Polyethylene and catalyst composition for polyethylene synthesis

FIELD: chemistry.

SUBSTANCE: polyethylene in form of ethylene homopolymers and copolymers of ethylene with α-olefins and having molecular weight distribution range Mw/Mn from 6 to 100, density from 0.89 to 0.97 g/cm3, weight-average molecular weight Mw from 5000 g/mol to 700000 g/mol and from 0.01 to 20 branches/1000 carbon atoms and at least 0.5 vinyl groups/1000 carbon atoms, where the fraction of polyethylene with molecular weight less than 10000 g/mol has degree of branching from 0 to 1.5 branches on the side chains, longer than CH3/1000 carbon atoms. The catalyst composition for synthesis of polyethylene in paragraph 1 consists of at least two different polymerisation catalysts, from which A) is at least one polymerisation catalyst based on monocyclopentadienyl complex of a group IV-VI metal, in which the cyclopentadienyl system is substituted by an uncharged donor (A1) of formula Cp-Zk-A-MA (II), where variables assume the following values: Cp-Zk-A is , MA is a metal which is selected from a group consisting of titanium (III), vanadium, chromium, molybdenum and tungsten, and k equals 0 or 1, or with hafnocene (A2), and B) is at least one polymerisation catalyst based on a ferrous component with a tridentate ligand containing at least two ortho-, ortho-disubstituted aryl radicals (B).

EFFECT: obtaining polyethylene with good mechanical properties, possibility for processing and high content of vinyl groups.

27 cl, 12 ex, 2 tbl, 5 dwg

 

The present invention relates to new types of polyethylene, to a catalytic composition and method of production thereof, as well as fibers, molded articles, films or mixtures of polymers which contain polyethylene.

To the mechanical strength of the molded products based on polyethylene are increasingly high requirements. In particular, requires products with high resistance to cracking under stress, fracture toughness and hardness, which is particularly useful in the manufacture of hollow articles, and pressure pipes. The requirement for high resistance to cracking under stress and at the same time the stiffness is not easy to satisfy, since these properties contradict each other. While the hardness increases with increasing density polyethylene, resistant to cracking under stress decreases with increasing density.

The formation of cracks in plastics under load is a physico-chemical process in which molecules of the polymers does not change. It is called, among other things, the gradual formation or separation of bonded molecular chains. The cracks grow the harder it is, the more the average molecular weight, the wider the molecular weight distribution and higher the degree of branching of the molecules, i.e. lower density. They formed the harder the longer the chain. Surface-active substances, in particular Soaps, and thermal stress accelerate the formation of cracks under load.

Properties of bimodal polyethylene depend, first, on the properties of the elemental composition of the components. Secondly, the mechanical properties of polyethylene is particularly important as the mixing of high and low molecular weight components. Poor mixing leads inter alia to a low resistance to cracking and negatively affects the slow change of the properties of pressure pipes made of polyethylene blends.

It was found that for hollow products and pressure pipes is better to use a mixture of high molecular weight copolymer of ethylene and low-density and low-molecular homopolymer ethylene high density, which are very resistant to cracking under load, as described, for example, L.L.Bohm and others, Adv. Mater., 4, 234-238 (1992). Similar mixtures of polymers are disclosed in EP-A-100843, EP-A 533154, EP-A 533155, EP-A 533156, EP-A 533160 and USA 5350807.

Such mixtures bimodal polyethylenes often get in cascade reactors, i.e. in two or more series-connected reactors, polymerization, so that the polymerization of low molecular weight component is carried out in one reactor, and the polymerization of high-molecular component in the following (see, for example, M.Ratzsch, W.Neisl “Bimodal Polymerwerkstoffe auf der Basi PP von und PE” in “Ausbereiten von Polymeren mit neuartigen Properties”, pp.3-25, VDI-Verlag, Dusseldorf 1995). The disadvantage of this method is that to obtain a low molecular weight component is necessary to add relatively large amounts of hydrogen. Therefore, the polymers thus obtained, contain little of the vinyl end groups, especially in the low molecular weight component. In addition, it is technically difficult to avoid falling into the next reactor monomers added in one reactor, or added hydrogen, is introduced as a control.

It is known the use of catalytic compositions containing two or more different catalysts for the polymerization of olefins - ziperovich type or metallocene. For example, to obtain mixtures with a wide molecular weight distribution, you can use a combination of two catalysts, one of which is formed polymer, average weight which differs from the mass of product obtained at different catalyst (WO 95/11264). Copolymers of ethylene with more high molecular weight α-olefins such as propylene, 1-butene, 1-penten, 1-hexene or 1-octene, known as LLDPE (linear polymers low density), which are formed in the presence of classical catalysts of the Ziegler-Natta titanium-based, differ from LLDPE obtained in the presence of metallocene. The number of side chains, obtained by the introduction of another monomer, and their distribution is, known as SCBD (distribution of short branched chains) are very different in case of different catalytic systems. The number and distribution of the side chains have a decisive influence on the crystallization of ethylene copolymers. While the fluid properties and, consequently, the ability to process such copolymers of ethylene depend mainly on their molecular mass and molecular mass distribution, mechanical properties especially strongly depend on the distribution of short branched chains. However, the distribution of short branched chains plays an important role in the methods of processing of polymers, for example, extrusion film, in which the crystallization of copolymers of ethylene during cooling film extrudate is an important factor in determining the rate of formation and the quality of the processed film. Due to the large number of possible combinations of choosing the right combination of catalysts to obtain a balanced combination of catalysts and achieve a balance between mechanical properties and processing is a difficult task.

Supplementation of metal components, including metal end of the transition range, the catalysts for polymerization of olefins based on transition metals of the row start to increase their population stability has been repeatedly described (Herrmann, C.; Streck, R.; Angew. Makromol. Chem. 94 (1981), 91-104).

Was described the synthesis of branched polymers of ethylene without the use of comonomers in the presence of bimetallic catalysts, one of which leads to the oligomerization part of the ethylene and the other carries out the copolymerization of the resulting oligomers with ethylene (Bearch, David L.; Kissin Yury V.; J. Polym. Sci., Polym. Chem. Ed. (1984), 22, 3027-42. Ostoja-Starzewski, K.A.; Witte, J.; Reichert, K.H., Vasiliou, G. in Transition Metals and Organometallics as Catalysts for Olefin Polymerization. Kaminsky, W.; Sinn, H. (editors); Springer-Verlag; Heidelberg; 1988; pp.349-360). The last link is described, for example, the use of Nickel-containing oligomerization catalyst in combination with a chromium catalyst polymerization.

In WO 99/46302 described the composition of the catalysts on the basis of (a) one component - pyridine-bis-aminogenesis and (b) another catalyst type zirconocene or ziperovich catalyst and its use for the polymerization of ethylene and olefins.

Known mixture of ethylene copolymers leave much to be desired from the point of view of a combination of good mechanical properties and processing capabilities and often contain too little of the vinyl end groups, which serve as a tool for cross-linkage.

The aim of the present invention to provide a polyethylene with good mechanical properties and great potential for processing and a high proportion of vinyl groups.

Was evitando detected, this goal can be achieved by using a special composition of the catalysts, in the presence of which receive the polyethylene with good mechanical properties and great potential for processing and a high proportion of vinyl groups.

The authors obtained polyethylene, which contains the homopolymers of ethylene and copolymers of ethylene with α-olefins with a width of molecular weight distribution Mw/Mnfrom 6 to 100, a density of from 0.89 to 0.97 g/cm3, srednevekovoi molecular mass Mwfrom 5000 g/mol to 700000 g/mol and the number of branching of from 0.01 to 20 branches/1000 carbon atoms and at least a 0.5 vinyl groups/1000 carbon atoms, and 5-50 wt.% polyethylene of low molecular weight have a degree of branching less than 10 branches/1000 carbon atoms and 5-50 wt.% polyethylene with high molecular weight have a degree of branching of more than 2 branches/1000 carbon atoms.

The authors also received polyethylene, which contains the homopolymers of ethylene and copolymers of ethylene with α-olefins with a width of molecular weight distribution Mw/Mnfrom 6 to 100, a density of from 0.89 to 0.97 g/cm3, srednevekovoi molecular mass Mwfrom 5000 g/mol to 700000 g/mol and the number of branching of from 0.01 to 20 branches/1000 carbon atoms and at least a 0.5 vinyl groups/1000 carbon atoms,and a part of the polyethylene having a molecular weight of less than 10000 g/mol has a degree of branching of from 0 to 1.5 branching side chains - more than CH3/1000 carbon atoms.

The authors also received a mixture of polymers which contain at least one polyethylene obtained according to the present invention, as well as fibers, films and molded articles, in which an important component is polyethylene of the present invention.

Moreover, the authors used the polyethylene of the present invention to obtain fibers, films and molded articles.

The authors also found the catalytic system for producing polyethylenes of the present invention, a method of using a catalytic system for the polymerization of ethylene or copolymerization of ethylene with olefins and a method of producing polyethylene of the present invention by polymerization of ethylene or copolymerization of ethylene with olefins in the presence of catalytic systems.

The polyethylene of the present invention is characterized by wide molecular mass distribution Mw/Mnin the interval from 6 to 100, preferably from 11 to 60 and particularly preferably from 20 to 40. Density polyethylene of the present invention is in the range from 0.89 to 0.97 g/cm3preferably from 0.92 to 0,965 g/cm3and particularly preferably in the range from 0,941 to 0.96 g/cm3. Srednevekovaja molecular mass Mwthe polyethylene of the present invention is located is in the range of from 5000 g/mol to 700000 g/mol, preferably from 30,000 g/mol to approximately 550 000 g/mol and particularly preferably from 70000 g/mol to 450,000 g/mol.

Molecular weight distribution of the polyethylene of the present invention can be modal, bimodal or polymodal. In the application of the present invention modal molecular weight distribution means that the molecular weight distribution has a single maximum. Bimodal molecular weight distribution means, for the purposes of the application of the present invention, the molecular weight distribution has at least two inflection points on the same branch, starting from the maximum. Preferably, the molecular weight distribution was modal or bimodal, especially bimodal.

The polyethylene of the present invention contains from 0.01 to 20 branches/1000 carbon atoms, preferably from 1 to 15 branches/1,000 carbon atoms, and especially preferably from 3 to 10 branches/1000 carbon atoms. Number of branches/1000 carbon atoms is determined by the method of13With NMR, as described by James C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and refer to the total content of CH3groups/1000 carbon atoms.

The polyethylene of 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 determined by the method of IR-spectroscopy according to ASTM D 6248-98. For these purposes, the expression "vinyl group" refers to the groups-CH=CH2; this expression does not cover vinylidene group and internal olefinic groups. The vinyl groups are usually caused by the reaction of chain termination after the introduction of ethylene and vinylidene end groups are usually formed by the reaction of chain termination after the introduction of the copolymer. Vinylidene and vinyl groups can then be functionalitywith or transversely to sew, and vinyl groups are usually more suitable for such subsequent reactions. Therefore, the polyethylene of the present invention is particularly applicable when it is desired subsequent functionalization or cross-stitching, for example, for the preparation of pipes or adhesives. Preferred is a content of at least 0,2 vinyl groups/1000 carbon atoms, preferably from 0.5 to 10 vinyl groups/1000 carbon atoms and particularly preferably from 0.7 to 5 vinyl groups/1000 carbon atoms, present in an amount of 20 wt.% in the polyethylene with the lowest molecular weights. Preferably, the number of vinyl groups/1000 carbon atoms, present in an amount of 20 wt.% in the polyethylene with the lowest molecular mass was greater than the number of inilah groups/1000 carbon atoms in the polyethylene (not fractionated). It can be defined by fractionation on a different faction on Holtrup, as described in W.Holtrup, Macromol. Chem. 178, 2335 (1977) and by the method of IR-spectroscopy, and the number of the vinyl groups are determined according to ASTM D 6248-98. As solvents for fractionation used xylene and diethyl ether of ethylene glycol at 130°C. Using a 5 g polyethylene, which was divided into 8 fractions.

The polyethylene of the present invention preferably contains at least 0,05 vinylidene groups/1000 carbon atoms, in particular from 0.1 to 1 vinylidene groups/1000 carbon atoms and particularly preferably from 0.15 to 0.5 vinylidene groups/1000 carbon atoms. The determination is carried out in accordance with ASTM D 6248-98.

5-50 wt.% one type of polyethylene of the present invention containing the low molecular weight, preferably 10-40 wt.% and particularly preferably 15-30 wt.%, characterized by a degree of branching less than 10 branches/1000 carbon atoms. This degree of divergence in terms of polyethylene, containing the most low molecular weight, is preferably from 0.01 to 8 branches/1000 carbon atoms and particularly preferably from 0.1 to 4 branches/1000 carbon atoms. 5-50 wt.% the polyethylene of the present invention, containing the highest molecular weight, preferably 10-40 wt.% and especially predpochtitel is about 15-30 wt.% have a degree of branching of more than 2 branches/1000 carbon atoms. This degree of branching in part of polyethylene containing the highest molecular weight, is preferably from 2 to 40 branches/1000 carbon atoms and particularly preferably from 5 to 20 branches/1000 carbon atoms. The proportion of polyethylene with the lowest or the highest molecular weights can be determined by fractionation in a solvent or without him, later called fractionation Holtrup, as described in W.Holtrup, Macromol. Chem. 178, 2335 (1977), and by IR and NMR spectroscopy of the various factions. As solvents for fractionation used xylene and diethyl ether of ethylene glycol at 130°Capolavori 5 g of polyethylene, which was divided into 8 fractions. The degree of branching in different fractions of the polymers may be determined by the method13With NMR, as described by James C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989). The degree of branching is called a full group content of CH3/1000 carbon atoms in the fractions of low and high molecular weight (including end groups).

The polyethylene of the present invention preferably has from 0.01 to 20 branches of side chains longer than CH3/1000 carbon atoms, preferably side chains from C2-C6/1000 carbon atoms and particularly preferably from 2 to 8 branched side chains longer than CH3/1000 at the MOU carbon preferably side chains from C2-C6/1000 carbon atoms. Branching of the side chains longer than CH3/1000 carbon atoms, define method13With NMR, as described by James C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and referred to the total content of the side chains longer than CH3/1000 carbon atoms (no limit). Particularly preferably be polyethylene, containing as α-olefins, 1-butene, 1-hexene or 1-octene, from 0.01 to 20 ethyl, Budilnik or exiling lateral branches/1000 carbon atoms, preferably from 1 to 15 ethyl, Budilnik or exiling lateral branches/1000 carbon atoms and particularly preferably from 2 to 8 ethyl, Budilnik or exiling lateral branches/1000 carbon atoms. This applies to the content of ethyl, Budilnik or exiling side chains per 1000 carbon atoms without end groups.

Part of the polyethylene of the present invention with a molecular weight of less than 10000 g/mol, preferably less than 20,000, characterized by the degree of branching of from 0 to 1.5 branches of side chains larger than CH3/1000 carbon atoms, preferably side chains from C2-C6/1000 carbon atoms. Particular preference is given to the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20000, to ora characterized by the degree of branching of from 0.1 to 0.9 branching of the side chains, longer than CH3/1000 carbon atoms, preferably side chains from C2-C6/1000 carbon atoms. Preferably, the polyethylene of the present invention with 1-butene, 1-hexene or 1-octene as α-olefins part of it with a molecular weight of less than 10000 g/mol, preferably less than 20000 had a degree of branching of from 0 to 1.5 ethyl, Budilnik or exiling branches of side chains per 1000 carbon atoms. Particular preference is given to the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20000, which is characterized by the degree of branching of from 0.1 to 0.9 ethyl, Budilnik or exiling branches of side chains per 1000 carbon atoms. It is also possible to determine the method described Holtrup/13C NMR (no limit).

Moreover, it is preferable that at least 70% of the branching side chains longer than CH3in the polyethylene of the present invention were 50 wt.% polyethylene with the highest molecular weights. It is also possible to determine the method described Holtrup/NMR13C.

Molecular weight distribution of the polyethylene of the present invention can be formally calculated from the overlap of two modal molecular weight distributions. Highs molecular weight low molecular weight component, preferred is entrusted are in the range from 3000 to 50000 g/mol, in particular from 5000 to 30000 g/mol. Highs molecular weight high molecular weight component is preferably in the range of 40,000 to 500000 g/mol, in particular from 50000 to 200000 g/mol. The difference between the individual peaks of the molecular weight distribution of the polyethylene of the present invention is preferably in the range from 30,000 to 400,000 g/mol, particularly preferably from 50000 to 200000 g/mol.

