Polyethylene for injection moulding

FIELD: chemistry.

SUBSTANCE: invention relates to polyethylene and articles made by injection moulding polyethylene. Polyethylene contains homopolymers of ethylene and/or copolymers with ethylene with molecular weight distribution Mw/Mn between 3 and 30, density of 0.945 - 0.965 g/cm3, average molecular weight Mw between 50000 g/mol and 200000 g/mol, high-load melt index (HLMI) between 10 and 300 g/10 min. The polymer contains 0.1-15 branches/1000 carbon atoms, where 1-15 wt % polyethylene with the highest molecular weight has degree of branching greater than 1 branch of side chains with length greater than CH3/1000 carbon atoms.The polyethylene is obtained using a catalyst composition which contains at least two different polymerisation catalysts, where A) is at least one hafnocene-based polymerisation catalyst (A2), and B) is at least one polymerisation catalyst based on an iron component, having a tridentate ligand which contains at least two ortho-, ortho-disubstituted aryl radicals (B). The disclosed polyethylene can be subjected to processing treatment on standard injection moulding apparatus.

EFFECT: articles obtained through injection moulding is uniform and can further be improved by increasing rate of injection moulding or high melting point.

9 cl, 2 tbl, 2 ex

 

The present invention relates to a new polyethylene, includes homopolymers of ethylene and/or copolymers of ethylene and 1-alkenes and having a molecular mass distribution Mw/Mnin the interval from 3 to 30, a density 0,945 to 0,965 g/cm3, srednevekovoy molecular weight of from 50000 g/mol to 200,000 g/mol, HLMI of from 10 to 300 g/10 min, which contains from 0.1 to 15 branches/1,000 carbon atoms, where from 1 to 15 wt.% polyethylene with high molecular masses has a degree of branching of more than 1 branches of side chains larger than CH3/1000 carbon atoms, the composition of the catalyst and the method of its production, and also to the products obtained injection molding, in which there is such a polyethylene.

Mixtures of different polyethylenes known and used for injection molding articles having high resistance to cracking under stress, as described in DE-C 3437116.

Earlier plastic mixture used in injection molding to obtain various types of screw closures. It is advisable to screw the paddles kept the size and shape during cooling after injection molding, i.e. did not give shrinkage (low shrinkage). Low shrinkage, combined with preservation of the shape is an important property of plastics that are intended for use, for example, for manufacturing is the service of screw closures with accurate tight. In addition, the method of injection molding is usually easier to carry out if the polyethylene composition to be molded, have a good flowability in the melt. To the mechanical strength of products made of polyethylene, obtained by injection molding, are constantly increasing requirements. On the other hand, needed a good adaptability to achieve high performance.

In the publication WO 00/71615 describes the containers received injection molding of the bimodal polyethylene with a density in the range from 0,950 to 0.98 g/cm3, a crystallinity in the range from 80 to 90%, consisting of at least 2 plastic components with different molecular weight distribution, where at least one component is a copolymer of ethylene. The polyethylene obtained with the use of cascade reactors or by extrusion of a melt of the two components.

Known ethylene copolymer mixture still leave much to be desired in terms of a combination of good mechanical properties, high melt fluidity and good optical properties.

Unexpectedly, it was found that this problem can be solved by using a specific catalyst composition, which can be obtained polyethylene having good mechanical properties, x is the Roshi adaptability and good optical properties.

Accordingly, applicants was obtained polyethylene, includes homopolymers of ethylene and/or copolymers of ethylene with 1-alkenes having a molecular weight distribution Mw/Mnin the interval from 3 to 30, a density in the range from 0,945 to 0,965 g/cm3, srednevekovoy molecular mass Mwin the range of from 50000 to 200000 g/mol, HLMI in the range from 10 to 300 g/10 min, which contains from 0.1 to 15 branches/1,000 carbon atoms, where from 1 to 15 wt.% polyethylene with high molecular masses have a degree of branching of more than 1 branch of the side chains of more than CH3/1000 carbon atoms.

Applicants have also created products manufactured by injection moulding, caps and closures, in which the polyethylene according to the present invention is present as a main component. In addition, applicants have found the use of polyethylenes according to the present invention for obtaining products using injection molding.

Applicants have also created a catalytic system for receiving the polyethylenes according to the present invention. The invention also relates to the use of catalytic systems for polymerization of ethylene and/or copolymerization of ethylene with 1-alkenes and method for producing a polyethylene according to the present invention by polymerization of ethylene or copolymerization of ethylene with 1-alkene is mi in the presence of a specified catalyst system.

Molecular mass distribution Mw/Mnpolyethylene according to the present invention is in the range from 3 to 30, preferably in the range from 5 to 20 and particularly preferably in the range from 6 to 15. Density polyethylene according to the present invention is in the range from 0,945 to 0,965 g/cm3, preferably in the range from 0,947 to 0.96 g/cm3especially preferably in the range from 0,948 to 0,955 g/cm3. Srednevekovaja molecular mass Mwpolyethylene according to the invention is in the range of from 50000 g/mol to 200,000 g/mol, preferably in the range of from 70000 g/mol to 150000 g/mol and particularly preferably in the range from 80000 g/mol to 120,000 g/mol. HLMI of polyethylene according to the present invention is in the range from 10 to 300 g/10 min, preferably in the range from 50 to 200 g/10 min and particularly preferably in the range from 70 to 150 g/10 min. In the description of the present invention, the term “HLMI” is used in its well-known meaning and refers to the index of the melt at high shear stress, which is defined at 190°c load of 21.6 kg 190°C/21,6 kg) according to ISO 1133.

Density [g/cm3] determined in accordance with ISO 1183. Determination of molecular mass distributions, mean values of Mn, Mwand their derived values of Mw/Mnwas carried out is by using high temperature gel permeation chromatography apparatus WATERS 150 C using the method based on DIN 55672, and series-connected columns 3× SHODEX AT 806 MS, 1× SHODEX UT 807 and 1× SHODEX AT-G under the following conditions: solvent is 1,2,4-trichlorobenzene (stabilized of 0.025 wt.% 2,6-di-tert-butyl-4-METHYLPHENOL), flow rate: 1 ml/min, volume of 500 ál injection, the temperature of 135°C., calibration using PE Standards. The evaluation was conducted using WIN-GPC.

The polyethylene according to the present invention contains from 0.1 to 15 branches/1,000 carbon atoms, preferably from 0.2 to 8 branches/1000 carbon atoms, particularly preferably from 0.3 to 3 branches/1000 carbon atoms. Number of branches/1000 carbon atoms specified by using the13C-NMR as described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and means the total content of CH3groups/1000 carbon atoms.

Further, the polyethylene according to the present invention contains from 1 to 15 wt.% polyethylene with a high molecular mass, preferably from 2 to 12 wt.%, and particularly preferably from 3 to 8 wt.%, with the degree of branching of more than 1 branch of the side chains of more than CH3/1000 carbon atoms, preferably in the range from 2 to 20 branching of the side chains of more than CH3/1000 carbon atoms and particularly preferably in the range from 5 to 15 branching of the side chains of more than CH3/1000 atoms of carbon is and. This characteristic can be defined solvent-resolvent fractionation, which was later called fractionation of Holtrop and described in the publication W. Holtrup, Makromol. Chem. 178, 2335 (1977), in combination with IR-study of the various factions. As solvent fractionation was used xylene and etilenglikolevye ether at 130°C. the sample of polyethylene by weight of 5 g was divided into 8 fractions. Faction has consistently investigated13C-NMR spectroscopy. The branching of the different fractions of the polymer can be defined using the13C-NMR in accordance with the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989). CDBI polyethylene according to the present invention is preferably less than 50%, in particular in the range from 10 to 45%. The method of determining the CDBI is described, for example, in WO 93/03093. TREF method is described, for example, in the publication of Wild, Advances in Polymer Science, 98, p.1-47, 57 p. 153, 1992. CDBI is defined as the percentage of copolymer molecules based on mass, in which the content of co monomer is ±25% of the average total molar content of co monomer. Branching of the side chains of more than CH3means the content of side chains per 1000 carbon atoms without end groups.

Molecular weight distribution of polyethylene according to the present invention can b the th modal, bimodal or multimodal. The term "modal molecular weight distribution" in the description of the present invention means that the molecular weight distribution has a single maximum. The term "bimodal molecular weight distribution" in this application means that the molecular weight distribution has at least two inflection points on the profile starting from the maximum. Molecular weight distribution is preferably modal or bimodal, particularly preferably bimodal.

From 1 to 15 wt.% polyethylene according to the invention with the high molecular mass, preferably from 2 to 12 wt.%, particularly preferably 3 to 8 wt.% the fractionation gel permeation chromatography (GPC) with subsequent analysis by the method of fractionation by elution with increasing temperature (analytical temperature rising elution fractionation technique - TREF) preferably does not show the peak of high density polyethylene with a maximum above 80°C, preferably above 85°C. and particularly preferably above 90°C. the Concentration of polymer in the fractions obtained at different temperatures, determined by infrared spectroscopy. TREF can also be calibrated using preparative dedicated polyethylene fractions with a certain number of short the chain branching. TREF method is described, for example, in the publication of Wild, Advances in Polymer Science, 98, p.1-47, 57 p. 153, 1992.

When the polyethylene according to the present invention is analyzed by the TREF method, fractions of the maximum above 80°C, preferably above 85°C. and particularly preferably above 90°C during the analysis of the GPC is preferably show a polyethylene with a molecular mass below 1 Mio g/mol unlike polyethylenes obtained with conventional Ziegler catalysts.

The polyethylene according to the present invention has a degree of long chain branching λ (lambda) in the interval from 0 to 2 long-chain branches/10000 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) is determined by light scattering as described, for example, in ACS publications Series 521, 1993, Chromatography of Polymers, Ed. Theodore Provder, Simon Pang and Alfred Rudin: Size-Exclusion Chromatographic Assessment of Long-Chain Branch Frequency in Polyethylenes, page 254-269.

Preferably 5-50 wt.% polyethylene according to the invention, having the lowest molecular weight, preferably 10-40 wt.% and particularly preferably 15-30 wt.%, have a degree of branching less than 10 branches/1000 carbon atoms. The degree of branching part of the polyethylene having the lowest molecular weight, is preferably from 0.01 to 9 branches/1000 atoms angle of the ode and particularly preferably from 0.1 to 6 branches/1000 carbon atoms. This characteristic can be determined using a known method of Holtrop/13C-NMR. The degree of branching/1000 carbon atoms is defined by13C-NMR as described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and means the total content of CH3groups/1000 carbon atoms.

The polyethylene according to the present invention contains 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 is defined by using the infrared spectrum in accordance with ASTM D 6248-98. In the description of the present invention, the expression "vinyl group" refers to-CH=CH2groups; vinylidene group and internal olefinic groups are not included in this term. The vinyl groups are usually reactions breakage of the polymer chain after the introduction of ethylene, while vinylidene end groups are usually formed after the reaction of breakage of the polymer chain after the introduction of the co monomer.

The polyethylene according to the present invention preferably contains from 0.01 to 20 branches of side chains of more than CH3/1000 carbon atoms, preferably side chains With2-C6/1000 carbon atoms, preferably from 1 to 15 from whom Evleri side chains of more than CH 3/1000 carbon atoms, preferably side chains With2-C6/1000 carbon atoms, particularly preferably from 2 to 8 branches of side chains of more than CH3/1000 carbon atoms, preferably side chains With2-C6/1000 carbon atoms. The number of branches of side chains more CH3/1000 carbon atoms specified by using the13C-NMR in accordance with the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and the term refers to the total content of the side chains of more than CH3groups/1000 carbon atoms (no limit). Particularly preferably, the polyethylene with 1-butene, 1-hexene or 1-octene as the α-olefin contained from 0.01 to 20 ethyl, Budilnik or exiling side branches/1000 carbon atoms, preferably from 1 to 15 ethyl, Budilnik or exiling side branches/1000 carbon atoms and particularly preferably from 2 to 8 ethyl, Budilnik or exiling side branches/1000 carbon atoms. This applies to the content of ethyl, Budilnik or exiling side chains per 1000 carbon atoms without end groups.

In the polyethylene according to the present invention the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20,000, preferably has a degree of branching of from 0 to 1.5 branches sides of the x chains more CH 3/1000 carbon atoms, preferably side chains With2-C6/1000 carbon atoms. Especially preferably the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20,000, has a degree of branching of from 0.1 to 0.9 branching of the side chains of more than CH3/1000 carbon atoms, preferably side chains With2-C6/1000 carbon atoms. Preferably the polyethylene according to the invention with 1-butene, 1-hexene or 1-octene as a 1-alkene portion of the polyethylene with a molecular weight of less than 10000 g/mol, preferably less than 20,000 g/mol, preferably has a degree of branching of from 0 to 1.5 ethyl, Budilnik or exiling branches of side chains per 1000 carbon atoms. Especially preferred part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20,000, having a degree of branching of from 0.1 to 0.9 ethyl, Budilnik or exiling branching side chains per 1000 carbon atoms. This value can also be determined by the method of Holtrop/13C-NMR mentioned above.

Further, it is preferable that at least 70% of the branches of side chains more CH3in the polyethylene according to the invention are present in 50 wt.% polyethylene with high molecular masses. It can also be determined by the method of Holtrop/13WITH YAM WHO, above.

The polyethylene according to the present invention preferably has the quality of mixing, defined in accordance with ISO 13949, less than 3, in particular from 0 to 2.5. This value is defined for polyethylene, taken directly from the reactor, i.e. polyethylene powder without prior melting in the extruder. This polyethylene powder may preferably be obtained by polymerization in a single reactor.

As 1-alkenes, representing the comonomers which may be present in the ethylene copolymers alone or in mixture with one another, in addition to ethylene in parts of ethylene copolymers of polyethylene according to the invention can be applied to all 1-alkenes containing from 3 to 12 carbon atoms, for example propene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene and 1-mission. Ethylene copolymer preferably comprises 1-alkenes containing from 4 to 8 carbon atoms, for example 1-butene, 1-penten, 1-hexene, 4-methylpentene or 1-octene in copolymerizing form as a level of co monomer. Particularly preferably, the application of 1-alkenes selected from the group consisting of 1-butene, 1-hexene and 1-octene. The polyethylene according to the invention comprises preferably from 0.01 to 5 wt.%, preferably from 0.1 to 3 wt.% the co monomer.

The polyethylene according to the invention may optionally include from 0 on the 6 wt.%, preferably from 0.1 to 1 wt.% auxiliary components and/or additives known in the art, such as stabilizers, processing stabilizers against the effects of light or high temperatures, conventional additives, such as increasing the slip, antioxidants, antiadhesive and antistatics, and also, if appropriate, dyes. A qualified specialist will know the type and quantity of such additives.

Further, it was found that the processing properties of the polyethylenes according to the present invention can be further enhanced by the addition of small amounts of forecasters or thermoplastic polyesters. Such forecaster known as additives that improve the technological properties, and are commercially available, e.g. under the trade names Viton® and Dynamar® (see also, for example, US-A-3125547). They are preferably added in an amount of from 10 to 1000 ppm, particularly preferably from 20 to 20 ppm based on the total weight of the polymer mixture according to the invention.

Typically the mixture of additives and polyethylenes according to the invention can be carried out by all known methods. It can be done, for example, the introduction of the powder components in the granulating apparatus such as kneader machine with dual auger (ZSK), mixing is Chou machine Farrel (Farrel) or kneader machine Koba (Kobe). The granulated mixture can also technologically processed directly on the plant for the production of films.

The applicants of the present invention was also provided a method of using polyethylene according to the invention for the manufacture of articles by injection molding and provided the obtained injection-molded product, preferably a screw closures, caps, flanges, fittings and technical details, in which the polyethylene according to the invention is present as a main component.

The product obtained injection molding, screw closures and caps, flanges, fittings and technical details, in which the polyethylene according to the present invention is present as a main component, represent products that contain from 50 to 100 wt.%, preferably from 60 to 90 wt.% polyethylene according to the invention is based on the whole polymer material used for production. In particular, these include products obtained injection molding, screw closures and caps, in which one of the layers contains from 50 to 100 wt.% polyethylene according to the present invention.

