, reduces energy consumption, requires no additional Blend processes and allows a simple control of the molecular weight distributions, and the Polymer components of different molecular weight. In addition, will achieved a thorough mixing of the polymer.

The Parameters used in this application were as follows certainly:

Intrinsic viscosity [dl / g]

The Determination of the intrinsic viscosity η, which is the Limit value of the viscosity number given extrapolation of the polymer concentration to zero, was carried out with an automatic Ubbelohde viscometer (Lauda PVS 1) with decalin as a solvent at 135 ° C according to ISO 1628.

Width of the molecular weight distribution:

Gel permeation chromatography (GPC) was carried out at 140 ° C. in 1,2,4-trichlorobenzene using a GPC apparatus 150C from Waters. The evaluation of the data was done with the software Win-GPC of the company HS-Entwicklungsgesellschaft for scientific hard- and software mbH, Ober-Hilbersheim. The calibration of the columns was carried out by means of polyethylene standards with molecular weights of 100 to 10 ⁷ g / mol. There were determined mass average (M _w ) and number average (M) of the molecular weights of the polymers and the ratio of weight average to number average (M _w / M _n ).

Density and comonomer content:

Density and comonomer content were determined by IR spectroscopy. The IR spectra were measured on films having a thickness of 0.1 mm, prepared by pressing at 180 ° C for 15 minutes. The correlation of the IR spectra to the density of the polymer samples was obtained via a chemical calibration against polymer standards whose density had been determined by measuring the buoyancy density according to ISO 1183. The correlation of the IR spectra to the comonomer content of the polymer samples was obtained via a chemical calibration against polymer standards whose hexene content had been determined by an evaluation of NMR spectra. To measure the NMR spectra, the polymer standards were filled under inert gas and melted down. The internal standard used in the ¹ H and ¹³ C NMR spectra were the solvent signals whose chemical shift was converted to TMS.

Branches / 1000 carbon atoms were determined by ¹³ C-NMR as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2 & 3), 201-317 (1989) describe and refer to the total CH ₃ group content per 1000 carbon atoms.

Melting temperature [° C]:

The melting temperature T _m was determined by DSC measurement according to ISO 3146 with a first heating at a heating rate of 20 ° C per minute up to a temperature of 200 ° C, a dynamic crystallization with a cooling rate of 20 ° C per minute up to a temperature of 25 ° C and a second heating at a heating rate of 20 ° C per minute turn up to a temperature of 200 ° C determined. The melting temperature is then the temperature at which the enthalpy versus temperature curve measured at the second heating has the maximum.

All These documents are expressly incorporated by reference this application. All quantities and ratios relate to this application based on the weight of the total weight of the corresponding Mixtures, unless stated otherwise.

in the The following is the invention with reference to examples, without to limit these to it.

Examples

Examples 1-3 and Comparative Example

verwendet.As transition metal compound was 3-methyl- (2-pyridyl-1-methyl) indenyl) chromium dichloride)

used.

3-aminopropyltrimethoxysilane was purchased from the company Aldrich.

polymerization

It was in a 1 liter flask with stirrer and gas inlet tube at 40 ° C polymerized under argon. To a solution of the in Table 1 and 2 indicated amount of the corresponding complex in 250 ml of toluene the appropriate amount of MAO (10% solution in toluene) was added and at 40 ° C heated. Then the modifier was added. Just before the ethylene addition in each case 3 ml of hexene were submitted. Subsequently was Ethylene at a flow rate of about 20 to 40 l / h at atmospheric pressure passed through. It was under constant flow of ethylene and under further addition of witches for the times indicated in Table 1 polymerized. After the suspension recognizably assumed a "mushy" consistency In order to exclude diffusion effects, the polymerization was carried out Addition of methanolic HCl solution (15 ml concentrated hydrochloric acid in 50 ml of methanol). Subsequently, 250 ml of methanol admitted, the resulting white Polymer filtered off, washed with methanol and dried at 70 ° C.