Preferably, the index HLMI for polyethylene of the present invention were in the range from 0 to 200 g/10 min, preferably from 5 to 50 g/10 min. For the purposes of the present invention, the expression "HLMI" means "the index of the high content of the melt and is determined at 190°C at a load of 21.6 kg 190°C/21,6 kg) according to ISO 1133.

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

The polyethylene of the present invention preferably has a degree of branching of long chains of λ (lambda) from 0 to 2 long chains/10000 carbon atoms and particularly preferably from 0.1 to 1.5 long chains/10,000 carbon atoms. Stephen the branching of long chains of λ (lambda) can be determined from the scattering, as described, for example, in ACS Series 521, 1993, Chromatography of Polymers, Ed. Theodore Provder; Simon Pang and Alfred Rudin: Size-Exclusion Chromatographic Assessment of Long-Chain Branch Frequency in Polyethylenes, R. 254-269.

The polyethylene of the present invention preferably has a CDBI of less than 50%, in particular from 10 to 45%. The method of determining the CDBI is described, for example, in WO 93/03093. Method TREF described, for example, Wild, Advances in Polymer Science, 98, p.1-47, 57 p.153, 1992. Figure CDBI is defined as the mass percent of a copolymer containing comonomer in the amount of ±25% of the average total molar content of co monomer.

The sustainability of the polyethylene of the present invention to cracking under load is preferably 50 hours, more preferably at least 160 hours. Resistance to cracking under load is determined at 50°C for all samples in the form of a disc (diameter: 38 mm, thickness (height): 1 mm notch length of 20 mm and a depth of 0.2 mm), which is immersed in a 5% solution of lutensol pressure of 3 bar. Measure the time of occurrence of cracks voltage (expressed in hours).

As α-olefins, i.e. possible comonomers which may be present individually or in mixtures with each other along with ethylene in the copolymer with ethylene as part of the polyethylene of the present invention, it is possible to use all α-olefins with 3 to 12 carbon atoms, for example propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene and Dean. Copolymers of ethylene preferably include α-olefins with 4 to 8 carbon atoms, for example 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten or 1-octene in the form of a copolymer as a single comonomers. Especially preferred are α-olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene.

The polyethylene of the present invention may also consist of a mixture of polymers. Thus, for example, can be mixed with each other two or three different copolymer of ethylene, which can vary the density and/or molecular weight distribution and/or distribution of branching of short circuits.

Suitable mixtures of polymers containing (P1) from 20 to 99 wt.% one or more kinds of polyethylene according to the invention and (P2) from 1 to 80 wt.% polymer, which is different from (P1), and wt.% refer to the total weight of the mixture of polymers.

Especially often use a mixture of polymers containing

(E) from 30 to 95 wt.% one type of polyethylene according to the invention, particularly preferably from 50 to 85 wt.% and

(F) from 5 to 70 wt.% polyolefin which is different from (P1), particularly preferably from 15 to 50 wt.%, moreover, wt.% refer to the total weight of the mixture of polymers.

The type of other components of the polymer (P2) in the mixture depends on the nature of further use of the mixture. The mixture can be obtained, for example, by the mixing of the aqueous or more additional LLDPEs, or HDPEs, or LDPEs, or PPs, or polyamides, or polyesters. The mixture of polymers can also be obtained by simultaneous polymerization in the presence of a catalytic system, which is active in the polymerization of olefins. Catalysts suitable for the preparation of polymers for blending or for carrying out simultaneous polymerization are, in particular, classical catalysts of the Ziegler-Natta titanium-based, classical catalysts firm Phillips on the basis of the oxides of chromium, metallocene, in particular metal complexes 3-6 groups of the Periodic table of the elements containing one, two or three cyclopentadienyls, indanilnykh and/or fluoroaniline systems, complexes with hard geometry (see, for example, EP AND 0416815 or EP AND 0420436), bis-imine complexes of Nickel and palladium (preparation see WO 9803559 A1) or pyridine bis-imine compounds of iron and cobalt (preparation see WO 9827124 A1). Polymerization catalysts can be applied to the same substrate or on different substrates.

A mixture of polyethylenes of this invention can also contain two or three other polymer or olefin copolymer. This can be, for example, LDPEs (their mixtures are described, for example, in DE-A1-19745047) or polyethylene homopolymers (a mixture thereof are described, for example, in EP-B-100843) or LLDPEs (as described, for example, in EP-B-728160 or WO-A-90/03414) or a mixture of LLDPE/LDPE (WO 95/27005 or ER-IN-662989).

Copolymers of ethylene and mixtures of polymers can also contain known per se additives and/or additives, for example stabilizers for processing stabilizers, providing resistance to the action of light and heat, customary additives type lubricants, antioxidants, antiadhesive and antistatics, and also the appropriate dyes. Experts know the types and amounts of these additives.

It was further established that the processing of polyethylenes of this invention can be expanded by the introduction of small amounts of fluorine-containing elastomers or thermoplastic polyesters. Such fluorine-containing elastomers are known as processing AIDS and are issued by the industry, for example, under the trademark Viton® and Dynamar® (see also, for example, US-A-3125547). They are preferably added in quantities of from 10 to 1000 ppm, particularly preferably from 20 to 200 ppm, calculated on the total weight of the mixture of the polymers obtained according to this invention.

The polyethylene of the present invention can also be modified by fixing, cross-stitching, hydrogenation, functionalization, or other functionalization reactions, well known to the experts.

Mixtures of polymers can be obtained by mixing all the known ways. This can be done, for example, the introduction of the powder components in the apparatus to which regulirovaniya, for example, in a twin-screw mixer (ZSK), Farrel mixer or mixer Kobe. Granulated mixture can also be treated directly in the device to retrieve the film.

Various types of polyethylene and mixtures of the polymers of this invention are quite suitable, for example, for the manufacture of films in high-performance devices for reception of films by extrusion with blowing and casting from solution. Films of mixtures of polymers have very good mechanical properties, high impact resistance and high tensile strength combined with very good optical properties, in particular transparency and gloss. In particular, they are suitable for packaging, for example, as termoskleivaniya films for large bags, and food containers. In addition, the film is poorly glued together and therefore can be used in machines with small additives of the type lubricants or antiadhesion.

Due to the good mechanical properties of different types of polyethylene of the present invention suitable for the production of fibers and molded products, in particular tubes and link pipe. They are also suitable for molding under pressure, centrifugal casting and injection molding. They are also suitable as components for compounding, bonding means and additives for polypropylene, in particular in wt the bathrooms are materials based on polypropylene, with high impact strength.

Fibers, films and molding, in which an important component is polyethylene of the present invention, contain it in an amount of from 50 to 100 wt.%, preferably from 60 to 90 wt.% in the calculation on the entire polymer used for their production. In particular, these include film and forming, in which one of the layers contains from 50 to 100 wt.% the polyethylene of the present invention.

Preference is given to fibers containing polyethylene of the present invention with a density in the range of 0.94-0.96 g/cm3. These fibers preferably have MI5about 0.5-5 g/10 see the Preferred molding containing the polyethylene of the present invention with a density in the range from 0.93 to 0,965 g/cm3. These moulding preferably have MI5about 5 g/10 see Among these molds particular preference is given to pipes, large hollow articles with a volume of 10 l and bottles. Particularly preferred polyethylene pipes of the present invention with a density in the range from 0.93 to 0,955 g/cm3. These tubes preferably have MI5the order of 0-1 g/10 see Especially preferred large hollow body made of polyethylene of the present invention with a density in the range from 0.94 to 0,955 g/cm3. Such large hollow articles preferably have MI5the order of 0-1 g/10 see Especially repectfully bottles made of polyethylene of the present invention with a density in the range from 0,945 to 0,955 g/cm 3. These bottles preferably have MI5about 0.5-5 g/10 see Especially preferred product obtained by molding under pressure polyethylene of the present invention with a density in the range from 0.95 to 0,965 g/cm3. These products preferably have MI5about 2-60 g/10 cm

The polyethylene of the present invention receive in the presence of a catalytic system of the present invention and, in particular, its preferred options.

The present invention also provides a catalyst composition containing at least two different polymerization catalyst, of which (A) represents at least one polymerization catalyst based on monotsiklopentadienil complex metal from 4-6 groups of the Periodic table of elements, in which cyclopentadienyls system is substituted by an uncharged donor (A1), or garretsen (A2) and C) is at least one polymerization catalyst based on iron with a tridentate ligand containing at least two ortho, ortho-disubstituted aryl radicals ().

In addition, the invention provides a method for the polymerization of olefins in the presence of catalytic compositions of this invention.

For the purpose of the present invention uncharged donor is an uncharged functional group containing an element Yi 16th group in the Periodic table.

Garrity in the composition of the catalyst are, for example, cyclopentadienyls complexes. Cyclopentadienyls complexes can be, for example, bridge or nesostykovki bis-cyclopentadienyls complexes, as described, for example, in EP 129368, EP 561479, EP 545304 and EP 576970, mononitrobenzene complexes, such as bridge aminocyclopentane complexes are described, for example, in EP 416815, polynuclear cyclopentadienyls complexes as described in EP 632063, tetrahydroindene with PI-ligand substituents, as described in EP 659758, or tetrahydroindene with PI-ligand substituents, as described in EP 661300.

Preference is given monosyllabically complexes (A1)containing the following structural elements of the General formula Cf-YmMA(I)in which the variables mean:

Cf means cyclopentadienyls system

Y means the Deputy, which is associated with Cf and contains at least one uncharged donor containing at least one atom from 15 or 16 groups of the Periodic table,

MAmeans titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, in particular chromium, and

m is 1, 2 or 3.

Suitable monosyllabically complexes (A1) containing a structural element of the General formula Cf-YmMA(I)in which lane the term defined above. Other ligands can be bound to the metal atom MA. A number of other ligands depends on the oxidation state of the metal atom. These ligands are not cyclopentadienyls systems. Suitable ligands include monoamine and gianinni ligands, as described, for example, to H. in Addition, with the Central atom M can also be related to Lisovskii bases, such as amines, ethers, ketones, aldehydes, esters, sulfides or phosphines. Monosyllabically complexes can be Monomeric, dimeric or oligomeric. Preferred Monomeric monosyllabically complexes.

MAis a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten. Oxidation number of transition metals MAin catalytically active complexes is generally known in the art. Chromium, molybdenum and tungsten with high probability have oxidation number +3, zirconium and hafnium oxidation state +4 and the titanium oxidation state +3 or +4. However, you can use complexes, in which the oxidation state of the metal atom does not coincide with the degree of oxidation in the active catalyst. Such complexes can then respectively be restored or oxidize with suitable activators. It is preferable that the M Awas titanium in oxidation state 3, vanadium, chromium, molybdenum or tungsten. Special preference is given to chromium in the oxidation States 2, 3 and 4 and especially 3.

m can be 1, 2 or 3 (1, 2 or 3 donor groups can be associated with Cf, which in the case of 2 or 3 of the groups Y may be identical or different. Preferred is one donor group Y associated with 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 heteroaromatic cyclic system. Donor Y can be associated with the transition metal MAintermolecular or intramolecular or may not be associated with him. Preferably, the donor Y was associated with intramolecular Central atom MA. Especially preferred are monosyllabically complexes containing the structural element of the General formula Cf-Y-MA.

Cp is cyclopentadienyls system, which can be substituted in any way and/or condensed with one or more of the romantic, aliphatic, heterocyclic or heteroaromatic cycles with 1, 2 or 3 substituents, preferably with 1 Deputy, which was founded by a group Y, and/or 1, 2 or 3 substituents, preferably 1 Deputy, replaced by a group Y and/or aromatic, aliphatic, heterocyclic, or heteroaromatic condensed cycles containing 1, 2 or 3 substituent, preferably 1 substituent. Cyclopentadienyls the frame itself is a cycle C56 π-electrons, in which one of the carbon atoms may also be replaced by nitrogen or phosphorus, preferably phosphorus. Preference is given to systems based on the cycle C5not substituted by a heteroatom. This cyclopentadienyls frame may, for example, be condensed with a heteroaromatic cycle containing at least one atom from the group consisting of N, P, O and S, or aromatic cycle. In this context, "condensed" means a heterocycle and cyclopentadienyls frame are two common atoms, preferably two carbon atoms. Cyclopentadienyls system associated with MA.

Especially satisfy all requirements monosyllabically complexes (A1), in which the group Y is formed by a group-Zk-A-, and together with cyclopentadienyls system Cp and MAthey form mootsikapun adenylyl complex, containing the structural element of the General formula Cp-Zk-A-MA(II)in which the variables have the following meanings:

CD ZK-A represents a

where the variables have the following meanings:

E1A-E5Aeach represent a carbon or from the E1Ato E5Anot more than phosphorus,

R1A-R4Aeach, independently of one another represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR5A2N(SiR5A3)2, OR5A, OSiR5A3, SiR5A3, BR5A2in which the organic radicals R1A-R4Acan also be substituted by Halogens and two vicinal radicals R1A-R4Acan also be connected with the formation of five-, six - and semichronic cycle, and/or two vicinal radicals R1A-R4Aassociated with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, the radicals R5Aeach, independently of one another represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in alkylsulfate and 6-20 carbon atoms in the aryl part and two genialnyh radical R 5Acan also be connected with the formation of five - or six-membered cycle,

Z is a divalent bridge between A and Cp, which are 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 silicon or germanium,

R6A-R11Aeach, independently of one another represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR12A3where the organic radicals R6A-R11Acan also be substituted by Halogens and two genialnyh or vicinal radicals R6A-R11Acan also be connected with the formation of five - or six-membered cycle and

the radicals R12Aeach, independently of one another represent hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, With1-C10-alkoxy or C6-C10-aryloxy and two radicals R12Acan also be connected with the formation of five - or chesticle the aqueous cycle, and

A is an uncharged donor group containing one or more atoms 15 and/or 16 groups of the Periodic table of elements, preferably unsubstituted, substituted or condensed heteroaromatic cyclic system,

MArepresents a metal chosen from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten, in particular chromium, and

k is 0 or 1.

In the preferred cyclopentadienyls systems Cp all groups from the E1Ato E5Aare carbon atoms.

Polymerization in the presence of metal complexes depends on the substituents R1A-R4A. The number and type of substituents can affect the availability of the metal atom M to the polymerized olefins. Thus, it is possible to vary the activity and selectivity of the catalyst in relation to different monomers, especially bulk monomers. Because deputies can also affect the reaction rate of chain termination in the growing polymer chain, the molecular weight of the resulting polymers may also change. Therefore, to achieve the desired results and obtain a desired catalyst system can be varied chemical structure of the substituents from R1Ato R4Awithin wide limits. Possible organic R1A-R4Asubstituents are the I, for example: 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 can in turn 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 by other alkyl groups, such as phenyl, naphthyl, diphenyl, antoanela, 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 by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and two of the radicals from R1Ato R4Acan also be connected with the formation of 5-, 6 - or 7-membered cycles and/or vicinal radicals R1A-R4Amo is ut to connect with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and/or the organic radicals R1A-R4Awhich may be substituted by halogen atoms, for example fluorine, chlorine or bromine. Moreover, R1A-R4Amay represent an amino group NR5A2or N(SiR5A3)2alkoxyl or aryloxy OR5Afor example dimethylamino, N-pyrrolidinyl, picoline, methoxy, ethoxy or isopropoxy group. The radicals R5Ain organosilicon substituents SiR5A3can be the same carbon-containing organic radicals described above for R1A-R4Aand 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. These radicals SiR5A3can also join cyclopentadienyls the skeleton via an oxygen atom or nitrogen, for example, trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylcyclohexyl. 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, diphenyl and anthranol. Possible organosilicon substituents are, in particular, trialkylsilyl group with 1-10 carbon atoms in the alkyl radical, in particular trimethylsilyl group.