Matte polyethylene and products obtained injection molding according to the present invention, a thickness of 1 mm is preferable, as determined in accordance with ASTM D 1003-0 on the device BYK Gardener Haze Guard Plus Device, at least 5 pieces of film 10×10 cm below 94%, preferably ranges from 10 to 92% and particularly preferably in the range from 50 to 91%. Resistance to cracking under stress (full creep testing cut - full notch creep test - FNCT) polyethylene and products obtained injection molding, as determined according to ISO DIS2 16770 with a pressure of 3.5 Mbar at 80°C in 2 wt.% the solution Akropal (N=10) in water, is preferably at least 5 hours, preferably is in the range from 6 to 80 hours, particularly preferably in the range from 7 to 20 hours. Polyethylene and products obtained injection molding according to the present invention, a thickness of 1 mm have the preferred impact strength equal to at least 12 j, as defined by the impact test drop weight mechanism according to ISO 6603 at -20°C.

The polyethylene can be processed on standard injection molding apparatus. The texture of the products obtained injection molding, is homogeneous and can be further improved by increasing the speed of injection molding or by increasing the melting temperature.

Characteristics of fluidity in terms of the technological treatments were established by determining the yield strength in spiral form. The polyethylene was injected at a certain temperature, pressure and sorostitute screw in a form for injection molding to obtain spirals with different wall thickness. The length of the resulting helix can be considered as a measure of fluidity. Determination of yield strength in spiral form was performed with the apparatus Demag ET100-310 c locking pressure of 100 t and a mouthpiece 3 mm.

The stability of the size and shape of the polyethylene according to the invention was tested by injection molding at a temperature of from 180 to 270°C caps with thread with thread diameter of 28.2 mm, Then cover cooled and measured the diameter of the thread 50 samples, calculate the average value of the diameter and compared with the original diameter of the thread. The additional samples were examined visually on the stability of shape and size.

The polyethylene according to the invention showed high performance fluidity lengths of the spiral more than 40 cm, measured at an initial temperature of 250°C, injection pressure of 1000 bar, the speed of rotation of the screw 90 mm/s, the melting point of 30°C and a wall thickness of 2 mm.

The product obtained injection molding, preferably closures, lids and screw closures and screw caps, flanges, fittings and technical details, in which the polyethylene according to the invention is present as a main component, represent products that contain from 50 to 100 wt.%, preferably from 60 to 90 wt.% polyethylene according to the invention is based on the whole polymer material used for their production. Caps, sat the ry are preferably used for bottles, preferably bottles for soft drinks.

The polyethylene according to the invention can be obtained using the catalytic system according to the invention and in particular its preferred embodiments.

The present invention additionally relates to a catalytic composition comprising at least two different polymerization catalyst, of which (A) represents at least one polymerization catalyst based on monotsiklopentadienil complex metal 4-6 groups of the Periodic table of elements, in which cyclopentadienyls system is substituted by an uncharged (electroneutral) donor (A1) or harricana (A2), and b represents at least one polymerization catalyst based on iron component, comprising a tridentate ligand that contains at least two ortho, ortho-disubstituted aryl radical ().

The present invention relates also to a method for the polymerization of olefins in the presence of a catalytic composition according to the invention.

In accordance with the present invention uncharged donor is an uncharged (electroneutral) functional group containing an element of group 15 or 16 of the Periodic table.

Hafniensia components of the catalyst are, is, for example, cyclopentadienyls complexes. Cyclopentadienyls complexes may represent, for example, bridge or namashikaye biscyclopentadienyl complexes are described, for example, in the publications EP 129368, EP 561479, EP 545304 and EP 576970, monosyllabically complexes, such as bridge aminocyclopentane complexes are described, for example, in the publication EP 416815, multicore cyclopentadienyls complexes, which are described in EP 632063, PI-ligand-substituted tetrahydroindane, which are described in the publication EP 659758, or PI-ligand-substituted tetrahydroindene, which are described in EP 661300.

Preferred monosyllabically complexes (A1)containing the following structural distinguishing features of the General formula Cf-YmMA(I)where the variables have the following meanings:

Cf is cyclopentadienyls system

Y represents a Deputy, which is associated with Cf and contains at least one uncharged donor containing at least one atom of group 15 and 16 of the Periodic table,

MAndis titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, especially chromium,

m is 1, 2 or 3.

Suitable monosyllabically complexes (A1) containing a structural element of the General formula Cf-YmMA(I)where the variables take the up value, defined above. Thus, additional ligands can be bound to the metal atom MAnd. The number of additional ligands depends on the oxidation state of the metal atom. These ligands are not additional cyclopentadienyls systems. Suitable ligands include monoamine and gianinni ligands, for example, the ligands described for X. in Addition, the Central metal M may be connected to the base of the Lewes, such as amines, ethers, ketones, aldehydes, esters, sulfides or phosphines. Monosyllabically complexes can exist in Monomeric, dimeric or oligomeric form. Monosyllabically complexes are preferably presented in a Monomeric form.

MAndrepresents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten. The oxidation number of transition metals MAndin catalytically active complexes is usually well known to the skilled technician in the art. Chromium, molybdenum and tungsten likely present with oxidation state +3, zirconium and hafnium with oxidation state +4 and titanium - with oxidation state +3 or +4. However, it is possible to use complexes, the oxidation of which is not in accordance with the degree of oxidation of the asset is on the catalyst. Such complexes may then be subjected to a suitable recovery or oxidation with suitable activators. MAndpreferably is titanium with oxidation state 3, vanadium, chromium, molybdenum or tungsten. Particular preference is given with chromium oxidation States 2, 3 and 4, especially 3.

m may be equal to 1, 2 or 3, that is, Cf can be attached to 1, 2 or 3 donor groups Y, and when there are 2 or 3 groups Y, they may be the same or different. Preferably, only one donor group Y is linked to Cf (m=1).

Uncharged donor Y is an uncharged functional group containing an element of group 15 and 16 of the Periodic table, for example, Amin, Amin, carboxamide, ester of carboxylic acid, ketone (oxo), a simple ether, thioketone, phosphine, postit, phosphine oxide, sulfonyl, sulfonamide or unsubstituted, substituted or condensed partially unsaturated heterocyclic or aromatic heterocyclic system. Donor Y can be associated intermolecular or intramolecular bonds with the transition metal MAndor may not contact him. Preferably the donor Y is associated with intramolecular transition metal MAnd. Especially preferred monosyllabically complexes containing the structural element of the General formula Cf-Y mMA.

Cf is cyclopentadienyls system, which can be substituted in any manner and/or may be condensed with one or more aromatic, aliphatic cycles, heterocycle or aromatic heterocycle contains 1, 2 or 3 substituent, preferably 1 Deputy, formed by a group Y, and/or 1, 2 or 3 substituent, preferably 1 Deputy, replaced by a group Y and/or aromatic, aliphatic, heterocyclic, or heteroaromatic condensed cycle containing 1, 2 or 3 substituent, preferably 1 substituent. Cyclopentadienyls structure itself represents a C5the cyclic system containing 6 π electrons, in which one of the carbon atoms may also be replaced by a nitrogen atom or phosphorus, preferably phosphorus atom. Preferably the application With5cyclic systems without substitution of a heteroatom. This cyclopentadienyls structure can be, for example, condensed with heteroaromatic structure containing at least one atom selected from the group consisting of atoms N, P, O and S, or an aromatic structure. In the context of the present invention, the term "condensed" means a heterocycle and cyclopentadienyls structure have two common atom, preferably an atom is carbon. Cyclopentadienyls the system is connected with MAnd.

Particularly suitable mononitrobenzene complexes (A1) are complexes in which Y is formed by a group-Zk-A - and together with cyclopentadienyls system Cf and MAndforms monosyllabically complex containing a structural element of the General formula CR-Zk-A-MA(II)where the variables have the following meanings:

CR-Zk-A represents a

where the variables have the following meanings:

E1A-E5Aeach represent a carbon atom or not more than one of the E1A-E5Arepresents a phosphorus atom.

R1A-R4Aeach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR5A2N(SiR5A3)2, OR5A, OSiR5A3, SiR5A3, BR5A2where the organic radicals R1A-R4Acan be substituted by Halogens and two vicinal radicals R1A-R4Acan be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R1A-R4Acan be combined with education is the use of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S,

the radicals R5Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two pairs of radicals R5Aalso can be connected with the formation of five - or six-membered cycle,

Z represents a divalent bridge between a and CP, which is selected from the following groups:

BR6A-, -BNR6AR7A-, -AlR6A- -Sn-, -O-, -S-, -SO-, -SO2-, -NR6A-, -CO-, -PR6A- or-P(O)R6A-,

where

L1A-L3Aeach, independently of one another, represent an atom of silicon or germanium,

R6A-R11Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR12Awhere the organic radicals R6A-R11Amay be substituted by halogen, or two pair or vicinal radicals of R6A-R11Aalso can be connected with the formation of five - or six-membered cycle,

the radicals R 12Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl or alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, With1-C10-alkoxy or6-C10-aryloxy, and two radicals R12Acan be connected with the formation of five - or six-membered cycle,

And is uncharged donor containing one or more atoms 15 and/or 16 groups of the Periodic table of elements, preferably unsubstituted, substituted or condensed aromatic heterocyclic system,

MAndrepresents a metal selected from the group consisting of titanium with the oxidation state 3, vanadium, chromium, molybdenum and tungsten, in particular chromium, and

k is 0 or 1.

In the preferred cyclopentadienyls systems Cf all E1A-E5Arepresent a carbon atom.

On the curing properties of the metal complexes can be influenced by various substituents R1A-R4A. The number and type of substituents can affect the availability of the metal atom M to olefins, subject to polymerization. In this case, you can modify the activity and selectivity of the catalyst with respect to the various monomers, in particular the volume of monomers. As deputies are also which influence the rate of reaction is complete, the growth of the polymer chain, thus, you can modify the molecular weight of the produced polymers. Therefore, the chemical structure of the substituents R1A-R4Amay vary in a wide range to achieve the desired result and to obtain a catalytic system with the desired properties. Possible operatingincome substituents R1A-R4Aare, for example, the following: hydrogen, C1-C22-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain as Deputy C1-C10is an alkyl group and/or C6-C10-aryl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R1A-R4Acan also be connected with the formation of 5-, 6 - or 7-membered cycle and/or two vicinal radicals of R1A-R4Acan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S, and/or the organic radicals R1A-R4Acan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R1A-R4Amay be an amino group, NR5A2or N(SiR5A3)2, alkoxy or aryloxy OR5Afor example dimethylamino, N-pyrrolidinyl, picoline, methoxy, ethoxy or isopropoxy. The radicals R5Ain organosilicon substituents SiR5A3can be uglerodosoderzhaschie radicals described above for R1A-R4Awhere two radicals R5Acan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. Radicals SiR5A3can also join the change to cyclopentadienyls the structure via an oxygen atom or nitrogen, and represent, for example, trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylsilane. Preferred radicals R1A-R4Aare 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 dichlorsilane family, trialkyl or trichlorsilane family, naphthyl, biphenyl and anthranol. Possible organosilicon substituents are, in particular, trialkylsilyl group containing from 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl group.

Two vicinal radicals of R1A-R4Atogether with the containing E1A-E5Acan form a heterocycle, preferably a heteroaromatic containing at least one atom selected from the group consisting of nitrogen atoms, phosphorus, oxygen and sulfur, particularly preferably nitrogen and/or sulfur, and E1A-E5Apresent in the heterocycle or aromatic heterocycle, preferably represent carbon atoms. Preference is given to compounds and heteroaromatic cycles containing 5 or 6 atoms in the cycle. Examples of 5-membered heterocycles, which apart from carbons can contain in a loop from one to four nitrogen atoms and/or sulfur atom Il is oxygen, are 1,2-dihydrofuran, furan, thiophene, pyrrole, isoxazol, 3-isothiazol, 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 which may contain one to four nitrogen atoms and/or phosphorus atom, are pyridine, postabortal, pyridazine, pyrimidine, pyrazin, 1,3,5-triazine 1,2,4-triazine or 1,2,3-triazine. 5-membered and 6-membered heterocycles may also be substituted C1-C10-alkyl, C6-C10-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogen, such as fluorine, chlorine or bromine, dialkylamino, alkylolamides, diarylamino, alkoxy or aryloxy or may be condensed with one or more aromatic or heteroaromatic cycles. Examples of benzo-condensed 5-membered heteroaryl groups are indole, indazole, benzofuran, benzothiophene, benzothiazole, benzoxazole and benzimidazole. Examples of benzo-condensed 6-membered heteroaryl groups are Roman, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, hinzelin, cinoxacin, 1,10-phenanthrolin and hemolysin. Names and numbering of the atoms of the heterocycles were taken from the publication Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979. Heterocycles/Goethe is aromaticheskie cycles are preferably condensed with cyclopentadienyls structure through C-C double bond of the heterocycle/heteroaromatic cycle. Heterocycles/aromatic heterocycles containing one heteroatom, preferably are 2,3 - or b-condensed.

Cyclopentadienyls systems Cp, condensed with a heterocycle include, for example, thiopental, 2-methylthiophenol, 2-ethylthiophene, 2-isopropylthioxanthone, 2-n-butylthioethyl, 2-tert-butylthiophenol, 2-trimethylsilylmethyl, 2-phenylthiophene, 2-aftercapture, 3-methylthiophenol, 4-phenyl-2,6-dimethyl-1-thiopental, 4-phenyl-2,6-diethyl-1-thiopental, 4-phenyl-2,6-aminobutiramida 1-thiopental, 4-phenyl-2,6-di-n-butyl-1-thiopental, 4-phenyl-2,6-ditrimethylol-1-thiopental, isopentane, 2-methylisophthalic, 2-atlasapollo, 2-isopropylnaphthalene, 2-n-butylacetate, 2-trimethylsilylacetamide, 2-phenylazophenyl, 2-naphthylacetate, 1-phenyl-2,5-dimethyl-1-isopentane, 1-phenyl-2,5-diethyl-1-isopentane, 1-phenyl-2,5-di-n-butyl-1-isopentane, 1-phenyl-2,5-di-tert-butyl-1-isopentane, 1-phenyl-2,5-di-trimethylsilyl-1-isopentane, 1-tert-butyl-2,5-dimethyl-1-aspendale, oxapentane, phosphopentose, 1-phenyl-2,5-dimethyl-1-phosphopentose, 1-phenyl-2,5-diethyl-1-phosphopentose, 1-phenyl-2,5-di-n-butyl-1-phosphopentose, 1-phenyl-2,5-di-tert-butyl-1-phosphopentose, 1-phenyl-2,5-di-trimethylsilyl-1-phosphopentose, 1-methyl-2,5-dimethyl-1-phosphopentose, 1-tert-butyl-2,5-dimethyl-1-phosphopentose, 7-cyclopent[1,2]thiophene[3,4]cyclopentadiene or 7-qi is lapenta[1,2]pyrrole[3,4]cyclopentadiene.

In additional preferred cyclopentadienyls systems Cp four radical R1A-R4Ai.e. two pairs of vicinal radicals formed by two heterocycle, in particular aromatic heterocycle. Heterocyclic systems are systems described above.

Cyclopentadienyls system Cp containing two condensed heterocycle, represents, for example, 7-cyclopentadien, 7-cyclopentadienyl or 7-cyclopentadien.

The synthesis of such cyclopentadienyls systems condensed with a heterocycle described, for example, in the above-mentioned publication WO 98/22486. In the publication "Metalorganic catalysts for synthesis and polymerisation", Springer Verlag 1999, Ewen et al., p. 150 also describes the synthesis of such cyclopentadienyls systems.

Particularly preferred substituents R1A-R4Aare uglerodosoderzhaschie substituents described above and uglerodosoderzhaschie substituents, which form a condensed cyclic system, i.e. with E1A-E5A-cyclopentadienyls structure, preferably C5-cyclopentadienyls structure, form, for example, unsubstituted or substituted indenolol, besindario, phenanthroline, fluoroanilino or tetrahydroindole system, and, in particular, their preferred options for implementation.

Examples of such CEC is pentadienyl systems (without a group-Z-A-, which usually is in position 1)are 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3-isopropylcyclopentadienyl, 3-tert-butylcyclopentadienyl, dialkylacrylamide, such as tetrahydroindene, 2,4-dimethylcyclopentane or 3-methyl-5-tert-butylcyclopentadienyl, trialkylsilanes, such as 2,3,5-trimethylcyclopentanone, or tetraalkyllead, such as 2,3,4,5-tetramethylcyclopentadienyl and indenyl, 2-methylindenyl, 2-ethylidene, 2-isopropylphenyl, 3-methylindenyl, benzinger and 2-methylbenzhydryl. Condensed cyclic system can optionally contain C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR5A2N(SiR5A3)2, OR5A, OSiRSA3or SiR5A3for example , 4-methylindenyl, 4-ethylidene, 4-isopropylphenyl, 5-methylindenyl, 4-phenylindane, 5-methyl-4-phenylindane, 2-methyl-4-phenylindane or 4-naphthylidine.

