Polyethylene for injection moldings

[0001] The present invention relates to a new polyethylene which contains ethylene homopolymers and / or copolymers of ethylene with 1-alkenes and has a molar mass distribution width Mw / Mn of 3 to 30, density ₃ from 0.945 to 0.965 g / cm³, weight average molar mass Mw from 50,000 g / mol to 200,000 g / mol, HLMI (flow index under load) from 10 to 300 g / 10 min and has from 0.1 to 15 branches / 1000 carbon atoms, in which 1 to 15% by weight polyethylene having the highest molar masses has a branching degree greater than 1 side chain branching greater than CH3 / 1000 carbon atoms, catalyst composition and method for its preparation, and moldings in which this polyethylene is present.

[0002] Blends of various polyethylenes are known and used to produce moldings with high resistance to slow crack propagation as disclosed in DE-C 34 37 116.

[0003] Recently, polyethylene blends have been used in injection molding to produce many types of threaded closures. It is advantageous if the threaded closures retain their dimensions and shape during cooling after the injection molding procedure, i.e. they do not shrink (low shrinkage). Low shrinkage, together with shape retention, is an important property of plastics that are to be used, for example, to produce threaded closures with exact fit. In addition, the injection molding method is usually easier to perform if the polyethylene injection compositions have good melt flowability. Even higher demands are placed on the polyethylene-containing molded parts. On the other hand, good processability is required to achieve high throughputs.

[0004] WO 00/71615 discloses injection-molded containers of bimodal polyethylene having ₃ density from 0.950 to 0.98 g / cm³, crystallinity from 60 to 90%, consisting of at least 2 polyethylene components with different molar mass distributions, and in which at least one component is an ethylene copolymer. Polyethylene is obtained from a cascade of reactors or by melt extrusion of two components.

[0005] Known ethylene copolymer blends still leave much to be desired in terms of a combination of good mechanical properties, high melt flowability and good optical properties.

[0006] It has been surprisingly found that this goal can be achieved by using a specific catalyst composition with which polyethylene having good mechanical properties, good processability and good optical properties can be obtained.

[0007] We found polyethylene, respectively, which contains ethylene homopolymers and / or copolymers of ethylene with 1-alkenes and has a molecular weight distribution Mw / Mn from 3 to 30, density from 0.945 to 0.965 ₃ g / cm³, weight average molar mass Mw from 50,000 g / mol to 200,000 g / mol, HLMI from 10 to 300 g / 10 min and from 0.1 to 15 branches / 1000 carbon atoms, in which 1 to 15% by weight of the highest polyethylene molar masses have a degree of branching greater than 1 branching side chains greater than CH3 / 1000 carbon atoms.

[0008] We have also found moldings, caps and closures in which the polyethylene of the invention is present as a significant component. In addition, we have found the use of the polyethylenes of the inventions to produce moldings.

[0009] We also found a catalyst system for the preparation of polyethylenes according to the invention, the use of a catalyst system for the polymerization of ethylene and / or copolymerization of ethylene with 1-alkenes and a method for producing the polyethylene according to the invention by polymerization of ethylene and / or copolymerization of ethylene with 1-alkenes in the presence of a catalyst system .

[0010] The polyethylene according to the invention has a molar mass distribution width Mw / Mn in the range from 3 to 30, preferably from 5 to 20 and in particular preferably from 6 to 15. The density of the polyethylene according to the invention 33 is in the range from 0.945 to 0.965 g / cm³, preferably from 0.947 to 0.96 g / cm³ and in particular ₃ preferably in the range of from 0.948 to 0.955 g / cm³. The weight average molar mass Mw of the polyethylene according to the invention ranges from 50,000 g / mol to 200,000 g / mol, preferably from 70,000 g / mol to 150

000 g / mol and in particular preferably from 80,000 g / mol to 120,000 g / mol. The HLMI of the polyethylene according to the invention is in the range from 10 to 300 g / 10 min, preferably from 50 to 200 g / 10 min, particularly preferably in the range from 70 to 150 g / 10 min. For the purposes of the present invention, the expression "HLMI" refers, as is known, to "high load melt index" and is defined in

190 ° C under a load of 21.6 kg (190 ° C / 21.6 kg) in accordance with ISO 1133.

₃ [0011] Density [g / cm³] determined in accordance with ISO 1183. Determination of molar mass distributions and their mean Mn, Mw, and Mw / Mn derivatives was carried out by means of high-temperature gel permeation chromatography on WATERS 150 C using the method based on DIN 55672 and the following columns connected in series: 3x SHODFJC AT 806 MS, 1x SHODEX UT 807 and 1x SHODEX AT-G under the following conditions: solvent: 1,2,4-trichlorobenzene (stabilized by 0.025% by weight 2,6-di-tert-butyl-4-methylphenol), flow rate: 1 ml / min, 500 ml injection volume, temperature: 135 ° C. Calibration using PE standards. The estimation was carried out using WIN-GPC.

[0012] The polyethylene of the invention has from 0.1 to 15 branches / 1000 carbon atoms, preferably from 0.2 to 8 branches / 1000 carbon atoms and in particular preferably from 0.3 to 3 branches / 1000 carbon atoms. Branches / 1000 carbon atoms determined by¹³C-NMR as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2 & 3), 201-317 (1989), and this applies to the total content of CH3 groups / 1000 carbon atoms.

[0013] Furthermore, the polyethylene of the invention has 1 to 15% by weight of polyethylene having the highest molar masses, preferably 2 to 12% by weight and in particular preferably 3 to 8% by weight has a degree of branching greater than 1 branching of the side chains greater than CH3 / 1000 carbon atoms, preferably in the range of 2 to 20 branching of side chains larger than CH3 / 1000 carbon atoms and particularly preferably in the range of 5 to 15 branching of side chains larger than CH3 / 1000 carbon atoms. This can be determined by solvent fractionation non-solvent, later called Holtrup fractionation as described in W. Holtrup,

Makromol. Chem. 178, 2335 (1977) coupled with IR measurement of various fractions. Xylene and ethylene glycol diethyl ether at 130 ° C were used as fractionation solvents. 5 g of 13 polyethylene were used and divided into 8 fractions. Fractions were subsequently analyzed by spectroscopy¹³C13

NMR. The degree of branching in the different polymer fractions can be determined by¹³C-NMR as

EP 1 753 791 B1 was described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2 & 3), 201-317 (1989). The polyethylene of the invention preferably has a CDBI (ratio of composition distribution) less than 50%, in particular 10 to 45%. The method of determining CDBI is described, for example in WO 93/03093. The TREF method is described, for example, in Wild, Advances in Polymer Science, 98, pp. 1-47, 57 pp. 153, 1992. CDBI was determined as the weight percentage of copolymer molecules having a comonomer content of +/- 25% of the average total molar comonomer content. Side chain branches larger than CH3 refer to side chain content / 1000 carbon atoms without end groups.

[0014] The molar mass distribution of the polyethylene of the invention may be monomodal, bimodal or multimodal. In this patent application, the monomodal molar mass distribution means that the molar mass distribution has a single maximum. Bimodal molar mass distribution means, for the purposes of this patent application, that the molar mass distribution has at least two inflection points on one side, starting from the maximum. The molar mass distribution is preferably monomodal or bimodal, in particular bimodal.

[0015] 1 to 15% by weight of the polyethylene according to the invention having the highest molar masses, preferably 2 to 12% by weight and in particular preferably 3 to 8% by weight when separated into fractions by means of gel permeation chromatography (GPC), and then this fraction using "analytical temperature rising elution fractionation technique" (TREF), (analytical technique for fractional elution with increasing temperature) preferably showed no high density polyethylene peak with a maximum above 80 ° C, preferably above 85 ° C and in particular preferably above 90 ° C. The polymer concentration in the fractions obtained at different temperatures is measured by infrared spectroscopy. The TREF result can also be calibrated using preparatively isolated polyethylene fractions having a specified number of short chain branches. The TREF method is described, for example, in Wild, Advances in Polymer Science, 98, pp. 1-47, 57 pp. 153, 1992.

[0016] When the polyethylene of the invention is tested by TREF, fractions with a maximum above 80 ° C, preferably above 85 ° C and in particular preferably above 90 ° C, when tested by GPC, preferably only show polyethylene with molar masses below 1 Mil . g / mol as opposed to polyethylenes obtained with typical Ziegler catalysts.

[0017] The polyethylene of the invention preferably has a long chain branching λ (lambda) from 0 to 2 long chain branches / 10,000 carbon atoms and particularly preferably from 0.1 to 1.5 long chain branches / 10,000 carbon atoms. The degree of long-chain branching λ (lambda) was measured by light scattering as described, for example, in ACS Series 521, 1993. Chromatography of Polymers, Ed. Theodore Provder; Simon Pang and Alfred Rudin: Size-Exclusion Chromatographic Assessment of Long-Chain Branch Frequency in Polyetyloenes, pp. 254-269.

[0018] Preferably, 5-50% by weight of the polyethylene of the invention having the lowest molar masses, preferably 10-40% by weight and particularly preferably 15-30% by weight, has a branching degree of less than 10 branches / 1000 carbon atoms. This degree of branching in a portion of the polyethylene having the lowest molar masses is preferably from 0.01 to 9 branches / 1000 carbon atoms and particularly preferably from 0.1 to 6 branches / 1000 carbon atoms. This can be determined by the Holtrup method described 13 /¹³C-NMR. Branches / 1000 carbon atoms determined by¹³CNMR, as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2 & 3), 201-317 (1989), and

They relate to the total content of CH3 / 1000 carbon atoms.

[0019] The polyethylene of the invention has at least 0.2 vinyl groups / 1000 carbon atoms, preferably from 0.7 to 5 vinyl groups / 1000 carbon atoms and particularly preferably from 0.9 to 3 vinyl groups / 1000 carbon atoms. The content of vinyl groups / 1000 carbon atoms was determined by IR, ASTM D 6248-98. For the purposes of this invention, the expression vinyl groups refers to CH = CH2; vinylidene groups and internal olefinic groups are not covered by this expression. Vinyl groups are usually assigned to the polymer termination reaction after introducing ethylene, while vinylidene end groups are usually formed after the polymer termination reaction after introducing the comonomer.

[0020] The polyethylene according to the invention preferably has from 0.01 to 20 branches of side chains larger than CH3 / 1000 carbon atoms, preferably side chains from C2-C6 / 1000 carbon atoms, preferably from 1 to 15 branches of side chains larger than CH3 / 1000 carbon atoms, preferably side chains from C2-C6 / 1000 carbon atoms and particularly preferably from 2 to 8 branches of side chains larger than CH3 / 1000 carbon atoms, preferably side chains from C2-C6 / 1000 carbon atoms. Side chain branches larger than CH3 / 1000 carbon atoms are determined by ¹³C-NMR, as defined by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2 & 3), 201317 (1989), and referred to the total content of side chains larger than CH3 groups / 1000 carbon atoms (without end groups). It is particularly preferred that polyethylene with 1-butene, 1-hexene or 1-octene as the α-olefin have 0.01 to 20 ethyl, butyl or hexyl side branches / 1000 carbon atoms, preferably from 1 to 15 ethyl, butyl or hexyl side branches / 1000 carbon atoms and particularly preferably from 2 to 8 ethyl, butyl or hexyl side branches / 1000 carbon atoms. This applies to the content of ethyl, butyl or hexyl side chains / 1,000 carbon atoms without end groups. [0021] In the polyethylene of the invention, a portion of the polyethylene having a molar mass of less than 10,000 g / mol, preferably less than 20,000, preferably has a degree of branching from 0 to 1.5 branches of side chains larger than CH3 / 1000 carbon atoms, preferably chains side from C2-C6 / 1000 carbon atoms. Particularly, a portion of polyethylene having a molar mass of less than 10,000 g / mol, preferably less than 20,000, having a branching degree from 0.1 to 0.9 branching of side chains larger than CH3 / 1000 carbon atoms, preferably side chains from C2 is preferred -C6 / 1000 carbon atoms. Preferably the polyethylene of the invention with 1-butene, 1-hexene or 1-octene as 1-alkene, a portion of the polyethylene having a molar mass of less than 10,000 g / mol, preferably less than 20,000, preferably has a degree of 0 to 1.5 ethyl , butyl or hexyl side chain branches / 1000 carbon atoms. Particularly, a portion of polyethylene having a molar mass of less than 10,000 g / mol, preferably less than 20,000, having a degree of branching from 0.1 to 0.9 ethyl, butyl or hexyl branching side chains / 1000 carbon atoms is preferred. This can also be determined using the Holtrup / method described¹³C-NMR.

[0022] Furthermore, it is preferred that at least 70% of the side chain branches larger than

CH3 in the polyethylene of the invention was present in 50% by weight of the polyethylene having the highest molar masses. This can also be determined using the Holtrup / method described¹³C-NMR.

[0023] The polyethylene according to the invention preferably has a mixing quality measured according to ISO

EP 1 753 791 B1

13949 less than 3, in particular from 0 to 2.5. This value is based on polyethylene taken directly from the reactor, i.e. polyethylene powder without prior melting in the extruder. This polyethylene powder can preferably be obtained by polymerization in a single reactor. [0024] As 1-alkenes, which are comonomers that can be present in ethylene copolymers, either alone or in a mixture with another, in addition to ethylene in the ethylene copolymer part of the polyethylene of the invention, all 1-alkenes having from 3 to 12 carbon atoms, e.g., propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. The ethylene copolymer preferably contains 1-alkenes having from 4 to 8 carbon atoms, e.g., 1-butene, 1-pentene, 1-hexene, 4-methylpentene or 1-octene, in copolymerized form, as a comonomer unit. In particular, it is preferred to use 1-alkenes selected from the group consisting of 1-butene, 1-hexene and 1-octene. Preferably, the polyethylene of the invention contains 0.01 to 5% by weight, preferably 0.1 to 3 by weight of comonomer.

[0025] The polyethylene of the invention may further contain from 0 to 6% by weight, preferably 0.1 to 1 by weight of known auxiliaries and / or additives, e.g., processing stabilizers, stabilizers against the influence of light and heat, typical additives such like lubricants, antioxidants, anti-blocking and anti-electrostatic agents, and also, if appropriate, dyes. The skilled person will know the type and amount of these additional measures.

[0026] In addition, it has been found that the polyethylene processing properties of the invention can be further improved by incorporating small amounts of fluoroelastomers or thermoplastic polyesters. Such fluoroelastomers are known as processing aids and are commercially available, for example, under the trade names Viton® and Dynamar® (see also, for example, US-A-3125547). They are preferably added in amounts of from 10 to 1000 ppm, particularly preferably from 20 to 200 ppm, based on the total weight of the polymer blend according to the invention.

[0027] In general, the mixing of additives and polyethylene according to the invention can be carried out by all known methods. This can be done, for example, by introducing powdered ingredients into a granulation apparatus, e.g. a twin-screw kneader (ZSK), Farrel kneader or Kobe kneader. The granulated mixture can also be processed directly at the film production plant.

[0028] We have also found the use of the polyethylenes of the invention for the production of compacts, and injection molding, preferably threaded closures, caps, tube flanges and technical parts in which the polyethylene of the invention is present as a significant component.

[0029] Moldings, threaded closures and caps, tube flanges and technical parts in which the polyethylene according to the invention is present as a significant component are those which contain from 50 to 100% by weight, preferably from 60 to 90% by weight, of the polyethylene according to the invention, relative to the total polymer material used for manufacture. In particular, moldings, threaded closures and caps are also included in which one of the layers contains from 50 to 100% by weight of the polyethylene according to the invention.

[0030] The polyethylene and compacts according to the invention having a thickness of 1 mm preferably have haze, as determined according to ASTM D 1003-00 with a BYK Gardener Haze Guard Plus device on at least 5 10x10 cm film samples below 94%, preferably from 10 to 92 % and particularly preferably

From 50 to 91%. Resistance to slow crack propagation (full notched creep test (FNCT)) of polyethylene and compacts as determined according to ISO DIS2 16770 at 3.5 Mbar at 80 ° C in a 2% by weight solution of Akropal N (N = 10) in water, is preferably at least 5 hours, preferably from 6 to 80 hours. and in particular preferably from 7 to 20 hours. The polyethylene and compacts according to the invention with a thickness of 1 mm preferably have an impact strength as determined in accordance with the instrumental impact test by the falling weight method according to ISO 6603 at -20 ° C of at least 12 J.

[0031] Polyethylene can be processed using conventional injection molding machines. The finish of the molded parts is homogeneous and can be further improved by increasing the injection speed or increasing the mold temperature.

[0032] The flow properties under treatment conditions were determined by means of a spiral test. Polyethylene is injected at a specified temperature, pressure and speed of the screw into a spiral mold to obtain coils with different wall thicknesses. The length of the obtained coil can be considered as a measure of flow. The spiral test was performed on a Demag ET100-310 with a clamping pressure of 100 t and a 3 mm nozzle.