Two vicinal radicals R1A-R4Aalong with containing groups E1A-E5Acan form a heterocycle, preferably a heteroaromatic cycle containing at least one atom from the group consisting of nitrogen, phosphorus, oxygen and sulfur, particularly preferably nitrogen and/or sulfur, and E1A-E5Ain the heterocycle and heteroaromatic cycle are preferably carbon atoms. Preferred are heterocyclic compounds and heteroaromatic cycles with 5-6 atoms in the cycle. Examples of 5-membered heterocycles which can contain one to four nitrogen atoms and/or sulfur, or oxygen in the loop in addition to carbon atoms, 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, are pyridine, postabortal,pyridazine, the 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 with 1-10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl atoms or halogen, for example fluorine, chlorine or bromine, dialkylamino, alkylammonium, diarylamino, alkoxyl or aryloxides or condensed with one or more aromatic or heteroaromatic compounds. Examples of 5-membered heteroaryl group fused with a benzene cycle, are indole, indazole, benzofuran, benzothiophene, benzothiazole, benzoxazole and benzimidazole. Examples of 6-membered heteroaryl group fused with a benzene cycle, are chroman, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, hinzelin, cinoxacin, 1,10-phenanthrolin and hemolysin. Name heterocycles and numbering of atoms taken from Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979. Heterocycles/heteroaromatic compounds preferably condense with cyclopentadienyls skeleton double bond of the heterocycle/heteroaromatic compounds. Heterocycles/heteroaromatic compounds with one heteroatom preferably condensed in the 2,3 - or b-position.

Cyclopentadienyls system Cp, kondensirovannye is with heterocycles, 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-terpentin, 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-cyclopent[1,2]pyrrole[3,4]cyclopentadiene.

In other preferred cyclopentadienyls Cp systems four of the radical R1A-R4Ai.e. two pairs of vicinal radicals, form two heterocycle which, in particular heteroaromatic compounds. Heterocyclic system are the same as described above.

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

The synthesis of such cyclopentadienyls systems containing condensed heterocycle described, for example, in the above WO 98/22486. Other syntheses of these cyclopentadienyls systems described in "Metalorganic catalysts for synthesis and polymerisation", Springer Verlag 1999, Ewen et al., p.150.

Particularly preferred substituents R1A-R4Aare the above-described carbon-containing organic substituents and the carbon-containing organic substituents, which form a condensed cyclic system, i.e. with cyclopentadienyls skeleton E1A-E5Apreferably, with the frame C5form, for example, unsubstituted or substituted indenyl, benzinger, phenanthrene, fluorene or tetrahydroindene and also, in particular, their preferred options.

Examples of such cyclopentadienyls systems (without a group-Z-A-, which is preferably localized in position 1) are 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3-isopropylcyclopentadienyl, 3-tert-butylcyclopentadienyl, dialkylacrylamide, for example 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 also indenyl, 2-methylindenyl, 2-ethylidene, 2-isopropylphenyl, 3-methylindenyl, benzinger and 2-methylbenzhydryl. Condensed cyclic system may contain1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR5A2N(SiR5A3)2, OR5A, OSiR5A3or 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, one of the substituents R1A-R4Apreferably R2Arepresents a C6-C22-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, preferably C6-C22-aryl, for example phenyl, naphthyl, diphenyl, anthracene or phenanthrene, and aryl can be substituted by N-, P-, O - or S-containing substituents, C1-C22-alkyl, C2-C22-alkenyl, halogen or halogenation Il what halogenosilanes with 1-10 carbon atoms, 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-florfenicol, o-, m-, p-chlorophenyl, o-, m-, p-cryptomaterial, 2,3-, 2,4-, 2,5- or 2,6-differenial, 2,3-, 2,4-, 2,5 - or 2,6-dichlorophenyl, or 2,3-, 2,4-, 2,5 - or 2,6-di(trifluoromethyl)phenyl. Substituents containing N, P, O or S, C1-C22-alkyl, C2-C22alkenyl, halogen or halogenated or galogenidy with 1-10 carbon atoms in the aryl radical, preferably located in the para-position with respect to communication with cyclopentadienyls cycle. Aryl Deputy can be in a vicinal position relative to the substituent-Z-A or two Deputy located relative to each other in the 1,3 positions cyclopentadienyls cycle.

As in the case of metallocenes, monosyllabically complexes (A1) can be chiral. One of the substituents RiA-R4Acyclopentadienyls frame can have one or more chiral centers or herself cyclopentadienyls system Cp may be a while, so that chirality is induced only when a bond with the transition metal M (about formalism related to cyclopentadienyls connections, see the R.Halterman, Chem. Rev. 92, (1992), 965-994).

The bridge Z between cyclopentadiene enoi 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 components. On the activity of the catalyst can be influenced by changing the length of the bridge between cyclopentadienyls system and a Group Z preferably is associated with cyclopentadienyls frame adjacent to the condensed heterocycle or a condensed aromatic group. Thus, if a heterocycle or aromatic group condensed in positions 2,3 cyclopentadienyls skeleton, then Z should preferably be located in positions 1 or 4 cyclopentadienyls of the skeleton.

Possible carbon-containing organic substituents R6A-R11Awhen communication Z include, for example, the following: 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 contains 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 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 may be substituted by alkyl groups, e.g. phenyl, naphthyl, diphenyl, antoanela, 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 may be substituted by alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and two of the radicals from R6Ato R11Acan also be connected with the formation of 5 - or 6-membered cycle, for example cyclohexane, and the organic radicals R6A-R11Amay also be substituted by halogen atoms, for example fluorine, chlorine or bromine, for example pentafluorophenyl or bis-3,5-triptorelin-1-yl, and alkyl or aryl.

The radicals R12Ain organosilicon substituents SiR12A3can be the same radicals as described above for R6A-R11Aand two radicals R12Acan 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, vinyl, allyl, benzyl, phenyl, ortho-dialkyl - or-dichlorsilane family, trialkyl or trichlorsilane family, naphthyl, diphenyl 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 by other alkyl groups, such as phenyl, naphthyl, diphenyl, antoanela, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil-1st, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil-1-Ohm, or arylalkyl, which can be substituted by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl and two of the radicals from R6Ato R11Acan also be connected with the formation of 5 - or 6-Lenogo cycle, for example cyclohexane, and the organic radicals R6A-R2Bmay be substituted by halogen atoms, for example fluorine, chlorine or bromine, especially fluorine, for example pentafluorophenyl or bis-3,5-triptorelin-1-yl, and alkyl or aryl. Especially preferred methyl, ethyl, 1-propyl, 2-isopropyl, 1-butyl, 2-tert-butyl, phenyl and pentafluorophenyl.

Z is preferably a group-CR6A R7A-, -SiR6AR7A-in particular-Si(CH3)2-, -CR6AR7ACR8AR9A-, -SiR6AR7ACR8AR9Aor substituted or unsubstituted 1,2-phenylene, and in particular CR6AR7A-. Preferred options described above substituents R6A-R11Aare the same preferred option in this case. Preference is given-CR6AR7A-including-CHR6A-, -CH2- or-C(CH3)2- group. Group-SiR6AR7Ain L1AR6AR7ACR8AR9A- may be associated with cyclopentadienyls system or A. This group-SiR6AR7Aor her preferred option preferably associated with Cp.

k is 0 or 1; in particular, k is equal to 1 or can also be equal to 0, when A is an unsubstituted, substituted or condensed heterocyclic system. Preferred k is equal to 1.

A is an uncharged donor containing 15 or 16 atom groups of the Periodic table, preferably one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen or phosphorus, preferably nitrogen and phosphorus. Donor function in A can be related to intermolecular or intramolecular metal MA. Donor And preferably is associated with M intramolecular. Potential donors are zarajennye functional group, the containing element 15 or 16 groups of the Periodic table, such as amine, Imin, carboxamide, ester of carboxylic acid, ketone (oxo), a simple ether, thioketone, phosphine, postit, phosphine oxide, sulfonyl, sulfonamide or unsubstituted, substituted or condensed heterocyclic systems. You can attach And cyclopentadienyls the radical and Z synthetically, for example by a method similar to that described in WO 00/35928.

A is preferably a group selected from-OR13A-, -SR13A-, -NR13AR14A-, -PR13AR14A-, -C=NR13Aand unsubstituted, substituted or condensed heteroaromatic systems, in particular,- NR13AR14A- ,- (C=NR13Aand unsubstituted, substituted or condensed heteroaromatic systems.

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 can in turn contain as Deputy C6-C10-aryl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C20-al is Anil, 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 by other alkyl groups, such as phenyl, naphthyl, diphenyl, antoanela, 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, arylalkyl, which may contain 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and can be replaced by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl or SiR15A3, and the organic radicals R13A-R14Acan also be substituted by halogen atoms, for example fluorine, chlorine or bromine, or nitrogen-containing groups, and, in addition, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR15A3groups and two vicinal radicals R13A-R14Acan also be connected with the formation of five - or six-membered cycle and the radicals R15Acan also be connected with the formation of five - and chesticles the th cycle.

NR13AR14Ais an amide substituent. Preferably it 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, Diisobutylene, 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-isopropylacrylamide, N-tert-butylcyclohexylamine, dicyclohexylamine, pyrrolidine, piperidine, hexamethylenimine, decahydroquinoline, diphenylamine, N-methylaniline or N-ethylaniline.

In aminogroup-C=NR13A, R13Apreferably represents C6-C20-aryl radical which may be substituted by other alkyl groups, such as phenyl, naphthyl, diphenyl, antoanela, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil-1-yl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil-1-yl.

A preferably represents an unsubstituted, substituted or condensed heteroaromatic cyclic system, which in addition to carbon atoms in the cycle can contain heteroatoms from the group consisting whom her from oxygen, sulfur, nitrogen or phosphorus. Examples of 5-membered heteroaryl groups which may contain one to four nitrogen atoms and/or one to three nitrogen atoms and/or sulfur or oxygen along with carbon atoms are 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 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 can be substituted C1-C10-alkyl, C6-C10-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogen, for example fluorine, chlorine or bromine or be fused with one or more aromatic or heteroaromatic compounds. Examples of 5-membered heteroaryl group fused with a benzene cycle is 2-indolyl, 7-indolyl, 2-coumaroyl, 7-Kumar the Nile, 2-thionaphthene, 7-thionaphthene, 3-indazole, 7-indazole, 2-benzimidazolyl and 7 benzimidazolyl. Examples of condensed with the benzene ring cycle 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-fenesin. The name and numbering of atoms in molecules heterocycles taken from L. Fieser and M. Fieser, Lehrbuch der organischen Chemie, 3rdrevised edition, Verlag Chemie, Weinheim 1957.

Among these heteroaromatic systems A special preference is given to unsubstituted, substituted and/or condensed six-membered heteroaromatic compounds with 1, 2, 3, 4 or 5 nitrogen atoms in the heteroaromatic part, in particular substituted and unsubstituted 2-pyridyl or 2-Honolulu. Therefore, A preferably represents a group of formula (IV)

in which

E6A-E9Aeach, independently from each other represents a carbon or nitrogen,

R16A-R19Aeach, independently of one another represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and SiR20A3, and the organic radicals R16A-R19Acan also be substituted by halogen atoms is in or nitrogen and, in addition, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR20Aand two vicinal radicals R16A-R19Aor R16Aand Z can also be connected with the formation of five - or six-membered cycle and

the radicals R20Aeach, independently of one another represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part 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-E9Arepresents nitrogen and is 1 when E6A-E9Ais the carbon.

In particular, 0 or 1 for E6A-E9Arepresents nitrogen and the rest of the carbon. Particularly preferably, when a represents 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, 6-methyl-4-pyrimidyl, 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.

BL is due to the ease of obtaining the preferred combinations of Z and A are such in which Z is unsubstituted or substituted 1,2-phenylene and A is NR16AR17Aand those in which Z represents-CHR6A-, -CH2-, -C(CH3)2or-Si(CH3)2and A represents an unsubstituted or substituted 2-chinolin or unsubstituted or substituted 2-pyridyl. System without bridge Z in which k is equal to 0, it is also very easy to synthesize. In this case, A preferably represents unsubstituted or substituted 8-chinolin. In addition, when k = 0, R2Apreferably represents C6-C22-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, preferably C6-C22-aryl, for example phenyl, naphthyl, diphenyl, anthracene or phenanthrene, and aryl may also be substituted by N-, P-, O - or S-containing groups, C1-C22-alkyl, C2-C22-alkenyl, halogen or halogenation with 1-10 carbon atoms.

Preferred options for the above variables are also preferred in these preferred combinations.

MArepresents a metal chosen from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten, preferably titanium in the oxidation state 3, and chromium. Special preference is given to x the WMD in the oxidation States 2, 3 and 4, especially 3. The metal complexes, in particular the chromium complexes, can be obtained simply by the reaction of the corresponding metal salts such as metal chlorides, with the anion of the ligand (for example, in a manner analogous to the examples in DE 19710615).

Among suitable monosyllabically complexes (A1) preference is given to complexes of the formula Cp-YmMAXn(V)in which the variables Cp, Y, A, m and MAdefined above, and their preferred variants are those in this case:

XAeach independently represents a fluorine, chlorine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C20-aryl, alkylaryl with 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 uncoordinated 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 represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the arilje the second part, SiR23A3, and the organic radicals R21A-R22Acan also be substituted by halogen atoms or nitrogen - and oxygen-containing groups and two radicals R21-R22Acan also be connected with the formation of five - or six-membered cycle,

the radicals R23Aeach, independently of one another represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 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.

The above options and preferred options for Cp, Y, Z, A, m, and MAalso applicable individually or in combination to these preferred monosyllabically complexes.

The ligands XAdetermined, for example, by selecting the appropriate starting compounds of the metals used for the synthesis of monosyllabically complexes, but can also continue to vary. Possible ligands XAare in particular halogen, for example fluorine, chlorine, bromine or iodine, especially chlorine. Also good ligands XAare methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl. In addition, the ligands XAyou can specify just as the e examples no claim to completeness, are triptorelin, BF4-PF6-and also poorly coordinated or coordinatewise anions (see, for example, S. Strauss in Chem. Rev. 1993, 93, 927-942), for example B(C6F5)4-.

Other particularly suitable ligands XAare amides, alkoxides, sulfonates, carboxylates and β-diketonates. Varying the radicals R21Aand R22Ayou can further adjust, for example, physical properties such as solubility. Possible carbon-containing organic substituents R21A-R22Ainclude the following, for example: 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-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 Il is cyclooctadiene, C6-C22-aryl which can be substituted by other alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl, diphenyl, antoanela, 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 by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and R21Aand R22Acan also be connected with the formation of 5 - or 6-membered cycle and organic radicals R21A-R22Amay be substituted by halogen atoms, for example fluorine, chlorine or bromine. Possible radicals R23Ain organosilicon substituents SiR23A3are the same radicals which have been mentioned above for R21A-R22Aand two radicals R23Acan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, trialkylsilyl, triphenylene or dimethylphenylsilane. As radicals R21Aand R22Apreference is given to using C1-C10-alkyl, for example methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentile, n-hexyl, n-heptyl, n-octyle and also vinyl, allyl, benzyl and phenyl. Particularly preferably used is SQL some of these substituted ligands X, as they get cheap and readily available starting materials. Thus, particularly preferred is one in which XAis 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. Thus, the number n cannot be expressed in General form. Usually specialists known oxidation number of transition metals MAin catalytically active complexes. It is highly likely that chromium, molybdenum and tungsten are present in the oxidation States +3 and the vanadium in oxidation state +3 or +4. However, you can use complexes, in which the oxidation number does not match the degree of oxidation in the active catalyst. Such complexes can then respectively be restored or oxidize with suitable activators. Preference is given to complexes of chromium in oxidation state +3, and complexes of titanium in the oxidation state 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)-3-(4-harfe the sludge)of cyclopentadienyl(III), dichloride, 1-(8-chinolin)-2-methyl-3-vinylcyclopentane(III)dichloride, 1-(8-chinolin)-2-methyl-3-(1-naphthyl)cyclopentadienyl(III)dichloride, 1-(8-chinolin)-2-methyl-3-(4-triptoreline)cyclopentadienyl(III)dichloride, 1-(8-chinolin)-2-methyl-3-(4-chlorophenyl)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-phenylindolizine(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-pyridyl-methyl)Ingenieria, 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).