In a particularly preferred embodiment of the invention one of the substituents R1A-R4Apreferably R2Arepresents a C6-C22-aryl or alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 atoms angle of the ode in the aryl part, preferably C6-C22-aryl, such as phenyl, naphthyl, biphenyl, anthracene or phenanthrene, where the aryl may also be substituted by N-, P-, O - or S-containing substituents, C1-C22-alkyl, C2-C22-alkenyl, halogen or halogenation or halogenosilanes containing 1-10 carbon atoms, and represent, for example, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, o-, m-, p-dimethylaminophenyl, o-, m-, p-methoxyphenyl, o-, m-, p-forfinal, o-, m-, p-chlorophenyl, o-, m-, p-triptoreline, 2,3-, 2,4-, 2,5 - or 2,6-differenl, 2,3-, 2,4-, 2,5 - or 2,6-dichlorophenyl, or 2,3-, 2,4-, 2,5 - or 2,6-di(trifluoromethyl)phenyl. N-, P-, O - or S-containing substituents, C1-C22-alkyl, C2-C22alkenyl, halogen or halogenated or galogenidy containing 1-10 carbon atoms as substituents on the aryl radical, preferably located in the para-position relative to the connection with cyclopentadienyls ring. Aryl Deputy can join in vicinal position relative to the substituent-Z-A or two Deputy located relative to each other in the 1,3-positions on cyclopentadienyls ring. -Z-A and aryl Deputy preferably are located in the 1,3-positions relative to each other on cyclopentadienyls ring.

If metal is ENES monosyllabically complexes (A1) can be chiral. Thus, one of the substituents R1A-R4Acyclopentadienyls structure may have one or more chiral centers, or itself cyclopentadienyls system Cp may be a while, so that the chirality is introduced only when it is linked to the transition metal M (rules of chirality in cyclopentadienyls connections, see publication R. Halterman, Chem. Rev. 92, (1992), 965-994).

The bridge Z between cyclopentadienyls system Cp and uncharged donor A is a divalent organic bridge (k=1), which preferably consists of carbon and/or silicon and/or boron-containing units, forming a bridge. On the activity of the catalyst can be influenced by changing the length of the connection between cyclopentadienyls system and A. Z is preferably connected with cyclopentadienyls structure next to condensed heterocycle or a condensed aromatic cycle. Thus, when the heterocycle or aromatic cycle condensed in the 2,3-positions cyclopentadienyls patterns, then Z preferably is in position 1 or 4 cyclopentadienyls structure.

Possible operatingincome substituents R6A-R11Aon the bridge Z are, for example, the following substituents: hydrogen, C1-C20-alkyl which may be linear or branched, for example methyl, e is Il, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C6-C10-aryl group as substituent, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C20alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C20-aryl which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimethylpent-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylpent-1-yl, or arylalkyl, which can be substituted for more alkyl groups, and represent, for example, benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where two of R6A-R11Acan also be connected with the formation of 5 - or 6-membered cycle, for example cyclohexane, and the organic radicals R6A-R11Acan also be substituted by Halogens such as fluorine, chlorine or bromine, and represent, for example pentafluorophenyl or bis-3,5-trifter etilen-1-yl, and alkyl or aryl.

The radicals R12Ain organosilicon substituents SiR12A3can represent the same radicals listed above for R6A-R11Awhere two radicals R12Acan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. Preferred radicals R6A-R11Aare 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 finely, trialkyl - or trichloro-substituted finely, naphthyl, biphenyl and anthranol.

Particularly preferred substituents R6A-R11Aare hydrogen, C1-C20-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, C6-C20-aryl which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimethylpent-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylpent-1-yl, or arylalkyl, which can be substituted for more alkyl groups, for example benzyl, -, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R6A-R11Acan also be connected with the formation of 5 - or 6-membered cycle, for example cyclohexane, and the organic radicals R6A-R2Bcan also be substituted by Halogens such as fluorine, chlorine or bromine, in particular fluorine, and represent, for example pentafluorophenyl or bis-3,5-triptoreline-1-yl, and alkyl or aryl. Especially preferred are methyl, ethyl, 1-propyl, 2-isopropyl, 1-butyl, 2-tert-butyl, phenyl and pentafluorophenyl.

Z preferably represents a group-CR6AR7A-, -SiR6AR7A-in particular

-Si(CH3)2, -CR6AR7ACR8AR9A-, -SiR6AR7ACR8AR9A-, or substituted or unsubstituted 1,2-phenylene, in particular CR6AR7A-. Preferred variants of the substituents R6A-R11Adescribed above are the preferred option in this case. Preferred CR6AR7Aare-CHR6A-,CH2- or-C(CH3)2group.

Group-SiR6AR7Ain L1AR6AR7ACR8AR9A- can be attached to cyclopentadienyls system or to A. This group-SiR6AR7Aor her preferred option preferably attached to the Cp.

k is 0 or 1; in particular, k is 1 or, when A p is ecstasy unsubstituted, substituted or condensed heterocyclic ring system may also be 0. Preferably k is 1.

A represents an uncharged donor containing an atom of group 15 and 16 of the Periodic table, preferably one or more atoms selected from the group consisting of atoms of oxygen, sulfur, nitrogen and phosphorus, preferably nitrogen and phosphorus. Donor functional group in A may be joined to the metal M via intermolecular or intramolecular bonds. The donor in A preferably associated with M. intramolecular Potential donors are uncharged functional group containing an element of group 15 and 16 of the Periodic table, for example, Amin, Amin, carboxamide, ester of carboxylic acid, ketone (oxo), a simple ether, thioketone, phosphine, postit, phosphine oxide, sulfonyl, sulfonamide or unsubstituted, substituted or condensed heterocyclic ring system. Accession And cyclopentadienyls the radical and Z can be synthetically, for example by way of synthesis, similar to that described in WO 00/35928.

And preferably represents a group selected from-OR13A-, -SR13A-,

-NR13AR14A-,

-PR13AR14A- ,- (C=NR13Aand unsubstituted, substituted or condensed aromatic heterocyclic systems, the company is and

-NR13AR14A- ,- (C=NR13A-, and unsubstituted, substituted or condensed aromatic heterocyclic system.

R13Aand R14Aeach, independently of one another, represent hydrogen, C1-C20-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C6-C10-aryl group as substituent, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C20alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C20-aryl which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimethylpent-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylpent-1-yl, alkylaryl, which contains from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and can be replaced by the additional is skillname groups, for example, benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl or SiR15A3where the organic radicals R13A-R14Acan also be substituted by Halogens such as fluorine, chlorine or bromine, or nitrogen-containing groups and additional C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR15A3group and two vicinal radicals R13A-R14Acan also be connected with the formation of five - or six-membered cycle, and the radicals R15Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl or alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R15Acan also be connected with the formation of five - or six-membered cycle.

NR13AR14Ais amide Deputy. It preferably is a secondary amide, such as dimethylamide, N-ethylmethylamino, diethylamide, N-methylpropylamine, N-methylisophthalic, N-ethylisopropylamine, dipropylamine, Diisopropylamine, N-methylbutylamine, N-ethylbutylamine, N-methyl-tert-butylamide, N-tert-butylenediamine, dibutylamine, di-sec-butylamide, Diisobutyl the amide, tert-amyl-tert-butylamide, dipentine, N-methylhexane, vexille, tert-amyl-tert-octylated, dioctylamine, bis(2-ethylhexyl)amide, dodecylamine, N-methyloctadecane, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexane, N-tert-butylcyclohexylamine, dicyclohexylamine, pyrrolidine, piperidine, hexamethylenimine, decahydroquinoline, diphenylamine, N-methylaniline or N-ethylaniline.

In aminogroup-C=NR13AR13Apreferably represents C6-C20-aryl radical which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimethylpent-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylpent-1-yl.

A preferably represents an unsubstituted, substituted or condensed aromatic heterocyclic system, which in addition to carbon atoms, may contain in the cycle heteroatoms selected from the group consisting of atoms of oxygen, sulfur, nitrogen and phosphorus. Examples of 5-membered heteroaryl groups which can contain as atoms of the cycle in addition to carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and atom and/or sulfur or oxygen, are 2-furyl, 2-thienyl, 2-pyrrolyl, 3-isoxazolyl, 5-isoxazolyl, 3-isothiazole, 5-isothiazole, 1-pyrazolyl, 3-pyrazolyl, 5-a feast which was Salil, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl and 1,2,4-triazole-3-yl. Examples of 6-membered heteroaryl groups which may contain one to four nitrogen atoms and/or phosphorus atom are 2-pyridinyl, 2-phosphobenzene, 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. 5-membered and 6-membered heteroaryl group may also be substituted C1-C10-alkyl, C6-C10-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogen, such as fluorine, chlorine or bromine, or may be condensed with one or more aromatic or heteroaromatic groups. Examples benzododecinium 5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumaroyl, 7-coumarinyl, 2-thionaphthene, 7-thionaphthene, 3-indazole, 7-indazole, 2-benzimidazolyl and 7 benzimidazolyl. Examples benzododecinium 6-membered heteroaryl groups are 2-chinolin, 8-chinolin, 3-cinnolin, 8-cinnamyl, 1-ftalazol, 2-chinadoll, 4-chinadoll, 8-chinadoll, 5-Minoxidil, 4-acridin, 1-phenanthridine and 1-fedasil. The nomenclature and numbering of heteros the clov taken from the publication L.Fieser and M. Fieser, Lehrbuch der organischen Chemie, 3rdrevised edition, Verlag Chemie, Weinheim 1957.

Among these heteroaromatic systems A particularly preferred unsubstituted, substituted and/or condensed six-membered heteroaromatic group containing 1, 2, 3, 4 or 5 nitrogen atoms in the heteroaromatic part, in particular substituted and unsubstituted 2-pyridyl or 2-chinolin. Thus, A preferably represents a group of formula (IV)

where

E6A-E9Aeach, independently of one another, represent carbon or nitrogen,

R16A-R19Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR20A3where the organic radicals R16A-R19Acan also be substituted by Halogens or nitrogen and an additional C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR20A3and two vicinal radicals of R16A-R19Aor R16Aand Z can also be connected with the formation of five - or six-membered cycle and

the radicals R20A each, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl or alkylaryl containing from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R20Acan also be connected with the formation of five - or six-membered cycle and

p is 0 when E6A-E9Arepresent a nitrogen atom, and is 1 when E6A-E9Arepresent a carbon atom.

In particular 0 or 1 E6A-E9Arepresent the nitrogen atom and the others are carbon atoms. Particularly preferably, A is 2-pyridyl, 6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl, 3-pyridil, 4 pirimidil, 2-pyrazinyl, 6-methyl-2-pyrazinyl, 5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethylpyrazine, 3,5,6-trimethyl-2-pyrazinyl, 2-chinolin, 4-methyl-2-chinolin, 6-methyl-2-chinolin, 7-methyl-2-chinolin, 2-Minoxidil or 3-methyl-2-Minoxidil.

Thanks to the ease of obtaining the preferred combinations of Z and A are those in which Z represents unsubstituted or substituted 1,2-phenylene and A is NR16AR17Aand in which Z is-CHR6A-, -CH2-, -C(CH3)2or-Si(CH3)2and A is unsubstituted or substituted 2-chinolin or unsubstituted or is ewenny 2-pyridyl. System without bridge Z in which k is 0, are particularly simple to synthesize. In this case, A preferably represents unsubstituted or substituted 8-chinolin. In addition, when k is 0, R2Apreferably represents C6-C22-aryl or alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, preferably C6-C22-aryl, such as phenyl, naphthyl, biphenyl, anthracene or phenanthrene, where the aryl may also be substituted by N-, P-, O - or S-containing substituents, C1-C22-alkyl, C2-C22-alkenyl, halogen or halogenation or halogenosilanes containing 1-10 carbon atoms.

Preferred options described above for variables, also preferred in such preferred combinations.

MArepresents a metal selected from the group consisting of titanium with the oxidation state 3, vanadium, chromium, molybdenum and tungsten, preferably titanium with a degree of oxidation of 3 and chrome. Particularly preferred chromium with the oxidation States 2, 3 and 4, in particular 3. The metal complexes, in particular the chromium complexes, can be obtained in a simple way by the interaction of the appropriate metal salts, for example chlorides of the metals, with the ligand anion (for example, using a method similar to that described what the examples in the publication DE 19710615).

Among suitable monosyllabically complexes (A1) is preferred complexes of the formula Cp-YmMAXn(V)where the variables Cp, Y, A, m and MAtake the values defined above and their preferred options, which are also preferred, and in this case, and:

XAeach, independently of one another, represents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C20-aryl, alkylaryl containing 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR21AR22A, OR21A, SR21A, SO3R21A, OC(O)R21A, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion, or two radicals XAform a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals XAcan connect to each other,

R21A-R22Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR23A3where the organic radicals R21A-R22Acan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R21AR 22Acan also be connected with the formation of five - or six-membered cycle,

the radicals R23Aeach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R23Acan also be connected with the formation of five - or six-membered cycle and

n is 1, 2, or 3.

Options for implementation and preferred embodiments of described above for Cp, Y, Z, A, m, and MAalso apply separately and in conjunction with these preferred mononitrobenzene complexes.

The ligands XAget, for example, by selection of suitable starting compounds of the metals used for the synthesis of monosyllabically complexes, but can also be changed after that. Possible ligands XAare, in particular, halogen, such as fluorine, chlorine, bromine or iodine, especially chlorine. Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, and phenyl or benzyl are preferred ligands XA. In addition, as additional examples of ligands XAbut without the constraints can be specified triptorelin, BF4-PF6-and weakly coordinating the e or coordinarussia anions (see, for example, S. Strauss, Chem. Rev. 1993, 93, 927-942), for example B(C6F5)4-.

Amides, alkoxides, sulfonates, carboxylates and β-diketonates are also particularly appropriate ligands XA. Changing the radicals R21Aand R22Aallows you to subtly adjust the physical properties, such as solubility. Possible operatingincome substituents R21A-R22Aare, for example, the following: C1-C20-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C6-C10-aryl group as substituent, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C20alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C20-aryl which can be substituted for more alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, 2-methoxyphenyl, 2-N,N-dimethylaminophenyl or arylalkyl where arylalkyl can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where R21Acan also be connected with R22Awith the formation of 5 - or 6-membered cycle, and organic radicals R21A-R22Acan also be substituted by Halogens such as fluorine, chlorine or bromine. Possible radicals R23Ain organosilicon substituents SiR23A3are the radicals specified above for R21A-R22Awhere two R23Acan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, trialkylsilyl, triphenylene or dimethylphenylsilane. Preferably the use of C1-C10-alkyl, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, as well as vinyl, allyl, benzyl and phenyl as radicals R21Aand R22A. Some of these substituted ligands X are particularly preferred because they can be obtained from cheap and readily available starting materials. Thus, particularly preferred is a variant in which Ais dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluensulfonate, acetate or acetylacetonate.

The number n of ligands XAdepends on the oxidation state of the transition metal MA. Therefore, the number n can not lead in the General description. The oxidation number of transition metals MAin catalytically active complexes is well known to the skilled technician in the art. Chromium, molybdenum and tungsten, it is highly likely to be present with oxidation state +3, vanadium - with oxidation state +3 or +4. However, it is possible to use complexes, the degree of oxidation which does not correspond to the oxidation state of the active catalyst. Such complexes may then appropriately be subject to recovery or oxidation with suitable activators. Preferably the application of the chromium complexes with oxidation state +3 and complexes of titanium with a degree of oxidation 3.