[0033] The durability of the polyethylene form and size according to the invention was tested by injection molding at 180 to 270 ° C screw caps with a thread diameter of 28.2 mm. The caps were cooled and the thread diameter of 50 samples was measured, the mean counted and compared to the diameter of the original thread. The samples were also visually inspected for form stability and size.

[0034] The polyethylene of the invention showed high flow properties, with spiral lengths above 40 cm, measured at a batch temperature of 250 ° C, an injection pressure of 1000 bar, a screw speed of 90 mm / s, a mold temperature of 30 ° C and a wall thickness of 2 mm.

[0035] Moldings, preferably closures, threaded caps and closures and caps, tube flanges and technical parts in which the polyethylene according to the invention is present as a significant component are those containing from 50 to isotropic by weight, preferably from 60 to 90% by weight, polyethylene according to the invention, relative to the total polymer material used for production. The caps and closures are preferably used for bottles, preferably beverage bottles.

[0036] The polyethylene of the invention can be obtained using the catalyst system of the invention and in particular its preferred embodiments.

[0037] The present invention further provides a catalyst composition comprising at least two different polymerization catalysts, of which A) is at least one polymerization catalyst based on a monocyclopentadienyl metal group 4-6 metal table of the periodic table, whose cyclopentadienyl system is substituted with a uncharged donor (A1 ) or hafnocene (A2) and B) is at least one polymerization catalyst based on an iron component, having a tridentate ligand containing at least two ortho, ortho-disubstituted aryl (B) substituents.

[0038] The invention further provides a process for the polymerization of olefins in the presence of a catalyst composition according to the invention.

[0039] For the purposes of the present invention, the uncharged donor is an uncharged functional group containing an element from group 15 or 16 of the periodic table.

[0040] The components of the hafnocene catalyst are, for example, cyclopentadienyl complexes.

EP 1 753 791 B1

Cyclopentadienyl complexes can be, for example, bridged or non-bridged biscyclopentadienyl complexes as described, for example, in EP 129 368, EP 561479, EP 545 304 and EP 576 970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes described in, for example, EP 416 815, multinucleated cyclopentadienyl complexes as described in EP 632 063, tetrahydropentalenes with a pi-substituted ligand as described in EP 659 758 or tetrahydroindenes with a pi-substituted ligand as described in EP 661 300.

[0041] Preference is given to monocyclopentadienyl (A1) complexes having the following structural feature of the general formula Cp-YmM^AND (1), where the variables have the following meanings:

Cp is the cyclopentadienyl system,

Y is a substituent that is bound to Cp and contains at least one uncharged donor containing at least one atom from group 15 or 16 of the periodic table,

M^AND means titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, in particular chromium, and m means 1, 2 or 3.

[0042] Suitable monocyclopentadienyl complexes (A1) contain a structural element of the general formula Cp-YmM^AND (I), where the variables are as defined above. Subsequent ligands can therefore be bound to the metal atom M^AND. The number of subsequent ligands depends, for example, on the degree of oxidation of the metal atom. These ligands are not subsequent cyclopentadienyl systems. Suitable ligands include monoanionic and dianionic ligands as described, for example, for X. In addition, Lewis bases such as amines, ethers, ketones, aldehydes, esters, phosphine sulfides can also be bonded to the M metal center. Monocyclopentadienyl complexes monomeric, dimeric or oligomeric. Monocyclopentadienyl complexes are preferably in monomeric form.

[0043] M^AND means a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten. Oxidation state of transition metals M^AND in catalytically active complexes it is usually known to the skilled person. Chromium, molybdenum and tungsten are very likely present on the +3 oxidation state, zirconium and hafnium on the +4 oxidation state and titanium on the +3 or +4 oxidation state. However, it is also possible to use complexes whose oxidation state does not correspond to that of an active catalyst. Such complexes can then be appropriately reduced or oxidized by means of suitable activators. M^AND is preferably titanium in oxidation state 3, vanadium, chromium, molybdenum or tungsten. In particular, chromium is preferred in oxidation states 2, 3 and 4, in particular 3.

[0044] m can be 1, 2 or 3, i.e. 1, 2 or 3 Y donor groups can be bonded to Cp, and they can be identical or different when 2 or 3 Y groups are present. Only one is preferred donor group Y associated with CP (m = 1).

[0045] The uncharged donor Y is an uncharged functional group containing an element from group 15 or 16 of the periodic table, e.g. amine, imine, carboxamide, carboxylic ester, ketone (oxo), ether, thioketone, phosphine, phosphite, phosphine oxide, sulfonyl , sulfonamide or unsubstituted, substituted or fused, partially unsaturated heterocyclic

EP 1 753 791 B1 or heteroaromatic ring systems. The Y donor can be intermolecular or intramolecular to M transition metal^AND or unrelated to him. Donor Y is preferably intramolecularly bonded to the metallic center M^AND. Particularly preferred are mono-cyclopentadienyl complexes containing a structural element of the general formula Cp-YM^AND.

[0046] Cp is a cyclopentadienyl system which can be substituted in any way and / or be fused with one or more aromatic, aliphatic, heterocyclic or heteroaromatic rings with 1, 2 or 3 substituents, preferably 1 substituent formed by the group Y and / or 1, 2 or 3 substituents, preferably 1 substituent substituted with a Y group and / or an aromatic, aliphatic ring, heterocyclic or heteroaromatic condensed containing 1, 2 or 3 substituents, preferably 1 substituent. The cyclopentadienyl skeleton itself is a C5 ring system having 6 π electrons in which one of the carbon atoms can also be replaced by nitrogen or phosphorus, preferably phosphorus. It is preferred to use C5 ring systems without being replaced by a heteroatom. This cyclopentadienyl backbone may be, for example, fused to a heteroaromat containing at least one atom from the group consisting of N, P, O and S or with an aroma. In this context, fused means that the heterocycle and the cyclopentadienyl backbone share two atoms, preferably carbon atoms. The cyclopentadienyl system is associated with M^AND.

[0047] Particularly well suited monocyclopentadienyl complexes (A1) are those in which Y is formed by the group Zk-A- and together with the Cp and M cyclopentadienyl system^AND forms a monocyclopentadienyl complex containing a structural element of the general formula Cp-Zk-AM^AND(II), where the variables have the following meanings:

Cp-Zk-A means

<img file="PL1753791T3_D0001.tif" />

where variables have the following meanings:

Each of E^1A-E^5A is carbon or no more than one E^1A to E^5A phosphorus, each R^1A-R^4A is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl substituent and 6-20 carbon atoms in the aryl substituent, NR^5A2, N (SiR^5A3)₂, OR^5A, OSiR^5A3, SiR^5A3, BR^5A2, where organic substituents R^1A-R^4A they may also be substituted with halogens and two vicinal R substituents^1A-R^4A they may also be combined to form a five-, six- or seven-membered ring, and / or two vicinal R substituents^1A-R^4A are connected to form a five-, six- or seven-membered heterocycle,

EP 1 753 791 B1 containing at least one atom from the group consisting of N, P, O and S,

5A each of R substituents^5A is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the 5A aryl part and two geminal R substituents^5A they can also be combined to form a five or six membered ring,

Z is a divalent bridge between A and Cp, which is selected from the following group

<img file="PL1753791T3_D0002.tif" />

-BR^6A-, -BNR^6AR^7A-, -AlR^6A-, -Sn-, -O-, -S-, -SO-, -SO2-, -NR^6A-, -CO-, -PR^6A- or -P (O) R^6A- where each of L^1A-L^3A means, independently of each other, silicon or germanium, each of R^6A-R^11A is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR^12A3, where organic substituents R^6A-R^11A they may also be substituted with halogens and two geminal or vicinal R substituents^6A-R11A can also be combined to form a five or six membered ring and

12A each of the substituents R^12A is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the 12A aryl part, C1-C10-alkoxy or C6-C10-aryloxy and two R substituents^12A they can also be combined to form a five- or six-membered ring, and

A is an uncharged donor group containing one or more atoms of the 15 and / or 16 group of the periodic table, preferably unsubstituted, substituted or fused,

EP 1 753 791 B1 heteroaromatic ring system,

M^AND is a metal selected from the group consisting of titanium with oxidation state 3, vanadium, chromium, molybdenum and tungsten, in particular chromium, and k is 0 or 1.

[0048] In preferred Cp cyclopentadienyl systems, all E^1A to E^5A means carbon.

[0049] The polymerization behavior of metal complexes can be influenced by changing substituents

R^1A-R^4A. The number and type of substituents may affect the availability of the metal atom M for olefins to be polymerized. In this way, the activity and selectivity of the catalyst can be modified for various monomers, in particular, spatial monomers. Since substituents can also affect the rate of completion of the growing polymer chain, the molar mass of the polymers formed can also be changed in this way. Chemical structure of R substituents^1A to R.^4A it can therefore vary widely to achieve the desired results and to obtain a tailored catalyst system. Possible carboorganic substituents R^1A-R^4A are, for example, the following: hydrogen, C1-C22-alkyl which may be linear or branched, e.g. 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 may in turn contain a group

C1-C10-alkyl and / or C6-C10-aryl as a substituent, e.g. cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl. C2-C22-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C22-aryl which may be substituted by further alkyl groups, e.g., 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 which may be substituted by further alkyl groups, e.g. benzyl, o-, m, p-methylbenzyl, 1- or 2- ethylphenyl, where two R substituents^1A to R.^4A they may also be combined to form a 5-, 6- or 7-membered ring and / or two vicinal R substituents^1A-R^4A they can be combined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S and / or organic substituents R^1A-R^4A they may also be substituted with halogens such as fluorine, chlorine or bromine.

In addition, R^1A-R^4A may be amine NR^5A2 or N (SiR^5A3)₂, alkoxy or aryloxy OR^5A. For example, 5A dimethylamine, N-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy. Substituents R^5A in 5A SiR organosilicon substituents^5A3 may be the same carboorganic substituents as described above for R^1A-R^4Awhere two R substituents^5A they may also be combined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tritertbutylsilyl, 5A triallylsilyl, triphenylsilyl or dimethylphenylsilyl: these SiR substituents^5A3 they can also be combined to form a cyclopentadienyl skeleton by oxygen or nitrogen, for example trimethylsilyloxy, triethylsilyloxy, butyl dimethyl silyloxy, tributyl silyloxy or tritert-butylsilyloxy. Preferred substituents for R^1A-R^4Aare 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. Possible organosilicon substituents are, in particular, trialkylsilyl groups having 1 to 10 carbon atoms in the alkyl substituent, in

In particular trimethylsilyl groups.

[0050] Two vicinal R substituents^1A-R^4A together with E.^1A-E^5A containing them may form a heterocycle, preferably heteroaromatic, containing at least one atom from the group consisting of nitrogen, phosphorus, oxygen and sulfur, particularly preferably nitrogen and / or sulfur, with E^1A-E^5A preferably present in the heterocycle or heteroaromat being carbon. Heterocycles and heteroaromats having a ring size of 5 or 6 atoms are preferred. Examples of 5-membered heterocycles that may contain one to four nitrogen atoms and / or sulfur or oxygen as ring atoms in addition to carbon atoms 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 and 1,2,4-triazole. Examples of 6-membered heteroaryl groups that can contain from one to four nitrogen atoms and / or a phosphorus atom are pyridine, phosphabenzene, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine 1,2,4-triazine or 1,2,3 triazine. The 5-membered and 6-membered heterocycles may also be substituted by C 1 -C 10 -alkyl, C 6 -C 10 aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl, or halogenated fluorides such as fluorine, chlorine or bromine, dialkylamide, alkylarylamide, diarylamide, alkoxy or aryloxy or be conjugated to one or more aromatics or heteroaromatics. Examples of benzofused 5-membered heteroaryl groups are indole, indazole, benzofuran, benzothiophene, benzothiazole, benzoxazole and benzimidazole. Examples of benzo-fused 6-membered heteroaryl groups are chroman, benzopyran, quinoline, isoquinoline, cinoline, phthalazine, quinazoline, quinoxaline, 1,10-phenanthroline and quinolizine. Nomenclature and numbering of heterocycles based on Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979. Heterocycles / heteroaromats are preferably conjugated to the cyclopentadienyl backbone via the CC double heterocycle / heteroaromat.

Heterocycles / heteroaromats having one heteroatom are preferably 2,3- or b-conjugated.

[0051] Cp cyclopentadienyl systems having a fused heterocycle are, for example, thiapentalene, 2-methylthiapentalene, 2-ethylthiapentalene, 2-isopropylthiapentalene, 2-n-butylthiapentalene, 2-tert-butyl-thiapentalene, 2-trimethylphenylthilyl 2-naphthylthiapentalene, 3-methylthiopentalene, 4-phenyl-2,6-dimethyl-1-thiopentalene, 4-phenyl-2,6-diethyl-1-thiopentalene, 4-phenyl-2,6-diisopropyl-1-thiopentalene, 4-phenyl- 2,6-di-n-butyl-1-tiopentalen, 4-phenyl-2,6-dithrimethylsilyl-1-thiopentalene, azapentalene, 2-methylazapentalene, 2-ethylazapentalene, 2-isopropyl azapentalene, 2-n-butylazapentalene, 2-trimethylsilylazapentalene, 2-phenylazapentalene, 2-naphthyl phenyl 2.5-dimethyl-1-azapentalene, 1-phenyl-2,5-diethyl-1-azapentalene, 1-phenyl-2,5-di-n-butyl-1-azapentalene, 1-phenyl-2,5- di-tert-butyl-1-azapentalene, 1-phenyl-2,5-di-trimethylsilyl-1-azapentalene, 1-tert-butyl-2,5-dimethyl-1-azapentalene, oxapentalene, phosphapentalene, 1-phenyl-2,5-dimethyl-1-phosphapentalene, 1-phenyl 2.5-diethyl-1-phosphapentalene, 1-phenyl-2,5-di-n-butyl-1-phosphapentalene, 1-phenyl-2, 5-di-tert-butyl-1-phosphapentalene, 1-phenyl-2,5-di-trimethylsilyl-1-phosphapentalene, 1-methyl-2,5-dimethyl-1-phosphapentalene, 1-tert-butyl-2,5-dimethyl- 1-phosphapentalene, 7-cyclopenta- [1,2] thiophene [3,4] cyclopentadiene or 7-cyclopenta [1,2] pyrrolo [3,4] cyclopentadiene.

[0052] In further preferred Cp cyclopentadienyl systems, four R substituents^1A-R^4A, i.e. two pairs of vicinal substituents, form two heterocycles, in particular heteroaromatic. Heterocyclic systems are the same as those described above.

[0053] Cp cyclopentadienyl systems having two conjugated heterocycles are, for example, 7-cyclopentadithiophene, 7-cyclopentadipyrole or 7-cyclopentadiphosphol.

[0054] The synthesis of such cyclopentadienyl systems having a fused heterocycle is described, for example, in WO 98/22486, mentioned above. The "metalorganic catalysts for synthesis and polymerization", Springer Verlag 1999, Ewen et al., P. 150 further describes the synthesis of these cyclopentadienyl systems.

[0055] Particularly preferred R substituents^1A-R^4A are the carboorganic substituents described above and the carboorganic substituents that form the cyclic condensed ring system, i.e. together with the E backbone^1A-E^5A-cyclopentadienyl, preferably a C5cyclopentadienyl backbone, form, for example, an unsubstituted or substituted indenyl, benzindenyl, phenantrenylyl, fluorenyl or tetrahydroindenyl system as well as, in particular, their preferred embodiments.

[0056] Examples of such cyclopentadienyl systems (without the -ZA- group, which is preferably located at the 1 position) are 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3isopropylcyclopentadienyl, 3-tert-butylcyclopentadienyl, dialkylalkylcyclopentadienyl, dimethylcyclopentadienyl, or 3-methyl-5-tert-butylcyclopentadienyl, trialkylcyclopentadienyl such as 2,3,5-trimethylcyclopentadienyl or tetraalkyl-cyclopentadienyl such as

2,3,4,5-tetramethylcyclopentadienyl, and also indenyl, 2-methylindenyl, 2-ethylindenyl, 2-isopropylindenyl, 3-methylindenyl, benzindenyl and 2-methylbenzindenyl. The conjugated ring systems may further contain C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl portion and 6-20 carbon atoms in the aryl portion, NR^5A2, N (SiR^5A3)₂, OR^5A, OSiR^5A3 or SiR^5A3, e.g. 4-methylindenyl, 4-ethylindenyl, 4-isopropylindenyl, 5-methylindenyl, 4-phenylindenyl, 5-methyl-4-phenylindenyl, 2-methyl-4-phenylindenyl or 4-naphthylindenyl.