The method of synthesis of such functionally-substituted cyclopentadienyls of known ligands. Different methods of synthesis included sobrasada ligands described, for example, in M. Enders and others, in Chem. Ber. (1996), 129, 459-463 or P. Jutzi and U. Siemeling in J. Orgmet. Chem. (1995), 500, 175-185.

Such complexes can be synthesized by methods known per se, by reaction of the appropriately substituted, cyclic hydrocarbon anions preferably with halides of titanium, vanadium or chromium. Examples of appropriate preparative methods of synthesis are described, for example, in Journal of Organometallic Chemistry, 369 (1989), 359-370 and in EP-A-1212333.

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

in which the substituents and indices have the following meanings:

XBrepresents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C15-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, -OR6or-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 can be connected to each other,

E1B-E5Brepresent carbon or not more than one of the E1B-E5Brepresents a phosphorus or nitrogen, preferably carbon,

t is 1, 2 or 3 depending on the valence Hf takes values such that the metallocene comp the CEN General formula (VI) is uncharged,

and

R6Band R7Beach represents a C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, foralkyl or ferril with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and

R1B-R5Beach, independently of one another represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which in turn may contain substituents: C1-C10-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR8B2N(SiR8B3)2, OR8B, OSiR8B3, SiR8B3, and the organic radicals R1B-R5can also be substituted by halogen atoms and/or two radicals R1-R5in particular vicinal radicals, may also be connected with the formation of five-, six-or semichasnoho cycle and/or two vicinal radicals R1D-R5Dcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and

the radicals R8Bmay be the same or different and each of them can be a C1-C10-alkyl, C3-C10-cycloalkyl, C6 -C15-aryl, C1-C4-alkoxy or C6-C10-aryloxy and

Z1Bis a XBor

moreover, the radical

R9B-R13Beach, independently of one another represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which in turn can contain as Deputy C1-C10-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR142N(SiR143)2, OR14B, OSiR14B3, SiR14B3, and the organic radicals R9B-R13Bcan also be substituted by halogen atoms and/or two radicals R9B-R13Bin particular vicinal radicals, may also be connected with the formation of five-, six - or semichasnoho cycle and/or two vicinal radicals R9B-R13Bcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and

the radicals R14Bmay be the same or different and each represents a C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl, C1-C4-alkoxy or C6 -C10-aryloxy,

E6B-E10Beach represents a carbon or not more than one of the E68-E10Brepresents a phosphorus or nitrogen, preferably carbon,

or the radicals R4Band Z1Btogether form a group-R15BV-A1B-and

R15Brepresents a

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

and

R16B-R21Bare the same or different and each represents a hydrogen atom, halogen atom, trimethylsilyloxy group, group C1-C10-alkyl, C1-C10-foralkyl, C6-C10-ferril, C6-C10-aryl, C1-C10-alkoxy, a C7-C15-alkylacrylate, C2-C10alkenyl, C7-C40-arylalkyl, C8-C40-arylalkyl or C7-C40-alkylaryl or two adjacent radicals together with the atoms connecting them, form a saturated or unsaturated cycle with 4 to 15 carbon atoms and

M2B-M4Beach represents a silicon, germanium or tin, or preferably silicon,

A1Brepresents a

-NR22B2, -PR22B2or unsubstituted, substituted or kondensierten the Yu heterocyclic system, and

the radicals R22Veach, independently from each other represents 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 in turn can contain as Deputy C1-C4-alkyl or C3-C10-cycloalkyl,

v is equal to 1 or can also be equal to 0 when A1Bis unsubstituted, substituted or condensed heterocyclic system,

or the radicals R4Band R12Vtogether form a group-R15V-.

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 heterocyclic aromatic cycle, which may contain in addition to carbon atoms of the ring heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus. Examples of 5-membered heteroaryl groups which contain from one to four nitrogen atoms and/or sulfur, or oxygen in the loop along with the carbon atoms are 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-oxazo the sludge, 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 can contain as substituents C1-C10-alkyl, C6-C10-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl atoms or halogen, for example fluorine, chlorine or bromine, or may be condensed with one or more aromatic or heteroaromatic compounds. Examples of condensed with the benzene ring cycle 5-membered heteroaryl are 2-indolyl, 7-indolyl, 2-coumaroyl, 7-coumarinyl, 2-thionaphthene, 7-thionaphthene, 3-indazole, 7-indazole, 2-benzimidazolyl and 7 benzimidazolyl. Examples of condensed with the benzene ring cycle 6-membered heteroaryl 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 name and numbering of atoms in the heterocycle is taken from L.Fieser and M. ieser, Lehrbuch der organischen Chemie, 3rdrevised edition, Verlag Chemie, Weinheim 1957.

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

Such complexes can be synthesized by methods known per se, preferably by reaction of the corresponding substituted cyclic hydrocarbon anions with halides of hafnium. Examples of appropriate preparative methods are described, for example, in Journal of Organometallic Chemistry, 369 (1989), 359-370.

Garrity can be used in Rac or pseudo-Rac form. The term pseudo-Rac refers to complexes in which two cyclopentadienyls ligand are Rac-position relative to each other independently of all other substituents in the complex.

Examples of suitable guarracino (A2) are, inter alia, dichloride (methylene)-bis(cyclopentadienyl)hafnium, dichloride (methylene)-bis(3-methylcyclopentadienyl)hafnium, dichloride (methylene)-bis(3-n-butylcyclopentadienyl)hafnium, dichloride (methylene)-bis(indenyl)hafnium, dichloride (methylene)-bis(tetrahydroindene)hafnium, dichloride (isopropylidene)-bis(cyclopentadienyl)hafnium, dichloride (isopropylidene)-bis(3-trimethylsilylcyanation)hafnium, dichloride (isopropylidene)bis(3-methylcyclopentadienyl)hafnium, dichloride (isopropylidene-bis(3-n-butylcyclohexane ITIL)hafnium, dichloride (isopropylidene)-bis(3-vinylcyclopentane)hafnium, dichloride (isopropylidene)-bis(indenyl)hafnium, dichloride (isopropylidene)-bis(tetrahydroindene)hafnium, dichloride (dimethylsilane)-bis(cyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(indenyl)hafnium, dichloride (dimethylsilane)-bis(tetrahydroindene)hafnium, dichloride, (ethylene)bis(cyclopentadienyl)hafnium, dichloride, (ethylene)bis(indenyl)hafnium, dichloride, (ethylene)bis(tetrahydroindene)hafnium, dichloride (tetramethylethylene)-9-fluorenylacetamide, dichloride (dimethylsilane)-bis(tetramethylcyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(3-trimethylsilylcyanation)hafnium, dichloride (dimethylsilane)-bis(3-methylcyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(3-n-butylcyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(3-tert-butyl-5-methylcyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(3-tert-butyl-5-ethylcyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(2-methylindenyl)hafnium, dichloride (dimethylsilane)-bis(2-isopropylphenyl)hafnium, dichloride (dimethylsilane)-bis(2-tert-butylidene)hafnium, dichloride (diethylsilane)-bis(2-methylindenyl)hafnium, dichloride (dimethylsilane)-bis(3-methyl-5-methylcyclopentadienyl)hafnium, dichloride (dimethylsilane)-bis(3-ethyl-5-isopropylcyclopentadienyl the l)hafnium, dichloride (dimethylsilane)-bis(2-ethylidene)hafnium, dichloride (dimethylsilane)-bis(2-methyl-4,5-benzinger)hafnium, dichloride (dimethylsilane)-bis(2-ethyl-4,5-benzinger)hafnium, dichloride (methylphenylsulfonyl)-bis(2-methyl-4,5-benzinger)hafnium, dichloride (methylphenylsulfonyl)-bis(2-ethyl-4,5-benzinger)hafnium, dichloride (diphenylsilanediol)-bis(2-methyl-4,5-benzinger)hafnium, dichloride (diphenylsilanediol)-bis(2-ethyl-4,5-benzinger)hafnium, dichloride (diphenylsilanediol)-bis(2-methylindenyl)hafnium, dichloride (dimethylsilane)-bis(2-methylphenylimino)hafnium, dichloride (dimethylsilane)-bis(2-ethyl-4-phenylindane)hafnium, dichloride (dimethylsilane)-bis(2-methyl-4-(1-naphthyl)indenyl)hafnium, dichloride (dimethylsilane)-bis(2-ethyl-4-(1-naphthyl)indenyl)hafnium, dichloride (dimethylsilane)-bis(2-propyl-4-(1-naphthyl)indenyl)hafnium, dichloride (dimethylsilane)-bis(2-isobutyl-4-(1-naphthyl)indenyl)hafnium, dichloride (dimethylsilane)-bis(2-propyl-4-(9-phenanthrol)indenyl)hafnium, dichloride (dimethylsilane)-bis(2-methyl-4-isopropylidene)hafnium, dichloride (dimethylsilane)-bis(2,7-dimethyl-4-isopropylidene)hafnium, dichloride (dimethylsilane)-bis(2-methyl-4,6-diisopropylphenol)hafnium, dichloride (dimethylsilane)-bis(2-methyl-4[p-triptoreline]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-methyl-4-[3',5'-dimetilfenil]indenyl)hafnium, dichloride (dimethyle anvil)-bis(2-methyl-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (diethylsilane)-bis(2-methyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-ethyl-4-[4-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-propyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane-bis(2-n-butyl-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-hexyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-isopropylaniline)(2-methyl-4-phenylindane)hafnium, dichloride (dimethylsilane)-bis(2-isopropyl-(1-naphthyl)indenyl)(2-methyl-4-(1-naphthyl)indenyl)hafnium, dichloride (dimethylsilane)-bis(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)(2-methyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)(2-ethyl-4-[4'-tert-butylphenyl]indenyl)hafnium, dichloride (dimethylsilane)-bis(2-isopropyl-4-[4-tert-butylphenyl]indenyl)(2-methyl-4-[3',5'-bis-tert-butylaniline)hafnium, dichloride (dimethylsilane)-bis(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 the corresponding derivatives dimethylamine, monochloro-mono(alkylacrylate)hafnium and di(alkylacrylate)hafnium. The complex is s can be used in the form of rac-shape, meso-form or mixtures thereof.

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

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

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

t is 1 or 2, preferably 2,

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

R9B-R13Beach represent hydrogen, C1-C8-alkyl, C6-C8-aryl, NR14B2, OSiR14B3or Si(R14B)3or in each case two radicals R1Bto R5Band/or R9Vto R13Btogether with the cycle C5form indenyl, fluorenyl or substituted indenyl or fluorenyl.

Especially applicable Garrity formula (VII) with the same cyclopentadienyls radicals.

Examples of particularly suitable compounds D) of the formula (VII) are inter alia: dichloride, bis(cyclopentadienyl)hafnium, dichloride, bis(indenyl)hafnium, dichloride, bis(fluorenyl)hafnium, dichloride, bis(tetrahydroindene)hafnium, dichloride, bis(pentamethylcyclopentadienyl)hafnium, dichloride is IP(trimethylsilylcyanation)hafnium, dichloride, bis(trimethoxysilylmethyl)hafnium, dichloride, bis(ethylcyclopentadienyl)hafnium, dichloride, bis(isobutyrylacetate)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-butylcyclopentadienyl)hafnium, dichloride, (cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)hafnium, dichloride, bis(tetramethylcyclopentadienyl)hafnium and related derivatives dimethylamine.

Other examples are appropriate hafniensia compounds in which one or two chloride ligand is replaced by bromide or iodide.

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

in which the variables have the following meanings:

E1Crepresents nitrogen or phosphorus, especially nitrogen,

E2C-E4Ceach, independently of one another represent a carbon, nitrogen or phosphorus, especially carbon,

R1C-R3Ceach, independently of one another represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R1C-R3Cmay be substituted by halogen atoms 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 N, P, O and S,

R4C-R7Ceach, independently of one another represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, SiR19C3, and the organic radicals R4C-R7Ccan be is substituted by halogen atoms and/or two genialnyh or vicinal radicals R 4C-R7Ccan also be connected with the formation of five-, six - or semichasnoho cycle and/or two genialnyh or vicinal radicals R4C-R9Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and when v is 0, R6Cis the relationship with L1Cand/or R7Cis the relationship with L2Cand L1Cforms a double bond with the carbon atom associated with R4Cand/or L2Cforms a double bond with the carbon atom associated with R5C,

u = 0 when E2C-E4Crepresents a nitrogen or phosphorus and is 1 when E2C-E4Cis carbon

L1C-L2Ceach, independently of one another represents nitrogen or phosphorus, especially nitrogen,

R8C-R11Ceach, independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R8C-R11Ccan also be substituted by halogen atoms and/or two vicinal radicals R8C-R17Ccan also be connected with the formation of five-, six - or semiline what about the cycle and/or two vicinal radicals R 8C-R17Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S,

R12C-R17Ceach, independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R8C-R17Ccan also be substituted by halogen atoms 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 N, P, O and S,

the indices v, each, independently of one another are 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 with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR18C, SO3R18C, OC(O)R18C, CN, SCN, β-diketonate CO, BF4-PF6-or surround coordinatewise anion and the radicals XCcan connect to each other,

the radicals R18Ceach, independently of one another represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3, and the organic radicals R18Ccan also be substituted by halogen atoms 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 represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3, and the organic radicals R19Ccan also be substituted by halogen atoms or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - or six-membered cycle,

s is equal to 1, 2, 3 or 4, especially 2 or 3,

D is an uncharged donor and

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

Three atoms from the E2Cto E4Cin the molecule may be the same or p is knowledge. If E1Cis phosphorus, then it is preferable that each E2Cto E4Crepresented the carbon. If E1Cis nitrogen, then it is preferable that the group of E2Cto E4Ceach represented a nitrogen or carbon, especially carbon.

The substituents R1C-R3Cand R8C-R17Ccan vary in a wide interval. Possible carbon-containing organic substituents R1C-R3Cand R8C-R17Cinclude the following, for example: 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 may in turn 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 bytesneeded alkyl groups, such as phenyl, naphthyl, diphenyl, antoanela, 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 may be substituted by alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and two of the radicals from R1Cto R3Cand/or two vicinal radicals R8C-R17Ccan also be connected with the formation of

5-, 6 - or 7-membered cycle or two vicinal radicals R1C-R3Cand/or two vicinal radicals R8C-R17Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and/or the organic radicals R1C-R3Cand/or R8C-R17Cmay also be substituted by halogen atoms, for example fluorine, chlorine or bromine. Moreover, R1C-R3Cand R8C-R17Ccan be an amino group NR18C2or N(SiR19C3)2alkoxyl or aryloxy OR18Cfor example dimethylamino, N-pyrrolidinyl, picoline, methoxyl, ethoxyl or isopropoxy, or halogen, for example fluorine, chlorine or bromine. Possible radicals R19Cin organosilicon substituents SiR19C3are the same carbon-containing organic radicals, which have been described Visele R 1C-R3Cand two radicals 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 radicals SiR19C3 may be connected in E2C-E4Cthrough oxygen or nitrogen, such as trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylcyclohexyl.

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, diphenyl and anthranol. Particularly preferred organosilicon substituents are trialkylsilyl group with 1-10 carbon atoms in the alkyl radical, especially 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, especially hydrogen. In particular, R13Cand R16Ceach represents a methyl, trifluoromethyl, ethyl, n-PR is drank, 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 is a hydrogen atom.

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 represents a C1-C22-alkyl which may be substituted by halogen atoms, in particular C1-C22-n-alkyl which may be substituted by halogen atoms, for example methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen, for example fluorine, chlorine or bromine and R9Cand R11ceach represents a halogen, for example fluorine, chlorine or bromine. Special preference is given to R8Cand R10C, each of which represents a C1-C22-alkyl which may be substituted by halogen atoms, in particular C1-C22-n-alkyl which may be substituted by halogen atoms, for example methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, and R9Cand R11ceach represents a halogen, for example fluorine, chlorine or the rum.

In particular, R12C, R14C, R15Cand R17Care the same, R13Cand R16Care the same, R9Cand R11Care the same and R80and R10Care the same. This circumstance is preferable in the above-described preferred embodiments.