Preferred mononitrobenzene complexes (A1) of this type are dichloride, 1-(8-chinolin)-3-vinylcyclopentane(III)dichloride, 1-(8-chinolin)-3-(1-naphthyl)cyclopentadienyl(III)dichloride, 1-(8-chinolin)-3-(4-triptoreline)cyclopentadienyl(III)dichloride, 1-(8-chinolin)-2-methyl-3-vinylcyclopentane(III)dichloride, 1-(8-chinolin)-2-methyl-3-(1-naphthyl)cyclopentane is nichrome(III), dichloride, 1-(8-chinolin)-2-methyl-3-(4-triptoreline)cyclopentadienyl(III)dichloride, 1-(8-chinolin)-2-phenylindolizine(III)dichloride, 1-(8-chinolin)-2-phenylbenzimidazole(III)dichloride, 1-(8-(2-medicinalis))-2-methyl-3-vinylcyclopentane(III)dichloride, 1-(8-(2-medicinalis))-2-fenilalanina(III), dichloride, 1-(2-pyridylmethyl)-3-vinylcyclopentane(III)dichloride, 1-(2-pyridylmethyl)-2-methyl-3-vinylcyclopentane(III)dichloride, 1-(2-chenailler)-3-vinylcyclopentane, dichloride, 1-(2-pyridylethyl)-3-vinylcyclopentane, dichloride, 1-(2-pyridyl-1-methylethyl)-3-vinylcyclopentane, dichloride, 1-(2-pyridyl-1-phenylmethyl)-3-vinylcyclopentane, dichloride, 1-(2-pyridylmethyl)-Ingenieria(III)dichloride, 1-(2-chenailler)Ingenieria, dichloride, 1-(2-pyridylethyl)Ingenieria, dichloride, 1-(2-pyridyl-1-methylethyl)Ingenieria, dichloride, 1-(2-pyridyl-1-phenylmethyl)Ingenieria, dichloride, 5-[(2-pyridyl)methyl]-1,2,3,4-tetramethylcyclopentadienyl and dichloride, 1-(8-(2-medicinalis))-2-methylbenzenamine(III).

Methods of obtaining such functional cyclopentadienyls of known ligands. Different ways of synthesis of such complexing ligands are described, for example, in the publication M. Enders et al., Chem. Ber. (1996), 129, 459-463 or in publications P. Jutzi and U. Siemeling, J. Orgmet. Chem. (1995), 500, 175-185.

The synthesis of these complexes can be FPIC is the means which are known per se, preferably by the interaction of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, vanadium or chromium. Examples of suitable methods are described, for example, in the publication Journal of Organometallic Chemistry, 369 (1989), 359-370 and in EP-A-1212333.

Especially preferred hipnotizame (A2) are complexes of hafnium General formula (VI)

where the substituents and indices have the following meanings:

XBrepresents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C15-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, -OR6Bor-NR6BR7Bor two radicals XBform a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals XBare the same or different and may join to each other,

E1B-E5Beach represent a carbon atom or one of the E1B-E5Brepresents an atom of phosphorus or nitrogen, preferably represents a carbon atom,

t is 1, 2 or 3 and depends on the valency Hf, so that the metallocene complex of General formula (VI) is uncharged,

where

R6Band R7Beach represent C1-C10 -alkyl, C6-C15-aryl, alkylaryl, arylalkyl, foralkyl or ferril, each of which contains from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part;

R1B-R5Beach, independently of one another, represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which can, in turn, contain a C1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl containing from 1 to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR8B2N(SiR8B3)2, OR8B, OSiR8B3, SiR8B3where the organic radicals R1B-R5Bcan also be substituted by Halogens and/or two radicals of R1B-R5Bin particular vicinal radicals, may also be connected with the formation of five-, six - or semichasnoho cycle and/or two vicinal radicals of R1D-R5Dcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S, where

the radicals R8Bmay be the same or different and each may represent C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-the reel, C1-C4-alkoxy or C6-C10-aryloxy and

Z1Bis XBor

where the radicals

R9B-R13Beach, independently of one another, represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which can, in turn, contain a C1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl containing from 1 to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR14B2N(SiR14B3)2, OR14B, OSiR14B3, SiR14B3where the organic radicals R9B-R13Bcan also be substituted by Halogens and/or two radicals of R9B-R13Bmore precisely vicinal radicals, may also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R9B-R13Bcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O and S, where

the radicals R14Bare the same or different and each represents C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl, C1-C4-alkoxy or C6-C10-aryloxy,

6B-E10Beach represent a carbon atom or one of the E6B-E10Brepresents a phosphorus atom or a nitrogen atom, and preferably represents a carbon atom,

or where the radicals R4Band Z1Btogether form-R15B-A1Bgroup,

R15Bis

=BR16B, =BNR16BR17B, =AlR16B, -Ge-, -Sn-, -O- -S-, =SO, =SO2, =NR16B, =CO, =PR16Bor =P(O)R16B,

where

R16B-R21Bare the same or different and each represents a hydrogen atom, halogen atom, trimethylsilyloxy group, C1-C10is an alkyl group, a C1-C10-alkyl fluoride group, a C6-C10-porarily group, C6-C10-aryl group, a C1-C10-CNS group, C7-C15-alkylresorcinol group, C2-C10-alkenylphenol group, C7-C40-arylalkyl group, C8-C40-arylalkyl group or a C7-C40-alcylaryl group, or two adjacent radicals together with the atoms connecting them form a saturated or unsaturated cycle containing from 4 to 15 carbon atoms, and

M2B-M4Beach represents an atom of silicon, germanium or tin, preferably silicon,

A1Bis

-NR22B 2, -PR22B2or unsubstituted, substituted or condensed heterocyclic system, where

the radicals R22Beach, independently of one another represent C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, C7-C18-alkylaryl or Si(R23B)3,

R23Brepresents hydrogen, C1-C10-alkyl, C6-C15-aryl, which may, in turn, contain a C1-C4-alkyl groups as substituents, or C3-C10-cycloalkyl,

v is 1 or when A1Bis unsubstituted, substituted or condensed heterocyclic system may also be 0;

or where the radicals R4Band R12Btogether form-R15Bgroup.

A1Bmay, for example, together with bridge R15Bto form an amine, a simple ether, thioether or phosphine. However, A1Bcan also be an unsubstituted, substituted or condensed aromatic heterocyclic system, which in addition to carbon atoms, may contain in the cycle heteroatoms selected from the group consisting of atoms of oxygen, sulfur, nitrogen and phosphorus. Examples of 5-membered heteroaryl groups which, besides carbon atoms, can contain in a loop from one to four nitrogen atoms and/or sulfur atom or oxygen, are the I 2-furyl, 2-thienyl, 2-pyrrolyl, 3-isoxazolyl, 5-isoxazolyl, 3-isothiazole, 5-isothiazole, 1-pyrazolyl, 3-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl and 1,2,4-triazole-3-yl. Examples of 6-membered heteroaryl groups which may contain a loop from one to four nitrogen atoms and/or phosphorus atom are 2-pyridinyl, 2-phosphobenzene, 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. 5-membered and 6-membered heteroaryl group may also be substituted C1-C10-alkyl, C6-C10-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogen, such as fluorine, chlorine or bromine, or may be condensed with one or more aromatic or heteroaromatic groups. Examples benzododecinium 5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumaroyl, 7-coumarinyl, 2-thionaphthene, 7-thionaphthene, 3-indazole, 7-indazole, 2-benzimidazolyl and 7 benzimidazolyl. Examples benzododecinium 6-membered heteroaryl groups are 2-chinolin, 8-chinolin, 3-cinnolin, 8-cinnamyl, 1-ftalazol, 2-imazalil, 4-chinadoll, 8-chinadoll, 5-Minoxidil, 4-acridin, 1-phenanthridine and 1-fedasil. The nomenclature and numbering of the compounds taken from the publication L.Fieser, M. Fieser, Lehrbuch der organischen Chemie, 3rdrevised edition, Verlag Chemie, Weinheim 1957.

The radicals XBin the General formula (XIV) are preferably the same and preferably represent fluorine, chlorine, bromine, C1-C7is alkyl or aralkyl, in particular chlorine, methyl or benzyl.

The synthesis of such complexes can be carried out by known methods, preferably by engagement of suitable substituted cyclic hydrocarbon anions with halides of hafnium. Examples of suitable synthesis methods are described, for example, in Journal of Organometallic Chemistry, 369 (1989), 359-370.

Garrity can be used in racemic or pseudoracemic form. The term "pseudoracemic form" refers to complexes in which two cyclopentadienyls ligand are racemic manner relative to each other, when all other substituents of the complex is not taken into account.

Examples of suitable guarracino (A2) are, among others, the following:

dichloride Methylenebis(cyclopentadienyl)hafnium, the dichloride Methylenebis(3-methylcyclopentadienyl)hafnium, the dichloride Methylenebis(3-n-butylcyclopentadienyl)hafnium, the dichloride methylenbis(indenyl)hafnium, the dichloride methylenbis(tetrahydroindene)creating the, dichloride isopropylene(cyclopentadienyl)hafnium, the dichloride isopropylidenebis(3-trimethylsilylcyanation)hafnium, the dichloride isopropylidenebis(3-methylcyclopentadienyl)hafnium, the dichloride isopropylidenebis(3-n-butylcyclopentadienyl)hafnium, the dichloride isopropylidenebis(3-vinylcyclopentane)hafnium, the dichloride isopropylidenebis(indenyl)hafnium, the dichloride isopropylidenebis(tetrahydroindene)hafnium, the dichloride dimethylselenide(cyclopentadienyl)hafnium, the dichloride dimethylselenide(indenyl)hafnium, the dichloride dimethylselenide(tetrahydroindene)hafnium, the dichloride ethylenebis(cyclopentadienyl)hafnium, the dichloride ethylenebis(indenyl)hafnium, the dichloride ethylenebis(tetrahydroindene)hafnium, the dichloride tetramethylethylene-9-fluorenylacetamide, the dichloride dimethylselenide(tetramethylcyclopentadienyl)hafnium, the dichloride dimethylselenide(3-trimethylsilylcyanation)hafnium, the dichloride dimethylselenide(3-methylcyclopentadienyl)hafnium, the dichloride dimethylselenide(3-n-butylcyclopentadienyl)hafnium, the dichloride dimethylselenide(3-tert-butyl-5-methylcyclopentadienyl)hafnium, the dichloride dimethylselenide(3-tert-butyl-5-ethylcyclopentadienyl)hafnium, the dichloride dimethylselenide(2-methylindenyl)hafnium, the dichloride dimethylselenide(2-isopropylphenyl)hafnium, the dichloride dimethylselenide(2-tert-BU Ilinden)hafnium, dibromide determinatives(2-methylindenyl)hafnium, the dichloride dimethylselenide(3-methyl-5-methylcyclopentadienyl)hafnium, the dichloride dimethylselenide(3-ethyl-5-isopropylcyclopentadienyl)hafnium, the dichloride dimethylselenide(2-ethylidene)hafnium, the dichloride dimethylselenide(2-methyl-4,5-benzinger)hafnium, the dichloride dimethylselenide(2-ethyl-4,5-benzinger)hafnium, the dichloride methylphenylethylamine(2-methyl-4,5-benzinger)hafnium, the dichloride methylphenylethylamine(2-ethyl-4,5-benzinger)hafnium, the dichloride diphenylsilanediol(2-methyl-4,5-benzinger)hafnium, the dichloride diphenylsilanediol(2-ethyl-4,5-benzinger)hafnium, the dichloride diphenylsilanediol(2-methylindenyl)hafnium, the dichloride dimethylselenide(2-methyl-4-phenylindane)hafnium, the dichloride dimethylselenide(2-ethyl-4-phenylindane)hafnium, the dichloride dimethylselenide(2-methyl-4-(1-naphthyl)indenyl)hafnium, the dichloride dimethylselenide(2-ethyl-4-(1-naphthyl)indenyl)hafnium, the dichloride dimethylselenide(2-propyl-4-(1-naphthyl)indenyl)hafnium, the dichloride dimethylselenide(2-isobutyl-4-(1-naphthyl)indenyl)hafnium, the dichloride dimethylselenide(2-propyl-4-(9-phenanthrol)indenyl)hafnium, the dichloride dimethylselenide(2-methyl-4-isopropylidene)hafnium, the dichloride dimethylselenide(2,7-dimethyl-4-isopropylidene)hafnium, the dichloride dimethylselenide(2-methyl-4,6-diisopropylphenol)hafnium, dig arid dimethylselenide(2-methyl-4[p-triptoreline]indenyl)hafnium, dichloride dimethylselenide(2-methyl-4-[3',5'-dimetilfenil]indenyl)hafnium, the dichloride dimethylselenide(2-methyl-4-[4'-tert-butylphenyl]indenyl)hafnium, the dichloride determinatives(2-methyl-4-[4'-tert-butylphenyl]indenyl)hafnium, the dichloride dimethylselenide(2-ethyl-4-[4'-tert-butylphenyl]indenyl)hafnium, the dichloride dimethylselenide(2-propyl-4-[4'-tert-butylphenyl]indenyl)hafnium, the dichloride dimethylselenide(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride dimethylsilanol(2-isopropyl-4-phenylindane)(2-methyl-4-phenylindane)hafnium, dichloride dimethylsilanol(2-isopropyl-4-(1-naphthyl)indenyl)(2-methyl-4-(1-naphthyl)indenyl)hafnium, dichloride dimethylsilanol(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)(2-methyl-4-(4'-tert-butylphenyl]indenyl)hafnium, dichloride dimethylsilanol(2-isopropyl-4-[4'-tert-butylphenyl]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, and appropriate connections dimethylamine, monochloramine(alkylacrylate)hafnium and di(alkylacrylate)hafnium. The complexes may be used in racemic form, mesopore or mixtures thereof.

Among guarracino General formula (VI), preferred are the compounds of formula (VII)

Among the compounds of formula (VII) are preferred compounds, in the which

XBrepresents fluorine, chlorine, bromine, C1-C4-alkyl or benzyl, or two radicals XBform a substituted or unsubstituted butadienyl ligand,

t is 1 or 2, preferably 2,

R1B-R5Beach represent hydrogen, C1-C8-alkyl, C6-C8-aryl, NR8B2, OSiR8B3or Si(R8B)3and

R9B-R13Beach represent hydrogen, C1-C8-alkyl or C6-C8-aryl, NR14B2, OSiR14B3or Si(R14B)3

or in each case two radicals of R1B-R5Band/or R9B-R13Btogether with C5cycle form indenyl, fluorenyl or substituted indenolol or fluorenyl system.

Especially applicable Garrity formula (VII), in which cyclopentadienyls radicals are the same.

Examples of particularly suitable compounds D) of the formula (VII) are, among others, the following:

dichloride, bis(cyclopentadienyl)hafnium, dichloride, bis(indenyl)hafnium, dichloride, bis(fluorenyl)hafnium, dichloride, bis(tetrahydroindene)hafnium, dichloride, bis(pentamethylcyclopentadienyl)hafnium, dichloride, bis(trimethylsilylethynyl)hafnium, dichloride, bis(trimethoxysilylmethyl)hafnium, dichloride, bis(ethylcyclopentadienyl)hafnium, dichloride, bis(isobutyrylacetate the l)hafnium, dichloride, bis(3-butylcyclopentadienyl)hafnium, dichloride, bis(methylcyclopentadienyl)hafnium, dichloride, bis(1,3-di-tert-butylcyclopentadienyl)hafnium, dichloride, bis(triftormetilfullerenov)hafnium, dichloride, bis(tert-butylcyclopentadienyl)hafnium, dichloride, bis(n-butylcyclopentadienyl)hafnium, dichloride, bis(vinylcyclopentane)hafnium, dichloride, bis(N,N-dimethylaminobenzylidene)hafnium, dichloride, bis(1,3-dimethylcyclopentane)hafnium, dichloride, bis(1-n-butyl-3-methylcyclopentadienyl)hafnium, dichloride, (cyclopentadienyl)(methylcyclopentadienyl)hafnium, dichloride, (cyclopentadienyl)(n-butylcyclopentadienyl)hafnium, dichloride (methylcyclopentadienyl)(n-butyl)cyclopentadienyl)hafnium, dichloride, (cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)hafnium, dichloride, bis(tetramethylcyclopentadienyl)hafnium, and appropriate connections dimethylamine. Other examples are the compounds of garretsen in which one or two of the chloride ligands are replaced bromidum or production by iodide.

Suitable catalysts (B) are complexes of transition metals, at least one ligand of the General formula XV-XIX,

where the variables have the following meanings:

E1Crepresents a nitrogen atom or phosphorus, in particular nitrogen,

E2C-E4Ceach is ezavisimo from each other, represent a carbon atom, nitrogen or phosphorus, in particular carbon,

R1C-R3Ceach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R1C-R3Ccan also be substituted by Halogens and/or two vicinal radicals of R1C-R3Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R1C-R3Ctogether with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O and S,

R4C-R7Ceach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, SiR19C3where the organic radicals R4C-R7Ccan also be substituted by Halogens and/or two pairs or vicinal radicals of R4C-R7Ccan also be connected with the formation of five-, six - or what michinaga cycle, and/or two pairs or vicinal radicals of R4C-R9Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S, and when v is 0, R6Crepresents the relationship of L1Cand/or R7Crepresents the relationship of L2Cso L1Cforms a double bond with the carbon atom that is attached to R4Cand/or L2Cforms a double bond with the carbon atom that is attached to R5C,

u is 0 when E2C-E4Crepresent a nitrogen atom or a phosphorus atom, and is 1 when E2C-E4Crepresent a carbon atom,

L1C-L2Ceach, independently of one another, represent a nitrogen atom or a phosphorus atom, in particular nitrogen,

R8C-R11Ceach, independently of one another represent C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R8C-R11Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal the radical of R 8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S,

R12C-R17Ceach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R12C-R17Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S,

the indices v, each, independently of one another, represent 0 or 1,

the radicals XCeach, independently of one another represent fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C20-aryl, arylaryl containing 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, OR18C, SR18C, SO3R18C/sup> , OC(O)R18C, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion and the radicals XCcan be connected to each other,

the radicals R18Ceach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3where the organic radicals R18Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R18Ccan also be connected with the formation of five - or six-membered cycle,

the radicals R19Ceach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R19Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - or six-membered cycle,

s is 1, 2, 3 or 4, in particular 2 or 3,

D is electrically neutral donor and

t represents an integer from 0 to 4, in particular 0, 1 or 2.