[0057] In a particularly preferred embodiment, one of the substituents R^1A-R^4A, preferably R^2A, is C6-C22-aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl portion and 6-20 carbon atoms in the aryl portion, preferably C6-C22-aryl such as phenyl, naphthyl, biphenyl, anthracenyl or phenantrenyl, where aryl may also be substituted

N-, P-, O or S-containing substituents, C1-C22-alkyl, C2-C22-alkenyl, halogens or haloalkyls or haloaryls having 1-10 carbon atoms, for example o-, m-, pmethylphenyl, 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-, pchlorophenyl, 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. Substituents containing N-, P-, Oalbo S-, C1-C22-alkyl, C2-C22-alkenyl, halogens or haloalkyls or haloaryls having 1-10 carbon atoms as substituents on the aryl substituent are preferably located in the para position relative to the ring bond cyclopentadienyl. The aryl substituent may be bonded in the vicinal position relative to the -ZA substituent or the two substituents are located relative to each other at positions 1,3 in the cyclopentadienyl ring. -Z-A1 and the aryl substituent are preferably present at positions 1,3 relative to each other in the cyclopentadienyl ring.

[0058] As with metallocenes, monocyclopentadienyl complexes (A1) may be

Chiral. Thus, one of the R substituents^1A-R^4A the cyclopentadienyl skeleton may have one or more chiral centers, or the Cp cyclopentadienyl system itself may be enantiomedic such that chirality is only induced when it is associated with the M transition metal (for formalism regarding chirality in cyclopentadienyl compounds, see R. Halterman, Chem. Rev 92, (1992), 965-994).

[0059] The Z bridge between the Cp cyclopentadienyl system and the uncharged donor A is a divalent organic bridge (k = 1), which preferably consists of carbon- and / or silicon- and / or boron-containing bridge members. The activity of the catalyst may be affected by a change in the binding length between the cyclopentadienyl system and A. Z is preferably linked to the cyclopentadienyl backbone next to the conjugated heterocycle or conjugated aroma. Thus, if the heterocycle or aroma is condensed at the 2,3 positions of the cyclopentadienyl skeleton, then Z is preferably located at the 1 or 4 position of the cyclopentadienyl skeleton.

[0060] Possible carbonorganic substituents R^6A-R^11A on the Z bond are, for example, the following: hydrogen, C 1 -C 20 -alkyl, which may be linear or branched, e.g. 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, a 5- to 7-membered cycloalkyl which may in turn contain a C6-C10 aryl group as a substituent, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C20-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g., vinyl, 1-allyl, 2- allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C20-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphen-1, 2,3,4-, 2, 3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphen-1-yl or arylalkyl which may be substituted by further alkyl groups, e.g. , benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where two R^6A to R.^11A they may also be combined to form a 5- or 6-membered ring, for example cyclohexane, and R substituents^6A-R^11A they may also be substituted with halogens such as fluorine, chlorine or bromine, e.g. pentafluorophenyl or bis-3,5-trifluoromethylphen-1-yl and alkyl or aryl.

12A 12A [0061] Substituents R^12A in SiR organosilicon substituents^12A3 may be the same substituents as those listed above for R^6A-R^11Awhere two R substituents^12A they can also be combined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl, butyl dimethylsilyl, tributylsilyl, tritert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. Preferred substituents for R^6A-R^11A are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, nheptyl, n-octyl, benzyl, phenyl, ortho-dialkyl- or dichloro-substituted phenyls , trialkyl- or trichlorosubstituted phenyls, naphthyl, biphenyl and anthranyl.

[0062] In particular preferred R substituents^6A to R.^11A are hydrogen, C 1 -C 20 -alkyl which may be linear or branched, e.g. 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, C6-C20-aryl which may be further substituted with alkyl groups, e.g. 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 which

EP 1 753 791 B1 can be substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl where two R substituents^6Ato R.^11A they can also be combined to form a 5- or 6-membered ring, for example cyclohexane, and R substituents^6A-R^2B they may also be substituted with halogens such as fluorine, chlorine or bromine, in particular fluorine, e.g. pentafluorophenyl or bis-3,5-trifluoromethylphen-1-yl and alkyl or aryl. Particularly, methyl, ethyl, 1-propyl, 2-isopropyl, 1-butyl, 2-tert-butyl, phenyl and pentafluorophenyl are preferred.

[0063] Z is preferably a -CR group^6AR^7A-, -SiR^6AR^7A-, in particular -Si (CH3) 2-, -CR^6AR^7ACR^8AR^9A-, SiR^6AR^7ACR^8AR^9A- either substituted or unsubstituted 1,2-phenylene and in particular -CR^6AR^7A. Preferred embodiments of R substituents^6A to R.^11A the above described are likewise preferred embodiments. -CR is preferred^6AR^7A- being a group -CHR^6A-, -CH2- or -C (CH3) 2-.

[0064] The -SiR group^6AR^7A - in -L^1AR^6AR^7ACR^8AR^9A- may be associated with the cyclopentadienyl system or A. This group is SiR^6AR^7A- or its preferred embodiment is preferably associated with Cp.

[0065] k has a value of 0 or 1; in particular, k is 1 or, when A is unsubstituted, substituted or fused, the heterocyclic ring system may also be 0. Preferred k is 1.

[0066] A is a non-charged donor containing an atom of group 15 or 16 of the periodic table, preferably one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus, preferably nitrogen and phosphorus. The donor functional group in A can be intermolecular or intramolecular to metal M^AND. Donor wA is preferably intermolecularly bound to M. Possible donors are uncharged groups containing an element from group 15 or 16 of the periodic table, e.g., amine, imine, carboxamide, carboxylic acid ester, ketone (oxo), ether, thioketone, phosphine, phosphite , phosphine oxide, sulfonyl, sulfonamide or unsubstituted, substituted or conjugated heterocyclic ring systems. Attachment of an Ado cyclopentadienyl and Z substituent can be carried out synthetically by, for example, a method analogous to that described in WO 00/35928. [0067] A is preferably a group selected from -OR^13A-, -SR^13A, -NR^13AR^14A, -PR^13AR^14A-. -C = NR^13Aand unsubstituted, substituted or fused heteroaromatic ring systems, in particular -NR^13AR^14A-, -C = NR^13A- and unsubstituted, substituted or fused heteroaromatic ring systems.

[0068] Each of R^13A and R^14A, independently of one another, is hydrogen, C1-C20-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, nheptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-to 7 - a cycloalkyl group which may in turn contain a C6-C10 aryl group as a substituent, e.g. which double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6C20-aryl which may be substituted by further alkyl groups, e.g., 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 which has from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and may be substituted by further alkyl groups, e.g., benzyl, o-, m- , pmethylbenzyl, 1- or 2-ethylphenyl or SiR^15A3, where organic substituents R^13A-R^14A they can also

May be substituted by halogens such as fluorine, chlorine or bromine or nitrogen containing groups and further C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR group^15A3 and two vicinal substituents R^13A-R^14A they may also be joined to form a five- or six-membered ring and each of the R substituents^15A, independently of each other, is hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl or alkylaryl having from 1 15A to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two substituents R^15A they may also be joined to form a five or six membered ring.

[0069] NO^13AR^14A is an amide substituent. It is preferably a secondary amide such as dimethylamide, N-ethylmethylamide, diethylamide, N-methylpropylamide, N-methylisopropylamide, Netylisopropylamide, dipropylamide, diisopropylamide, N-methylbutylamide, N-ethylbutylamide, N-methyl-tert-butylamide, N-tert-butyl dibutylamide, di-sec-butylamide, diisobutylamide, tert-amyl-tert-butylamide, dipentylamide, N-methylhexylamide, dihexylamide, tert-amyl-tertoctylamide, dioctylamide, bis (2-ethylhexyl) amide, didecylamide, N-methyloctadecylamide, N-methylcyclohexylamide, N-ethylcyclohexylamide, N-isopropylcyclohexylamide, N-tert-butylcyclohexylamide, dicyclohexylamide, pyrrolidine, piperidine, hexamethylenimine, decahydroquinoline, N-diphenylamide, or N-methylamine

13A 13A [0070] In the imino group, -C = NR^13A, R^13A is preferably a C6-C20-aryl substituent which may be substituted by - further alkyl groups, e.g. 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. [0071] A is preferably an unsubstituted, substituted or fused heteroaromatic ring system which may contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus in addition to ring carbons. Examples of 5-membered heteroaryl groups that can contain from one to four nitrogen atoms or from one to three nitrogen atoms and / or a sulfur or oxygen atom as ring members in addition to carbon atoms are 2-furyl, 2-thienyl, 2-pyrrolyl , 3-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2 -imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl and 1,2,4-triazol-3-yl. Examples of 6-membered heteroaryl groups that can contain from one to four nitrogen atoms and / or a phosphorus atom are 2-pyridinyl, 2-phosphabenzenyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3, 5-triazine-2-yl and 1,2,4-triazine-3-yl, 1,2,4-triazine-5-yl and 1,2,4-triazine-6-yl. The 5-membered and 6-membered heteroaryl groups may also be substituted by C1-C10-alkyl, C6-C10-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl portion and 6-10 carbon atoms in the aryl portion, trialkylsilyl or such halogens like fluorine, chlorine or bromine or be coupled with one or more aromas or heteroaromatics. Examples of benzo-fused 5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumararonyl, 7-coumararonyl, 2-thionaftenyl, 7-thionaftenyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl and 7-benzimidazolyl. Examples of benzo-fused 6-membered heteroaryl groups are 2-quinolyl,

8-quinolyl, 3-cynolyl, 8-cynolyl, 1-phthalazine, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl, 5-quinoxalyl, 4-acrydyl, 1-phenanthridil and 1-phenynyl. Nomenclature and numbering of heterocycles based on L.Fieser and M. Fieser, Lehrbuch der organischen Chemie, revised 3rd edition, Verlag Chemie, Weinheim 1957.

[0072] Of these heteroaromatic systems, unsubstituted are particularly preferred,

Substituted and / or conjugated six-membered heteroaromatics having 1, 2, 3, 4 or 5 nitrogen atoms in the heteroaromatic part, in particular substituted and unsubstituted 2-pyridyl or 2-quinolyl. A is therefore preferably a group of formula (IV),

<img file="PL1753791T3_D0003.tif" />

where

Each E^6A-E^9A, independently of each other, means carbon or nitrogen,

Each R^16A-R^19A, independently of each other, is hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR^20A3, where organic substituents R^16A-R^19A they may also be substituted with halogens or nitrogen and further C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR^20A3 and two vicinal R substituents^16A-R^19A or R^16A and Z may also be combined to form a five or six membered ring and each of the R substituents^20A is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl substituent and 6-20 carbon atoms in the aryl substituent and two R substituents^20A they can also be combined to form a five- or six-membered ring and p is 0 when E^6A-E^9A is nitrogen and means 1 when E^6A-E^9A is coal.

[0073] In particular, 0 or 1 E^6A-E^9A means nitrogen and the residue is carbon. A is particularly preferably 2-pyridyl, 6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl, 3- pyridazin, 4-pyrimidyl, 2-pyrazinyl, 6-methyl-2-pyrazinyl, 5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethyl-pyrazinyl, 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.

[0074] For ease of synthesis, preferred combinations of Z and A are those in which Z is unsubstituted or substituted 1,2-phenylene and A is NR^16AR^17A and those wherein Z is CHR^6A-, -CH2-, -C (CH3) 2 or -Si (CH3) 2- and A is unsubstituted or substituted 2-quinolyl or unsubstituted or substituted 2-pyridyl. Systems without a Z bridge, in which k is 0, are also in particular very easy to obtain. A is preferably unsubstituted or 2A substituted 8-quinolyl in this case. In addition, when k is 0, R^2A is preferably C6-C22aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl portion and 6-20 carbon atoms in

Aryl, preferably C6-C22-aryl such as phenyl, naphthyl, biphenyl, anthracenyl or phenantrenyl, where aryl can also be substituted with substituents containing N-, P-, O- or S-, C1-C22alkyl, C2-C22-alkenyl, halogens or haloalkyls or haloaryls having 1-10 carbon atoms.

[0075] The preferred embodiments described above for the variables are also preferred in these preferred combinations.

[0076] M^AND is a metal selected from the group consisting of titanium in oxidation state 3, vanadium, chromium, molybdenum and tungsten, preferably titanium in oxidation state 3 and chromium. Particularly, chromium is preferred at oxidation levels 2, 3 and 4, in particular 3. Metal complexes, in particular chromium complexes, can be obtained simply by reacting with appropriate metal salts, e.g., metal chlorides, with an anionic ligand (e.g. , using a method analogous to the examples in DE 197 10615).

[0077] Of the suitable monocyclopentadienyl complexes (A1), those of formula Cp-Ym-M are preferred^ANDXn (V) where the variables Cp, Y, A, m and M^AND are as defined above and their preferred embodiments are also preferred here, and:

Every X^AND, independently of each other, means fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C20-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the part aryl, NR^21AR^22A, OR^21A, SR^21A, SO3R^21A, OC (O) R^21A, CN, SCN, β-diketonate, CO, BF4^-, PF6or non-coordinate spatial anion or two X substituents^AND form a substituted or unsubstituted diene ligand, in particular 1,3-diene ligand, and X substituents^AND can be connected with each other,

21A 22A each with R^21A-R^22A is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part,

23A 21A 22A

SiR^23A3, where organic substituents R^21A-R^22A they can also be substituted with halogens either

21A 22A nitrogen and oxygen containing groups and two R substituents^21A-R^22Athey can also be combined to form a five- or six-membered ring,

23A each of the R substituents^23A is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 atoms in the carbon part

23A aryl and two R substituents^23A they can also be combined to form a five- or six-membered ring and is 1, 2 or 3.

[0078] Embodiments and preferred embodiments described above for Cp, Y, Z, A, m and M^ANDcan also be used alone and in combination with these preferred monocyclopentadienyl complexes.

[0079] Ligands X^AND result, for example, from the selection of the appropriate starting metal compounds used in the synthesis of monocyclopentadienyl complexes, but may also be changed later. Possible X ligands^AND there are, in particular, halogens such as fluorine, chlorine, bromine or iodine, especially chlorine. Alkyl substituents such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl are also preferred X ligands^AND. Further ligands X^AND which may be mentioned, purely by way of example and not exhaustively, are trifluoroacetate, BF4^- , PF6^- and also weakly coordinating or non-coordinating anions

EP 1 753 791 B1 (cf., e.g., S. Strauss in Chem. Rev. 1993, 93, 927-942), e.g., B (C6F5) 4^-.

[0080] Amides, alkoxylates, sulfonates, carboxylates and β-diketonates are also in particular

A 21A 22A useful ligands X^AND. Change of substituents R^21A and R^22A it enables, for example, the exact adjustment of properties such as solubility. Possible carbonorganic substituents

21A 22A

R^21A-R^22A are, for example, the following: C 1 -C 20 -alkyl which can be linear or branched, e.g. 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, a 5- to 7-membered cycloalkyl which may in turn contain a C6-C10 aryl group as a substituent, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C20-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl , 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C20-aryl which may be substituted by further alkyl groups and / or substituents containing N- or O-, e.g. 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, 2-methoxyphenyl, 2-N, N-dimethylaminophenyl or arylalkyl, where arylalkyl may be substituted further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 121A 22A or 2-ethylphenyl, where R^21A it can also be attached to R^22A to form a 5- or 6-membered 21A 22A ring and R substituents^21A-R^22A they can also be substituted with halogens such as

23A 23A fluorine, chlorine or bromine. Possible substituents R^23A in SiR organosilicon substituents^23A3 are those 21A 22A 23A substituents themselves as those mentioned above for R^21A-R^22Awhere two R^23A they can also be combined to form a 5- or 6-membered ring, e.g., trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. The use of C 1 -C 10 -alkyl such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and also vinyl is preferred

21A 22A allyl, benzyl and phenyl as substituents R^21A and R^22A. Some of these substituted X ligands are particularly advantageously used since they can be obtained from cheap and readily available substrates. Thus, a particularly preferred embodiment is that in which X^AND is dimethylamide, methoxylate, ethoxylate, isopropoxylate, phenoxylate, naphthoxylate, triflate, ptoluenesulfonate, acetate or acetylacetonate.

[0081] Number n of X ligands^AND depends on the oxidation state of the transition metal M^AND. The number n may therefore not be given in general terms. Oxidation degree of transition metals M^AND in catalytically active complexes it is usually known to those skilled in the art. Chromium, molybdenum and tungsten are very likely to be present in the +3 oxidation state, vanadium in the +3 or +4 oxidation state. However, it is also possible to use complexes whose oxidation state does not correspond to that of an active catalyst. Such complexes can therefore be appropriately reduced or oxidized by means of suitable activators. It is preferable to use chromium complexes on the + 3 oxidation state and titanium complexes on the 3 oxidation state.