The substituents R4C-R7Ccan vary in a wide interval. Possible carbon-containing organic substituents R4C-R7Cinclude the following, for example: 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 may in turn 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 may be substituted ALK is lname groups, such as phenyl, naphthyl, diphenyl, antoanela, 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 may be substituted by alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and two radicals R4Cto R7Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle or two genialnyh radical R4C-R7Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and/or the organic radicals R4C-R7Cmay also be substituted by halogen atoms, for example fluorine, chlorine or bromine. Moreover, R4C-R7Ccan be an amino group NR18C2or N(SiR19C3)2for example dimethylamino, N-pyrrolidinyl or picolinic. Possible radicals R19Cin organosilicon substituents SiR19C3are the same carbon-containing organic radicals, which have been described above for R1C-R3Cand 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 glad the Kala SiR 19C3can be linked through the nitrogen atom with the carbon atom. When v is 0, R6Cis the relationship with L1Cand/or R7Cis the relationship with L2Cso L1Cforms a double bond with the carbon atom associated with R4Cand/or L2Cforms a double bond with the carbon atom associated with 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, diphenyl and anthranol. The preferred amide Vice-NR18C2especially secondary Amida, 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-terbutaline, 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, Pyrrhus is lidin, the piperidine, hexamethylenimine, decahydroquinoline, diphenylamine, N-methylaniline or N-ethylaniline.

L1Cand L2Ceach, independently from each other represents a nitrogen or phosphorus, especially nitrogen, and when v is 0, may form a double bond with the carbon atom associated with R4Cor R5C. In particular, when v is 0, L1Cand/or L2Ctogether with the carbon atom associated with R4Cor R5Cforming aminogroup-CR4C=N - or-CR5C=N-. When v is equal to 1, L1Cand/or L2Ctogether with the carbon atom associated with R4Cor R5Cforms, in particular, aminogroup-CR4CR6C-N or CR5CR7C-N.

The ligands XCdepend, for example, from the selection of the appropriate starting compounds of the metals used for the synthesis of iron complexes, but subsequently, the ligands can be replaced. Possible ligands XCare, in particular, halogen atoms such as fluorine, chlorine, bromine or iodine, especially chlorine. Also suitable ligands XCare methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl. In addition, the ligands XCthat can be specified simply as examples, do not pretend to completeness, are triptorelin, BF4-PF6-and poorly coordinated or coordinatewise anions (see, for example, S. Strauss in Chem. Re. 1993, 93, 927-942), for example B(C6F5)4-. Other particularly suitable ligands XCare amides, alkoxides, sulfonates, carboxylates and β-diketonates. Particularly preferable to use some of these substituted ligands X, as derived from cheap and readily available starting materials. Thus, particularly preferred is one in which XCis dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluensulfonate, acetate or acetylacetonate.

Varying the radicals R18Ccan finely be adjusted, for example, physical properties such as solubility. Possible carbon-containing organic substituents R18Cinclude the following, for example: 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-C22alkenyl, which may be linear, cyclic or branched and in which the double bond may b the th 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 by other alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl, diphenyl, antoanela, 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 by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and R18Ccan also be connected with the formation of 5 - or 6-membered cycle and organic radicals R18Cmay be substituted by halogen atoms, for example fluorine, chlorine or bromine. Possible radicals R19Cin organosilicon substituents SiR19C3are the same radicals as described above for R18Cand 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. Preference is given to using as radicals R18CC1-C10-alkyl, for example methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentile, n-hexyl, n-HepB is sludge, n-octyle and also vinyl, allyl, benzyl and phenyl.

The number s of the ligands XCdepends on the degree of iron oxidation. The number of s cannot be defined in General terms. The oxidation state of iron in catalytically active complexes is generally known in the art. However, you can use complexes, in which the oxidation state of the metal does not match the degree of oxidation in the active catalyst. Such complexes can properly repair or oxidize with suitable activators. Preference is given to using iron complexes in the oxidation state +3 or +2.

D is an uncharged donor, in particular uncharged Lisowski base or Lewis acid, for example, it can be amines, alcohols, ethers, ketones, aldehydes, esters, sulfides or phosphines that may be associated with iron atom or remain as residual solvents used in the synthesis of iron complexes.

The number t of ligands D can range from 0 to 4, and often depends on the nature of the solvent, in which he received the iron complex, and the time during which dried the resulting complexes, and therefore can be non-integer number, for example of 0.5 or 1.5. In particular t is equal to from 0.1 to 2.

In a preferred embodiment, the complexes have the formula

in the cat the swarm

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

R1C-R3Ceach, independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R1C-R3Ccan also be substituted by halogen atoms 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 N, P, O and S,

R4C-R5Ceach, independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, SiR19C3, and the organic radicals R4C-R5Ccan also be substituted by Halogens,

u = 0 when E2C-E4Cis nitrogen or phosphorus and is 1 when EC -E4Cis carbon

L1C-L2Ceach, independently from each other represents a nitrogen or phosphorus, especially nitrogen,

R8C-R11Ceach, independently from each other represents C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R8C-R11Ccan also be substituted by halogen atoms 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 N, P, O and S,

R12C-R17Ceach, independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R12C-R17Ccan also be substituted by halogen atoms and/or two vicinal radicals R8C-R17Ct is the train to connect 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 N, P, O and S,

the indices v, each, independently from each other 0 or 1,

the radicals XCeach, independently of one another represent fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C20-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, OR18C, SiR18C, SO3R18C, OC(O)R18C, CN, SCN, β-diketonate, CO, BF4-PF6-or surround coordinatewise anion and the radicals XCcan connect to each other,

the radicals R18Ceach, independently of one another represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3, and the organic radicals R18Ccan also be substituted by halogen atoms and the nitrogen - and oxygen-containing groups and two radicals R18Ccan also be connected with the formation of five - and six-membered cycle,

the radicals R19Ceach, independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, and the organic radicals R19Ccan also be substituted by halogen atoms or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - and six-membered cycle,

s is equal to 1, 2, 3 or 4, especially 2 or 3,

D is an uncharged donor and

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

Options and preferred options described above are also applicable to E2C-E4C, R1C-R3CXC, R18Cand R19C.

The substituents R4C-R5Ccan vary in a wide interval. Possible carbon-containing organic substituents R4C-R5Cinclude the following, for example: 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 may in turn contain as Deputy C1-C10is an alkyl group and/or C6-C10-aryl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona electromedical, 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 may be substituted by alkyl groups, e.g. phenyl, naphthyl, diphenyl, antoanela, 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 may be substituted by alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and the organic radicals R4C-R5Cmay also be substituted by halogen atoms, for example fluorine, chlorine or bromine. Moreover, R4C-R5Ccan be an amino group NR18C2or N(SiR19C3)2for example dimethylamino, N-pyrrolidinyl or picolinic. Possible radicals R19Cin organosilicon substituents SiR19C3are the same carbon-containing organic radicals, which have been described above for R1C-R3Cand two R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, t is iillililli, triphenylsilane or dimethylphenylsilane. These radicals SiR19C3can be linked through the nitrogen atom with the carbon 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, especially methyl.

The substituents R8C-R17Ccan vary in a wide interval. Possible carbon-containing organic substituents R8C-R17Cinclude the following, for example: 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 may in turn 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 may be substituted by alkyl groups, e.g. phenyl, naphthyl, diphenyl, antoanela, 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 may be substituted by alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, and two radicals R8C-R17Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle or two vicinal radicals R8C-R17Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and/or the organic radicals R8C-R17Cmay also be substituted by halogen atoms, for example fluorine, chlorine or bromine. Moreover, R8C-R17Ccan be a halogen atom such as fluorine, chlorine, bromine, amino group NR18C2or N(SiR19C3)2alkoxyl or aryloxy OR18Cfor example dimethylamino, N-pyrrolidinyl, picoline, methoxyl, ethoxyl or isopropoxy. Possible radicals R19Cin organosilicon substituents SiR19C3are the same carbon-containing organic radicals, which have been given above for R1C-R3Cand two R19Ccan also be connected with the formation of 5 - or 6-members of the tion cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These radicals SiR19C3can be linked through oxygen or nitrogen, such as trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylcyclohexyl.

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, especially hydrogen. In particular, R13Cand R16Geach 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 and bromine, and R12C, R14C, R15Cand R17Ceach is hydrogen.

Preferred radicals R8C-R11Crepresent 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 represents a C1-C22-alkyl which may be substituted by halogen atoms, in particular C1-C22-n-alkyl, which may be the also substituted by halogen atoms, for example, methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen, for example fluorine, chlorine and bromine, and R9Cand R11Ceach represents a halogen, for example fluorine, chlorine or bromine. Particularly preferred R8Cand R10Cand each being C1-C22the alkyl may be substituted by halogen atoms, in particular C1-C22-n-alkyl which may be substituted by halogen atoms, for example methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, and R9Cand R11Ceach is a halogen atom 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. This fact is also preferred in the preferred embodiments described above.

Obtaining the compounds (B) are described, for example, in J. Am. Chem. Soc. 120, p.4049 ff. (1998), J. Chem. Soc, Chem. Commun. 1998, 849, and WO 98/27124. Preferred complexes (B) 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-methylphenylimino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,6-diisopropylaminoethyl]peridiniales(II), dichloride, 2,6-bis[1-(2,6-dichlorophenylamino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,6-diisopropylaniline)methyl]peridiniales(II)dichloride, 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-dibromopyridine)ethyl]peridiniales(II) or the corresponding dibromide or tribromide.

In a subsequent 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 using the complex of the transition metal (A) as a catalyst under the reaction conditions of homopolymerization or copolymerization of ethylene, it leads to a higher Mwcompared with the complex of (B)used as a catalyst in the same reaction conditions. Preferred uses of the complexes (A1), (A2) and (B) are combined complexes (A1) and (B), and complex (A2) and (B).

These catalysts provide a very uniform particles of polymers with similar molecular weight distribution of various particles, especially particles of different sizes, when colorometric M wpreferably less than 10% compared with Mwthe entire polymer. Preferably, the average diameter of the polymer particles ranged from 0.1 to 2 mm and the value of Mwand Mw/Mndetermined by the GPC method for individual particles sieved fractions of these particles were constant in the range of greater than or less than 20%, preferably 15%, and especially preferably 10% of Mwand Mnthe total weight polyethylene (whole weight substances).

The catalytic composition of this invention can be used by itself or together with other components as catalytic systems for polymerization of olefins. In addition, the authors have developed a catalytic system for the polymerization of olefins, including:

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),

at least one polymerization catalyst based on an iron complex with a tridentate ligand containing at least two ortho, ortho-disubstituted aryl radicals,

optionally one or more activators,

optionally one or more organic or inorganic carriers,

E) optionally one is or more compound of the metal 1, 2 or group 13 of the Periodic table.

In a subsequent 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 using the complex of the transition metal (A) as the sole catalyst under the reaction conditions of homopolymerization or copolymerization of ethylene Mwthe resulting polymer is higher than in the case of complex (B) when used as the sole catalyst in the same conditions. Preferred uses of the complexes (A1), (A2) and (B) are combined complexes (A1) and (B), and combining complexes (A2) and (B).

Monosyllabically complexes (A1), garretsen (A2) and/or the iron complex (B) sometimes show low activity in the polymerization, and therefore, to obtain good activity in polymerization is used together with one or more activators, such as component (C). Therefore, the catalytic system optionally contains, as component (C) one or more activators (C). The catalytic system of the present invention preferably contains one or more activator (S). is based on the combination of (A) and (B) effective is one or more activators (C). The complex of the transition metal (A) and the iron complex (B) in the catalytic composition can be activated using the same activator or a mixture of activators or different activators. Often for both catalysts (A) and (B) it is better to use the same activator (C).

In the composition of the catalysts of this invention can in each case to use the activator or activators (C) in any amount in the calculation of the complexes (A) and (B). It is preferable to use them in excess or in stoichiometric amounts in each case calculated on an activated complexes (A) or (B). The amount of activator depends on the type of activator (C). Usually the molar ratio of the complex transition metal (A) and activator (C) may be from 1:0.1 to 1:10000, preferably from 1:1 to 1:2000. The molar ratio of the iron complex (B) and activator (C) is also usually in the range of 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) and turn them into a catalytically active or more active compounds are, for example, such compounds as alumoxane, a strong uncharged lisowska acid, an ionic compound containing a cation of the Lewis acid or an ionic compound, steriade is as cation Pentecostal acid.

As alumoxanes can be used, for example, compounds described in WO 00/31090. Particularly suitable alumoxane with an open-chain or cyclic alumoxane General formula (X) or (XI),

in which R1D-R4Deach, independently of one another represents a C1-C6-alkyl, preferably methyl, ethyl, butyl or isobutyl, and I is an integer from 1 to 40, preferably from 4 to 25.

Particularly suitable alumoxanes is methylalumoxane.

These oligomeric alumoxane usually obtained by controlled reaction solution trialkylamine, in particular trimethylaluminum with water. Usually get oligomeric alumoxane in the form of mixtures of linear and cyclic chain molecules of different lengths, so I should be considered as an average value. Alumoxane may also be present as impurities in other metallurgical, usually aluminiurn. Alumoxane, suitable as component (C), issued by the industry.

In addition, instead of alumoxane formula (X) or (XI) can also be used as component (C) modified alumoxane, in which some of the hydrocarbon radicals substituted by hydrogen atoms or CNS, aryloxyalkyl, siloxane or amide radicals.

It was found that better COI is lesofat complex transition metal (A) or the iron complex (B) and alumoxane in such quantities, so that the atomic ratio of aluminum in alumoxane, including aluminiumgie, and 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. The atomic ratio of aluminum in alumoxane, including aluminiumgie, and iron complex (B) is in the range from 1:1 to 2000:1, preferably from 10:1 to 500:1 and in particular in the range from 20:1 to 400:1.

The following class of suitable activators (C) includes hydroxyalkoxy. They can be prepared, for example, by adding from 0.5 to 1.2 equivalents. water, preferably from 0.8 to 1.2 equivalents. water 1 EQ. aluminum, alkylamino, 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 atomic ratio of aluminum in hydroxyadamantane and 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 and in particular in the range from 20:1 to 40:1. Preference is given to using monotsiklopentadienil metallvillaga compound (A1) or dialkylamino (A2).

As strong, uncharged Lewis sites preferred acids are compounds of General formula (XII)

M2DX1DX2DX3D (XII)

in which

M2Dis an element of group 13 of the Periodic table of elements, in particular B, Al or Ga, preferably B,

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

Other examples of strong, uncharged Lewis sites acids described in WO 00/31090.

Compounds particularly suitable as component (C)are boron and braccini, for example, trialkylborane, trainborn or trimethylboroxine. Particularly preferred boron, which contain at least two perfluorinated aryl radical. Special preference is given to compounds of the General formula (XII)in which X1DX2Dand X3Dthe 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, Tris(3,5-differenl)borane or Tris(3,4,5-tryptophanyl)borane. Preferred is Tris(pentafluorophenyl)borane.

Suitable compounds (C) preferably receives the reaction of the compounds of al the MINIA or boron formula (XII) with water, alcohols, derivatives of phenol, derivatives thiophenol or aniline derivatives, with halogenated and especially perfluorinated alcohols and phenols, which are particularly important. 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 Pentecoste acids are, in particular, trimethylaluminum/pentafluorophenol, trimethylaluminum/1-bis(pentafluorophenyl)methanol, trimethylaluminum/4-hydro-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, for example, in Baranovich (RB(OH)2and Voronovich (R2B(OH)) acids. Particularly noteworthy boranova acid containing perfluorinated aryl radicals, for example (C6F5)2BOH.

Uncharged strong Lisovskii acid, are suitable as activators (C)also include the reaction products Bronevoy acid with two equivalents of aluminiumrail or the reaction products of aluminiumrail with two equivalents of an acidic fluorinated, in particular perfluorinated, organic is soedineniya, for example pentafluorophenol or bis(pentafluorophenyl)boric acid.

Suitable ionic compounds containing cations lucovsky acid include saltlike compounds of the cation of the General formula (XIII)

[((M3D)a+)Q1Q2...Qz]d+(XIII)

in which

M3Dis the item 1-16 groups of the Periodic table of elements

Q1-Qzare simply negatively charged radicals, such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, halogenated, halogenared, each with 6-20 carbon atoms in the aryl part and 1-28 carbon atoms in the alkyl part, C3-C10-cycloalkyl, which may contain as substituents C1-C10-alkyl, halogen, C1-C28-alkoxyl, silyl or mercaptal,

a is an integer from 1 to 6 and

z is an integer from 0 to 5,

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

Particularly suitable cations are the cations of Carbonia, hydronium and sulfone and cationic complexes of transition metals. It is important to mention triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocene cation. Preferably, they had coordinatewise counterions, in particular boron compounds, which are also mentioned is in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.