Three atoms of E2C-E4Cmolecule may be the same or different. If E1Crepresents a phosphorus atom, then E2C-E4Ceach preferably represent a carbon atom. If E1Crepresents a nitrogen atom, then E2C-E4Ceach preferably represent a nitrogen atom or carbon, in particular carbon.

The substituents R1C-R3Cand R8C-R17Ccan vary within wide limits. Possible operatingincome substituents R1C-R3Cand R8C-R17Care, for example, the following: C1-C22-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as substituents, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C22aryl that may be substituted additionally the additional alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R1C-R3Cand/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle, and/or two vicinal radicals of R1C-R3Cand/or two vicinal radicals of R8C-R17Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom selected from the group consisting of atoms N, P, O and S, and/or the organic radicals R1C-R3Cand/or R8C-R17Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R1C-R3Cand R8C-R17Ccan also be an amino group NR18C2or N(SiR19C3)2, alkoxy or alloctype OR18Cfor example dimethylamino, N-pyrrolidinyl, picoline, methoxy, ethoxy or isopropoxy or halogen, such as fluorine, chlorine or bromine. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals, which have been described above for R -R3Cwhere two R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These SiR19C3radicals can also join the E2C-E4Cthrough an oxygen atom or nitrogen, and represent, for example, trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylsilane.

Preferred radicals R1C-R3Care hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl - or dichlorsilane family, trialkyl or trichlorsilane family, naphthyl, biphenyl and anthranol. Particularly preferred organosilicon substituents are trialkylsilyl group containing from 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl group.

Preferred radicals R12C-R17Care hydrogen, 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 hydrogen. In particular, R13Cand R16Ceach pre whom represent 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 or bromine, and R12C, R14C, R15Cand R17Ceach represent hydrogen.

Preferred radicals R8C-R11Care 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, R8Cand R10Ceach represent C1-C22-alkyl, which can also be substituted by Halogens, in particular With1-C22-n-alkyl, which can also be substituted by Halogens, such as methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen, such as fluorine, chlorine or bromine, and R9Cand R11Ceach represent halogen, such as fluorine, chlorine or bromine. Particularly preferred R8Cand R10C, each of which represents a C1-C22-alkyl, which can also be substituted by Halogens, in particular C1-C22-alkyl, which can also be substituted by Halogens, such as methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, and R9Cand R11Ceach represent halogen, such as fluorine, chlorine or bromine.

In particular, R1C , R14C, R15Cand R17Care the same, R13Cand R16Care the same, R9Cand R11Care the same and R8Cand R10Care the same. It is also preferable in all the preferred embodiments described above.

The substituents R4C-R7Ccan also vary within wide limits. Possible operatingincome substituents R4C-R7Care, for example, the following: C1-C22-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as substituent, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, such as FeNi is, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl where arylalkyl can be substituted for more alkyl groups, and represent, for example, benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R4C-R7Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle, and/or two pairs radical of R4C-R7Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O and S, and/or the organic radicals R4C-R7Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R4C-R7Ccan be an amino group of the formula NR18C2or N(SiR19C3)2for example dimethylamino, N-pyrrolidinyl or picolinic. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals described above for R1C-R3Cwhere two R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These SiR19C3RA is Italy can also join the carbon atom, which is connected through the nitrogen atom. When v is 0, R6Crepresents the relationship of L1Cand/or R7Crepresents the relationship of L2Cso L1Cforms a double bond with the carbon atom that is attached to R4Cand/or L2Cforms a double bond with the carbon atom that is attached to R5C.

Preferred radicals R4C-R7Care hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, ortho-dialkyl - or dichlorsilane family, trialkyl or trichlorsilane family, naphthyl, biphenyl and anthranol. Preferred amide substituents NR18C2in particular, secondary amides, such as dimethylamide, N-ethylmethylamino, diethylamide, N-methylpropylamine, N-methylisophthalic, N-ethylisopropylamine, dipropylamine, Diisopropylamine, N-methylbutylamine, N-ethylbutylamine, N-methyl-tert-butylamide, N-tert-butylenediamine, dibutylamine, di-sec-butylamide, Diisobutylene, tert-amyl-tert-butylamide, dipentine, N-methylhexane, vexille, tert-amyl-tert-octylated, dioctylamine, bis(2-ethylhexyl)amide, dodecylamide, N-methyloctadecane, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexane, N-tert-butylcyclohexylamine, dicyclohexylamine, pyrrolidine, piperidine, hexamethylenimine is, decahydroquinoline, diphenylamine, N-methylaniline or N-ethylaniline.

L1Cand L2Ceach, independently of one another, represent a nitrogen atom or phosphorus, in particular nitrogen, and when v is 0, can form a double bond with the carbon atom that is attached to R4Cor R5C. In particular, when v is 0, L1Cand/or L2Ctogether with the carbon atom that is attached to R4Cor R5Cform aminogroup-CR4C=N - or-CR5C=N-. When v is 1, L1Cand/or L2Ctogether with the carbon atom that is attached to R4Cor R5Cform, in particular, aminogroup-CR4CR6C-N or CR5CR7C-N.

The ligands XCare the result of, for example, selection of suitable starting compounds of the metal used for the synthesis of iron complexes, but can also be modified after synthesis of the complexes. Possible ligands XCare, in particular, halogen, such as fluorine, chlorine, bromine or iodine, in particular chlorine. Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl, are also applicable ligands XC. As examples of additional ligands XCcan be specified, but without limitation only by them, triptorelin, BF4-PF6-and weakly coordinating or ncoordinates the anions (see, for example, S. Strauss, Chem. Rev. 1993, 93, 927-942), such as B(C6F5)4-. Amides, alkoxides, sulfonates, carboxylates and β-diketonates are also particularly applicable ligands XC. Some of these substituted ligands X are particularly preferable because they can be obtained from inexpensive and readily available starting materials. Thus, particularly preferred is a variant in which XCis dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluensulfonate, acetate or acetylacetonate.

Changing the radicals R18Cyou can, for example, to accurately adjust physical properties such as solubility. Possible operatingincome substituents R18Care, for example, the following: C1-C20-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain as Deputy C6-C10-aryl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C20alkenyl, which may be linear, cyclic or p is swellendam and in which the double bond may be internal or terminal, for example vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C20-aryl which can be substituted for more alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, 2-methoxyphenyl, 2-N,N-dimethylaminophenyl, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals R18Ccan also be connected with the formation of 5 - or 6-membered cycle, and organic radicals R18Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. Possible radicals R19Cin organosilicon substituents SiR19C3are radicals described above for R18Cwhere two radicals R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, trialkylsilyl, triphenylene or dimethylphenylsilane. Preferably used as the radical R18CC1-C10-alkyl, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, as well as vinyl, Allie is a, the benzyl and phenyl.

The number of ligands XCdepends on the degree of oxidation of iron, so it may not be cited in the General description. The oxidation state of iron in catalytically active complexes is well known to the skilled technician in the art. However, you can apply complexes, the degree of oxidation which does not correspond to the oxidation state of the active catalyst. Such complexes may then be subjected to appropriate recovery or oxidation with suitable activators. Preferably the use of iron complexes with oxidation state +3 or +2.

D is electrically neutral donor, in particular not support a charge of a Lewis base or Lewis acid, such as amines, alcohols, ethers, ketones, aldehydes, esters, sulfides or phosphines which can be connected to the Central iron atom or present as solvent remaining after obtaining complexes of iron.

The number t of ligands D can range from 0 to 4, and often depends on the solvent in which it was received the iron complex, and the time during which dried the resulting complexes, and therefore it may be not a whole number, such as 0.5 or 1.5. In particular, t is 0, 1-2.

In a preferred embodiment,

where

E2C-E4Ceach, independently of one another, represent a carbon atom, nitrogen or phosphorus, in particular carbon atom,

R1C-R3Ceach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R1C-R3Ccan also be substituted by Halogens and/or two vicinal radicals R1C-R3Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R1C-R3Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O and S,

R4C-R5Ceach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, SiR19C3where the organic radicals R4C-R5Ccan also be substituted by Halogens,

u is 0 when E2C-E4Crepresent the nitrogen atom and the and phosphorus, and is equal to 1 when E2C-E4Crepresent a carbon atom,

L1C-L2Ceach, independently of one another, represent a nitrogen atom or phosphorus, in particular nitrogen atom,

R8C-R11Ceach, independently of one another represent C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R8C-R11Ccan also be substituted by Halogens and/or two vicinal radicals R8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O and S,

R12C-R17Ceach, independently of one another, represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R12C-R17Ccan also be substituted by Halogens, and/or DV is vicinal radicals R 8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O or S,

the indices v, each, independently of one another, represent 0 or 1,

the radicals XCeach, independently of one another represent fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C20-aryl, alkylaryl containing 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, OR18C, SR18C, SO3R18C, OC(O)R18C, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion and the radicals XCcan be connected to each other,

the radicals R18Ceach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3where the organic radicals R18Ccan also be substituted by Halogens and nitrogen - and oxygen-containing groups and two radicals R18Ccan also be connected with the formation of the five - or six-membered cycle,

the radicals R19Ceach, independently of one another, represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R19Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - or six-membered cycle,

s is 1, 2, 3 or 4, in particular 2 or 3,

D represents an uncharged donor and

t takes values from 0 to 4, in particular 0, 1 or 2.

Options and preferred options for implementation, described above, also apply to E2C-E4C, R1C-R3CXC, R18Cand R19C.

The substituents R4C-R5Ccan vary in a wide area. Possible operatingincome substituents R4C-R5Care, for example, the following: hydrogen, C1-C22-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as to cover the El, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, 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, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where the organic radicals R4C-R5Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R4C-R5Ccan be an amino group NR18C2or N(SiR19C3)2for example dimethylamino, N-pyrrolidinyl or picolinic. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals described above for R1C-R3Cwhere two radicals R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example rimacillin, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. Such SiR19C3radicals can join the carbon atom on which they are located, through the nitrogen atom.

Preferred radicals R4C-R5Care hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or benzyl, in particular methyl.

The substituents R8C-R17Ccan vary in a wide area. Possible operatingincome substituents R8C-R17Care, for example, the following: C1-C22-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as substituent, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, 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, Huck is Anil, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R8C-R17Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle, and/or two vicinal radicals of R8C-R17Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of atoms of N, P, O and S, and/or the organic radicals R8C-R17Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R8C-R17Ccan be a halogen, such as fluorine, chlorine, bromine, amino group NR18C2or N(SiR19C3)2, alkoxy or aryloxy OR18Cfor example dimethylamino, N-pyrrolidinyl, picoline, methoxy, ethoxy or isopropoxy. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals, which have been indicated above for R1C-R3Cwhere two RA is hiccuping R 19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These SiR19C3radicals can also join via an oxygen atom or nitrogen, and represent, for example, trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylsilane.

Preferred radicals R12C-R17Care hydrogen, 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 hydrogen. In particular, R13Cand R16Ceach represent 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 or bromine, and R12C, R14C, R15Cand R17Ceach represent hydrogen.

Preferred radicals R8C-R11Care 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, R8Cand R10Ceach represent C1-C22-alkyl, which is also what can be substituted by halogen, in particular, C1-C22-n-alkyl, which can also be substituted by Halogens, such as methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen, such as fluorine, chlorine or bromine, and R9Cand R11Ceach represent halogen, such as fluorine, chlorine or bromine. Particularly preferably, R8Cand R10Ceach represent C1-C22-alkyl, which can also be substituted by Halogens, in particular C1-C22-n-alkyl, which can also be substituted by Halogens, such as methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, and R9Cand R11Ceach represent halogen, such as fluorine, chlorine or bromine.

In particular, R12C, R14C, R15Cand R17Care the same, R13Cand R16Care the same, R9Cand R11Care the same and R8Cand R10Care the same. It is also preferable in the preferred embodiments described above.

Obtaining the compounds (B) are described, for example, J. Am. Chem.-Soc. 120, p. 4049 ff. (1998), J. Chem. Soc., Chem. Commun. 1998, 849, and in WO 98/27124. Preferred complexes (B) are:

dichloride, 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,4,6-trimethylaniline)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2-chloro-6-were the Mino)ethyl]peridiniales(II), dichloride, 2,6-bis[1-(2,6-diisopropylaniline)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,6-dichlorophenylamino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,6-diisopropylaniline)methyl]peridiniales(II), 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,6-diftorhinolonom)ethyl]peridiniales(II)dichloride, 2,6 bis[1-(2,6-diftorhinolonom)ethyl]peridiniales(II) or the corresponding dibromide or tribromide.

Further, the reference to the complex of the transition metal (A) or catalyst (A) means monosyllabically complex (A1) and/or garrote (A2). The molar ratio of the complex transition metal (A) to the polymerization catalyst (B) is usually in the range from 1:100 to 100:1, preferably in the range from 1:10 to 10:1 and particularly preferably in the range from 1:5 to 5:1. When the complex of the transition metal (A) is used as the sole catalyst in the same reaction conditions of homopolymerization or copolymerization is preferably results in a higher Mwthan in the application of complex (B) as the only complex in the same reaction conditions. Preferred options complexes (A1), (A2) and (B) are also preferable combinations of the complex (A1) with (B) and combined complex (A2) with (B).

The catalytic composition according to the invention can be applied to the AMA on its own or together with additional components as catalytic systems for polymerization of olefins. In addition, applicants have developed a catalytic system for the polymerization of olefins, including

A) at least one polymerization catalyst based on monotsiklopentadienil complex metal 4-6 groups of the Periodic table of elements, in which cyclopentadienyls system is substituted by an uncharged donor (A1) or harricana (A2),

C) at least one polymerization catalyst based on iron component containing tridentate ligand, which includes at least two ortho, ortho-disubstituted aryl radicals,

C) optionally one or more activating compounds,

D) optionally one or more organic or inorganic carriers,

E) optionally one or more compounds of metals 1, 2 or 13 group of the Periodic table of elements.

Further, the reference to the complex of the transition metal (A) or catalyst (A) means monosyllabically complex (A1) and/or garrote (A2). The molar ratio of the complex transition metal (A) to the 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 the complex of the transition metal (A) is used as the sole catalyst in the same reaction conditions in homopolymerization or copolymerization of ethylene, this is predpochtitelno leads to higher M wthan in the application of complex (B) as the only complex when carrying out the reaction under the same conditions. Preferred options complexes (A1), (A2) and (B) are also preferable combinations of complexes (A1) and (B) and in combination complexes (A2) and (B).

Monosyllabically complexes (A1), garretsen (A2) and/or the iron complex (B) sometimes have only a low polymerization activity and in this case are contacting with one or more activators, in particular component (C)to facilitate the manifestation of good polymerization activity. Thus, the catalyst system optionally further includes as a component (C) one or more activating compounds, preferably one or two activating compounds (C). The catalytic system according to the invention preferably includes one or more activators (C). Depending on the combinations of catalyst components (A) and (B) the priority is the application of one or more activating compounds (C). Activation of the complex transition metal (A) and the iron complex (B) a catalytic composition may be carried out using the same activator, or a mixture of activators, or using different activators. Often predominantly use one of the same activator (C) for both catalysts (A) and (B).

The activator or activators (C) can in each case be used in any amount is based on the complexes (A) and (B) a catalytic composition according to the invention. Preferably they are used in excess or in stoichiometric amounts, in each case based on the complex (A) or (B)that they activate. The number of trigger(s) connection(s)intended for use depends on the type of activator (C). Usually the molar ratio of the complex transition metal (A) to the activating compound (C) may be in the range from 1:0.1 to 1:10000, preferably from 1:1 to 1:2000. The molar ratio of the iron complex (B) activating the compound (C) is usually in the range from 1:0.1 to 1:10000, preferably from 1:1 to 1:2000.