[0082] Preferred monocyclopentadienyl (A1) complexes of this type are 1- (8-quinolyl) -3-phenylcyclopentadienyl-chromium (III) dichloride, 1- (8-quinolyl) -3- (1-naphthyl) cyclopentadienyl-chromium (III) dichloride, 1- (8) dichloride -quinolyl) -3- (4-trifluoromethylphenyl) cyclopentadienylchrome (III), 1- (8-quinolyl) -2-methyl-3-phenylcyclopentadienylchrome (III) dichloride, 1- (8-quinolyl) -2-methyl-3 dichloride - (1-naphthyl) cyclopentadienylchromium (III), 1- (8-quinolyl) -218 dichloride

Methyl-3- (4-trifluoromethylphenyl) cyclopentadienylchromium (III), 1- (8-quinolyl) -2-phenylindenylchromium (III) dichloride, 1- (8-quinolyl) -2-phenylbenzindenylchromium (III) dichloride, dichloride 1- (8- (2-methylquinolyl)) - 2-methyl-3-phenylcyclopentadienylchromium (III), 1- (8- (2-methylquinolyl)) -2-phenylindenylchromium (III) dichloride, 1- (2-pyridylmethyl) -3-dichloride phenylcyclopentadienylchrome (III), 1- (2-pyridylmethyl) -2-methyl-3-phenylcyclopentadienylchrome (III) dichloride, 1- (2-quinolylmethyl) -3-phenylcyclopentadienylchromium dichloride, 1- (2-pyridylethyl) -3-phenylcyclopentadienylchromium dichloride, 1- (2-pyridyl-1-methylethyl) -3-phenylcyclopentadienylchloryl-1-pyridylmethyl) ) -3-phenylcyclopentadienyl-chromium, 1- (2-pyridylmethyl) indenylchromium (III) dichloride, 1- (2-quinolylmethyl) indenylchromium dichloride, 1- (2-pyridylethyl) indenylchromium dichloride, 1 (2-pyridylethyl dichloride) indenylochromu, 1- (2-Pyridyl-1-phenylmethyl) indenylchromium dichloride, 5 - [(2-pyridyl) methyl] -1,2,3,4-tetramethylcyclopentadienylchromium dichloride and 1- (8- (2-methylquinolyl)) - 2-methylbenzindenyl dichloride -chromu (III).

[0083] The synthesis of such functional groups of cyclopentadienyl ligands is known. Various synthetic routes to obtain these complexing ligands are described in, for example, 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.

[0084] The synthesis of such complexes can be carried out by known methods, by reacting suitably substituted cyclic hydrocarbon anions with preferred halogens of titanium, vanadium or chromium. An example of suitable preparative methods is described, for example, in Journal of Organometallic Chemistry, 369 (1989), 359-370 and in EP-A-1212333.

[0085] In particular, suitable hafnocenes (A2) are hafnium complexes of general formula (VI)

<img file="PL1753791T3_D0004.tif" />

in which substituents and coefficients have the following meanings:

_B

X^B is fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C15-aryl, alkylaryl 6B having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the part aryl, -OR^6B6B 7B B or -NR^6BR^7B, or two substituents X^B form a substituted or unsubstituted diene ligand, w _B in particular 1,3-diene ligand, and X substituents^B are identical or different and can be combined with each other,

1B 5B 1B 5B each with E^1B-E^5B is carbon or no more than one E^1B to E^5B is phosphorus or nitrogen, preferably carbon,

T is 1, 2 or 3 and is, depending on the Hf valence, such that the metallocene complex of general formula (VI) is uncharged, where

6B 7B each with R^6B and R^7B is C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each of them has from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part and 1B 5B each R^1B to R.^5B is, independently of each other, hydrogen, C1-C22-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may in turn contain C1-C10-alkyl groups as substituents, C2-C22-alkenyl, C6C22-aryl, arylalkyl having from 1 up to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR^8B2, N (SiR^8B3)₂, OR^8B, OSiR^8B3, SiR^8B3, where organic substituents R^1B-R^5B may 1B 5B also be substituted with halogens and / or two R substituents^1B-R^5B, in particular vicinal substituents, may also be combined to form a five-, six- or seven-membered ring, and / or two vicinal substituents R^1D-R^5D they can be combined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S, where R^8B may be identical or different and each of them may be C1-C10-alkyl, C3C10-cycloalkyl, C6-C15-aryl, C1-C4-alkoxy or C6-C10-aryloxy and

FROM^1B means XB or

<img file="PL1753791T3_D0005.tif" />

where

9B 13B each of the substituents R^9B to R.^13B is, independently of one another, hydrogen, C1-C22-alkyl, a 5- to 7-membered cycloalkyl or cycloalkenyl which may in turn contain C1-C10-alkyl groups as substituents,

C2-C22-alkenyl, C6-C22-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6-21 carbon atoms in the aryl part, NR^14B2, N (SiR^14B3)₂, OR^14B, OSiR^14B3, SiR^14B3, where organic substituents 9B 13B 9B 13B

R^9B-R^13B they may also be substituted with halogens and / or two R substituents^9B-R^13B, in particular vicinal substituents, may also be combined to form a five-, six- or 9B 13B seven-membered ring, and / or two vicinal substituents R^9B-R^13B they can be combined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S, where

14B substituents R^14B are identical or different and each represents C1-C10-alkyl, C3-C10-cycloalkyl,

C6-C15-aryl, C1-C4-alkoxy or C6-C10-aryloxy,

6B 10B 6B 10B each with E^6B-E^10B is carbon or no more than one E^6B to E^10B is phosphorus or nitrogen, 4B 1B 15B 1B preferably carbon, or where R is^4B and Z^1B together they form a group -R^15B-AND^1B- where R^15B means

EP 1 753 791 B1

<img file="PL1753791T3_D0006.tif" />

<img file="PL1753791T3_D0007.tif" />

BR =^16B= BNR^16BR^17B, = AlR^16B, -Ge-, -Sn-, -O-, -S-, = SO, = SO₂, = NR^16B, = CO, PR^16B or = P (O) R^16Bwhere

16B 21B

R^16B-R^21B are identical or different and each represents a hydrogen atom, a halogen atom, a trimethylsilyl group, a C1-C10 alkyl group, a C1-C10 fluoroalkyl group, a C6-C10 fluoroaryl group,

C6-C10-aryl, C1-C10-alkoxy, C1-C15-alkylaryloxy, C2-C10-alkenyl, C7C40-arylalkyl, C8-C40-arylalkenyl or C7-C40-alkylaryl or two adjacent substituents together with atoms connecting them to form a saturated or unsaturated ring having from 4 to carbon atoms, and 2B 4B each with M^2B-M^4B is silicon, germanium or tin, or preferably silicon,

AND^1B means -O -, - S-,

<img file="PL1753791T3_D0008.tif" />

= O, = S, = NR^22B, -OR^22B, -NR^22B2, -PR^22B or unsubstituted, substituted or fused heterocyclic ring system wherein 22B each of R^22B is, independently of one another, C1-C10-alkyl, C6-C15-aryl, C3-C10 cycloalkyl, C7-C18-alkylaryl or Si (R^23B)3,

23B

R^23B is hydrogen, C1-C10-alkyl, C6-C15-aryl, which may in turn contain C1-C4-alkyl as substituents or C3-C10-cycloalkyl,

EP 1 753 791 B1

1B v is 1 or when A^1B is unsubstituted, substituted or fused heterocyclic ring system may also be 0 4B 12B 15B or where R^4B and R^12B together they form a group -R^15B-.

1B 15B [0086] A^1B maybe, for example, together with the R bridge^15B, form an amine, ether, thioether or phosphine. 1B

However, A.^1B it may also be an unsubstituted, substituted or fused aromatic heterocyclic ring system that may contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus in addition to ring carbons. Examples of 5-membered heteroaryl groups that may contain from one to four nitrogen atoms and / or sulfur or oxygen atoms as ring members in addition to carbon atoms 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, 5oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl and 1,2,4-triazol-3-yl Examples of 6-membered heteroaryl groups that can contain from one to four nitrogen atoms and / or a phosphorus atom are 2-pyridinyl, 2-phosphobenzenyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5- triazine-2-yl and 1,2,4-triazine-3-yl, 1,2,4-triazine-5-yl and 1,2,4-triazine-6-yl. The 5-membered and 6-membered heteroaryl groups may also be substituted by C 1 -C 10 -alkyl, C 6 -C 10 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl portion and 6-10 carbon atoms in the aryl portion, trialkylsilyl or halogens such as fluorine, chlorine or bromine or be conjugated to one or more aromas or heteroaromatics. Examples of benzofused 5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumararonyl, 7-coumararonyl,

2-thionaftenyl, 7-thionaftenyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl and 7-benzimidazolyl. Examples of benzo-fused 6-membered heteroaryl groups are 2-quinolyl, 8-quinolyl, 3-cininyl, 8-cinolyl,

1-phthalazine, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl, 5-quinoxalil, 4-acrydyl, 1-phenanthridil and 1-phenyzyl.

Nomenclature and numbering of heterocycles based on L.Fieser and M. Fieser, Lehrbuch der organischen

Chemie, 3rd Revised Edition, Verlag Chemie, Weinheim 1957.

_B [0087] Substituents X^B in general formula (XIV) they are preferably identical, and are preferably fluorine, chlorine, bromine, C1-C7-alkyl or aralkyl, in particular chlorine, methyl or benzyl. [0088] The synthesis of such complexes can be carried out by known methods, with the beneficial reaction of suitably substituted cyclic hydrocarbon anions with hafnium halogens. Examples of suitable preparative methods are described, for example, in Journal of Organometallic Chemistry, 369 (1989), 359-370.

[0089] Hafnocenes can be used in the form of Rac or pseudo-Rac. The term pseudo-Rac refers to complexes in which two cyclopentadienyl ligands are in a Rac arrangement relative to each other when all other substituents of the complex are omitted.

[0090] Examples of suitable hafnocenes (A2) are, amongst others, [0091] methylene bis (cyclopentadienyl) hafnium dichloride, methylene bis (3-methylcyclopentadienyl) hafnium dichloride, methylene bis (3-n-butylcyclopentadienyl) hafniene dichloride, methylene chloride methylene bis (tetrahydroindenyl) hafnium, isopropyloidobenic (cyclopentadienyl) hafnium dichloride, isopropyloidenobis (3-trimethylsilylcyclopentadienyl) hafnium dichloride, isopropylenebis (3-methylcyclopentadienyl) hafnium dichloride, isopropylenebis (3-n-butylcyclopentadienyl) hafnium dichloride, isopropylidene-bis dichloride (322

EP 1 753 791 B1 fenylocyklopentadienylo) hafnium dichloride izopropyloidenobis (indenyl) hafnium dichloride izopropyloidenobis (tetrahydroindenyl) hafnium dichloride, dimethylsilanediylbis (cyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, ethylenebis (cyclopentadienyl ) hafnium, ethylene bis (indenyl) hafnium dichloride, ethylene bis (tetrahydroindenyl) hafnium dichloride, dichloride, tetramethylethylene-9-fluorenylocyklopentadienylohafnu, dimethylsilandiylbis (tetramethyl pentadienylo) hafnium dichloride, dimethylsilanediylbis (3trimetylosililocyklopentadienylo) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-n-butylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-tert-butyl 5-methylcyclopentadienyl) hafnium, dimethylsilanediylbis (3-tert-butyl-5-ethylcyclopentadienyl) hafnium dichloride, dimethylsilandiylbis (2-methylindenyl) hafnium dichloride, dimethylsilanediylbis (2-isopropyl-indenyl) hafnium dichloride, dimethylsilanediylbis (2-tertbutyloindenylo) hafnium dibromide dietylosilanodiylobis (2-methylindenyl) hafnium dichloride, dimethylsilanediylbis (3-methyl-5-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-ethyl-5-isopropylcyclopentadienyl) hafnium, dimethylsilanediylbis (2-ethylindenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-4,5-benzindenyl) hafnium dichloride, dimethylsilanediylbis (2-ethyl-4,5-benzindenyl) hafnium dichloride, methylphenylsilanediylbis (2-methyl-4,5-benzindenyl) hafnioblene-dichloro-ethylene dichloride 4,5-benzindenyl) hafnium, diphenylsilanediylbis (2-methyl-4,5-benzindenyl) hafnium dichloride, diphenylsilanediylbis (2-ethyl-4,5-benzindenyl) hafnium dichloride, diphenylsilanediylbis (2-methylindenyl) dichloride dimethylsilanediylbis (2-methyl-4-phenylindenyl) hafnium dichloride, dimethylsilanediylbis (2-ethyl-4-phenylindenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-4- (1-naphthyl) ethylisilyl) ethylenylsylene) (1-naphthyl) indenyl) hafnium, dimethylsilanediylbis (2-propyl-4- (1-naphthyl) indenyl) hafnium dichloride, dimethylsilanediylbis (2-4-butyl-4- (1-naphthyl) indenyl) hafniyl dichloride di dimethyl dichloride (2-propyl-4- (9-phenanthryl) indenyl) hafnium dimethylsilanediylbis (2-methyl-4-isopropylindenyl) hafnium dichloride, dimethylsilanediylbis (2,7-dimethyl-4-isopropylindenyl) hafnium dichloride, dimethylsilanediylis (2-methyl-4,6-diisopropylindiyl) ethylisyldisyl) ethyl -trifluoromethylphenyl] indenyl) hafnium, dimethylsilanediylbis (2-methyl-4- [3 ', 5'-dimethylphenyl] indenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-4- [4'-tert-butylphenyl] indenyl) dichloride diethylsilanediylbis (2-methyl-4- [4'-tert-butylphenyl] indenyl) hafnium dichloride, dimethylsilanediylbis (2-ethyl-4- [4'-tert-butylphenyl] indenyl) hafnium dichloride, dimethylsilanediylbis (2-propyl-diyl) tert-butylphenyl] indenyl) hafnium, dimethylsilanediylbis (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) hafnium dichloride, dimethylsilanediyl (2-isopropyl-4-phenylindenyl) (2-methyl-4-phenylindenyl), dimethylsilanediyl (2-isopropo-4- (1-naphthyl) indenyl) (2-methyl-4- (1-naphthyl) indenyl) hafnium dichloride, dimethylsilanediyl (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) ( 2-methyl-4- [4'-tert-butylphenyl] indenyl) hafnium, dimethylsilanediyl (2-isopropyl-4- [4'-tertbutylphenyl] indenyl) (2-methyl-4- [1'-naphthyl] indenyl) hafnium dichloride and ethylene (2-isopropyl-4- [4'-tert-butylphenyl] indenyl) (2-methyl-4- [4'-tert-butylphenyl] indenyl) hafnium dichloride, and also the corresponding dimethyl hafnium compounds, monochloromono (alkylaryloxy) hafnium and di (alkylaryloxy) hafnium. Complexes can be

EP 1 753 791 B1 can be used in the form of flares, meso forms or mixtures thereof.

[0092] Of the hafnocenes of general formula (VI), those of formula (VII)

<img file="PL1753791T3_D0009.tif" />

are beneficial.

[0093] Of the compounds of formula (VII), those wherein BB are preferred

X^B is fluorine, chlorine, bromine, C1-C4-alkyl or benzyl, or two substituents X^B form a substituted or unsubstituted butadiene ligand, t is 1 or 2, preferably 2, each of R^1B to R.^5B means C1-C8-alkyl, C6-C6-aryl, NR^8B2, OSiR^8B3 or Si (R^8B) 3 and each of R^9B to R.^13B is hydrogen, C₁-C₈-alkyl or C₆-C₈-aryl, NR^14B2, OSiR^14B3 or Si (R^14B)₃1B 5B 9B 13B or in each case two R substituents^1B to R.^5B and / or R^9B to R.^13B together with ring C₅form an indenyl, fluorenyl or substituted indenyl or fluorenyl system.

[0094] Hafnocenes of formula (VII) in which the cyclopentadienyl substituents are identical are in particular preferred.

[0095] Examples of the corresponding compounds D) of formula (VII) in particular are, among others:

bis (cyclopentadienyl) hafnium dichloride, bis (indenyl) hafnium dichloride, bis (fluorenyl) hafnium dichloride, bis (tetrahydroindenyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, dichloromethane bis (ethylcyclopentadienyl) hafnium, bis (isobutylcyclopentadienyl) hafnium dichloride, bis (3-butenylcyclopentadienyl) hafnium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (1,3-di-tert-butylcyclopentadienyl) hafnium dichloride, bis (trifluoromethylcyclopentadienyl) hafnium dichloride, bis (tert-butylcyclopentadienyl) hafnium dichloride, bis (n-butylcyclopentadienyl) naphthylchloride, naphthylchloride) dimethylaminomethylcyclopentadienyl) hafnium, bis (1,3-dimethylcyclopentadienyl) hafnium dichloride, bis (1-n-butyl-3-methylcyclopentadienyl) hafnium dichloride, (cyclopentadienyl) (methylcyclopentadienyl) hafnium dichloride (cyclopentadienyl) (n-butylcyclopentadienyl) hafnium dichloride (methylcyclopentadienyl) (n-butylcyclopentadienyl) hafnium, (cyclopentadienyl) (1-methyl-3-n-butylcyclopentadiethylnaphthylnaphthylnaphthyl) naphthylchloride Further examples are suitable hafnocene compounds in which one or

Two chloride ligands were replaced by bromide or iodide.