Salt coordinatewise anions can also be obtained by combining the compounds of boron or aluminum, for example aluminiuim, with a second compound which can react with the formation of a relationship between two or more atoms of boron or aluminum, for example with water, and a third compound which forms a connection with boron or aluminum of an ionisable ionic compound, for example triphenylmethane, or optional with base, preferably an organic nitrogen-containing base, for example an amine, an aniline derivative or a nitrogen-containing heterocycle. In addition, you can add a fourth connection, which also reacts with the boron compound or aluminum, for example pentafluorophenol.

Ionic compounds containing pentecosta acids as cations and preferably contain coordinatewise counterions. Special preference is given to such Pentecostal acids as protonated amine or aniline derivatives. The preferred cations are N,N-dimethylaniline, N,N-dimethylcyclohexylamine and N,N-dimethylbenzylamine, as well as derivatives of these last.

As activators (C) are also suitable compounds containing anionic boron heterocycles as described in WO 9736937, in particular Borotbists Dimity aniline or Borotbists of triphenylmethyl.

Preferred ionic compounds C) include borates, which contain at least two perfluorinated aryl radical. Special preference is given tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline and especially tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylamine, tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylamine or tetracosapentaenoic of triphenylmethyl.

It is also possible that two or more borate anion connect with each other, as in dianion [(C6F5)2B-C6F4-B(C6F5)2]2-or the borate anion can be bound via a bridge with a corresponding functional group on the surface of the media.

Other suitable activators (C) indicated in WO 00/31090.

The number of strong uncharged Lewis sites acids, ionic compounds containing cations of Lewis sites of acids or ionic compounds containing as cations pentecosta acid, is preferably from 0.1 to 20 EQ., more preferably 1-10 EQ. and particularly preferably 1-2 equiv. in the calculation of the complex transition metal (A) or the iron complex (B).

Suitable activators (C) also include boron-aluminum compounds, for example di[bis(pentafluorobenzylbromide)]meillan. Examples of such boron-aluminum compounds are disclosed in WO 99/06414.

you Can also use a mixture of all the above activators (C). Preferred mixtures contain alumoxane, in particular methylalumoxane, and the ionic compound, in particular containing tetrakis(pentafluorophenyl)borate anion, and/or strong uncharged Lewis acid, in particular Tris(pentafluorophenyl)borane or noroxin.

As the complex of the transition metal (A)and the iron complex (B) and the activator (C) is preferably used in solution, preferably in an aromatic hydrocarbon from 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or mixtures.

Another possibility is to use the activator (C), which may simultaneously serve as a carrier (D). Such systems are, for example, of inorganic oxide-treated zirconium alkoxide followed by chlorination, for example, carbon tetrachloride. The receipt of such systems are described, for example, in WO 01/41920.

Particularly preferred combinations of preferred options (C) preferred options (A) and/or (B).

As a General activator (C) for the catalyst components (A) and (B) it is preferable to use alumoxane. As activator (C) for guarracino (A2) is preferred combination saltlike compounds with cations of General formula (XIII), in particular N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylamine the tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylamine tetrakis(pentafluorophenyl)borate or trityl tetranitronaphthalene, in particular in combination with alumoxane as activator (C) for the iron complex (B).

Another particularly applicable activator (S) are the reaction products of aluminum compounds of the formula (XII) with perfluorinated alcohols and phenols.

For polymerization processes in the gas phase or in suspension of a transition metal complexes (A) and the iron complex (B) it is often better to use in the form of solids, i.e. deposited on a solid carrier (D). In addition, applied complexes have high productivity. Therefore, the transition metal complexes (A) and/or the iron complex (B) can be optionally immobilized on an organic or inorganic carrier (D) and used in the polymerization in applied form. This allows, for example, to avoid deposits in the reactor and to control the morphology of the polymer. The preferred carriers are silica gel, magnesium chloride, aluminum oxide, mesoporous solids, aluminosilicates, hydrotalcite and organic polymers, such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene or polymers with polar functional groups, for example copolymers of ethylene and acrylic esters, acrolein or vinyl acetate.

Special preference is given to cat the political system, containing at least one complex of a transition metal (A)at least one iron complex (B)at least one activator (S) and at least one carrier (D).

The preferred catalytic composition according to the invention contains one or more carriers. Can be applied as a component with transition metal (A)and the iron complex (B), or may be applied only one of the two components. In the preferred embodiment, applied both component (A) and (B). In this case, the two components (A and B) can be in different media or together on the same media. It is preferable to apply the components (A) and (B) on the same carrier to be sure in relatively close spatial arrangement of the different catalytic centers and, consequently, in a good mix of the resulting polymers.

In the preparation of catalytic systems of the invention are preferred immobilization of one of the components (a) and one of the components (b) and/or activator (C) or media (D) by physical adsorption or by chemical reaction, e.g. by covalent binding components with reactive groups on the carrier surface.

The order in which combine media D), the complex of the transition metal (A), the iron complex (B) and activators (C)not important. After the division of the different stages of the various intermediate substance may 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 activator (C) can be mobilitat independently of one another, for example, sequentially or simultaneously. Thus, media (D) can first be brought into contact with the activator or activators (C) or you can lead the media (D) into contact with the complex transition metal (A) and/or the iron complex (B). Possible pre-activation complex of the transition metal (A) with one or more activators (C) before mixing with the carrier (D). Iron-containing component can, for example, be brought into contact simultaneously with the complex transition metal (A) together with the activator (C), or it can be activated separately by using the activator (C). Pre-activated iron complex (B) can be applied to the carrier before or after the application of pre-activated complex transition metal (A). In one possible embodiment, the complex of the transition metal (A) and/or the iron complex (B) can be prepared in the presence of the media. Another method of immobilization is a preliminary polymerization catalyst system in the presence of the carrier, or without it.

Immobilization is usually carried out in an inert solvent, which after immobilization can remove Phi is Tracia or evaporation. After separate stages, the solid can be washed with suitable inert solvents, for example aliphatic or aromatic hydrocarbons, and dried. However, you can also apply and wet deposited catalyst.

In a preferred method of preparation of the deposited catalytic system, at least one iron complex (B) is brought into contact with the activator (C) and then mixed with digidrirovanny or passivated by the media (D). The complex of the transition metal (A) is also brought into contact with at least one activator (C) in a suitable solvent, preferably with the formation of a soluble reaction product, an adduct or a mixture. The resulting preparation is then mixed with the immobilized complex of iron, which is used directly or after removal of the solvent, and then the solvent is completely or partially removed. Received caused the catalytic system is preferably dried to ensure that all or most of the solvent removed from the pores of the support. The applied catalyst is preferably obtained as a free flowing powder. Examples of industrial implementation of this method is described in WO 96/00243, WO 98/40419 or WO 00/05277. Another preferred option includes obtaining first activator (S) on the carrier (D) and then contacting this caused the frame connection with the complex of the transition metal (A) and the iron complex (B).

As the carrier (D) it is preferable to use finely crushed carriers, which can be any organic or inorganic substances. In particular, media (D) may be a porous media type talc, silicate scales or montmorillonite, mica or inorganic oxide or a finely divided powder of the polymer (e.g. polyolefin or a polymer with polar functional groups).

The media being used 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 of 1 to 500 μm. Preference is given to media with a specific surface area in the range from 50 to 700 m2/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 of from 10 to 150 microns.

The complex of the transition metal (A) is preferably used in an amount such that the end of the catalytic system, the concentration of the transition metal complex of the transition metal (A) ranged from 1 to 200 μmol, preferably from 5 to 100 μmol and particularly preferably from 10 to 70 μmol per gram of the carrier (D). The iron complex (B) is preferably used in such a quantity is as, to end the catalytic system, the concentration of iron in the iron complex (B) ranged from 1 to 200 μmol, preferably from 5 to 100 μmol and particularly preferably from 10 to 70 μmol per gram of the carrier (D).

Inorganic carrier can be subjected to heat treatment, for example, to remove the adsorbed water. Such drying is usually carried out at temperatures in the range from 50 to 1000°C, preferably from 100 to 600°C, preferably to carry out the drying at temperatures from 100 to 200°C under reduced pressure and/or inert gas (e.g. nitrogen), or inorganic carrier can be ignited at temperatures from 200 to 1000°C to obtain a desired structure of solids and/or the desired concentration of Oh-groups on the surface. The media can also be treated chemically using conventional sorbents, such as metallicity, preferably aluminiumgie, CHLOROSILANES or SiCl4or even methylalumoxane. Appropriate processing methods are described, for example, in WO 00/31090.

Inorganic carrier can also be chemically modified. For example, treatment of silica gel with NH4SiF6or other fluorinating reagents leads to fluorination of the silica gel surface, and the treatment of silica gels with silanes containing nitrogen-, fluorine - or sulfur-containing groups leads to correspondingly modificarea the major surfaces of the silica gels.

You can also use organic media such as powders finely crushed polyolefin (e.g. polyethylene, polypropylene or polystyrene), and preferably before you use are free from adsorbed water, residual solvents or other impurities and dried. You can also use functionalityand polymeric carriers, such as carriers on the basis of polystyrene, polyethylene, polypropylene or polybutylene; using functional groups such media, for example ammonium or hydroxyl, can be immobilized at least one of the catalyst components. You can also use a mixture of polymers.

Inorganic oxides suitable as a carrier (D), can be found 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 preferred oxides for use as carriers include silicon dioxide, aluminum oxide and mixed oxides of calcium, aluminum, silicon, magnesium or titanium, and a mixture of the corresponding oxides. Other inorganic oxides which can be used alone or in combination with the above preferred oxide carriers are, for example, MgO, CaO, AlPO4, ZrO2, TiO2B2O3or mixtures thereof.

Other predpochtitel is suspended inorganic carriers are inorganic halides, for example MgCl2or carbonates, for example Na2CO3, K2CO3, CaCO3, MgCO3, sulfates, for example Na2SO4, Al2(SO4)3, BaSO4, nitrates, for example KNO3, Mg(NO3)2or Al(NO3)3.

As carriers of (D) catalysts for the polymerization of olefins, preferred are silica gels, because of them it is possible to prepare the media with particles of the desired size and the desired patterns. It was found that particularly suitable for this purpose spray dried silica gels, which is a spherical agglomerates of relatively small granules, i.e. primary particles. Before using the silica gels can be dried and/or calcined.

Other preferred media (D) are the hydrotalcite and calcined hydrotalcite. In Mineralogy hydrotalcite called a natural mineral with the ideal formula

Mg6Al2(OH)16CO3·4 H2O

and with the structure type of structure of brucite Mg(OH)2. Brucite crystallizes in the form of scales, in which metal ions are in octahedral voids between the two layers of close-Packed hydroxyl ions, and is busy only every second layer of octahedral voids. In hydrotalcite some magnesium ions replaced by aluminum ions, resulting in packetloop acquires a positive charge. It is counterbalanced by anions, which are located between the layers together with molecules of water of crystallization.

Such layered structures are present not only in the hydroxides of magnesium-aluminium, but generally in mixed metal hydroxides of the General formula

M(II)2x2+M(III)23+(OH)4x+4A2/nnz H2O

with a layered structure, in which M(II) is a divalent metal such as Mg, Zn, Cu, Ni, Co, Mn, Ca and/or Fe and M(III) is a trivalent metal such as Al, Fe, Co, Mn, La, Ce and/or Cr, x is a number from 0.5 to 10 in increments of 0.5, A is an anion in internodes and n represents the charge of the anion in the internode, which can be from 1 to 8, usually from 1 to 4, and z is an integer from 1 to 6, in particular from 2 to 4. Possible anions in the internodes are organic anions, such as the anions of alkoxides, sulfates alilovic esters, sulfates arolovich esters or sulfates glycol ethers, inorganic anions such as, in particular, carbonate, bicarbonate, nitrate, chloride, sulfate or B(OH)4-or the anions of polyoxometallates, for example Mo7O246-or V10O286-. However, there is a mixture of several of such anions.

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

Calcined hydrotalcite can be obtained from hydrotalcite calcination, i.e. by heating, by which inter alia can set the content of hydroxyl groups. In addition, it also changes the crystal structure. Calcined hydrotalcite used in accordance with this invention, are obtained at temperatures higher than 180°C., Preferably ignited within 3-24 hours at temperatures from 250°C to 1000°C, in particular from 400°C to 700°C. you Can skip over solid air or inert gas or ignited in a vacuum.

When heated natural or synthetic hydrotalcite first lose water, i.e. dried. With further heating, i.e. when the actual annealing, the metal hydroxides are converted to metal oxides resulting from the removal of hydroxyl groups and interstitial anions; however, the OH group or interstitial anions such as carbonates, in the calcined hydrotalcite may still remain. A measure of this is the loss during annealing. The so-called weight loss of the sample, which is heated in two stages: first for 30 min at 200°C in a drying Cabinet and then for 1 hour at 950°C in a muffle furnace.

Thus, the calcined hydrotalcite used as component (D)are mixed oxides of divalent and trivalent meta is fishing M(II) and M(III), moreover, the molar ratio of M(II) and M(III) is usually in the range from 0.5 to 10, preferably from 0.75 to 8 and especially from 1 to 4. In addition, may also be present in normal amounts of impurities, such as Si, Fe, Na, Ca or Ti, as well as chlorides and sulphates.

The preferred calcined hydrotalcite (D) are mixed oxides, in which M(II) is magnesium and M(III) aluminum. Such mixed oxides of aluminum-magnesium receive from Condea Chemie GmbH (now Sasol Chemie), Hamburg, under the trademark Puralox Mg.

Preference is given to the calcined hydrotalcite in which the restructuring is completed or almost completed. The calcination, i.e. structural transformation can be confirmed, for example, by using the diffraction patterns.

The hydrotalcite, calcined hydrotalcite or silica gels are usually used in the form of finely ground powders with average particle diameter D50 of from 5 to 200 μm, preferably from 10 to 150 μm, particularly preferably from 15 to 100 μm and in particular from 20 to 70 μm, and usually with the volume of pores of from 0.1 to 10 cm3/g, preferably from 0.2 to 5 cm3/g and the value of specific surface area from 30 to 1000 m2/g, preferably from 50 to 800 m2/g and in particular from 100 to 600 m2/, Complex transition metal (A) is preferably used in an amount such that the final kataliticheskaya concentration of the transition metal complex of the transition metal (A) ranged from 1 to 100 μmol, preferably from 5 to 80 μmol and particularly preferably from 10 to 60 mmol per 1 g of the carrier (D).

The catalytic system may also contain an additional component (E) is a compound of the metal of General formula (XX),

MG(R1G)rG(R2G)SG (R3G)tG(XX)

in which

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

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

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

rGis an integer from 1 to 3

and

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

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

Among connected to the second metal General formula (XX) are preferred compounds, in which MGis lithium, magnesium, boron or aluminum, and R1Grepresents a 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, in particular n-butyl-n-octylamine, tri-n-hexylamine, triisobutylaluminum, tri-n-butylamine, triethylamine, dimethylammoniumchloride, dimethylaminophenyl. methylaluminoxane, methylaluminoxane, diethylaluminium and trimethylaluminum and mixtures thereof. You can also use the products of partial hydrolysis of aluminiumraw with alcohols.

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

In General, the compound of the metal (E) of General formula (XX) is used as a component of the catalytic system of the polymerization or copolymerization of olefins. Here is the link metal is a (E) can be used for example, to obtain the solid catalyst containing the medium (D), and/or added during the polymerization or before polymerization. Used metal link (E) may be the same or different. It is also possible, especially when the solid catalyst contains no activator (S)to the catalytic system contains in addition to the solid catalyst is one or more activators (C), which are identical or different from the compound (S)present in the solid catalyst.

Component (E) can be introduced into the reaction with components (A), (B) and optionally (C) and (D) in any order. Component (A), for example, you can enter into contact with components (C) and/or (D) before or after contact with the polymerized olefins. It is also possible pre-activation with one or more components (C) before mixing with the olefin and the subsequent addition of the same or another component (C) and/or (D) after this mixture is brought into contact with the olefin. Pre-activation is usually carried out at temperatures of 10-100°C, preferably at 20-80°C.