Suitable compounds (C)which are capable of interacting with the complex of the transition metal (A) or the iron complex (B) to turn it into a catalytically active or more catalytically active compound are, for example, such compounds as alumoxane, strong electrically neutral Lewis acid, an ionic compound containing a cation of a Lewis acid or an ionic compound containing the acid of Bronsted as cation.

As alumoxanes can be applied, for example, compounds described in the publication WO 00/31090. Especially applicable alumoks the us are alumoxane derived from open-chain or cyclic General formula (X) or (XI)

where R1D-R4Deach, independently of one another represent C1-C6is an alkyl group, preferably methyl, ethyl, butyl or isobutyl, and l represents an integer from 1 to 40, preferably from 4 to 25.

Especially applicable alumoxanes connection is methylalumoxane.

Such oligomeric alumoxane connections usually get controlled reaction solution trialkylamine, in particular trimethylaluminum with water. Usually obtained oligomeric alumoxane compounds are mixtures of cyclic and linear chain molecules of different lengths, so l should be considered as an average value. Alumoxane compounds may also be present in mixtures with other alkilani metals, usually alkilani aluminum. Alumoxane drugs that are suitable as component (C)are commercially available.

In addition, as the component (C) instead alumoxane compounds of the formula (X) or (XI) can be applied modified alumoxane, in which some of the hydrocarbon radicals substituted by hydrogen atoms or alkoxy, aryloxy, siloxy or amide radicals.

It was found that mainly the use of complex transition metal (A) or the iron complex (B) and alumoxane compounds in such quantity the Baltic States, to the ratio of the atomic mass of aluminum from alumoxane compounds, including any present alkyl aluminum to atomic mass of the transition metal complex of the transition metal (A) was in the range of from 1:1 to 2000:1, preferably from 10:1 to 500:1, and especially in the range from 20:1 to 400:1. Usually the ratio of the atomic mass of aluminum from alumoxane compounds, including any present alkyl aluminum to atomic mass of iron from the iron complex (B) is in the range from 1:1 to 2000:1, preferably from 10:1 to 500:1 and especially in the range from 20:1 to 400:1.

Further class of suitable activating component (C) are hydroxyalkoxy. They can be obtained, for example, by adding from 0.5 to 1.2 equivalents of water, preferably from 0.8 to 1.2 equivalents of water per equivalent of aluminum to alkylamino connection, in particular triisobutylaluminum, at low temperatures, usually below 0°C. Such compounds and their use in polymerization of olefins is described, for example, in WO 00/24787. The ratio of the atomic mass of aluminum from gidroksilaminov connection to the atomic mass of the transition metal complex of the transition metal (A) or the iron complex (B) is usually in the range from 1:1 to 100:1, preferably from 10:1 to 50:1, in particular in the range from 20:1 to 40:1. Preferably use mononitrobenzene what about the dialkyl metal (A1) or hafniensia dialkylamide soedineniya (A2).

As a strong electroneutral of Lewis acids preferred compounds of General formula (XII)

where

M2Drepresents an element of group 13 of the Periodic table of elements, in particular B, Al or Ga, preferably B,

X1DX2Dand X3Deach represent hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, halogenated or halogenared, each of which contains from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or fluorine, chlorine, bromine or iodine, in particular galogenidy, preferably pentafluorophenyl.

Additional examples of strong electroneutral of Lewis acids described in WO 00/31090.

Compounds which are particularly suitable for use as component (C)are boron and braccini, such as trialkylborane, trainborn or trimethylboroxine. Particularly preferred application Baranov that contain at least two perfluorinated aryl radical. Especially preferred compounds of General formula (XII)in which X1DX2Dand X3Dare the same, for example, triphenylboron, Tris(4-forfinal)borane, Tris(3,5-differenl)borane, Tris(4-formationl)borane, Tris(pentafluorophenyl)borane, Tris(tolyl)borane, Tris(3, 5dimethylphenyl)borane, Tr is(3,5-differenl)borane or Tris(3,4,5-tryptophanyl)borane. Preferably the use of Tris(pentafluorophenyl)borane.

Suitable compounds (C) is preferably produced by interaction of compounds of aluminum or boron formula (XII) with water, alcohols, derivatives of phenol, derivatives thiophenol or anisindione, and particularly preferably from halogenated and in particular perfluorinated alcohols and phenols. Examples of particularly suitable compounds are pentafluorophenol, 1,1-bis(pentafluorophenyl)methanol and 4-hydroxy-2,2',3,3',4',5,5',6,6'-nonaboriginal. Examples of combinations of compounds of the formula (XII) with acids of Bronstedt are, in particular, trimethylaluminum/pentafluorophenol, trimethylaluminum/1-bis(pentafluorophenyl)methanol, trimethylaluminum/4-hydroxy-2,2',3,3',4',5,5',6,6'-nonaboriginal, triethylaluminium/pentafluorophenol and triisobutylaluminum/pentafluorophenol and triethylaluminum/4,4'-dihydroxy-2,2',3,3',5,5',6,6'-octafluoropentyl.

Other suitable compounds of aluminum and boron of the formula (XII) R1Drepresents an OH group, such as, for example, in Baranovich acids and Borisovich acids. It is possible to emphasize Barinova acid containing perfluorinated aryl radicals, for example (C6F5)2BOH.

Strong electrically neutral Lewis acid suitable as activating compounds (C)include also the interaction products Boro the OIC acid with two equivalents of trialkylamine or interaction products trialkylamine with two equivalents of an acidic fluorinated, in particular perfluorinated, carbon compounds, such as pentafluorophenol - or bis(pentafluorophenyl)Barinova acid.

Suitable ionic compounds containing cations of a Lewis acid include solpadine compounds of the cation of the General formula (XIII)

where

M3Drepresents an item 1-16 groups of the Periodic table of elements

Q1-Qzpresent simple negatively charged radicals, such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, halogenated, halogenared, each of which contains 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 contain C1-C10-alkyl groups as substituents, halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptal,

a represents an integer from 1 to 6 and

z represents an integer from 0 to 5,

d corresponds to the difference a-z, but d is greater than or equal to 1.

Especially applicable cations are the cations of Carbonia, hydronium cations and cations of sulfone and cationic complexes of transition metals. Especially can be marked triphenylmethyl cation, the silver cation and the cation 1,1'-dimethylferrocene. They preferably contain coordinarussia (not about auusie coordination bonds) counterions, in particular, compounds of boron, which is also mentioned in the publication WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.

Salt containing coordinarussia anions, can be obtained by attaching compounds of boron or aluminum, for example alkylamine, with a second compound that can bind two or more atoms of boron or aluminum, for example, with water, and a third compound which forms a connection with boron or aluminum ionizing ionic compound, for example triphenylmethane, or optional with base, preferably an organic nitrogen-containing base, for example an amine, biliprotein or a nitrogen-containing heterocycle. In addition, there may be added a fourth connection, which likewise communicates with a compound of boron or aluminum, for example pentafluorophenol.

Ionic compounds containing acid of Bronsted as cations, preferably also contain coordinarussia counterions. As the acid of Bronsted preferred protonated amines or anisindione. The preferred cations are N,N-dimethylaniline N,N-dimethylcyclohexylamine and N,N-dimethylbenzylamine, as well as derivatives of the last two.

Compounds containing anionic boron heterocycles, which are described in WO 9736937, are also suitable as component (C), and the hour of the activities bratabandha dimethylaniline or trietilborazina.

Preferred ionic compounds C) include borates, which include at least two perfluorinated aryl radical. Especially preferred tetrakis(pentafluorophenyl)borate and N,N-dimethylaniline and especially tetrakis(pentafluorophenyl)borate and N,N-dimethylcyclohexylamine, tetrakis(pentafluorophenyl)borate and N,N-dimethylbenzylamine or tricityregionalchamber.

Two or more borate anions can be connected to each other, as in dianion [(C6F5)2B-C6F4-B(C6F5)2]2-or the borate anion can use bridge connection to join a suitable functional group on the surface of the media.

Other suitable activating compounds (C) are described in WO 00/31090.

The number of strong electroneutral of Lewis acids, ionic compounds containing cations of Lewis acids or ionic compounds containing acid of Bronsted 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 based on the complex of the transition metal (A) or the iron complex (B).

Suitable activating compounds (C) include boron-aluminum compounds such as di[bis(pentafluorobenzylbromide)]meillan. Examples of such biolumines the x compounds described in WO 99/06414.

You can also apply a mixture of the above-activating compounds (C). Preferred mixtures include alumoxane, in particular methylalumoxane, and the ionic compound, in particular a compound containing tetrakis(pentafluorophenyl)borate anion, and/or strong electroneutral a Lewis acid, in particular Tris(pentafluorophenyl)borane or noroxin.

The complex of the transition metal (A) or the iron complex (B) and the activating compound (C), preferably both, are used in a solvent, preferably an aromatic hydrocarbon containing from 6 to 20 carbon atoms, such as xylene, toluene, pentane, hexane, heptane or mixtures thereof.

You can also use the activating compounds (C), which can simultaneously act as a carrier (D). Such systems can be obtained, for example, of inorganic oxide-treated zirconium alkoxide followed by chlorination, for example, use of carbon tetrachloride. The receipt of such systems are described, for example, in WO 01/41920.

The combination of preferred options (C) preferred options (A) and/or (B) are particularly preferred.

As the United activator (C) for the catalyst components (A) and (B) preferably use alumoxane. Preferably as activator (C) for guarracino (A2) the conjunction is of Solodovnik compounds of the cation of the General formula (XIII), in particular tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline, tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylamine, tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylamine or tetranitropentaeritrita, especially in combination with alumoxane as activator (C) for the iron complex (B).

Especially applicable United activators (C) are the products of interaction of aluminum compounds of the formula (XII) with perfluorinated alcohols and phenols.

For the application of complex transition metal (A) and the iron complex (B) in gas-phase polymerization or suspension polymerization is often useful to use complexes in the form of solids, i.e. deposited on a solid carrier (D). In addition, supported on a carrier complexes have high productivity. Thus, the complex of the transition metal (A) and/or the iron complex (B) can optionally be immobilizates organic or inorganic carrier (D) and applied in the polymerization supported on a carrier form. This allows, for example, to prevent sedimentation in the reactor and to control the morphology of the polymer. As materials of the carrier preferably using silica gel, magnesium chloride, aluminum oxide, mesoporous materials, aluminosilicates, hydrotalcites and organic polymer clay is s, such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, or polymers containing functional groups, for example copolymers of Athena and esters of acrylic acid, acrolein or vinyl acetate.

Especially preferred catalytic system comprising at least one complex of a transition metal (A)at least one iron complex (B)at least one activating compound (C) and at least one component carrier (D).

The preferred catalytic composition according to the invention includes one or more carrier components. It is also possible that the component of the transition metal (a) and the iron complex (B), both supported on a carrier, or only one of the two components may be supported on a carrier. In the preferred embodiment, both components (a) and (b) supported on a carrier. Two components (a) and (b) in this case can be applied to different media or on one of the merged carrier. Components (a) and (b) is preferably applied to the merged carrier to provide a spatial proximity of different catalytic centers and, thus, ensure good mixing of the obtained polymers.

To obtain the catalytic systems according to the invention the preferred immobilization of one of the components (A) and a component (B) and the and the activator (C) or media (D) physical adsorption and by chemical reactions, for example, covalent binding components with reactive groups on the carrier surface.

The order in which the merged component (D), the complex of the transition metal (A), the iron complex (B) and the activating compound (C), does not matter. After the individual process steps of the various intermediate products can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons.

The complex of the transition metal (A), the iron complex (B) and the activating compound (C) can immobilizates independently from each other, for example, sequentially or simultaneously. Thus, the component carrier (D) may first be contacted with an activating compound or compounds (C), or component carrier (D) may first be contacted with the complex transition metal (A) and/or the iron complex (B). It is also possible pre-activation complex of the transition metal (A) with one or more activating compounds (C) before mixing with the carrier (D). Component iron can, for example, be subjected to interaction with a complex of a transition metal and an activating compound (C) or may be separately pre-activated using the latter. Pre-activated complex is iron (B) may be applied to the carrier before or after pre-activated complex transition metal (A). In one embodiment, the complex of the transition metal (A) and/or the iron complex (B) can also be obtained in the presence of material media. An additional method of immobilization is a preliminary polymerization catalyst system with the preliminary application or no application to the media.

Immobilization is usually conducted in an inert solvent, which can be removed by filtration or evaporation after immobilization. After the individual process steps, the solid may be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons, and dried. However, you can also use wet catalyst supported on a carrier.

In the preferred method of obtaining system catalyst on the carrier, at least one iron complex (B) is in contact with the activating compound (C) and successively mixed with digidrirovanny or passivated material media (D). The complex of the transition metal (S) in the same way it is in contact with at least one activating compound (C) in a suitable solvent, preferably to produce a soluble reaction product, an adduct or a mixture. The product, thus obtained, is then mixed with the immobilized complex of iron, which is used immediately or after which spartia of solvent, and the solvent is completely or partially removed. The resulting catalyst on the carrier is preferably dried to ensure that all or most of the solvent removed from the pores of the material medium. The catalyst on the carrier preferably receive in the form of a fluid (loose) powder. Examples of industrial application of the above method is described in WO 96/00243, WO 98/40419 or WO 00/05277. Another preferred option involves first obtaining activating compounds (C) on the component carrier (D) and the subsequent contacting of the connection on the media with complex transition metal (a) and the iron complex (B).

As a media component (D) preferably use finely ground carriers, which can be any organic or inorganic solid. In particular, the component carrier (D) may consist of a porous carrier, such as talc, film silicate such as montmorillonite, mica or inorganic oxide or a finely powdered polymer (e.g. polyolefin or a polymer containing polar functional groups).

Applied materials carrier preferably have a specific surface area in the range from 10 to 1000 m2/g, pore volume in the range from 0.1 to 5 ml/g and average particle size in the range from 1 to 500 μm. Site is ctically media with a specific surface area in the range from 50 to 700 m 2/g, pore volume in the range from 0.4 to 3.5 ml/g and an average particle size in the range from 5 to 350 μm. Particularly preferred carriers with a specific surface area in the range from 200 to 550 m2/g, pore volume in the range from 0.5 to 3.0 ml/g and an average particle size in the range from 10 to 150 microns.

The complex of the transition metal (A) is preferably used in such amounts that the concentration of the metal complex of the transition metal (A) in the final catalyst system is in the range from 1 to 200 μmol, preferably in the range from 5 to 100 μmol and particularly preferably in the range from 10 to 70 μmol per 1 g of the carrier (D). The iron complex (B) is preferably used in such amounts that the concentration of iron from the iron complex (B) in the final catalyst system is in the range from 1 to 200 μmol, preferably in the range from 5 to 100 μmol and particularly preferably in the range from 10 to 70 μmol per 1 g of the carrier (D).

The inorganic carrier may be subjected to heat treatment, for example to remove the adsorbed water. Such processing for drying is usually conducted at temperatures in the range from 50 to 1000°C, preferably from 100 to 600°C, and drying at temperatures in the range from 100 to 200°C, preferably carried out under reduced pressure and/or inert gas (e.g. nitrogen), or not the content of inorganic fillers media may be subjected to calcination at temperatures in the range from 200 to 1000°C to obtain the desired structure of the solid substances and/or achieve the desired OH concentration on the surface. The media may also be treated chemically using conventional driers such as alkali metals, preferably of Akilov aluminum, CHLOROSILANES or SiCl4or methylalumoxane. Suitable processing methods are described, for example, in WO 00/31090.

The inorganic material of the carrier may also be subjected to chemical modification. For example, treatment of silica gel with NH4SiF6or other fluorinating agents leads to fluorination of the silica gel surface, or treatment of silica gels with silanes containing nitrogen-, fluorine - or sulfur-containing groups leads to correspondingly modified silica surfaces.

Organic materials media, such as finely ground powders of polyolefins (e.g. polyethylene, polypropylene or polystyrene)can also be used preferably similarly exempt from the adhered moisture, residual solvents or other impurities appropriate methods of cleaning and drying before use. You can also apply functionalized polymeric carriers, the carriers on the basis of polystyrene, polyethylene, polypropylene or polybutylene, functional groups, for example ammonium or hydroxyl group, can serve to immobilize at least one of the components is now catalyst. You can also use polymer mixture.