[0096] Suitable catalysts B) are transition metal complexes with at least one general general ligand XV to XIX,

<img file="PL1753791T3_D0010.tif" />

where variables have the following meanings:

1C

E^1C is nitrogen or phosphorus, in particular nitrogen,

2C 4C each with E^2C-E^4C is, independently of one another, carbon, nitrogen or phosphorus, in particular carbon, 1C 3C each of R^1C-R^3C is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR^18C2, OR^18C, SiR^19C3, where organic substituents R^1C-R^3C they may also be 1C 3C substituted with halogens and / or two vicinal R substituents^1C-R^3C they can also be joined to form 1C 3C to form a five-, six- or seven-membered ring, and / or two vicinal substituents^1C-R^3C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S,

4C 7C each with R^4C-R^7C is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part,

18C 19C 4C 7C

NO^18C2, SiR^19C3, where organic substituents^4C-R^7C they may also be substituted with halogens and / or

4C 7C two geminal or vicinal substituents R^4C-R^7C they can also be combined to form a ring

4C 9C five-, six- or seven-membered and / or two geminal or vicinal R substituents^4C-R^9C are linked to form a five-, six- or seven-membered heterocycle containing at least one 6C 1C 1C atom from the group consisting of N, P, O and S, and when v is 0, R^6C is a bond with L^1C and / or R^1C is

2C 1C 2C binding with L^2C so that L^1C forms a double bond with the carbon atom containing R4C and / or L^2C

5C forms a double bond with the carbon atom containing R^5C,

2C 4C 2C 4C raises 0 when E^2C-E^4C is nitrogen or phosphoric acid when E^2C-E^4C means coal,

1C 2C each with L^1C-L^2C is, independently of each other, nitrogen or phosphorus, in particular nitrogen, each of R^8C-R^11C is, independently of one another, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR^18C2, OR^18C, SiR^18C3, where organic substituents R^8C-R^11C they can also be

Halogen substituted and / or two vicinal R substituents^8C-R^17C they may also be combined to form a five-, six- or seven-membered ring, and / or two vicinal R substituents^8C-R^17C are joined to form a five, six or seven membered heterocycle containing at least one atom from the group consisting of N, P, O and S,

12C 17C each with R^12C-R^17C is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the part

18C 18C 19C 12C 17C aryl, halogen, NR^18C2, OR^18C, SiR^19C3, where organic substituents R^12C-R^17C they may also be substituted with halogens and / or two vicinal R substituents^8C -R^17C they may also be combined to form a five-, six- or seven-membered ring, and / or two vicinal substituents^8C-R^17C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S, each of the factors v is, independently of each other, 0 or 1, _C each of the substituents X^C is, independently of each other, fluorine, chlorine, bromine, iodine, hydrogen, C1-C10alkyl, C2-C10-alkenyl, C⁶-C²⁰-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR¹⁸C2, OR^18C, SR^18C, SO3R^18C, OC (O) R^18C, CN, SCN, β-diketonate, CO, BF4^- , PF₆ or the spatial non-coordinating anion and the X substituents can be connected to each other, each of the R substituents^18C is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the part

19C 18C aryl, SiR^19C3, where organic substituents R^18C they may also be substituted with halogens or groups containing nitrogen- and oxygen- and two R substituents^18C they can also be combined to form a five- or six-member ring,

19C each of R substituents^19C is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the part

19C aryl, where organic substituents R^19C they may also be substituted with halogens or groups

19C containing nitrogen- and oxygen- and two R substituents^19C they can also be combined to form a five- or six-member ring, sma value of 1, 2, 3 or 4, in particular 2 or 3,

D is an uncharged donor and it has a value from 0 to 4, in particular 0, 1 or 2.

2C 4C 1C [0097] Three E atoms^2C to E^4C they can be identical or different in the molecule. If E^1C means phosphorus,

2C 4C 1C 2C then each of E^2C to E^4C is preferably carbon. If E^1C is nitrogen, then each of E^2C down

4C

E^4C preferably nitrogen or carbon, in particular carbon.

1C 3C 8C 17C [0098] Substituents R^1C-R^3C and R^8C-R^17C can vary widely. Possible 1C 3C 8C 17C carboorganic substituents R^1C-R^3C and R^8C-R^17C are, for example, the following -C1-C22-alkyl which may be linear or branched, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, e.g.entyl, n-hexyl, n- heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, a 5- to 7-membered cycloalkyl which may in turn contain a C1-C10-alkyl group and / or a C6-C10-aryl group as substituents, e.g. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C22-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g., vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl,

Cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C22-aryl which may be substituted by further alkyl groups, e.g., 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 which may be substituted by further alkyl groups, e.g., benzyl, o-, m-, p-methylbenzyl, 1- or 21C 3C 8C 17C ethylphenyl; where two R substituents^1C to R.^3C and / or two vicinal substituents R^8C-R^17C they can also

1C be joined to form a 5-, 6- or 7-membered ring and / or two of the vicinal R substituents^1C3C 8C 17C

R^3C and / or two of vicinal substituents R^8C-R^17C they can be combined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and

1C 3C 8C 17C

S and / or organic substituents R^1C-R^3C and / or R^8C-R^17C they may also be substituted with such halogens

1C 3C 8C 17C 18C like fluorine, chlorine or bromine. In addition, R^1C-R^3C and R^8C, R^17C may also be amino NR^18C2 or

19C 18C

N (SiR^19C3) 2, alkoxy or aryloxy OR^18C, e.g. dimethylamino, N-pyrrolidinyl, picolinyl, methoxy,

19C ethoxy or isopropoxy or halogen such as fluorine, chlorine or bromine. Possible substituents R^19C in 19C SiR organosilicon substituents^19C3 are the same carboorganic substituents as

1C 3C 19C described above for R^1C-R^3Cwhere two R^19C they can also be combined to form a 5- or ring

6-membered, e.g., trimethylsilyl, triethylsilyl, butyl dimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl,

2C 4C triphenylsilyl or dimethylphenylsilyl. These substituents may also be associated with E^2C-E^4C through oxygen or nitrogen, for example trimethylsilyloxy, triethylsilyloxy, butyl dimethylsilyloxy, tributylsilyloxy or tritert-butylsilyloxy.

1C 3C [0099] Preferred R substituents^1C-R^3C are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, nbutyl, 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. Particularly preferred organosilicon substituents are trialkylsilyl groups having from 1 to carbon atoms in the alkyl substituent, in particular trimethylsilyl groups.

12C 17C [0100] Preferred R substituents^12C-R^17C are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine,

13C 16C in particular hydrogen. In particular, each of R^13C and R^16C means methyl, trifluoromethyl, ethyl, npropyl, isopropyl, n-butyl, isobutyl, tertbutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinylallyl, benzyl, phenyl, fluorine, chloral or bromine and each of R^12C, R^14C, R^15C and R^17C means hydrogen.

[0101] Preferred R substituents^8C-R^11C are methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine. In particular, each of R^8C and R^10C is C1-C22-alkyl, which may also be substituted with halogens, in particular C1-C22-n-alkyl, which may also be substituted with halogens, e.g., methyl, trifluoromethyl, ethyl, n-propyl; n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl or halogen

9C 11C such as fluorine, chlorine or bromine and each of R^9C and R^11C is -halo, such as fluorine, chlorine or bromine. In particular, each R is preferred^8C and R^10C being C1-C22-alkyl, which may also be substituted with halogens, in particular C1-C22-n-alkyl, which may also be substituted with halogens, e.g., methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n- pentyl, n-hexyl, n-heptyl, n-octyl, vinyl and

9C 11C each with R^9C and R^11C is halogen such as fluorine, chlorine or bromine.

[0102] In particular, R^12C, R^14C, R^15C and R^17C are identical, R^13C and R^16C are identical, R^9C and R^11C are identical and R^8C and R^10C are identical. This is also preferred in the preferred described above

EP 1 753 791 B1 embodiments.

4C 7C [0103] Substituents R^4C-R^7C, also, can vary widely. Possible 4C 7C carboorganic substituents R^4C-R^7C are, for example, the following: C1-C22-alkyl, which may be linear or branched, e.g., 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 may in turn contain a C1-C10-alkyl group and / or a C6-C10-aryl group as a substituent, e.g., cyclopropyl, cyclobutyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C22-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g., vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C22-aryl which may be substituted with further alkyl groups, e.g., phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, 2 , 3,4-, 2,3,5-, 2,3,6, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl or arylalkyl, where arylalkyl may be substituted with further

4C alkyl groups, e.g., benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where two R^4C7C to R.^7C they can also be combined to form a 5-, 6- or 7-membered ring and / or two 4C 7C geminal R substituents^4C-R^7C they can be combined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S and / or 4C 7C organic R substituents^4C-R^7C they may also be substituted with halogens such as fluorine, chlorine or bromine. 4C 7C 18C 19C

In addition, R^4C-R^7C may be amine NR^18C2 or N (SiR^19C3)₂, for example dimethylamine, N-pyrrolidinyl 19C 19C or picolinyl. Possible substituents R^19C in SiR organosilicon substituents^19C3 are the 1C 19C carboorganic substituents themselves as described above for R^1C-R3C, where two R^19C they can also be combined to form a 5- or 6-membered ring, e.g., trimethylsilyl, trimethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These 19C SiR substituents^19C3 they can also be bonded through nitrogen to carbon containing them. When v 6C 1C 7C 2C 1C is 0, R^6C means bond to L^1C and / or R^7C is a bond to L^2Cso that L^1C forms a 4C 2C double bond with a carbon atom containing R^4C and / or L^2C forms a double bond with the 5C carbon atom containing R^5C.

4C 7C [0104] Preferred R substituents^4C-R^7C 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. 16C NR amide substituents are also preferred^16C2, in particular secondary amides, such as dimethylamide, Netylmethylamide, diethylamide, N-methylpropylamide, N-methylisopropylamide, N-ethylisopropylamide, dipropylamide, diisopropylamide, N-methylbutylamide, N-ethylbutylamide, N-methyl-tert-butylamide, Ntertamide , dibutylamide, di-sec-butylamide, diisobutylamide, tert-amyl-tert-butylamide, dipentylamide, N-methylhexylamide, dihexylamide, tert-amyl-tert-octylamide, dioctylamide, bis (2-ethylhexyl) amide, didecylamide, N-methyloctadecylamide, N-methylcyclohexylamide, Netylcyclohexylamide, N-isopropylcyclohexylamide, N-tert-butylcyclohexylamide, dicyclohexylamide, pyrrolidine, piperidine, hexamethylenimine, decahydroquinoline, diphenylamine, or N-methylanilide.

1C 2C [0105] Each of L^1C and L.^2C is, independently of each other, nitrogen or phosphorus, in particular nitrogen, and when v is 0 can form a double bond with the carbon atom containing R^4C or R^5C. IN

In particular, when v is 0, L^1C and / or L^2C together with the carbon atom containing R^4C or R^5C form an as- \ ή imino group -CR^4C= N- or -CR^5C= N-. When v is 1, L^1C and / or L^2C together with the carbon atom containing R^4C or R^5C forms, in particular, the amide group -CR^4CR^6C-N^-- or -CR^5CR^7C-N^--.

_C [0106] Ligands X^C are the result of, for example, the selection of appropriate metal compound substrates used for the synthesis of iron complexes, but can also be changed later. possible_C ligands X^C there are, in particular, halogens such as fluorine, chlorine, bromine or iodine, in particular chlorine.

Alkyl substituents such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl are also CC ligands X^Cthat can be used. As next ligands X^C, mention may be made, purely by way of example and not exhaustively, trifluoroacetate, BF4^-, PF6^- and weakly coordinating or non-coordinating anions (cf., for example, S. Strauss in Chem. Rev. 1993, 93, 927-942), e.g., B (C6F5) 4^-. Amides, alkoxylates, sulfonates,_C carboxylates and β-diketonates are also particularly preferred X ligands. Certain of these substituted X ligands are particularly advantageously used since they can be obtained from cheap and readily available substrates. Thus, a particularly preferred embodiment is that of_C which X^C is dimethylamide, methoxylate, ethoxylate, isopropoxylate, phenoxylate, naphthoxylate, triflate, p-toluenesulfonate, acetate or acetoacetate.

[0107] Change of R substituents^18C it allows, for example, to fine-tune physical properties such as solubility. Possible carboorganic substituents R^18C are, for example, the following: C1-C20-alkyl which may be linear or branched, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , n-nonyl, n-decyl or ndodecyl, a 5- to 7-membered cycloalkyl, which may in turn contain a C6-C10-aryl group as a substituent, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C20-alkenyl, which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g., vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C20-aryl which may be substituted by further alkyl groups and / or substituents containing N- or O-, e.g., 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, 2-methoxyphenyl, 2-N, N-dimethylaminophenyl, or arylalkyl which may be substituted by further alkyl groups, e.g., benzyl, o-, m-, p- methylbenzyl, 1- or 2-ethylphenyl, where two R substituents^18C they can also be combined to form a 5- or 6-membered ring and R substituents^18C they may also be substituted with halogens such as fluorine, 18C 19C chlorine or bromine. Possible substituents R^18C in SiR organosilicon substituents^19C3 are the 18C 19C substituents themselves which are described above for R^18Cwhere two R substituents^19C they may also be combined to form a 5- or 6-membered ring, e.g., trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. It is preferred to use C1-C10-alkyl such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and also vinylallyl, benzyl and phenyl as R substituent^18C.

_C [0108] The number s of ligands X^C depends on the degree of iron oxidation. The number s may therefore not be given in general. The degree of iron oxidation in catalytically active complexes is usually known to those skilled in the art. However, it is also possible to use complexes whose oxidation state does not correspond to that of an active catalyst. Such complexes can therefore be reduced accordingly either

EP 1 753 791 B1 oxidized with suitable activators. The use of iron complexes with an oxidation state of +3 or +2 is preferred.

[0109] D is an uncharged donor, in particular an uncharged Lewis base or Lewis's acid, for example, amines, alcohols, ethers, ketones, aldehydes, esters, sulfides or phosphines that may be associated with an iron center or otherwise still be present as a solvent residue from the synthesis of iron complexes.

[0110] The amount of t ligands D can be from 0 to 4 and it often depends on the solvent in which the iron complex was prepared and the time for which the complexes obtained were dried and can therefore also be an integer number such as 0.5 or 1.5. In particular, the value is 0, 1 to 2.

[0111] In a preferred embodiment they are

<img file="PL1753791T3_D0011.tif" />

where

2C 4C each with E^2C-E^4C is, independently of one another, carbon, nitrogen or phosphorus, in particular carbon, 1C 3C each of R^1C-R^3C is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR^18C2, OR^18C, SiR^19C3, where organic substituents R^1C-R^3C they may also be 1C 3C substituted with halogens and / or two vicinal R substituents^1C-R^3C they may also be joined to form 1C 3C to form a five-, six- or seven-membered ring, and / or two vicinal substituents R^1C-R^3C are bound to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S, each of R^4C-R^5C is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, 18C 19C 4C 5C

NO^18C2, SiR^19C3, where organic substituents R^4C-R^5C can also be substituted with halogens,

2C 4C 2C 4C decreases the value 0 when E^2C-E^4C is nitrogen or phosphorus and equals 1 when E^2C-E^4C is carbon each of R^8C-R^11C is, independently of one another, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR^18C2, OR^18C, SiR^19C3, where organic substituents R^8C-R^11C they may also be substituted with halogens and / or two vicinal R substituents^8C-R^17C they can also be connected to

To form a five-, six- or seven-membered ring, and / or two vicinal substituents R^8C-R^17C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S,

12C 17 C each with R^12C-R^17C is, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the 18C 18C 18C 12C 17C aryl part, halogen, NR^18C2, OR^18C, SiR^18C3, where organic substituents R^12C-R^17C they may also be substituted with fluoride and / or two vicinal R substituents^8C-R^17C they can also be combined to form a five-, six- or seven-membered ring, and / or two vicinal R substituents^8C-R^17C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O or S, each of the coefficients v is, independently of each other, 0 or 1, _C each of the substituents X^C means, independently of each other, fluorine, chlorine, bromine, iodine, hydrogen, C1-C10alkyl, C2-C10-alkenyl, C6-C20-aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the part aryl, NR¹⁸%, OR^18C, SR^18C, SO3R^18C, OC (O) R¹⁸C, CN, SCN, β-diketonate, CO, BF4^-,

PF 6^- or a noncoordinating spatial anion and _C X substituents^C they can be joined together, each of R substituents^18C is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the 19C 18C aryl part, SiR^19C3, where organic substituents R^18C they may also be substituted with halogen and nitrogen- and oxygen-containing groups and two R substituents^18C they can also be combined to form a five or six membered ring,

19C each of R substituents^19C is, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl,

C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the 19C aryl part, where the organic substituents R^19C they may also be substituted with halogens or 19C groups containing nitrogen- and oxygen- and two R substituents^19C they can also be combined to form a five or six membered ring, is 1, 2, 3 or 4, in particular 2 or 3,

It is an uncharged donor and it is from 0 to 4, in particular 0, 1 or 2.