In another preferred embodiment, the solid catalyst is prepared from components (A), (B), (C) and (D)as described above, and is brought into contact with the component (E) at the time at the beginning or immediately before the polymerisation.

It is preferable to first make contact (E) with α-what Levina, which will polimerizuet, and then add the solid catalyst containing components (A), (B), (C) and (D)as described above.

In another preferred embodiment, the carrier (D) is first brought into contact with the component (E), with components (A) and (B) and then with activator (C), and then proceed as described above.

It is possible, in which the first catalytic system used for the preliminary polymerization of α-olefins, preferably linear alkenes C2-C10and, in particular ethylene or propylene, and the resulting pre-sopolimerizacii solid catalyst is then used in the actual polymerization. The mass ratio of the solid catalyst used for the preliminary polymerization, and the monomer polymerized in his presence, is usually in the range from 1:0.1 to 1:1000, preferably from 1:1 to 1:200.

In addition, during the preparation of the catalytic system or after cooking, you can add a small amount of olefin, preferably α-olefin, such as vinylcyclohexane, styrene or phenyldimethylsilane, as modifying component, and an antistatic or a suitable inert compound such as a wax or oil. The molar ratio of additives and the amount of the transition metal compounds (A) and the iron complex (B) ordinary who is from 1:1000 to 1000:1, preferably from 1:5 to 20:1.

Catalyst composition or catalyst system of the present invention suitable for producing polyethylene of the present invention, which has a number of advantages when using and processing.

To obtain the polyethylene of the present invention, the ethylene will polimerizuet, as described above, together with α-olefins containing 3 to 12 carbon atoms.

In the method of copolymerization of the present invention, the ethylene will polimerizuet together with α-olefins containing 3 to 12 carbon atoms. Preferred α-olefins are linear or branched C2-C10-alkenes, for example ethylene, propylene, 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 polimerizuet a mixture of different α-olefins. Preference is given to polymerization of at least one olefin selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-Heptene, 1-octene and 1-mission. Particularly preferable to use a mixture of monomers containing at least 50 mol. % ethylene.

Polymerization of ethylene with α-olefins can be made in all known in the industry means pritemperature in the range from -60 to 350°C, preferably from 0 to 200°C and particularly preferably from 25 to 150°C at pressures from 0.5 to 4000 bar, preferably from 1 to 100 bar and particularly preferably from 3 to 40 bar. The polymerization can be conducted in a known manner in the volume, in suspension, in gas phase or in a supercritical medium in the conventional reactors used for the polymerization of olefins. It can be done in periodic mode or preferably in a continuous mode in one or more stages. It is possible to conduct the polymerization at a high pressure in tube reactors or autoclaves, in solution, in suspension, gas-phase methods with stirring and in a gas phase fluidized bed.

Usually the polymerization is carried out at temperatures in the range from -60 to 350°C, preferably in the range from 20 to 300°C and at pressures from 0.5 to 4000 bar. The average contact time is usually from 0.5 to 5 hours, preferably from 0.5 to 3 hours. The optimum pressure range and temperature for carrying out the polymerization is usually dependent on the method of polymerization. In the case of polymerization at high pressure, which typically ranges from 1000 to 4000 bar, in particular from 2000 to 3500 bar, temperature of polymerization, usually set high. The optimum range of temperature for polymerization at high pressure range from 200 to 320°C, in particular from 220 to 290°C. In the case of polymer clay is Itachi at low pressure usually set the temperature at least a few degrees below the softening temperature of the polymer. In particular, in these methods, the polymerization of the set temperature of 50 to 180°C, preferably from 70 to 120°C. the Polymerization in suspension is carried out preferably in an inert hydrocarbon, such as isobutane or a mixture of hydrocarbons, either in the environment of the monomers. The polymerization temperature is usually in the range from -20 to 115°C and a pressure in the range from 1 to 100 bar. The solids content in the suspension is usually from 10 to 80%. The polymerization can be conducted or periodically, for example, autoclave with stirring, or continuously, e.g. in a tubular reactor, preferably the reactor with circulation. Especially preferable to use the method of Phillips PF, as described in US-A 3242150 and US-A 3248179. Gas-phase polymerization is usually carried out in the range from 30 to 125°C at pressures from 1 to 50 bar.

Among the above methods of polymerization is particularly preferred is a gas-phase polymerization, in particular gas-phase polymerization reactors, fluidized bed, polymerization in solution and polymerization in suspension, in particular in the reactor circulation and in the apparatus with stirrer. Gas-phase polymerization can also be carried out in the condensed or sverhorganizovanny phase, in which a part of the circulating gas is cooled to a temperature below the dew point and served back to the reactor in view of the two-phase mixture. In addition, you can use the multi-zone reactor, in which two zones polymerization are connected to each other and polymer many times passed through these two areas in turn. In these two zones, you can set different conditions of polymerization. Such a reactor is described, for example, in WO 97/04015. Different or identical methods of polymerization, if desired, can be combined in series to form a cascade polymerization, for example, as in the way Hostalen®. It is also possible parallel arrangement of reactors for two or more identical or different ways. Moreover, when polymerization is possible to use molecular weight regulators, for example hydrogen, or conventional additives such as antistatics. To obtain a high proportion of vinyl groups, the polymerization is preferably carried out in the presence of low quantities of hydrogen or in his absence.

The polymerization is preferably carried out in one reactor, in particular in gas-phase reactor. Polymerization of ethylene with α-olefins containing 3 to 12 carbon atoms, in the presence of the catalyst of this invention leads to the polyethylene of the present invention. Powder of polyethylene, unloaded directly from the reactor, is highly homogeneous, so unlike the case of cascade processes here to obtain a homogeneous product does not need subsequent extrusion.

Receipt the polymer blends by uniform mixing of the individual components, for example by extrusion from the melt in the extruder or mixer (see, for example, "Polymer Blends" in Ullmann''s Encyclopedia of Industrial Chemistry, 6thEdition, 1998 Electronic Release), often associated with certain difficulties. The melt viscosity of high molecular weight and low molecular weight components of the double mixture of polyethylene vary greatly. At ordinary temperatures at which prepare the mixture (about 190-210°C), low-molecular component is a liquid, and high-molecular component is only slightly softened (producing the so-called "lentil soup"). Therefore, uniform mixing of the two components is very difficult. In addition, it is known that high molecular weight component can easily collapse under the action of heat load and shear stresses in the extruder, which adversely affects the properties of the mixture. Therefore, the quality of mixing of such polyethylene mixtures is often unsatisfactory.

The quality of mixing of polyethylene powder are discharged directly from the reactor, can be checked by examining a thin layer ("microtome slice") of a sample in an optical microscope. Heterogeneity is manifested in the form of grains or "white spots". Grains or "white spots" are mostly of high molecular weight viscous particles in the low-molecular weight polymer (see, for example, U. Burkhardt and others in the "Aufereiten von Polymeren mit neuartigen Properties", VDI-Verlag, Dusseldorf 1995, p.71). Such inclusions can reach a size up to 300 μm, leading to cracking and brittle fracture of the components. The higher the quality of mixing of the polymers, the less common and less on the size of the observed inclusions. The quality of mixing of the polymer is determined quantitatively according to ISO 13949. According to this method of measurement is prepared microtome slice of a polymer sample, determine the number and size of these inclusions and the quality of mixing of the polymer according to the established pattern tests.

An important application of bimodal polyethylene is their use for the production of pressure pipes for gas transportation, drinking water and wastewater. PE pressure pipes are increasingly replacing metal pipes. For such applications, it is important that the pipe had a long service life without aging and dangerous cracking. Even small cracks or scratches in the pressure pipe can be increased even at low pressure and lead to cracking, and this process can be accelerated by raising the temperature and/or under the action of aggressive chemical environments. It is therefore extremely important to reduce the number and size of cracks in the pipe, such as grains or "white spots".

Getting polyethylene of the present invention in the reactor reduces energy cost, does not require subsequent mixing and which allows you to adjust the molecular weight distribution and education in different polymer fractions with different molecular weight. In addition, achieved a good mix of different types of polyethylene.

Brief description of drawings

Figures 1-4 are schematic image of all stages of the test for resistance to cracking under load for polyethylene of the present invention;

Figure 5 shows the cross-section and, respectively, a top view of the measurement cell used to conduct the test for resistance to cracking under stress.

The following examples illustrate the invention without limiting the scope of the invention.

Given the measured values was defined as follows.

Samples for NMR analysis were placed in a tube in an atmosphere of inert gas, and optionally melted. The signals from the solvent served as internal standard for spectra1H and13C NMR, and the values of the chemical shifts were expressed in a scale relative to TMS.

The content of the vinyl groups is determined by the method of IR-spectroscopy according to ASTM D 6248-98. The content of the vinyl groups in 20 wt.% the polyethylene with the lowest molecular mass determined by the method Holtrup, as described in W.Holtrup, Makromol. Chem. 178, 2335 (1977), in combination with the method of IR according to ASTM D 6248-98.

Number of branches/1000 carbon atoms is determined by the method of13C NMR, as described in James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and refer to the total soda is the place of CH 3groups/1000 carbon atoms, including end groups. The number of side chains longer than CH3and especially ethyl, Budilnik and exiling branching side chains per 1000 carbon atoms excluding end groups determined in the same way.

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

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

Molecular mass distribution and obtained on the basis of the values of Mn, Mwand Mw/Mnwas determined by the method of high-temperature gel permeation chromatography on a WATERS instrument 150 C method DIN 55672, using the sequence of columns: 3x SHODEX AT 806 MS, 1x SHODEX UT 807 and 1x 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, the volume of the sample to 500 ál temperature 135°C, calibration PE Standards. The evaluation was performed using WIN-GPC.

TREF analysis was performed under the following conditions: solvent 1,2,4-trichlorobenzene, flow rate 1 ml/min, the heating rate of 1 C/min, the amount of polymer 5-10 mg, the carrier is diatomaceous earth.

For the purposes of the present invention, the expression "HLMI" refers, as generally accepted, the term "speed is of Otok melt under high load, and is always determined at 190°C under a load of 21.6 kg 190°C/21,6 kg) according to ISO 1133.

The CDBI values were determined as described in WO-A-93/03093.

Resistance to cracking under stress ESCR measured at 50°C on samples in the form of a round disk (diameter 38 mm, thickness (height) of 1 mm, notched on one side by a groove length of 20 mm and a depth of 0.2 mm), which was immersed in a 5% solution of lutensol at a pressure of 3 bar. Measured time to cracking (in hours). Samples for testing were prepared on a laboratory press URH 30 oil hydraulic laboratory WERNER&PFLEIDERER. Mold shown in figure 1. The punch of the mold is placed a square piece of film Hostafan or cellophane (l=210 mm, thickness 0.02 mm), in the middle of him placed approximately 12-18 g of the polymer sample; another piece of film is placed on top and cover the flat matrix. Both metal parts should be located one above the other with high accuracy. The samples are pressed at 180°C, a pressure of 50 bar for 5 min and then at 200 bar within 30 minutes of the Polymer plate is removed from the mold, remove the protruding part and pull from the sample both films. After keeping at least one day of pressed plates (h=1 mm) squeeze stamping five discs with a thickness of 1 mm ± 0.05 mm using a hollow punch (d=38 mm). The thickness of the test in advance at many points. For analysis use only the appropriate size test drives. On the ski alternately put a notch with pasechnogo apparatus, current dosed with the force of a punch, for example 1,5 kg Depth of the notches 200 μm (figure 2). Then drive again carefully removed from the block.

The measuring cell, an example of which is shown in figure 5, is placed in the holder and fill to the top of a 5% solution of lutensol of the gas washing bottle. The sample in the form of a disk placed in the measuring cell notch out. Care should be taken that the entire drive was in contact with hydrating reagent. Placed on top of the nut and snug it screw up (figure 3). In the press apparatus shown in figure 4, it is possible to seal to use nitrogen, the pressure of which is measured by the contact pressure gauge. The measuring cell is fixed in a press machine using a latch. The press apparatus is equipped with a level controller, which delivers deionized water to replace evaporated to was confident that during the test drive sample is always completely covered by the solution of constant concentration. The disk sample load pressure of 3 bar and start the time counter (figure 4). When the first sign of destruction, nitrogen leaked through the crack, the pressure drops and the time counter stops automatically. The calculation performed by the average time in hours for five samples.

The quality of mixing polyethylene determined according to ISO 13949. Prepare six microto the different slices (thickness: > to 0.060 mm, diameter: 3-5 mm) from six different parts of the same sample of polyethylene. The slices are placed under the microscope with a 100-fold magnification and determine the number and size of inclusions ("white spots", agglomerates, particles) on the square 0.7 mm2. According to ISO 13949 enable smaller than 0.005 mm are not taken into account. According to the classification table ISO 13949 set levels 0, 0,5, 1, 1,5, 2, 2,5, 3, 3,5, 4, 4,5, 5, 5,5, 6, 6,5 or 7 depending on the number and size of inclusions. The resulting indicator is defined as the average values for all 6 samples. The lower this value is, the smaller the number of inclusions in the polyethylene and the higher the quality of mixing polyethylene.

Abbreviations the following table 1:

Cat.Catalyst
T(poly)The temperature of polymerization
MwSrednevekovaja molecular weight
MnBrednikova molecular weight
DensityThe density of the polymer
Prod.The performance of the catalyst in g of polymer is at g catalyst per hour

CH3/1000C means the total number of groups CH3per 1000 carbon atoms (including end groups).

Branching >CH3/1000C<10000 means branching side chains longer than CH3per 1000C in molecular masses smaller than 10000 g/mol without end groups, in tables or ethyl Budilnik branching side chains.

Branching >CH3/1000C means branching side chains longer than CH3at 1000C without end groups, in tables or ethyl Budilnik branching side chains.

Polymer ex. means the polymer from example.

Obtaining individual components

Example 1

Synthesis of 2-methyl-3-(trimethylsilyloxy)cyclopent-2-Aenon

of 37.8 g (240 mmol) hexamethyldisilazane added to a mixture of 7.8 g (70 mmol) of 2-Methylcyclopentane-1,3-dione and of 0.29 g (4.4 mmol) of imidazole and the mixture then was heated at 120°C for 2 hours. The mixture allowed to cool to room temperature with stirring, and all volatile components were distilled. After distillation at 60-63°C and 3×10-3mbar obtained 12.7 g (68 mmol, 98%) 2-methyl-3-(trimethylsilyloxy)cyclopent-2-Aenon in the form of a colourless liquid.

1H-NMR (200,13 MHz, CDCl3): of 0.26 (9H, s, Me3Si)of 1.52 (3H, s, Me); 2,47-of 2.34 (4H, m, CH2).

1H NMR (50,1 MHz, CDCl3): 0,0 (Me3Si); 5,3 (Me); 25,6 (CH2); 32,9 (CH2); 120,1 (Calkene); 180,9; (the alkene-OTMs); 205,9 (C-O).

1.2. Obtaining 2-methyl-3-(8-chinolin)cyclopent-2-Aenon

A mixture of 38.7 g (186 mmol) of 8-brainline in 250 ml of tetrahydrofuran was cooled to -80°C and then added 74,4 ml n-utility (2.5m in hexane, 186 mmol) under stirring. Then the mixture was stirred for another 15 min and added with stirring to 49.9 g (186 mmol) of 2-methyl-3-(trimethylsilyloxy)cyclopent-2-Aenon. The mixture allowed to cool to room temperature with stirring and stirred another hour. Then the reaction mixture is hydrolyzed in a mixture of 40 g of ice and 30 ml of concentrated hydrochloric acid and the resulting mixture was boiled under reflux for 3 hours. The mixture allowed to cool to room temperature under stirring, and added ammonia solution to establish a pH of 12. Then the aqueous phase separated from the organic phase and the aqueous phase was twice Proektirovanie diethyl ether. The organic phases are combined, dried over magnesium sulfate, was filtered and the solvent was distilled. Thus obtained residue was distilled under 119-139°C and 2×10-2mbar and received 31.1 g (139,3 mmol, 74,9%) of 2-methyl-3-(8-chinolin)cyclopent-2-northward.