The results of the polymerizations carried out in Examples 1 to 3 and Comparative Example 1, as well as the properties of the resulting ethylene copolymers, are shown in Tables 1 below. The stated amount of C ₆ addition corresponds to the sum of the 3 ml of hexene introduced in each case and the hexene added during the polymerization. Table 1 example 1 Example 2 Example 3 Comparative example Weighed in cat [mg, (μmol)] 9.9 (28.9) 10.1 (29.4) 14.7 (42.8) 5.9 (17.2) C6 addition [ml], 5.5 9.25 15.0 10 excipient 3-aminopropyltrimethoxysilane Triethylboron (TEB) butyl methyl ether none Polymerization time [min] 12 28 14.5 25 Yield [g] 8.1 24.1 9.0 15.4 Activity [g / mmol h] 1400 1750 870 2140 Intrins. Visc. η [dl / g] 9.64 1.2 0.97 2.09 M _w [g / mol] 1,10 10 ⁶ 6.02 10 ⁴ 3.91 10 ⁴ 1.34 10 ⁵ M _w / M _n 3.9 2.7 2.7 3.6 Density [g / cm ³ ] 0.908 0.901 0.886 0.881 CH3 / 1000C 10.8 26.5 39.9 41.0 C6 content 6.4 12.1 18.5 17.1

As the comparison of the examples surprisingly shows, it is possible by choice of the auxiliary is specifically the comonomer incorporation behavior the active center of a catalyst or a catalyst component based on a monocyclopentadieny complex. This provides new degrees of freedom with regard to targeted control the product composition or product properties accessible. One is thus able to produce extremely different products to obtain with a catalyst system.

Claims (14)

Process for the polymerization of olefins in Presence of at least one catalyst containing an organo-transition metal complex, wherein the comonomer incorporation behavior of the catalyst by addition of a or more auxiliaries is controlled. The process of claim 1 wherein the at least one catalyst comprises a monocyclopentadienyl complex of the formula Cp-Y _m M ^A (I) wherein the variables are as defined below: Cp is a cyclopentadienyl system, Y is a Cp-bonded substituent containing at least one neutral donor D, which contains at least one atom of groups 15 or 16 of the Periodic Table, M ^{A is} titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, in particular chromium and m is 1, 2 or 3, The method of claim 1 or 2, wherein and the one or more auxiliaries are selected from the group consisting of a) silanes of the general formula R _a SiR ' _b or R _a Si (OR') _b , b) zinc dialylene of the general formula ZnR ' ₂ , c) ethers of the general formula R'-OR' and d) boron trialkyls of the general formula BR ' ₃ , where R is in each case identical or different and for a C ₁ -C ₂₀ -alkyl-, C ₆ -C ₂₀ - Aryl, C ₆ -C ₂₀ -arylalkyl or C ₆ -C ₂₀ -alkylaryl radical which has at least one polar group of the general formulas -NR '' ₂ , -OR '', -COR '' or -COOR '' R 'is in each case identical or different and is a C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -arylalkyl or C ₆ -C ₂₀ -alkylaryl radical, R' is in each case identical or different and is hydrogen or a C ₁ -C ₂₀ -alkyl-, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -arylalkyl- or C ₆ -C ₂₀ -alkylaryl radical, a is 1, 2, 3 or 4 and b is selected such that a + b = 4. Process according to Claim 3, in which the auxiliaries R in each case are identical or different and represent a C ₁ -C ₂₀ -alkyl radical which has at least one polar group of the general formulas -NR '' ₂ , -OR '', -COR ''or-COOR''is substituted, R' is in each case identical or different and is a C ₁ -C ₂₀ -alkyl radical, R '' in each case identical or different and is hydrogen or a C ₁ -C ₂₀ -alkyl radical, Process according to one of claims 3 or 4, wherein R is substituted by at least one polar group of general formula -NR " ₂ , wherein R" represents a C ₁ -C ₈ -alkyl radical. A process according to any one of claims 1 to 5, wherein the organo-transition metal complex in supported form or as a solid. Method according to one of the preceding claims, wherein the catalyst is a hybrid catalyst containing at least one another transition metal compound is. The method of claim 7, wherein the organo-transition metal complex and the other transition metal compounds together on a support cogeträgert be used. The method of claim 7 or 8, wherein the hybrid catalyst a monocyclopentadienyl complex and at least one other organotransition contains. A method according to any one of claims 7 to 9, wherein the hybrid catalyst contains a catalyst component, which has two cyclopentadienyl ligands. The method of claim 10, wherein the two cyclopentadienyl ligands containing catalyst component as transition metal titanium, zirconium, Hafnium, chromium or vanadium. A process according to any one of claims 7 to 11, wherein the hybrid catalyst contains a catalyst component of the general formula (X),