[0112] The embodiments and preferred embodiments described above are similarly applicable to E^2C-E^4C, R^1C-R^3C, XC, R^18C and R^19C.

[0113] Substituents R^4C-R^5C can vary widely. Possible carboorganic substituents R^4C-R^5C are, for example, the following: hydrogen, C1-C22-alkyl which may be linear or branched, e.g., 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 may in turn contain a C1-C10-alkyl group and / or a C6-C10-aryl group as a substituent, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C22-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g., vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C22-aryl which may be substituted by further alkyl groups, e.g., 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 which may be substituted by further groups

4C alkyl, e.g., benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where the organic substituents R^4C5C 4C 5C

R^5C they may also be substituted with halogens such as fluorine, chlorine or bromine. In addition, R^4C-R^5C

18C 19C may be the amine NR^18C2 or N (SiR^19C3) 2, for example dimethylamine, N-pyrrolidinyl or picolinyl. 19C 19C

Possible substituents R^19C in SiR organosilicon substituents^19C3 are the same carboorganic 1C 3C 19C substituents as described above for R^1C-R^3Cwhere two R substituents^19C they can also be combined to form a 5- or 6-membered ring, e.g., trimethylsilyl, triethylsilyl, butyl dimethylsilyl,

19C tributylsilyl, tritert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These SiR substituents^19C3 they may also be nitrogen-bonded to carbon containing them.

[0114] Preferred R substituents^4C-R^5C they are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or benzyl, in particular methyl.

[0115] Substituents R^8C-R^17C can vary widely. Possible carboorganic substituents R^8C-R^17C are, for example, the following: C1-C22-alkyl which may be linear or branched, e.g., 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, a 5- to 7-membered cycloalkyl which may in turn contain a C1-C10-alkyl group and / or a C6-C10-aryl group as a substituent, e.g., cyclopropyl, cyclobutyl, cyclopentyl , cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C2-C22-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g., vinyl, 1-allyl, 2-allyl, 3-allyl , butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C6-C22-aryl which may be substituted by further alkyl groups, e.g., 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 which may be substituted by further alkyl groups, e.g., benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where two R substituents^8C to R.^17Cthey may also be combined to form a 5-, 6- or 7-membered ring and / or two of the vicinal R substituents^8C-R^17C they can be combined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S and / or organic substituents R^8C-R^17C they may also be substituted with halogens such as fluorine, chlorine or bromine. In addition, R^6C-R^17C it may be a halogen such as fluorine, chlorine, bromine, amine NR^18C2 or N (SiR^19C3)₂, alkoxy or aryloxy OR^18C, e.g. dimethylamine, N-pyrrolidinyl, picolinyl, methoxy, ethoxy

19C 19C or isopropoxy. Possible substituents R^19C in SiR organosilicon substituents^19C3 they are like that

1C 3C 19C only the organic carbon substituents listed above for R^1C-R^3Cwhere two R substituents^19Cthey can also be combined to form a 5- or 6-membered ring, e.g., trimethylsilyl, triethylsilyl, butyl dimethylsilyl, tributylsilyl, tritert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. These

19C SiR substituents^19C3 they may also be bound by oxygen or nitrogen, for example trimethylsilyloxy, triethylsilyloxy, butyl dimethylsilyloxy, tributylsilyloxy or tritert-butylsilyloxy.

12C 17C [0116] Preferred R substituents^12C-R^17C are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine,

13C 18C in particular hydrogen. In particular, each R^13C and R^18C means methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine,

Chloro or bromi each with R^12C, R^14C, R^15C and R^17C means hydrogen.

[0117] Preferred R substituents^8C-R^11C are methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine. In particular, each of R^8C and R^10C is C1-C22-alkyl which may also be substituted with halogens, in particular and C1-C22-n-alkyl which may also be substituted with halogens, e.g., methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n- pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen such as

9C 11C fluorine, chlorine or bromine and each of R^9C and R^11C is halogen such as fluorine, chlorine or bromine. In particular, it is preferred that each R^8C and R^10C is C1-C22-alkyl which may also be substituted with halogens, in particular C1-C22-n-alkyl which may also be substituted with halogens, e.g., methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl , n-hexyl, n-heptyl, n-octyl, 9C 11C vinyls each R^9C and R^11C is halogen such as fluorine, chlorine or bromine.

[0118] In particular, R^12C, R^14C, R^15C and R^17C are identical, R^13C and R^16C are identical, R^9C and R^11C are identical and R^8C and R^10C are identical. This is also advantageous in the preferred embodiment described above.

[0119] The synthesis of compounds B) is described, for example, in J. Am. Chem. Soc. 120, p. 4049 ff. (1998), J. Chem. Soc., Chem. Commun. 1998, 849, and WO 98/27124. Preferred complexes B) chloride

2,6-Bis [1- (2,6-dimethylphenylimino) ethyl] pyridine iron (II), 2,6-Bis [1- (2,4,6-trimethylphenylimino) ethyl] pyridine iron (II) dichloride, 2,6-Bis dichloride [1- (2-Chloro-6-methylphenylimino) ethyl] pyridine iron (II), 2,6-Bis dichloride [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron (II), 2,6-Bis dichloride [1- (2, 6-dichlorophenylimino) ethyl] pyridine iron (II), 2,6-Bis [1- (2,6-diisopropylphenylimino) methyl] pyridine iron (II) dichloride, 2,6-Bis [1- (2,4-dichloro-6-methylphenylimino) ethyl] pyridine iron (II) dichloride, 2,6-Bis [1- (2,6-difluorophenylimino) ethyl] pyridine iron (II) dichloride, 2.6 dichloride -Bis [1- (2,6-dibromophenylamino) ethyl] pyridine iron (II) or the corresponding dibromides or tribromides.

[0120] In the following description, reference to the transition metal complex (A) or catalyst (A) means monocyclopentadienyl complex (A1) and / or hafnocene (A2). The molar ratio of transition metal complex A) to polymerization catalyst B) is usually in the range from 1: 100 to 100: 1, preferably from 1:10 to 10: 1 and particularly preferably from 1: 5 to 5: 1. When transition metal complex A) is used as the sole catalyst under the same reaction conditions in ethylene homopolymerization or copolymerization, it preferably produces higher Mw than complex (B) when it is used as the only complex under the same reaction conditions. Preferred embodiments of complexes (A1), (A2) and (B) are similarly preferred in combinations of complex (A1) and (B) and in combination of complex (A2) and (B).

[0121] The catalyst composition of the invention may be used alone or together with further components as an olefin polymerization catalyst system. In addition, we found olefin polymerization catalyst systems containing

A) at least one polymerization catalyst based on a monocyclopentadienyl metal complex of groups 4-6 of the periodic table of elements whose cyclopentadienyl system is substituted with a discharged donor (A1) or hafnocene (A2),

EP 1 753 791 B1

B) at least one iron-based polymerization catalyst having a tridentate ligand containing at least two ortho, ortho-disubstituted aryl substituents,

C) optionally one or more activating compounds,

D) optionally one or more organic or inorganic carriers,

E) optionally one or more metal compounds from Group 1, 2 or 13 metals from the periodic table.

[0122] Monocyclopentadienyl (A1), hafnocene (A2) and / or iron (B) complexes sometimes only have low polymerization activity and are then contacted with one or more activators, namely component (C), to allow good polymerization activity to be demonstrated . The catalyst system therefore optionally further comprises, as component (C), one or more activating compounds, preferably one or two activating compounds (C). The catalyst system according to the invention preferably contains one or more activators (C). Depending on the combination of catalyst (A) and (B), one or more activating compounds (C) are preferred. Activation of the transition metal complex (A) and iron complex (B) of the catalyst composition can be carried out using the same activator or mixture of activator or different activators. It is often preferred to use the same activator (C) for both catalysts (A) and (B).

[0123] The activator or activators (C) can in any case be used in any amount relative to the complexes (A) and (B) of the catalyst composition of the invention. They are preferably used in excess or in stoichiometric amounts, in each case relative to the complex (A) or (B) they activate. The amount of activating compound (s) to be used depends on the type of activator (C). Generally, the molar ratio of transition metal complex (A) to activating compound (C) may be from 1: 0.1 to 1: 10000, preferably from 1: 1 to 1: 2000. The molar ratio of iron complex (B) to activating compound (C) is also usually in the range from 1: 0.1 to 1: 10000, preferably from 1: 1 to 1: 2000.

[0124] Suitable compounds (C) that are able to react with the transition metal complex (A) or iron complex (B) to convert it into a catalytically active or more active compound are, for example, compounds such as aluminoxane, an uncharged Lewis acid, an ionic compound having a Lewis acid cation, or an ionic compound containing Bronsted acid as a cation.

[0125] As aluminoxanes, it is possible to use, for example, the compounds described in WO 00/31090. Especially useful aluminoxes are open chain or cyclic aluminoxane compounds of general formula (X) or (XI)

EP 1 753 791 B1

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4 · ο— wherever R^1D-R^4D is, independently of one another, a C1-C6-alkyl group, preferably methyl, ethyl, butyl or an isobutyl group, and is an integer from 1 to 40, preferably from 4 to 25.

[0126] In particular, the preferred aluminoxane compound is methylaluminoxane.

[0127] These oligomeric aluminoxane compounds are usually obtained in a controlled reaction of a solution of trialkylaluminum, in particular trimethylaluminum, with water. Generally, the oligomeric aluminoxane compounds obtained are in the form of mixtures of both linear and cyclic chain molecules of various lengths, so that they should be regarded as average. Aluminoxane compounds may also be present in admixture with other alkylmetals, usually glycoalkyls. Aluminoxane preparations suitable as component (C) are commercially available.

[0128] In addition, modified aluminoxanes in which some of the hydrocarbon substituents have been replaced by hydrogen or alkoxy, aryloxy, siloxyalbamide substituents may also be used instead of the aluminoxane compounds of formula (X) or (XI) as component (C).

[0129] It has been found to be advantageous to use transition metal complex A) or iron complex B) and aluminoxane compounds in such amounts that the atomic ratio of aluminum from aluminoxane compounds including any still present alkylalkyl to transition metal from transition metal complex (A) in the range from 1: 1 to 2000: 1, preferably from 10: 1 to 500: 1 and in particular in the range from 20: 1 to 400: 1. The atomic ratio of aluminum from aluminoxane compounds including any still present aluminum aluminum to iron of the iron complex (B) is usually in the range from 1: 1 to 2000: 1, preferably from 10: 1 to 500: 1 and in particular in the range from 20: 1 to 400 1. [0130] Another class of suitable activating ingredients (C) are hydroxyaluminoxanes. They can be prepared, for example, by the addition of 0.5 to 1.2 equivalents of water, preferably 0.8 to 1.2 equivalents of water, per aluminum equivalent, to an aluminum alkyl compound, in particular triisobutyl aluminum, at low temperatures, usually below 0 ° C. Such compounds and their use in olefin polymerization are described, for example, in WO 00/24787. The atomic ratio of aluminum from the hydroxyaluminoxane compound to the transition metal from the transition metal complex (A) or iron complex (B) is usually in the range from 1: 1 to 100: 1, preferably from 10: 1 to 50: 1 and in particular in the range from 20: 1 up to 40: 1. The use of a monocyclopentadienyl dialkyl metal compound (A1) or is preferred

EP 1 753 791 B1 dialkyl compound hafnocene (A2).

[0131] As strong, uncharged Lewis acids, compounds of general formula (XII) are preferred _M^2DX^1DX^2DX^3D_(XII) where

2D

M^2D is the element of group 13 of the periodic table, in particular B, Al or Ga, preferably B, each of X^1D, X^2D and X^3D is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl portion and from 6 to 20 carbon atoms in the aryl portion or fluorine, chlorine, bromine or iodine, in particular haloaryls, preferably pentafluorophenyl.

[0132] Further examples of strong uncharged Lewis acids are given in WO 00/31090.

[0133] The compounds that are particularly useful as component (C) are borates and boroxins such as trialkyl borate, triaryl borate or trimethyl boroxine. In particular, borates that contain at least two perfluorinated aryl substituents are preferred. Particularly preferred are compounds of general formula (XII) in which X^1D, X^2D and X^3D are identical, for example triphenylborate, tris (4-fluorophenyl) borate, tris (3,5-difluorophenyl) borate, tris (4-fluoromethylphenyl) borate, tris (pentafluorophenyl) borate, tris (tolyl) borate, tris (3,5 -dimethylphenyl) borate, tris (3,5-difluorophenyl) borate or tris (3,4,5-trifluorophenyl) borate. The use of tris (pentafluorophenyl) borate is preferred.

[0134] Suitable compounds (C) are preferably prepared by reacting the aluminum or boron compounds of formula (XII) with water, alcohols, phenol derivatives, thiophenol derivatives or aniline derivatives, with halogenated and especially perfluorinated alcohols and phenols being particularly important. Examples of particularly preferred compounds are pentafluorophenol, 1,1bis (pentafluorophenyl) methanol and 4-hydroxy-2,2 ', 3,3', 4 ', 5,5', 6,6'-nonafluorobiphenyl. Examples of combinations of compounds of formula (XII) with Broenstedt acids are, in particular, trimethylaluminum / pentafluorophenol, trimethylaluminum / 1-bis (pentafluorophenyl) methanol, trimethylaluminum / 4-hydroxy-2,2 ', 3,3', 4 ', 5 , 5 ', 6,6'-nonafluorobiphenyl, triethylaluminum / pentafluorophenol and triisobutylaluminum / pentafluorophenol and triethylaluminum / 4,4'dihydroxy-2,2', 3,3 ', 5,5', 6,6'-octafluorobiphenyl hydrate.

1D [0135] In further suitable aluminum and boron compounds of formula (XII), R^1D is an OH group such as, for example, in boronic acids and boric acids. In particular, boric acids having perfluorinated aryl substituents may be mentioned, for example (C6F5) 2BOH.

[0136] Strong uncharged Lewis acids suitable as activating compounds (C) also include reaction products of boronic acid reaction with two equivalents of trialkylaluminum or reaction products of trialkylaluminum with two equivalents of acidic fluorinated, in particular perfluorinated, carbon compound such as pentafluorophenol or bis (pentafluorophenyl) acid ) borinic. [0137] Suitable ionic compounds having Lewis acid cations include cation salt compounds of the general formula (XIII) [((M^3D)^{a +}) Q1Q2 ... Q z]^{d +} (XIII) where

3D

M^3D is the element from groups 1 to 16 of the periodic table,

Q1 to Qz are simply negatively charged substituents such as C1-C28-alkyl, C6-C15-aryl,

Alkylaryl, aralkyl, haloalkyl, each haloaryl having from 6 to 20 carbon atoms in the aryl part and from 1 to 28 carbon atoms in the alkyl part, C3-C10-cycloalkyl which may have C1-C10-alkyl groups as substituents, halogen, C1-6 C28-alkoxy, C6-C15-aryloxy, silyl or mercaptyl groups, a is an integer from 1 to 6 and a is an integer from 0 to 5, d corresponds to the difference az, but is greater than or equal to 1.

[0138] Particularly useful cations are carbonium cations, oxonium cations and sulfonium cations and also cationic transition metal complexes. In particular, triphenylmethyl carion, silver cation and 1,1'-dimethylferocenyl cation may be mentioned. They preferably have non-coordinating counterions, in particular boron compounds as also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.

[0139] Salts having non-coordinating salts can also be prepared by combining a boron or aluminum compound, e.g., an aluminum alkyl, with a second compound that can react to bond two or more boron or aluminum atoms, e.g., water, and a third compound that forms with a boron or aluminum compound, an ionizing ionic compound, e.g., triphenylchloromethane, or optionally a base, preferably a base containing organic nitrogen, e.g. an amine, aniline derivative or nitrogen heterocycle. In addition, a fourth compound that similarly reacts with the boron or aluminum compound, e.g., pentafluorophenol, can be added.

[0140] Ionic compounds containing Bronsted acids as cations preferably similarly have non-coordinating counterions. Like Bronsted acid, a protonated amine or aniline derivative is particularly preferred. N, N-dimethylanilicine, N, N-dimethylcyclohexylammonium and N, N-dimethylbenzylammonium and the latter two are preferred cations.