Inorganic oxides suitable as a media component (D)may be selected from among the oxides of the elements 2, 3, 4, 5, 13, 14, 15 and the 16th groups of the Periodic table of elements. Examples of oxides preferred as carriers include silicon dioxide, aluminum oxide and mixed oxides of calcium, aluminum, silicon, magnesium or titanium, as well as an appropriate mixture of oxides. Other inorganic oxides which can be used by themselves or in combination with the above preferred oxide carriers are, for example, MgO, CaO, AlPO4, ZrO2, TiO2B2O3or mixtures thereof.

Other preferred inorganic materials carriers are inorganic halides, such as MgCl2or carbonates, such as Na2CO3, K2CO3, CaCO3, MgCO3, sulphates, such as Na2SO4, Al2(SO4)3, BaSO4nitrates, such as KNO3, Mg(NO3)2or Al(NO3)3.

As a solid material carriers (D) catalysts for the polymerization of olefins, preferably the use of silica, the size and structure of particles which makes them suitable as materials from which can be obtained media for polymerization of olefins. It is established, that is particularly useful are silica gels, dried using spray drying, which are spherical agglomerates of relatively small granular particles, i.e. fundamental particles. Silica gels can be dried and/or calcined before use.

Other preferred media (D) are hydrotalcite and whether hydrotalcite. In Mineralogy hydrotalcite called natural mineral empirical formula

Mg6Al2(OH)16CO3·4H2O,

the structure of which is derived from the structure of brucite Mg(OH)2. Brucite crystallizes in a flat structure with metal ions in the octahedral cavities between two layers of close-Packed hydroxyl ions, and is populated only every second layer of octahedral cavities. In hydrotalcite some magnesium ions replaced by aluminium ions, resulting in a layer package acquires a positive charge. It is counterbalanced by anions, which are kept together with crystallohydrates water between layers.

Such flat structures are found not only in the hydroxides of magnesium, aluminum, but generally in mixed metal hydroxides of the General formula

M(II)2x2+M(III)23+(OH)4x+4·A2/nn·z H2O

which have a sheet structure and in which M(II) represents vocality metal, such as Mg, Zn, Cu, Ni, Co, Mn, Ca and/or Fe and M(III) represents a trivalent metal such as Al, Fe, Co, Mn, La, Ce and/or Cr, x is a number in the range from 0.5 to 10 in increments of 0.5, A is embedded anion, n represents the charge introduced anion, which can take values in the interval from 1 to 8, usually from 1 to 4, and z is an integer in the range from 1 to 6, in particular from 2 to 4. Possible embedded anions are organic anions such as alkoxide anions, sulphate simple alilovic esters, sulfates simple arolovich esters or sulfates simple glycol ethers, inorganic anions such as, in particular, carbonate, bicarbonate, nitrate, chloride, sulfate or B(OH)4-or anions polyoxides metals, such as Mo7O246-or V10O286-. However, you can also use many of these anions.

Accordingly, all such mixed metal hydroxides with a layered structure should be considered as hydrotalcite for the purposes of the present invention.

Whether hydrotalcite can be obtained from hydrotalcites calcining, for example, by heating, by means of what can be achieved desirable content of hydroxyl groups. In addition, it also changes the crystal structure. Getting calcinatory hydrocell is s, used according to the invention is usually carried out at temperatures above 180°C. Preferably, the calcination during the period of time from 3 to 24 hours at temperatures in the range from 250 to 1000°C., in particular from 400 to 700°C. you Can also pass air or inert gas over solid or apply vacuum at this time.

When heated, the natural or synthetic hydrotalcite first is the removal of water, i.e. drying. Upon further heating, the actual annealing the metal hydroxides are converted to metal oxides in the removal of hydroxyl groups and internal anions; OH group or internal anions, such as carbonate, may still be present in calcinatory hydrotalcite. Measure the calcination is no ignition. It represents a mass loss occurred in the sample, which was subjected to two-stage heat - first for 30 minutes at 200°C in a drying oven and then for 1 hour at 950°C in a muffle furnace.

Thus, whether hydrotalcite used as component (D)are mixed oxides of divalent and trivalent metals M(II) and M(III), in which the molar ratio of M(II) M(III) is usually in the range from 0.5 to 10, preferably from 0.75 to 8, especially from 1 to 4. In addition, t is the train to be some amount of impurities, for example, Si, Fe, Na, Ca or Ti, as well as chlorides and sulphates.

Preferred calculatevolume hydrotalcite (D) are mixed oxides, in which M(II) is magnesium and M(III) is aluminum. Such mixed alumomagnesium oxides available from Condea Chemie GmbH (now Sasol Chemie), Hamburg under the trade name Puralox Mg.

Preferred also whether hydrotalcite in which structural transformation is complete or virtually complete. The calcination, i.e. the transformation of the structure can be confirmed by, for example, using x-rays.

Used hydrotalcite, whether hydrotalcite or silica gels are usually applied in the form of finely ground powders with average particle diameter D50 in the range from 5 to 200 μm, preferably from 10 to 150 μm, particularly preferably in the range from 15 to 100 μm and in particular from 20 to 70 μm, with volumes then usually in the range of from 0.1 to 10 cm3/g, preferably in the range from 0.2 to 5 cm3/g and a specific surface in the range from 30 to 1000 m2/g, preferably in the range from 50 to 800 m2/g and in particular in the range from 100 to 600 m2/, Complex transition metal (A) is preferably used in such amounts that the concentration of the transition metal complex of the transition metal (A) in the final kataliticheski the th system is in the range from 1 to 100 μmol, preferably in the range from 5 to 80 μmol and particularly preferably in the range from 10 to 60 mmol per 1 g of the carrier (D).

The catalytic system may contain as an optional component (E) compound of the metal of General formula (XX)

where

MGrepresents Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gallium, indium, thallium, zinc, particularly Li, Na, K, Mg, boron, aluminum or Zn.

R1Grepresents hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl, each of which contains from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part,

R2Gand R3Geach represent hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy, each of which contains from 1 to 20 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or alkoxy with C1-C10-alkyl or C6-C15-aryl,

rGrepresents an integer from 1 to 3

and

sGand tGrepresent integers from 0 to 2, where the sum rG+sG+tGcorresponds to the valency of MG,

where component (E) is usually not identical to the component (C). You can also use mixtures of various metal compounds of the formula (XX).

Among the metal compounds of General forms of the crystals of (XX) the preferred connection, in which

MGis lithium, magnesium, boron or aluminum, and

R1Grepresents C1-C20-alkyl.

Especially preferred compounds of metals of the formula (XX) are motility, utility, n-utility, methylaniline, methylacrylamide, ethylaniline, ethylaniline, butylaniline, dimethylamine, diethylamine, dibutylamine, n-butyl-n-octylamine, n-butyl-n-heptylamine, especially n-butyl-n-octylamine, tri-n-hexylamine, triisobutylaluminum, tri-n-butylamine, triethylamine, dimethylammoniumchloride, dimethylaminophenyl, methylaluminoxane, methylaluminoxane, diethylaluminium and trimethylaluminum and mixtures thereof. Can also be applied to the products of partial hydrolysis of Akilov aluminum with alcohols.

When using a compound of the metal (E), it is preferably present in the catalyst system in such an amount that the molar ratio of MGfrom the formula (XX) to the amount of transition metal complex of the transition metal (A) and the iron complex (B) is in the range from 3000:1 to 0.1:1, preferably in the range from 800:1 to 0.2:1, particularly preferably in the range from 100:1 to 1:1.

Typically, the compound of the metal (E) of General formula (XX) is used as a component of the catalytic system for the polymerization or copolyme is Itachi olefins. In accordance with the present invention a compound of the metal (E) may, for example, be used to obtain the solid catalyst, comprising a carrier (D), and/or be added during polymerization or before polymerization. Used metal link (E) may be identical or different from each other. It is possible, especially when the solid catalyst does not contain an activating component (C), to include in the catalytic system in addition to the solid catalyst, one or more activating compounds (C), which are identical or different from any of the compounds (E)present in the solid catalyst.

Component (E) may similarly be interacting in any manner with the components (A), (B) and optionally (C) and (D). For example, component (A) may be contacted with the component(s) (C) and/or (D) either before or after contacting with the olefin to be cured. It is also possible pre-activation with one or more components (C) before mixing with the olefin and further addition of the same or another component (C) and/or (D) after contact of the mixture with the olefin. Pre-activation is usually carried out at temperatures in the range from 10 to 100°C, preferably in the range from 20 to 80°C.

In another preferred embodiment, the OS is supervising the solid catalyst, obtained from components (A), (B), (C) and (D)as described above, in contact with the component (E) in the polymerization process, at the beginning of the polymerization or before polymerization.

Preferably, first (E) is in contact with an α-olefin, subject to polymerization, and then added a solid catalyst comprising components (A), (B), (C) and (D)as described above.

In another preferred embodiment, the carrier (D) first contact with the component (E), and then employs the components (A) and (B) any other activator (C), as described above.

You can also pre-polymerization catalyst system with α-olefins, preferably linear C2-C10-1-alkenes, in particular ethylene or propylene, and then the pre-polymerized solid catalyst is used in the actual polymerization. The mass ratio of the solid catalyst used in the preliminary polymerization, the monomer polymerized in it, is usually in the range from 1:0.1 to 1:1000, preferably in the range from 1:1 to 1:200.

In addition, in the process of receiving or after receiving the catalyst system may be added a small amount of olefin, preferably α-olefin, such as vinylcyclohexane, styrene or phenyldimethylsilane, as modificy the ith component, an antistatic or a suitable inert component such as wax or oil as an additive. The molar ratio of additives to total amount of transition metal compounds (A) and the iron complex (B) is usually in the range from 1:1000 to 1000:1, preferably from 1:5 to 20:1.

Catalyst composition or catalyst system according to the invention is suitable for obtaining polyethylene according to the invention, which has useful application and useful technological properties.

To obtain a polyethylene according to the invention ethylene is subjected to polymerization, as described above, with α-olefins containing from 3 to 12 carbon atoms.

In the method of copolymerization according to the invention ethylene is subjected to polymerization with α-olefins containing from 3 to 12 carbon atoms. Preferred α-olefins are linear or branched C2-C12-1-alkenes, in particular linear C2-C10-1-alkenes, such as Eten, propene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene, 1-mission or branched C2-C10-1-alkenes such as 4-methyl-1-penten. Particularly preferred α-olefins are C4-C12-1-alkenes, in particular linear C6-C10-1-alkenes. You can also polymerizate mixture of different α-olefins. Preferably polymerized, at least one α-is Latin, selected from the group consisting of Athena, propene, 1-butene, 1-pentene, 1-hexene, 1-Heptene, 1-octene and 1-mission. Preferably the use of mixtures of monomers containing at least 50 mol.% Athena.

The method of polymerization of ethylene with α-olefins according to the invention can be carried out using all industrially known methods of polymerization at temperatures in the range from -60 to 350°C, preferably in the range from 0 to 200°C and particularly preferably in the range from 25 to 150°C and pressures in the range of from 0.5 to 4000 bar, preferably in the range from 1 to 100 bar and particularly preferably from 3 to 40 bar. The polymerization can be carried out in a known manner in the mass, in suspension or in the gas phase or supercritical in the conventional reactors used for the polymerization of olefins. It can be a periodic manner or preferably in a continuous way in one or several stages. Methods of polymerization at high pressure tubular reactors or autoclaves, methods of polymerization in solution, in suspension, methods of polymerization in the gas phase under stirring and methods of polymerization in the gas phase fluidized bed of catalyst are appropriate ways.

Polymerization is usually conducted at temperatures in the range from -60 to 350°C, preferably in the range from 0 to 300°C, and pressures in the range of from 0.5 to 4000 bar. The average values of the residence time of the feedstock in the reactor is typically in the range from 0.5 to 5 hours, preferably from 0.5 to 3 hours. Preferred pressure range and temperature for carrying out the polymerization is usually dependent on the method of polymerization. In the case of methods of polymerization at high pressures, which is usually carried out at a pressure in the range from 1000 to 4000 bar, in particular in the range from 2000 to 3500 bar, also supports high temperature polymerization. Preferred temperature ranges for methods of polymerization at high pressures range from 200 to 320°C, in particular from 220 to 290°C. In the case of methods of polymerization at low pressure is normally maintained temperature that at least a few degrees below the softening temperature of the polymer. In particular, these methods of polymerization are set temperature in the range from 50 to 180°C, preferably from 70 to 120°C. In the case of application of the method of suspension polymerization, the polymerization is usually carried out in a suspension medium, preferably in an inert hydrocarbon, such as isobutane, or mixtures of hydrocarbons, as well as among monomers. The polymerization temperature is usually in the range from -20 to 115°C, and the pressure is usually in the range from 1 to 10 bar. The solids content of the suspension is typically in the range from 10 to 80%. The polymerization can be conducted either periodic manner, for example, under stirring autoclaves or continuous manner, for example, in a tubular reactor, preferably the reactor with circulation. Particularly preferred application of the method of Phillips PF, which is described in US-A 3242150 and US-A 3248179. Gas-phase polymerization is usually carried out at temperatures in the range from 30 to 125°C and pressures in the range from 1 to 50 bar.

Among the above-mentioned methods of polymerization are particularly preferred gas-phase polymerization, in particular in gas-phase fluidized bed reactor catalyst, polymerization in solution and suspension polymerization, in particular in the reactor circulation and capacitive reactors with agitators. Gas-phase polymerization can also be condensed or sverhorganizovannym a way that part of the circulating gas is cooled to a temperature below the dew point and is returned as a two-phase mixture in the reactor. In addition, it is possible to apply multi-zone reactor, in which two zones polymerization is connected and the polymer is passed through these two zones several times. Two zones can also vary the conditions of polymerization. Such a reactor is described, for example, in WO 97/04015. Different or Eden the ranks methods of polymerization can optionally be connected in series with the formation of a polymerization cascade, for example, as in the way Hostalen®. It is also possible parallel arrangement of reactors using two or more identical or different methods of polymerization. In addition, the polymerization can also be applied molecular weight regulators, for example hydrogen, or conventional additives such as antistatics.

The polymerization preferably is carried out in a single reactor, in particular gas-phase reactor. Polymerization of ethylene with α-olefins containing from 3 to 12 carbon atoms, leads to the production of polyethylene according to the invention when using the catalyst according to the invention. Powdered polyethylene obtained directly from the reactor shows high homogeneity, so that in contrast to the processes carried out using a cascade of reactors, in this case, to obtain a homogeneous product subsequent extrusion is not necessary.

Obtaining polymer blends thorough mixing of the individual components, for example, by extrusion of the melt in the extruder or kneader machine (see, for example, "Polymer Blends", Ulimann''s Encyclopedia of Industrial Chemistry, 6thEdition, 1998 Electronic Release) is often particularly difficult. Melt viscosity of high molecular weight and low molecular weight components of the bimodal polyethylene mixture vary greatly. While low molecular weight com is ANENT is enough liquid usually at temperatures of about 190-210°C, used to obtain mixtures of high molecular weight component at these temperatures only softens ("consistency lentil soup"). Therefore, homogeneous mixing of the two components is very difficult. In addition, it is known that high molecular weight component can easily be damaged due to thermal load and under the action of the shearing forces of the extruder, so that the mixture properties can deteriorate. Therefore, the quality of mixing of such polyethylene mixtures is often unsatisfactory.

The quality of mixing powdered polyethylene obtained directly at the exit of the reactor, can be analyzed by examination of thin sections ("microtome sections") of the samples under an optical microscope. Heterogeneity is manifested in the form of spots or "white spots". Spots or white spots are predominantly high-molecular particles of high viscosity in a matrix of low viscosity (see, for example, U. Burkhardt et al., "Aufbereiten von Polymeren mit neuartigen Properties", VDI-Verlag, Düsseidorf 1995, p. 71). Such inclusions can reach a size up to 300 μm, they are the cause of cracks under tension and lead to brittle fracture of the components. With a higher quality of mixing of the polymer is observed fewer inclusions and smaller inclusions. The quality of mixing polymer quantitatively determined is carried out in accordance with ISO 13949. According to this method of determining from a sample of polymer is produced microtome slice, count the number of inclusions and determine their size and on the basis of these data and according to the attached diagram determine the indicator of the quality of mixing of the polymer. Indicator of the quality of mixing of the polyethylene obtained directly from the reactor in the form of polymer powder without extrusion, preferably less than 3.

Getting polyethylene according to the invention in the reactor reduces energy consumption, requires no subsequent mixing processes and simplifies the control of the molecular weight distributions and molecular mass fractions in various polymers. In addition, achieves a good mixing of the polyethylene.

The following examples illustrate the invention but without limiting its scope. Describes the measured values obtained in the following way.