wherein E ^2D independently of one another are carbon, nitrogen or phosphorus, in particular carbon, R ^20D and R ^24D independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ -alkenyl , C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, -NR ^26D ₂ or -SiR ^26D ₃ , wherein the organic radicals R ^26D and R ^24D also may be substituted by halogens, R ^21D to R ^{23D are} independently hydrogen, C ₁ -C ₂₀ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ alkenyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, halogen, -NR ^26D ₂ or -SiR ^26D ₃ , wherein the organic radicals R ^21D to R ^23D also may be substituted by halogens and / or each two vicinal radicals R ^21D to R ^{23D may} also be connected to a five-, six- or seven-membered ring, and / or two vici nals R ^21D to R ^{23D are connected} to a five-, six- or seven-membered heterocycle, which is at least one atom from the group N, P, O or S contains, u independently of one another 0 for E ^2D equal to nitrogen or phosphorus and 1 for E ^2D is carbon, R ^27D to R ^30D independently of one another C ₁ -C ₂₀ alkyl, 5- to 7-membered cycloalkyl or Cycloalkenyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₄₀ aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, halogen, -NR ^26D ₂ -OR ^26D or -SiR ^26D ₃ , wherein the organic radicals R ^27D to R ^{30D may} also be substituted by halogens and / or any two vicinal radicals R ^27D to R ^{30D may} also be connected to a five, six or seven membered ring, and / or two vicinal radicals R ^27D to R ^30D are bonded to a five-, six- or seven-membered heterocycle which contains at least one atom from the group N, P, O or S, R ^31D to R ^36D independently of one another are hydrogen, C ₁ -C ₂₀ alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C ₂ -C ₂₂ alkenyl, C ₆ -C ₄₀ aryl, arylalkyl having 1 to 10 C-Ato in the alkyl radical and 6-20 C atoms in the aryl radical, halogen, -NR ^26D ₂ , -OR ^26D or -SiR ^26D ₃ , wherein the organic radicals R ^31D to R ^{36D may} also be substituted by halogens and / or two vicinal ^Radicals R ^31D to R ^{36D may} also be connected to a five-, six- or seven-membered ring, and / or that two vicinal radicals R ^31D to R ^{36D are connected to} a five-, six- or seven-membered heterocycle which ^comprises at least one atom the group N, P, O or S contains, v independently of one another 0 or 1, X ^D independently of one another fluorine, chlorine, bromine, iodine, hydrogen, C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₆ -C ₄₀ -aryl, arylalkyl having 1-10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, -NR ^26D ₂ , -OR ^26D , -SR ^26D- SO ₃ R ² -OC (O) -R ^26D , -CN, -SCN, β-diketonate, CO, BF ₄ ^- , PF ₆ ^- , or bulky noncoordinating anions and the radicals X ^{D are} optionally joined together, R ^{26D are} 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, wherein the organic radicals R ^26D also by halogens or nitrogen - And oxygen-containing groups may be substituted and each two radicals R ^{26D may} also be connected to a five- or six-membered ring, s 1, 2, 3 or 4, in particular 2 or 3, D is a neutral donor and t 0 to 4, in particular 0, 1 or 2. A method according to any one of claims 1 to 12, wherein a polymer with a higher molecular weight and a lower molecular weight polymer component is prepared, the ratio the higher molecular weight polymer component to the lower molecular weight polymer component from 5% by weight to 95% Wt .-%, in particular from 10 wt .-% to 90 wt .-% is. A process according to any one of claims 1 to 13, wherein the polymerization in the gas phase or in suspension.