[0141] Compounds containing anionic boron heterocycles as described in WO 9736937 are also suitable as component (C), in particular dimethylanilinium boratabenzenes or trityl boratabenzenes.

[0142] Preferred ionic compounds C) contain borates that contain at least two perfluorinated aryl substituents. Particularly preferred is N, N-dimethylaniline tetrakis (pentafluorophenyl) borate and, in particular, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) boronate or tetracispentafluorylphenyl.

[0143] It is also possible for two or more borate anions to be connected to each other, as in

2dianion [[C6F5) 2B-C6F4-B (C6F5) 2]^2-, or the borate anion may be bonded via a bridge to a suitable functional group on the surface of the support.

[0144] Further suitable activating compounds (C) are listed in WO 00/31090.

[0145] The amount of strong, uncharged Lewis acids, ionic compounds having Lewis acid cations or ionic compounds containing Bronsted acids as cations is preferably from 0.1 to 20 equivalents, more preferably from 1 to 10 equivalents and particularly preferably from 1 to 2 equivalents, relative to the complex transition metal (A) or iron complex (B).

[0146] Suitable activating compounds (C) also include boron aluminum compounds such as

[Bis (pentafluorophenylboroxy)] methylalane. Examples of such boron aluminum compounds are those disclosed in

WO 99/06414.

[0147] It is also possible to use mixtures of all of the above activating compounds (C). Preferred mixtures contain aluminoxanes, in particular methylaluminoxanes, and an ionic compound, in particular those containing tetrakis (pentafluorophenyl) borate anion, and / or strong uncharged Lewis acid, in particular tris (pentafluorophenyl) borate or boroxin.

[0148] Both the transition metal complex (A) or iron complex (B) and activating compounds (C) are preferably used in a solvent, preferably an aromatic hydrocarbon having from 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or their mixture. [0149] Another possibility is to use an activating compound (C) which can be used simultaneously as carrier (D). Such systems were obtained, for example, from inorganic oxide treated with zirconium alkoxide and subsequently subjected to chlorination, e.g. with carbon tetrachloride. The preparation of such systems is described, for example, in WO 01/41920.

[0150] Combinations of preferred embodiments (C) with preferred embodiments (A) and / or (B) are particularly preferred.

[0151] It is preferred to use aluminoxane as a common activator (C) for catalyst component (A) and (B). Combination of cation salt compounds of general formula (XIII), in particular N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylcyclohexylammonium tetrakis, N, N-dimethylcyclohexylammonium tetrakis, N, N-tetrakis (pentafluorophenyl) borate dimethyl benzylammonium or tetrakispentafluorophenyl borate trityl as activator (C) for hafnocenes (A2), in particular in combination with aluminoxane as activator (C) for the iron complex (B).

[0152] Further particularly preferred common activators (C) are reaction products of aluminum compounds of formula (XII) with perfluorinated alcohols and phenols.

[0153] To allow the use of the transition metal complex (A) and iron complex (B) in gas phase or suspension polymerization processes, it is often preferable to use the solid complexes, i.e. to apply them to a solid support (D). In addition, the supported complexes have high performance. The transition metal complexes (A) and / or the iron complex (B) can therefore also optionally be immobilized on an organic or inorganic support (D) and used in supported polymerization. This makes it possible, for example, to avoid deposits in the reactor and to control the morphology of the polymer. As carrier materials, it is preferred to use silica gel, magnesium chloride, alumina, mesoporous substances, aluminosilicates, hydrotalcites and organic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene or polymers containing polar functional groups, for example copolymers of ethene and acrylic esters, acrole esters or vinyl acetate.

[0154] In particular, it is preferred that the catalyst system comprises at least one transition metal complex (A), at least one iron complex (B), at least one activating compound (C) and at least one support component (D).

[0155] A preferred catalyst composition according to the invention comprises one or more support components. It is possible for both transition metal component (A) and iron complex (B) to be on

The carrier or only one of the two components was supported. In a preferred embodiment, both components (A) and (B) are supported. The two components (A) and (B) may in this case be applied to different carriers or together in a common carrier. Components (A) and (B) are preferably overlaid with a common carrier to provide relatively large spatial proximity to the various catalytic centers and thus to ensure good mixing of the various polymers formed.

In order to prepare the catalyst systems according to the invention, it is preferred to immobilize one of the components (A) and one of the components (B) and / or activator (C) or carrier (D) by physical sorption or otherwise by means of a chemical reaction, i.e. is the covalent bond of components with reactive groups on the surface of the support.

[0157] The order in which the carrier component D), the transition metal complex (A), the iron complex (B) and the activating compounds (C) are combined is essentially irrelevant. After separate process steps, the various intermediates can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons.

[0158] The transition metal complex (A), the iron complex (B) and the activating compound (C) can be immobilized independently of one another, e.g., sequentially or simultaneously. Thus, the carrier component (D) may first be contacted with the activating compound (s) (C) or the carrier component (D) may first be contacted with the transition metal complex (A) and / or the iron complex (B). It is also possible to pre-activate transition metal complex A) with one or more activating compounds (C) before mixing with the carrier (D). The iron component may, for example, react simultaneously with the transition metal complex with the activating compound (C), or may be pre-activated separately with the latter. The pre-activated iron complex (B) can be applied to the carrier before or after the pre-activated transition metal complex (A). In one possible embodiment, the transition metal complex (A) and / or the iron complex (B) can also be prepared in the presence of a carrier substance. Another method of immobilization is pre-polymerization of the catalyst system with or without prior application to a support.

[0159] Immobilization is generally carried out in an inert solvent which can be removed by filtration or evaporation after immobilization. After separate process steps, the precipitate may be washed with suitably inert solvents such as aliphatic or aromatic hydrocarbons and dried. However, it is also possible to use a still moist, immobilized catalyst.

[0160] In a preferred method of preparing a supported catalyst system, at least one iron complex (B) is contacted with the activated compound (C) successively mixed with dehydrated or passivated support material (D). The transition metal complex (A) is similarly contacted with at least one activating compound (C) in a suitable solvent, preferably giving a soluble reaction product, adduct or mixture. The preparation obtained in this way is then mixed with the immobilized iron complex, which is used directly or after separation of the solvent, and the solvent is completely or partly removed. The resulting supported catalyst system is preferably dried to ensure that all or most of the solvent is removed from the pores of the support material. The supported catalyst is preferably obtained as free-flowing

Powder. Examples of industrial implementation of the above method are described in WO 96/00243, WO 98/40419 or WO 00/05277. Another preferred embodiment involves first producing the activating compound (C) on the carrier component (D) and subsequently contacting said compound on the carrier with the transition metal complex (A) and the iron complex (B).

[0161] As the carrier component (D), it is preferred to use subtly separated carriers, which may be any organic or inorganic solid. In particular, the support component (D) may be a porous support such as talc, a layered silicate such as montmorillonite, mica or inorganic oxide, or a finely separated powdered polymer (e.g., a polyolefin or a polymer having polar functional groups).

[0162] The carrier substances used preferably have a specific surface area in the range of 10 to ₂

1000 m / g, pore volume in the range from 0.1 to 5 ml / g and average particle size from 1 to 500 μm.

₂

Carriers having a specific surface area in the range from 50 to 700 m are preferred²/ g, pore volume in the range of 0.4 to 3.5 ml / g and average particle size in the range of 5 to 350 mm. In particular₂ carriers having a specific surface area in the range from 200 to 550 m are preferred²/ g, pore volume in the range from 0.5 to 3.0 ml / g and average particle size from 10 to 150 mm.

[0163] The transition metal complex (A) is preferably applied in an amount such that the concentration of transition metal from the transition metal complex (A) in the finished catalyst system is from 1 to 200 mmol, preferably from 5 to 100 mmol and particularly preferably from 10 to 70 mmol, per g carrier (D). The iron (B) complex is preferably applied in an amount such that the concentration of iron from the iron (B) complex in the finished catalyst system is from 1 to μ00 μmol, preferably from 5 to 100 mmol and particularly preferably from 10 to 70 mmol, of nag carrier (D ).

[0164] The inorganic carrier may be heat treated, e.g., to remove adsorbed water. [0165] Such drying is generally carried out at temperatures in the range from 50 to 1000 ° C, preferably from 100 to 600 ° C, with drying from 100 to 200 ° C preferably carried out under reduced pressure and / or under an inert atmosphere (e.g. , nitrogen), or the inorganic support can be calcined at temperatures from 200 to 1000 ° C to produce the desired solid structure and / or to determine the desired OH concentration on the surface. The carrier can also be chemically treated with conventional drying agents such as metalalkyls, preferably aluminumalkyls, chlorosilanes or SiCl4, or otherwise methylaluminoxane. Suitable processing methods are described, for example, in WO 00/31090.

[0166] The inorganic carrier material can also be chemically modified. For example, treatment of NH4SiF6 silica gel or other fluorinating agents leads to fluorination of the silica gel surface, or treatment of silicate gels with silanes containing nitrogen-, fluorine- or sulfur-containing groups leads to suitably modified silica gel surfaces.

[0167] Organic carrier substances such as finely divided polyolefin powders (e.g., polyethylene, polypropylene or polystyrene) may also be used and they are preferably similarly released from adherent moisture, solvent residues or other impurities by suitable purification and drying operations prior to use. It is also possible to use

Functional polymer supports, e.g., those based on polystyrene, polyethylene, polypropylene or polybutylene, through which functional groups, e.g. amino or hydroxyl groups, at least one of the catalyst components can be immobilized. It is also possible to use polymer blends.

[0168] Inorganic oxides suitable as carrier component (D) can be found among oxides of elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the periodic table. Examples of preferred oxides as carriers include silicon dioxide, alumina and mixed oxides of calcium, aluminum, silicon, magnesium or titanium, and also suitable mixtures of oxides. Other inorganic oxides that can be used alone or in combination with the preferred oxide carriers mentioned above are, for example, MgO, CaO, AlPO4, ZrO2, TiO2, B2O3 or mixtures thereof.

[0169] Further preferred inorganic support substances are inorganic halogens such as MgCl2 or carbonates such as Na2CO3, K2CO3, CaCO3, MgCO3, sulfates such as Na2SO4, Al2 (SO4) 3, BaSO4, nitrates such as KNO3, Mg (NO3) 2 or Al (NO3) 3.

[0170] As solid support materials (D) for olefin polymerization catalysts, the use of silica gels is preferred, since the particles whose size and structure make them suitable as supports for olefin polymerization can be made from this material. Spray-dried silica gels, which are relative spherical agglomerates of small granular particles, i.e., primary particles, have been found to be particularly preferred. The silica gels can be dried and / or calcined before use.

[0171] Further preferred carriers (D) are hydrotalcites and calcined hydrotalcites. In mineralogy, hydrotalcite is a natural mineral with an ideal formula

Mg6Al2 (OH) 16CO3 • 4 H2O whose structure is a derivative of Mg (OH) 2 brucite. Brucite crystallizes in a layered structure with metal ions in octahedral gaps between two layers of densely packed hydroxyl ions, occupying only every second layer of octahedral gaps. In hydrotalcite, certain magnesium ions are replaced by aluminum ions, resulting in a positive charge through the layer package. This is balanced by anions that are placed together with the water of crystallization in the layers between them.

[0172] Such layered structures are found not only in magnesium aluminum hydroxides, but generally in mixed metal hydroxides of the general formula

M (II) 2x²⁺M (III) 2³⁺(OH) 4x4 • A2 / nⁿ • zH2O which have a layered structure and in which M (II) means a divalent metal such as Mg, Zn, Cu, Ni, Co, Mn, Ca and / or Fe and M (III) means a trivalent metal such as Al, Fe, Co , Mn, La, Ce and / or Cr, x is a number from 0.5 to 10 in 0.5 steps, A is an interstitial anion and n is an interstitial anion charge, which can be from 1 to 8, usually from 1 to 4, and is an integer from 1 to 6, in particular from 2 to 4. Possible interode anions are organic anions such as alkoxy anions, alkyl ether sulfates, aryl ether sulfates or glycol ether sulfates, inorganic anions such as, in particular, carbonate, bicarbonate, nitrate, chloride, sulfate or B (OH) 4^- or polyoxometallic anions such as Mo7O24^6- or V10O28^6-. However, a mixture of many such anions is also possible.

[0173] Accordingly, all such mixed metal hydroxides having a layered structure should be considered as hydrotalcites for the purposes of the present invention.

[0174] Calcined hydrotalcites can be prepared, starting from hydrotalcites, by calcination, that is, heating by which, among other things, the desired hydroxyl content can be determined. In addition, the crystal structure also changes. The preparation of the calcined hydrotalcites used according to the invention is usually carried out at temperatures above 180 ° C. Calcining for 3 to 24 hours at temperatures from 250 ° C to 1000 ° C, in particular from 400 ° C to 700 ° C, is preferred. It is also possible to pass air or inert gas over the sludge or apply vacuum at the same time.

[0175] During heating, natural or synthetic hydrotalcites give off water first, i.e. drying. During further heating, proper calcination occurs, metal hydroxides are converted to metal oxides by eliminating hydroxyl groups and interlayer anions; OH groups or interlayer anions such as carbonate may also still be present in calcined hydrotalcites. The measure of this is weight loss during roasting. This is the weight loss experienced by the sample, which is heated in two stages, first for 30 minutes at 200 ° C in a dryer and then for 1 hour at 950 ° C in a muffle furnace.

[0176] The calcined hydrotalcites used as component (D) are therefore mixed divalent and trivalent metal oxides M (II) and M (III), with a molar ratio of M (II) to M (III) generally ranging from 0.5 to 10, preferably from 0.75 to 8 and in particular from 1 to 4. In addition, ordinary amounts of impurities, e.g. Si, Fe, Na, Ca or Ti, and also chlorides and sulfates may also be present.

[0177] Preferred calcined hydrotalcites (D) are mixed oxides in which M (II) is magnesium and M (III) is aluminum. Such mixed aluminum-magnesium oxides can be obtained from Condea Chemie GmbH (now Sasol Chemie), Hamburg under the trade name Puralox Mg.

[0178] Calcined hydrotalcites in which structural transformation is completed or practically completed are also preferred. Calcining, i.e., transforming the structure, can be confirmed, for example, by means of an X-ray diffraction pattern.

[0179] The hydrotalcites, calcined hydrotalcites or silica gels used are usually used as finely divided powders having an average particle diameter D50 from 5 to 200 mm, preferably from 10 to 150 mm, particularly preferably from 15 to 100 mm and in particular from 20 to 70 mm, and usually have a pore volume of 0.1 to 10 cm³/ g, preferably from 0.2 to 5 cm³/ g, and specific surfaces

2 2 from 30 to 1000 m²/ g, preferably from 50 to 800 m²/ g and in particular from 100 to 600 m²/ G. The transition metal complex (A) is preferably applied in an amount such that the concentration of the transition metal from the transition metal complex (A) in the finished catalyst system is from 1 to 100 mmol, preferably from 5 to 80 mmol and particularly preferably from 10 to 60 mmol, per g carrier (D).

[0180] The catalyst system may further comprise, as an additional component (E), a metal compound of general formula (XX),

M^G(R^1G) RG (R^2G) SG (R^3G) tG (XX) where

EP 1 753 791 B1

M^G means Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gal, indium, thallium, zinc, in particular Li, Na, K, Mg, boron, glinal or Zn, each R^1G is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, each of R^2G and R^3G is hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy having from 1 to 20 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or alkoxy together with C1-C10 -alkyl or C6-C15-aryl, r^G is an integer from 1 to 3 and

GGGGGG p^G it^G denote integers from 0 to 2, with the sum of r^G+ s^G+ t^G corresponding to the valence of M^Gwhere component (E) is usually not identical to component (C). It is also possible to use mixtures of various metal compounds of formula (XX).

[0181] Among the metal compounds of general formula (XX), those in which are preferred

M^G means lithium, magnesium, boralbo aluminum and

R^1G is C1-C20-alkyl.

[0182] In particular, preferred metal compounds of formula (XX) are methyllithium, ethyllithium, n-butyllithium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, n-butyl magnesium , n-butyl-nheptylmagnesium, in particular n-butyl-n-octylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, tri-n-butylaluminum, triethylaluminum, dimethylaluminium chloride, dimethylaluminium fluoride, methylaluminium dichloride, methyl aluminum sesquide, diethyl aluminum chloride and trimethyl aluminum, and mixtures thereof. Partial hydrolysis of alkyl aluminum with alcohols can also be used.

[0183] When a metal compound (E) is used, it is preferably present in the catalyst system in an amount such that the molar ratio M^G from formula (XX) to the sum of transition metals from the transition metal complex (A) and the iron complex (B) is from 3000: 1 to 0.1: 1, preferably from 800: 1 to 0.2: 1 and particularly preferably from 100: 1 up to 1: 1.