Samples for NMR spectra are placed in a test tube in an inert gas and, if necessary, is melted. The solvent signals serve as an internal standard in1H and13C-NMR spectra and chemical shift converted to values relative to TMS.

The content of the vinyl groups was determined by IR in accordance with ASTM D 6248-98. Number of branches/1000 carbon atoms was determined by using13C-NMR in accordance with the method, sunnym in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and based on the total content of CH3groups/1000 carbon atoms, including end groups. The number of side chains longer than CH3in particular, ethyl, Budilnik and exiling side branches/1000 carbon atoms, including end groups, are also determined by this method.

The branching of the individual polymer fractions were determined by the method of Holtrop (W. Holtrup, Makromol. Chem. 178, 2335 (1977)) in combination with13C-NMR as described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989).

Density [g/cm3] determined according to ISO 1183.

Determination of molecular mass distributions, mean values of Mn, Mwand their derived values of Mw/Mnconduct high-temperature gel chromatography apparatus WATERS 150 C using a method based on DIN 55672, using series-connected columns: 3× SHODEX AT 806 MS, 1× SHODEX UT 807 and 1× SHODEX AT-G under the following conditions: solvent: 1,2,4-trichlorobenzene (stabilized of 0.025 wt.% 2,6-di-tert-butyl-4-METHYLPHENOL), flow rate: 1 ml/min, volume of 500 ál injection, the temperature of 135°C, calibration using PE standards. The calculation is performed using WIN-GPC.

In this description, the term “HLMI” is used in its well-known meaning and refers to the melt index when p is increased shear stress, which is always determined at 190°c load of 21.6 kg 190°C/21,6 kg) according to ISO 1133.

Matte is determined in accordance with ASTM D 1003-00 on the device BYK Gardener Haze Guard Plus Device using at least 5 pieces of film size C cm and a thickness of 1 mm.

Impact strength is determined in accordance with an instrumental impact test drop weight mechanism according to ISO 6603 at -20°C.

Resistance to cracking under stress (full creep testing cut - full notch creep test - FNCT) is determined in accordance with ISO DIS2 16770 at a pressure of 3.5 Mbar and a temperature of 80°C in 2 wt.% the solution Akropal N (N=10) in the water.

Determination of yield strength in spiral form is performed on the machine Demag ET100-310 c locking pressure of 100 t and a mouthpiece 3 mm Demag ET 100-310 at an initial temperature of 250°C, injection pressure of 1000 bar, the speed of rotation of the screw 90 mm/s, the melt temperature of 30°C and a wall thickness of 2 mm.

Abbreviations

Cat.Catalyst
T(Polym.)The temperature of polymerization
MwSrednevekovaja molecular weight
MnSrednekislye molecular weight
Tight.The density of the polymer
The term "vinyl/1000C"refers to the number of vinyl groups per 1000 carbon atoms
The term "p/1000C"refers to the number of branches/1000 carbon atoms, which represents the number of CH3/1000 carbon atoms, including end groups
The term "times. 15% PE VM"refers to 15 wt.% polyethylene containing the high molecular weight with a degree of branching of the side chains more CH3/1000 carbon atoms, excluding end groups
Production.The performance of the catalyst in g of polymer obtained in g of used catalyst per hour
Udorn. durable.Impact strength, which is defined in accordance with the test method on the apparatus with the upper supply shock supply in accordance with ISO 6603 at -20°C

Getting separate components

Bis(n-butylcyclopentadienyl)carrigahorig commercially available from Crompton.

2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II)dichloride receive in accordance with the method described in publ the requirements Qian et al., Organometallics 2003, 22, 4312-4321. In accordance with this invention 65,6 g 2,6-diacetylpyridine (0.4 mol), 170 g of 2,4-dichloro-6-methylaniline (0,483 mol), 32 g of silica gel type 135 and 160 g of molecular sieves (4Å) is stirred in 1500 ml of toluene at 80°C for 5 hours, then add 32 g of silica gel type 135 and 160 g of molecular sieves (4Å). The mixture is stirred at 80°C for an additional 8 hours, the insoluble solid precipitate is filtered off and washed twice with toluene. The solvent is distilled off from the filtrate thus obtained, the residue is mixed with 200 ml of methanol and successively stirred at 55°C for 1 hour. Thus obtained suspension is filtered and the obtained solid product is washed with methanol from the solvent. The result is 95 g of 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine to yield 47%. Interaction with iron chloride(II) is carried out in accordance with the method of publication Qian et al., Organometallics 2003, 22, 4312-4321.

Getting mixed catalytic systems

Example 1

a) Pre-processing of the media

XPO 2107, silica gel, dried by spray drying, Grace, calcined at 600°C for 6 hours.

b) obtaining a mixed catalyst systems

A mixture of 1.43 g (2,37 mmol) dichloride 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II)9,98 g bis(n-butylcyclopentadienyl)carrigahorig and 443 ml MAO (of 4.75 M in toluene, 2.1 mol) was stirred at room temperature for 1 hour and, still stirring, add to 338 g of pre-treated material of the carrier (a) in 500 ml of toluene. The result 778,4 g of the catalyst in the form of a solid product, which still contains 23,9 wt.% solvent (based on the total weight with all components applied to the media).

Polymerization catalysts

The polymerization is carried out in a reactor with a fluidized bed with a diameter of 0.5 m with a total pressure of 20 bar. The polymerization temperature 95°C when using the catalyst of example 1, which is fed to the reactor with a velocity 38,97 g per hour. The ethylene fed into the reactor with a rate of 40.7 kg per hour, 1-hexene, with a speed of 410 g / h and hydrogen with a speed of 2.1 liters per hour. In the reactor also serves 4,62 kg of propane per hour, 0.33 kg of nitrogen per hour and 0.5 g of triisobutylaluminum per hour. The polymer discharged from the speed of 30.1 kg/hour. Properties of the obtained polymer are shown in table 1.

Comparative example 1

The catalyst of the Ziegler receive in accordance with the method of the publication EP-A-739937, the polymerization is conducted by the method of suspension polymerization in the cascade, using a mixture of ethylene/hydrogen in the first reactor and a mixture of ethylene/1-butene containing 0.8 wt.% 1-butene in the second reactor. Properties of the obtained product are shown in table 1.

Table 1
Cat. prima-RAProduction.[yoy]HLMI
[g/10 min]
Mw[g/mol]Mw/MnTight. [g/cm3]Vinyl/
1000 C
Times./ 1000 CTimes. 15% VM PE
1
C1
3792109
75
99000 1163007,9
10
0,953 0,9531,3
0,12
3,9
1
5
0,5

Obtained polymers formed into a small plate of thickness 1 mm in the injection molding apparatus. The temperature of extrusion is equal to 225°C, the rotation speed of the extruder 116 rpm and the speed of injection of 50 mm/s, the residence Time of material in the apparatus 20, the pressure in the apparatus 687 bar.

Table 2
Properties of polyethylenes
Example1V1
The length of the spiral, 250°C [cm] 47,636
FNCT (3.5 MPa, 80°C) [h]7,41,3
Haze [%]90,8094,20
Impact energy (-20°C) [j]12,4211,21

1. Bimodal polyethylene containing homopolymers of ethylene or copolymers of ethylene with 1-alkenes with molecular weight distribution Mw/Mnin the interval from 3 to 30, a density 0,945 to 0,965 g/cm3the average molecular mass Mwfrom 50000 g/mol to 200,000 g/mol, melt index at high shear stress (HLMI) of from 10 to 300 g/10 min, determined at 190°C. and a load of 21.6 kg according to ISO 1133, which contains from 0.1 to 15 branches/1,000 carbon atoms, where from 1 to 15 wt.% polyethylene having high molecular weight, have a degree of branching of more than 1 branch of the side chains is higher than CH3/1000 carbon atoms as determined by the method of Holtrop/C13 NMR, and 5-50 wt.% polyethylene having the lowest molecular weight, have a degree of branching less than 10 branches per 1000 carbon atoms, and where the part of the polyethylene having a molecular weight of less than 20000 has a degree of branching of from 0 to 1.5 resp the areas of the side chains is higher than CH3/1000 carbon atoms as determined by the method of Holtrop/C13 NMR, and the number of co monomer is from 0.01 to 5 wt.%, and the polyethylene obtained with the use of a catalytic composition comprising at least two different polymerization catalyst, where (A) is at least one polymerization catalyst based garretsen (A2), and b) is at least one polymerization catalyst based on iron component having a tridentate ligand that contains at least two ortho, ortho-disubstituted aryl radicals ().

2. The polyethylene according to claim 1, characterized in that it has at least a bimodal distribution of short-chain branching.

3. The polyethylene according to claim 1 or 2, characterized in that the degree of branching is in the range from 0.2 to 8 branches/1000 carbon atoms.

4. The polyethylene according to claim 1, characterized in that obtained in a single reactor.

5. The product, obtained by injection moulding of polyethylene according to any one of claims 1 to 4.

6. The product, obtained by injection molding, according to claim 5, characterized in that it is a matte finish, determined in accordance with ASTM D 1003-00, is less than 94%.

7. The product, obtained by injection molding, by any pp.5-6, characterized in that its resistance to cracking under stress (FNCT), defined in the accordance with ISO DIS2 16770 at a pressure of 3.5 Mbar and a temperature of 80°C in 2 wt.% the solution Akropal N (N=10) in water, is at least 5 hours

8. The product, obtained by injection molding, according to claim 5, characterized in that it is a cover, bolt, screw cap, screw bolt, flange sockets or technical detail.

9. Screw caps made of polyethylene according to any one of claims 1 to 4.



 

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37 cl, 5 dwg, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a polyethylene based composition capable of peroxide cross-linking, which is meant for making articles for various purposes at the end of the cross-linking process, e.g. cable insulation, machine housings, semiconductor protective screens and tubes. The method involves pre-mixing a liquid organic peroxide, a liquid antioxidant and a liquid light stabiliser. The obtained liquid mixture is then added to polyethylene powder at room temperature and stirred intensely, preferably at mixer rotational speed of 800-1500 rpm. The light stabiliser used is at least one liquid sterically hindered amine.

EFFECT: using simple technology to prepare a peroxide cross-linked polyethylene composition, which can be stored for up to four or more days at room temperature with preservation of its activity.

4 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method involves mixing nanofiller with binder, mechanical activation of the obtained mixture and final moulding of the mixture. The powdered filler and binder undergo combined preliminary mechanical activation to obtain a concentrate. The concentrate is a powdered mixture of components with ratio binder: filler equal to 50:50. Further, the obtained concentrate is mixed with binder in amount of 100 pts. wt binder per 0.1-2.0 pts. wt concentrate to obtain a second mixture. This mixture undergoes traditional mixture in a bead mill for a period of time sufficient for obtaining a homogeneous mixture. The powdered mixture is then hot-moulded at pressure and temperature at which the mixture turns into a fluid. Further, the mixture is kept under these conditions until complete solidification. The binder used is powdered polypropylene.

EFFECT: method enables to obtain antifriction material, characterised by high strength properties and wear resistance, elasticity and low brittleness.

1 cl, 7 ex, 6 dwg, 1 tbl

FIELD: construction engineering.

SUBSTANCE: moulding powder for making a porous sintered body contains polyethylene of molecular weight of polyethylene within approximately 600000 g/mol to 2700000 g/mol as specified in ASTM 4020. The average diametre of powder particles is within approximately more than 80 mcm to 1000 mcm. Polyethylene has the powder bulk density within approximately 0.10 to 0.29g/cm3. Herewith the porous sintered body has the bond strength 0.7 MPa and higher, and the pressure differential 6 Mbar or lower in a sample of diametre 140 mm and thickness 6.2-6.5 mm at the air current 7.5 m3/hour.

EFFECT: products show excellent porosity and high durability.

17 cl, 3 dwg, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition is based on secondary polypropylene which contains crushed polypropylene in form of flakes with size of not more than 10 mm, obtained from waste polypropylene objects used in contact with petroleum products and are separators of oil-water emulsion or different oil storage vessel. The composition contains, wt %: said crushed polypropylene - 40-45, low density primary polyethylene - 35-39, inorganic powder filler - 20-21.

EFFECT: wider range of cheap materials based on secondary polypropylene material.

2 cl, 4 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: proposed invention can be used in machine building for fabricating articles based on extremely-macromolecular polyethylene of varying purpose. Proposed method comprises preliminary cold forming from initial extremely-macromolecular polyethylene powder with subsequent moulding at 190°C and specific pressure of 10 to 15 MPa. Heated obtained article is placed into injection mold wherein laminating layer of polyoxymethylene is injected at 230°C. Now, the article is cooled.

EFFECT: reduced weight, higher hardness and wear resistance.

3 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing thermoplastic elastomer compositions, realised through dynamic vulcanisation of a mixture of components of a composition, meant for preparing sealing components, tubing, insulation for components of electric devices, used in aviation, automobile, cable and other industries. The method is realised by loading an ethylene-propylene-diene copolymer and target additives at the first step. Temperature is raised to 120°C and vulcanising agents are added. At temperature of 150°C, thermoplastics are added - polyethylene and polypropylene in amount of 30-50 wt % of their total content and stirring is done at temperature of 190°C. At the second step the remaining amount of thermoplastics is added to the obtained mixture.

EFFECT: obtaining a thermoplastic elastomer composition with improved mechanical, rheological and electrical characteristics.

3 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention can be used for making polymer pipes meant for carrying water and cables. The composition contains soot, finely dispersed silicon dioxide, secondary high-pressure polyethylene and secondary low-pressure polyethylene.

EFFECT: combination of components in a defined ratio increases mechanical strength, reduces cost of the polymer composition and partially solves the problem of recycling polethylene wastes.

8 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to techniques of producing high-strength thermosetting films. Proposed method comprises mechanical missing of granules of several types of polyethylene and film extrusion with its subsequent pneumatic expansion. Extrusion rate makes over 18 m/min. Mix of granules contains unimodal low-pressure polyethylene and bimodal high-pressure polyethylene.

EFFECT: optimum ratio of components allow optimum physicochemical parametres and increased strength.

2 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for hermetic seals for containers, as well as to hermetic seals for containers for carbonated drinks, which contain said compositions and which are designed such that, their cap can be easily turned. Composition for sealing crown caps contains from 20 to 70 wt % thermoplastic rubber, which is a linear copolymer of 70/30 butadiene and styrene, polymerised in solution, and from 80 to 30 wt % thermoplastic polymer. Thermoplastic polymer is chosen from a group consisting of polypropylene and a mixture of polyethylene and ethylene vinyl acetate copolymer.

EFFECT: improved holding of internal pressure, easier removal of hermetic seal when using the container.

18 cl, 10 ex

FIELD: construction.

SUBSTANCE: invention may be used to make protection elements in various equipment used for flaw detection, for medical purposes, for radioactive logging of oil and gas wells, in portable neutron generators, etc. Method includes polymerisation of ethylene on surface of elementary boron particles with average size of 3-8 mcm in presence of catalytic system immobilised on them, which consists of vanadium tetrachloride and aluminium-organic compound. First ethylene is pre-polymerised on surface of boron particles at 25-30° C and ethylene pressure of 1 at for 8-10 minutes, then temperature is increased up to 50-60°C, and ethylene polymerisation is continued at 50-60°C and pressure in the range from 1 to 10 at to produce layer of ultrahigh molecular polyethylene on them with molecular weight of at least 1·106 and thickness of 0.01-20 mcm. Radiation-protection composite material represents particles of elementary boron with polyolefin layer in the form of agglomerates of average size of 20-100 mcm.

EFFECT: produced composite material has even distribution of boron particles in polymer matrix, high strength, very high impact viscosity in wide range of temperatures, resistance to cracking and abrasion.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: group of inventions relates to control of reactions during transitions from an initial reaction to a target reaction with respect to reduction of the amount of off-grade product. The method of determining transition parametres in a polymerisation reactor from an initial reaction for production of a product whose properties satisfy a set of initial requirements to a target reaction for production of a product whose properties satisfy a set of target requirements involves the following steps: identification of a primary property by obtaining data which indicate instantaneous and average values for each of at least two different product properties before, during and after the transition, where each of the said different properties corresponds to the set of initial requirements at the beginning of the transition, and identification as a primary property, based on the said data, of one product property which can be a reason for production of a large amount of off-grade product during the transition compared to any other property; determination of initial conditions for transition, including the initial value of the primary property, which considerably reduce the amount of off-grade product produced during the transition; and determination of variable process control parametres for the transition which begins with the said initial conditions. Disclosed also is a method of identifying the primary property of the product produced in a polymerisation reactor with properties which satisfy the set of initial requirements.

EFFECT: more reliable control.

14 cl, 10 dwg

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