[0184] Generally, a metal compound (E) of general formula (XX) is used as a component of the olefin polymerization or copolymerization catalyst system. Here, the metal compound (E) may, for example, be used to prepare a solid catalyst containing the support (D) and / or be added during or shortly before polymerization. The metal compounds (E) used may be identical or different. It is also possible, in particular when the solid catalyst does not contain an activating component (C), that the catalyst system further comprises, in addition to the solid catalyst, one or more activating compounds (C) that are identical or different from any compounds (E) present in solid catalyst.

[0185] Component E) may similarly react in any order with components (A), (B) and optionally (C) and (D). Component (A) may, for example, be contacted with components (C) and / or (D) either before or after contact with the olefins to be polymerized. Pre-activation with one or more components (C) before mixing with olefin and subsequent addition of the same or different component (C) and / or (D) is also possible after which the mixture is contacted with olefin. Pre-activation is generally carried out at temperatures of 10-100 ° C, preferably 20-80 ° C.

[0186] In another preferred embodiment, the solid catalyst is prepared starting from components (A), (B), (C) and (D) as described above and they are contacted with component (E) during, at the beginning or shortly before polymerization.

[0187] It is preferable to first contact (E) with the α-olefin to be polymerized and subsequently add a solid catalyst containing components (A), (B), (C) and (D) as described above.

[0188] In another preferred embodiment, the carrier (D) is first contacted with component (E), and components (A) and (B) and any further activator (C) are then treated as described above. [0189] It is also possible for the catalyst system to be first prepolymerized with α-olefins, preferably linear C2-C10-1-alkenes and in particular ethylene or propylene, and the resulting solid prepolymerized catalyst is then used in actual polymerization. The weight ratio of the solid catalyst used in the prepolymerization to the polymerized monomer is usually in the range from 1: 0.1 to 1: 1000, preferably from 1: 1 to 1: 200.

[0190] Furthermore, a small amount of olefin, preferably α-olefin, for example vinylcyclohexane, styrene or phenyldimethylvinylsilane, as a modifying component, anti-electrostatic agent or a suitable inert compound such as wax or oil can be added as an additive during or after the preparation of the catalyst system. The molar ratio of additive agents to the sum of transition metal compound (A) and iron complex (B) is usually from 1: 1000 to 1000: 1, preferably from 1: 5 to 20: 1. [0191] The catalyst composition or catalyst system according to the invention is suitable for producing the polyethylene according to the invention which has advantageous application of processing properties.

[0192] To prepare the polyethylene of the invention, ethylene is polymerized as described above with α-olefins having from 3 to 12 carbon atoms.

[0193] In the copolymerization method of the invention, ethylene is polymerized with α-olefins having from 3 to 12 carbon atoms. Preferred α-olefins are linear or branched C₂-C₁₂-1alkenes, in particular linear C2-C10-1-alkenes such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or branched C2-C10-1-alkenes such as 4-methyl-1-pentene. Particularly preferred α-olefins are C₄-C₁₂-1-alkenes, especially linear C₆-C₁₀-1-alkenes. It is also possible to polymerize various α-olefins. The polymerization of at least one α-olefin selected group consisting of zetene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene is preferred. Monomer mixtures containing at least 50 mol% ethene are preferably used.

[0194] The process according to the invention for the polymerization of ethylene with α-olefins can be carried out by all known industrial polymerization methods at temperatures in the range from -60 to 350 ° C, preferably from 0 to 200 ° C and particularly preferably from 25 to 150 ° C, and at pressures from 0.5 to 4000 bar, preferably from 1 to 100 bar and particularly preferably from 3 to 40 bar. The polymerization can be carried out in a known manner in bulk, in suspension, in a gas phase or in a supercritical medium in typical reactors used for olefin polymerization. It can be carried out periodically or preferably continuously in one or more stages. All high-pressure polymerization processes in tubular reactors or autoclaves, solutions in suspension, methods in suspension, gas phase mixing methods and gas phase fluid method are possible.

[0195] Polymerizations are usually carried out at temperatures in the range from -60 to 350 ° C, preferably in the range from 20 to 300 ° C, and at pressures from 0.5 to 4000 bar. The average residence times are usually 0.5 to 5 hours, preferably 0.5 to 3 hours. The preferred pressure and temperature ranges for carrying out the polymerization usually depend on the polymerization method. For high pressure polymerization processes, which are usually carried out at pressures between 1000 and 4000 bar, in particular between 2000 and 3500 bar, generally high polymerization temperatures are also set. Preferred temperature ranges for these high pressure polymerization processes are from 200 to 320 ° C, in particular from 220 to 290 ° C. In the case of low-pressure polymerization methods, they are usually set to a temperature that is at least a few degrees below the softening point of the polymer. In particular, temperatures from 50 to 180 ° C, preferably from 70 to 120 ° C, are set in these polymerization methods. In the case of suspension polymerization, the polymerization is usually carried out in a dispersion medium, preferably an inert hydrocarbon such as isobutane or mixtures of hydrocarbons or other monomers themselves. Polymerization temperatures generally range from -20 to 115 ° C, and pressures generally range from 1 to 100 bar. The solids content of the suspension is generally in the range of 10 to 80%. The polymerization can be carried out either periodically, e.g., in stirred autoclaves, or continuously, e.g., in tubular reactors, preferably in loop reactors. In particular, it is preferred to use the Phillips PF process as described in US-A 3 242 150 and US-A 3 248179. Gas phase polymerization is generally carried out in the range from 30 to 125 ° C at pressures from 1 to 50 bar.

[0196] Of the abovementioned polymerization methods, gas phase polymerization, in particular in fluid phase gas phase polymerization reactors, solution polymerization and suspension polymerization, in particular loop reactors and stirred tank reactors is particularly preferred. Gas phase polymerization can also be carried out in a condensation or supercritical state in which part of the recycle gas is cooled below the dew point and is recycled to the reactor as a two-phase mixture. In addition, it is possible to use a multi-zone reactor in which two polymerization zones are connected to each other and the polymer alternates through these two zones many times. The two zones may also have different polymerization conditions. Such a reactor is described, for example, in WO 97/04015. Different or identical polymerization processes can also, if desired, be connected in series to form a polymerization cascade, for example as in the Hostalen® process. Parallel positioning of the reactors using two or more identical or different methods is also possible. In addition, molar mass regulators, for example hydrogen, or common additives such as anti-electrostatics can also be used in polymerizations.

[0197] The polymerization is preferably carried out in a single reactor, in particular a gas phase reactor. Polymerization of ethylene with α-olefins having from 3 to 12 carbon atoms gives polyethylene according to the invention when the catalyst according to the invention is used. Powdered polyethylene obtained directly from the reactor shows very high homogeneity, so that, unlike cascade processes, no further extrusion is necessary to obtain a homogeneous product.

[0198] Preparation of polymer blends by thoroughly mixing the individual ingredients, on

For example, melt extrusion in an extruder or kneader (cf., for example, "Polymer Blends" in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 1998, electronic edition), often has special difficulties. The melt viscosities of the high and low molecular weight components of the bimodal polyethylene blend are extremely different. While the low molecular weight component is quite fluid at the typical temperatures of around 190-210 ° C used to make mixtures, the high molecular weight component is only softened ("lentil soup"). It is therefore very difficult to mix the two components evenly. In addition, it is known that the high molecular weight component can be easily damaged as a result of thermal stress and by shear forces in the extruder, so that the blend properties are adversely affected. The mixing quality of such polyethylene blends is therefore often unsatisfactory.

[0199] The mixing quality of the polyethylene powder obtained directly from the reactor can be tested by assessing thin patches ("microtome cut-off") of the sample under an optical microscope. Inhomogeneities are revealed in the form of points or "white spots". Points or "white spots" have mainly high molecular weight, high viscosity particles in a low viscosity matrix (cf., for example, U. Burkhardt et al. In "Aufbereiten von Polymeren mit neuartigen

Eigenschaften ", VDIVerlag, Düsseldorf 1995, p. 71). Such inclusions can reach a size of up to 300 mm, cause stress cracking and result in brittle fracture of the components. The better the mixing quality of the polymer, the less and less the inclusions observed. Mixing quality the polymer is quantified in accordance with ISO 13949. According to the measurement method, a microtome cut-off body is prepared from the polymer sample, the number and size of these inclusions are counted and the degree of polymer mixing quality determined in accordance with the established evaluation scheme. The mixing quality in the polyethylene obtained directly from the reactor, the non-extruded polymer powder is preferably less than 3.

[0200] The preparation of the polyethylene of the invention in the reactor reduces energy consumption, requires no further mixing methods, and facilitates controlling the molecular weight distribution and molecular weight fraction of various possible polymers. In addition, good mixing of the polyethylene is obtained. [0201] The following examples illustrate the invention without limiting its scope.

[0202] The measured values ​​described were determined as follows:

[0203] NMR samples were placed in tubes under an inert atmosphere and, if appropriate, molten. Solvent signals served as the internal standard in the spectra¹H- and ¹³C-NMR and their chemical shift were converted to TMS values.

[0204] The content of vinyl groups was determined by IR in accordance with ASTM D 6248-98.

Branches / 1000 carbon atoms determined by ¹³C-NMR as described by James. C. Randall, JMSREV. Macromol. Chem. Phys., C29 (2 &amp; 3), 201-317 (1989), and based on the total content of CH3 groups / 1000 carbon atoms including end groups. Similarly, side chains longer than CH3 and especially ethyl, butyl and hexyl branch side chains / 1000 carbon atoms without end groups are thus determined.

[0205] The degree of branching in individual polymer fractions was determined by the Holtrup method (W.

Holtrup, Macromol. Chem. 178, 2335 (1977)) condensed with¹³C-NMR as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2 &amp; 3), 201-317 (1989).

EP 1 753 791 B1 ₃ [0206] Density [g / cm³] determined in accordance with ISO 1183.

[0207] Determination of molar mass distributions and average Mn, Mw, and Mw / Mn resulting therefrom was carried out using high temperature gel permeation chromatography on WATERS 150 C using a method based on DIN 55672 and the following columns connected in series: 3x SHODEX AT 806 MS, 1x SHODEX UT 807i 1x SHODEX AT-G under the following conditions: solvent:

1,2,4-trichlorobenzene (stabilized by 0.025% by weight 2,6-di-tert-butyl-4-methylphenol), flow: 1 ml / min, 500 μΐ injection volume, temperature: 135 ° C, calibration using PE standards . The estimation was carried out using WIN-GPC.

[0208] For the purposes of the present invention, the expression "HLMI" refers, as is generally known, to "high load melt flow rate" and is always determined at 190 ° C under a load of 21.6 kg (190 ° C / 21.6 kg) in accordance with ISO 1133.

[0209] Haze, as determined according to ASTM D 1003-00, on a BYK Gardener Haze Guard Plus device on at least 5 pieces of 10x10 cm 1 mm thick film.

[0210] Impact strength was determined in accordance with the instrumental impact test using the falling weight method according to ISO 6603 at -20 ° C.

[0211] Resistance to slow crack propagation (full notched creep test (FNCT)) was determined according to ISO DIS2 16770 at 3.5 Mbar at 80 ° C in a 2% by weight solution of Akropal N (N = 10) in water.

[0212] The spiral test was measured on a Demag ET100-310 with a clamping pressure of 100 t and a 3 mm nozzle and with a batch temperature of 250 ° C, injection pressure of 1000 bar, screw speed 90 mm / s, mold temperature 30 ° C and wall thickness of 2 mm.

Abbreviations in the table below:

<td colspan="2"> [0213]</td>

<td>Cat.</td><td>catalyst</td>

<td>T (poly)</td><td>temperaturapolimeryzacji</td>

<td>^Min</td><td>weight average molar mass</td>

<td>Mn</td><td>number average molar mass</td>

<td colspan="2">Density polymer density</td>

Vinyl / 1000C refers to the number of vinyl groups per 1000 carbon atoms b / 1000C refers to branching / 1000 carbon atoms, which is the number CH3 / 1000 carbon atoms including end groups br in 15% PE hmw refers to 15% by weight polyethylene having the highest molar masses with a degree of branching side chains larger than CH3 / 1000 carbon atoms without end groups Prod. Catalyst efficiency per polymer obtained per g of catalyst used per hour. Impact Impact as determined according to the instrumental impact test by the falling weight method according to ISO 6603 at -20 ° C

Preparation of Individual Ingredients [0214] Bis (n-butylcyclopentadienyl) hafnium dichloride is commercially available from Crompton.

[0215] 2,6-Bis [1- (2,4-dichloro-6-methylphenyl-imino) ethyl] pyridine iron (II) dichloride was prepared

EP 1 753 791 B1 according to the method of Qian et al., Organometallics 2003, 22, 4312-4321. Tu, 65.6 g of 2.6-diacetylpyridine (0.4 mol), 170 g of 2,4-dichloro-6-methylaniline (0.483 mol ), 32 g of type 135 silica gel and 160 g of molecular sieves (4A) were mixed in 1500 ml of toluene at 80 ° C for 5 hours and further 32 g of type 135 silica gel and 160 g of molecular sieves (4A) are successively added. The mixture was stirred at 80 ° C for a further 8 hours, insoluble solids were filtered off and washed twice with toluene. The solvent was evaporated from the filtrate thus obtained, the residue was mixed with 200 ml of methanol and successively stirred at 55 ° C for 1 hour. The suspension thus formed was filtered off and the resulting precipitate was washed with methanol and the solvent was evaporated. This gave 95 g of 2,6-Bis [1- (2,4-dichloro-6-methylphenylimino) ethyl] pyridine in a 47% yield. Cancer with iron (II) chloride was performed as described by Qian et al., Organometallics 2003, 22, 43212-4321.

Preparation of mixed catalyst systems

Example1

a) Carrier pretreatment [0216] XPO-2107, spray dried silica gel from Grace, fired at 600 ° C for 6 hours.

b) Preparation of mixed catalyst systems [0217] A mixture of 1.43 g (2.37 mmol) 2,6-bis [1- (2,4-dichloro-6-methylphenylimino) ethyl] pyridine iron (II) dichloride, 9.98 g dichloride bis (n-butylcyclopentadienyl) hafnium and 443 ml MAO (4.75 M in toluene, 2.1 mol) were stirred at room temperature for 1 hour and successively added to stirring 338 g of pre-treated carrier material in 500 ml toluene. The resulting solid gave 778.4 g of catalyst that still contained 23.9% by weight of solvent (based on total weight and calculated relative to the total application of all components on the substrate). Polymerization with catalysts [0218] Polymerization was carried out in a fluidized bed reactor having a diameter of 0.5 m and a total pressure of 20 bar. The polymerization temperature was 95 ° C using the catalyst of example 1, which was fed at a rate of 38.97 g per hour into the reactor. Ethylene was fed into the reactor at a rate of 40.7 kg per hour, 1-hexene at a rate of 410 g per hour and hydrogen at a rate of 2.11 per hour. 4.62 kg of propane per hour, 0.33 kg of nitrogen per hour were also fed into the reactor. and 0.5 g triisobutylaluminum per hour The polymer was discharged at a rate of 30.1 kg / h. The properties of the polymers obtained are summarized in Table 1.

Comparative Example 1 [0219] Ziegler catalyst was prepared as described in EP-A-739937 and suspension cascade polymerization was carried out using ethylene / hydrogen in the first reactor and ethylene / 1-butene with 0.8% by weight of 1-butene in the second reactor. Product data is shown in Table 1.

Table 1:

<td>Angle. FROM Ex.</td><td>prod [G / g]</td><td>HLMI [G / 10 min]</td><td>mw [G / mol]</td><td>Mw / Mn</td><td>density [G / cm³]</td><td>vinyl/ 1000C</td><td>Branched. / 1 000C</td><td>Br in 15% PE hmw</td>

<td> 1</td><td> 3792</td><td> 109</td><td> 99000</td><td> 7,9</td><td> 0,953</td><td> 1,3</td><td> 3,9</td><td> 5</td>

<td>C1</td><td></td><td> 75</td><td> 116300</td><td> 10</td><td> 0,953</td><td> 0,12</td><td> 1</td><td> 0,5</td>

[0220] Each of the polymers was formed into small 1 mm thick plates in an Engel injection molding machine.

EP 1 753 791 B1

The extrusion temperature was 225 ° C, the screw speed 116 rpm and the injection speed 50 mm / s. Holding time was 20 s, clamping pressure 687 bar.

Table 2: Properties of polyethylenes

<td>Example</td><td> 1</td><td>V1</td>

<td>Spiral length, 250 ° C [cm]</td><td> 47,6</td><td> 36</td>

<td>FNCT (3.5 MPa, 80 °) [hours]</td><td> 7,4</td><td> 1,3</td>

<td>haze [%]</td><td> 90,80</td><td> 94,20</td>

<td>Impact strength (-20 ° C) [J]</td><td> 12,42</td><td> 11,21</td>

EP 1 753 791 B1