1H NMR (200,13 MHz, CDCl3): 1,69 (3H, t, Me); of 2.58 (2H, m, CH2); of 3.12 (2H, m, CH2); 7,39 (1H, DD, H3); 7,47-of 7.60 (2H, m, CHhinely); of 7.82 (1H, DD, CHhinely); is 8.16 (1H, DD, H4); 8,87 (1H, DD, H2). MS (El)m/e (%): 223 (8) [M+]; 195 (32) [M+ -2CH2]; 180(100) [M+-2CH2-CH3].

1.3. Synthesis of 3-hydroxy-2-methyl-3-phenyl-1-(8-chinolin)cyclopentene

A mixture of 2.4 g (of 10.75 mmol) of 2-methyl-3-(8-chinolin)cyclopent-2-Aenon and 100 ml of tetrahydrofuran was cooled to -90°C and then added to 7.2 ml finelite (1.8m in cyclohexane/diethyl ether, 12.9 mmol) under stirring. The mixture was stirred at this temperature for another one hour and added 1 ml of ethyl acetate. Then the mixture allowed to warm to room temperature with stirring, was heated under reflux for 10 min and after cooling to room temperature, was added 100 ml of water. Then the separated aqueous phase from the organic phase and the aqueous phase was twice Proektirovanie diethyl ether. The organic phases are combined, dried over magnesium sulfate, was filtered and drove the solvent. The residue was dissolved in 5 ml of toluene and then mixed with 80 ml of hexane. The precipitate was filtered and dried. Got 1,874 g (6,22 mmol, yield 57,9%) 3-hydroxy-2-methyl-3-phenyl-1-(8-chinolin)cyclopentene.

1H NMR (200,13 MHz, CDCl3): to 1.48 (3H, m, Me); to 2.57 (2H, m, CH2); 2,98 (1H, m, CH2); 3,2 (1H, m, CH2); or 4.31 (1H, s, OH); 7,39 (1H, DD, H3); 7,25-7,81 (9H, m, CHchinolin+phenyl); is 8.16 (1H, DD, H4); 8,88 (1H, DD, H2).

1.4. Synthesis of 2-methyl-3-phenyl-1-(8-chinolin)cyclopentadiene

A mixture of 5 ml water and 5 ml of concentrated hydrochloric acid was added and the solution 1,717 g (5.7 mmol) of 3-hydroxy-2-methyl-3-phenyl-1-(8-chinolin)cyclopentene in 100 ml of tetrahydrofuran. The mixture was stirred at room temperature for 90 min and then added to the ammonia solution to establish a pH of 12. Then the separated aqueous phase from the organic phase and the aqueous phase was twice Proektirovanie diethyl ether. The organic phases are combined, dried over magnesium sulfate, was filtered and the solvent was distilled. The obtained residue was distilled under 157-170°C and 2×10-2mbar and obtained 1.12 g (3.95 mmol, 69.3 percent) of 2-methyl-3-phenyl-1-(8-chinolin)cyclopentadiene.

1H NMR (200,13 MHz, CDCl3): 1,2 (3H, d, Me); a 2.01 (3H, m, Me); 2,10 (3H, m, Me); the 3.65 (2H, m, CH2); 3,9 (2H, m, CH2); 4,78 (1H, CHMe); to 6.58 (1H, m, CpH); only 6.64 (1H, m, CpH); 7,01 (1H, m, CpH); 7,03 (1H, m, CpH); 7.23 percent-7,87 (27H, m, CHchinolin+phenyl); 8,13 is 8.22 (3H, m, H4); 8,97-9,05 (3H, m, H2).

1.5. Synthesis dichloride (2-methyl-3-phenyl-1-(8-chinolin)cyclopentadienyl)chromium

To a solution of 1.09 g (of 3.85 mmol) of 2-methyl-3-phenyl-1-(8-chinolin)of cyclopentadiene in 40 ml of tetrahydrofuran was added a suspension of) 0.157 g (of 3.85 mmol) of potassium hydride in 20 ml of tetrahydrofuran. Then the reaction mixture was stirred at room temperature for 6 hours and then added to a solution of 1.44 g (of 3.85 mmol) trichloro-Tris(tetrahydrofuran)chromium in 50 ml of tetrahydrofuran under stirring. The mixture was stirred at room temperature for another 12 h, then the solvent was distilled and the residue washed 3 times with hexane and 3 times caluromysiops components obtained residue was extracted with methylene chloride and the solution was filtered. Was distilled from the filtrate the solvent and the residue was dried under reduced pressure. Got 0,969 g (2,39 mmol) dichloride (2-methyl-3-phenyl-1-(8-chinolin)cyclopentadienyl)chromium (62%).

1H NMR (200,13 MHz, CDCl3): -53,3 (1H, H4); -16,5 (1H, H5-7); 11,2 (3H, Me); 14,8 (1H, H5); 49,4 (1H,H3).

MS (El)m/e (%): 404 (100) [M+]; 369 (76) [M+-Cl]; 332; (92) [M+-2HCl]; 280 (48) [M+-2HCl-Cr].

Example 2

2.1. Synthesis of 3-hydroxy-2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentene

A solution of 3.51 g (15.6 mmol) of 4-bromobenzonitrile in 80 ml of tetrahydrofuran was cooled to -90°C and added with stirring to 6.2 ml of n-utility (2.5m in hexane, 15.6 mmol). After stirring at this temperature for 15 min was added with stirring a solution of 2.9 g (13 mmol) of 2-methyl-3-(8-chinolin)cyclopent-2-northward (see example 1.2) in 40 ml of tetrahydrofuran. The mixture was stirred at this temperature for another one hour and then added 1 ml of ethyl acetate. Mixture allowed to warm to room temperature with stirring and then added 100 ml of water. Then the aqueous phase separated from the organic phase and the aqueous phase was twice Proektirovanie diethyl ether. The organic phases are combined, dried over magnesium sulfate, was filtered and the solvent was distilled. The residue was dissolved in 5 ml of toluene and then mixed with 80 ml of hexane. The precipitate was filtered and dried. Got 2,69 g (7,28 mmol) 3-hydroxy-2-METI the-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentene. After cooling the mother liquor received a second fraction (1.42 g, of 3.84 mmol, total yield of 85.4%).

1H NMR (200,13 MHz, CDCl3): of 1.42 (3H, m, Me); 2,52 (2H, m, CH2); 2,98 (1H, m, CH2); 3,18 (1H, m, CH2); 4,10 (1H, s, OH); 7,39 (1H, DD, H3); 7,56-7,84 (7H, m, CHchinolin+aryl); 8,18 (1H, DD, H4); 8,89 (1H, DD, H2).

MS (El)m/e (%): 369 (9) [M+]; 351 (100) [M+-H2O]; 336 (12) [M+-H2O-Me]; 181 (72) [M+-H2O-Me-chinolin-CH2].

2.2. Synthesis of 2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentadiene

A mixture of 5 ml water and 5 ml of concentrated hydrochloric acid was added to the solution 3,61 g (9.8 mmol) of 3-hydroxy-2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentene in 100 ml of Tetra-hydrofuran. The mixture was stirred at room temperature for 90 min and then added to the ammonia solution to establish a pH of 12. Then the aqueous phase separated from the organic phase and the aqueous phase was twice Proektirovanie diethyl ether. The organic phases are combined, dried over magnesium sulfate, was filtered and the solvent was distilled. The obtained residue was distilled under 169-176°C and 2×10-2mbar and got 2,09 g (5.9 mmol, 60,2%) of 2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentadiene.

1H NMR (200,13 MHz, CDCl3): of 1.13 (3H, d, Me); of 1.97 (3H, m, Me); 2,03 (3H, m, Me); 3,62 (2H, m, CH2); a 3.87 (2H, m, CH2); to 4.81 (1H, square, CHMe); 6,59 (1H, m, CpH); 6,66 (1H, m, CpH); 7,07 (1H, m, CpH); 7,26 (1H, m, CpH); 7,31-7,88 (24H, m, CH chinolin+aryl); 8,14-8,24 (3H, m, H4); 8,93-9,02 (3H, m, H2).

MS (El)m/e (%): 351 (100) [M+]; 167 (72) [M+-F3CC6H4-C3H3].

2.3. Synthesis dichloride 2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentadienyl)chromium

A solution of 2.09 g (5,95 mmol) of 2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)of cyclopentadiene in 40 ml of tetrahydrofuran was added to a suspension 0,242 g (5,95 mmol) of potassium hydride in 20 ml of tetrahydrofuran. Then the reaction mixture was stirred at room temperature for 6 hours and then added to a solution of 2.23 g (5,95 mmol) trichloro-Tris(tetrahydrofuran)chromium in 50 ml of tetrahydrofuran under stirring. The mixture was stirred for another 12 h at room temperature, then the solvent was distilled and the residue washed 3 times with hexane and 3 times with toluene. The obtained residue was Proektirovanie 3 times with methylene chloride and the solution was filtered. The combined extracts with methylene chloride removed the solvent, the residue was washed and dried under reduced pressure. Got 1,58 g (3,34 mmol) dichloride (2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentadienyl)chromium (56,1%).

1H NMR (200,13 MHz, CDCl3): -54,1 (1H, H4); -17,1 (1H, H5); 13,5 (3H, Me); 14,9 (1H, H6); 48,8 (1H, H3).

MS (El)m/e (%): 472 (100) [M+]; 437 (82) [M+-Cl]; 400 (49) [M+-2HCl]; 380 (22) [M+-2HCl-Cr-HF]; 348 (23) [M+-2HCl-Cr]

Example 4

2,6-Bis[1-(2-chloro-6-methylphenylimino)ethyl]pyridine was obtained as in example 2 in WO 98/27124, and similarly introduced into reaction with ferric chloride(II); received dichloride, 2,6-bis[1-(2-chloro-6-methylphenylimino)ethyl]peridiniales(II)as disclosed in WO 98/27124.

Example 5

2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II) obtained according to the method of Qian and others, Organometallics 2003, 22, 4312-4321. This 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) was stirred in 1500 ml of toluene at 80°C for 5 h and then added 32 g of silica gel type 135 and 160 g of molecular sieves (4Å). The mixture was stirred at 80°C for another 8 hours, nerastvorimaya solid was filtered and washed twice with toluene. From the obtained filtrate was distilled solvent, the residue was mixed with 200 ml of methanol and then stirred at 55°C for 1 Casabranca suspension was filtered and the obtained solid was washed with methanol and solvent removed. Got 95 g of 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine to yield 47%. Reaction with ferric chloride(II) was carried out as described by Qian and others, Organometallics 2003, 22, 4312-4321.

Example 6

Dichloride, bis(n-butylcyclopentadienyl)hafnium can be purchased at the company Crompton.

Example 7

Dichloride [1-(8-chinolin)indenyl]chromium(III) received as opisanoj WO 01/12641.

a) Pre-processing of the media

XPO 2107, spray dried silica gel from Grace, was probalily at 600°C for 6 hours.

b) Pre-processing of the media

XPO 2107, spray dried silica gel from Grace, was probalily at 600°C for 6 h and then mixed with 3 mmol of MAO on g of calcined silica gel and then the solvent was removed under reduced pressure.

Getting mixed catalytic systems

Example 8

A mixture of 632 mg (1,042 mmol) dichloride, 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II)of 4.38 g (8,903 mmol) dichloride, bis(n-butylcyclopentadienyl)hafnium and 188 ml of MAO (4,75M in toluene, 895 mmol) was stirred at room temperature for 30 min, then added with stirring to 147,9 g of pre-treated media (a) and the mixture was stirred at room temperature for another 2 hours (Fe+Hf:Al=1:90). The solid was dried under reduced pressure to friable state. Got 310,4 g of catalyst containing 34 wt.% solvent (based on the total weight of the assumption of the full introduction of all components on the carrier).

Example 9

2.9 litres MAO (4,75M in toluene) was added with stirring to 3,24 kg pre-treated media (b), suspended in 70 l of toluene. Added a mixture of 15 g of the dichloride of 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II) and 46 g of the dichloride [1-(8-hinai is)indenyl]chromium(III) and the mixture was stirred at room temperature for 3 hours. The solid was filtered, washed twice with toluene and dried under reduced pressure to friable state.

Example 10

160,6 ml MAO (4,75M in toluene, 763 mmol) was added under stirring to 84,8 g of pre-treated media (b), suspended in 700 ml of toluene. Added a mixture of 560 mg (0,924 mmol) dichloride 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II) and 1.35 g (2,84 mmol) dichloride (2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentadienyl)chromium and the mixture was stirred at room temperature for 3 h (Fe+Cr:Al=1:140). The solid was filtered, washed twice with toluene and dried under reduced pressure to friable state. Got 144,4 g of the catalyst, which contained a 27.6 wt.% solvent (based on the total weight of the assumption of the full introduction of all components on the carrier).

Example 11

155,7 ml MAO (4,75M in toluene, 739,5 mmol) was added under stirring to 157,2 g of pre-treated media (b), suspended in 1300 ml of toluene. Added the mixture 1229 mg (2,028 mmol) dichloride 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales (II) and 2,938 g (6.21 mmol) dichloride (2-methyl-3-(4-benzotrifluoride)-1-(8-chinolin)cyclopentadienyl)chromium and the mixture was stirred at room temperature for 2 hours (Fe+Cr:Al=1:138). The solid was filtered, washed twice with toluene and dried at p is low pressure to friable state. Got 306,8 g of the catalyst, which contained a 34.2 wt.% solvent (based on the total weight of the assumption of the full introduction of all components on the carrier).

Mass spectroscopic analysis showed: 0.11 g Cr/100 g of catalyst, 0.04 g Fe/100 g of catalyst and 16.2 g Al/100 g of catalyst.

Polymerization in the presence of catalysts 8-11

The polymerization was carried out in a fluidized bed reactor with a diameter of 0.5 M. the reaction Temperature, output, productivity, and composition of the gas in the reactor are shown in table 1; the pressure in the reactor was 20 bar. In each case, was added 0.1 g of triisobutylaluminum per hour. The reaction was carried out in the presence of catalysts of examples 8-11. Properties of the obtained polymers are summarized in table 2.

Table 1
The results of polymerization
The catalyst from exampleOutput[g/l]The polymerization temperature [°C]Capacity [g/g cat]Ethylene [vol.%]HEXEN [vol.%]H2[vol.%]
83,594 180741,970,17-
9 (pri.)394,463935,781,680,62
9 (Deut.)2,79450432,271,651,61
103/49479833,461,940,42
113,193,962330.63 per1,98-

Comparative example 1

Dried by spraying the silica gel ES70X from Crossfield was probalily at 600°C for 6 h and then mixed with 3 mmol of MAO on g of calcined silica gel. A mixture of 36.2 mg (0,069 mmol) dichloride 2,6-bis[1-(2,4,6-trimethylaniline)ethyl]peridiniales(II), 106,3 mg (0,271 mmol) dichloride bis-intercircle (obtained from Crompton) and a 3.87 ml MAO (4,75M in toluene of 27.9 mmol who) was stirred at room temperature for 20 min and added with stirring to 8 g of pre-treated media suspended in 60 ml of toluene; the mixture was stirred at room temperature for 3 h ((Fe+Zr):Al(all)=1:140). The solid was filtered, washed with toluene and dried under reduced pressure to friable state. Mass spectroscopic analysis showed: 0.21 g Zr/100 g of catalyst, 0.03 g Fe/100 g of catalyst and 11.5 g Al/100 g of catalyst.

Polymerization

400 ml of isobutane, 30 ml of 1-hexene and 60 mg triisobutylaluminum was placed in a 1-liter autoclave the atmosphere of inert gas (argon) and, finally, introduced 54 mg of the solid catalyst obtained in example V. the Polymerization was conducted for 60 min at 90°C and a pressure of 40 bar of ethylene. The polymerization was stopped by pressure relief. Got 90 g of polyethylene. Performance: 1670 g of PE/g of solid catalyst. Properties of the obtained polymer are summarized in table 2.

Comparative example 2

The Ziegler catalyst prepared as described in example 32 in WO 99/46302. 4.5 g of the catalyst of the Ziegler suspended in 20 ml of toluene and stirred with 4,95 ml MAO (4,75M in toluene, 23,51 mmol) at room temperature for 30 minutes, the Solid was filtered, washed with toluene and dried under reduced pressure to friable state. The obtained solid is suspended in 20 ml of toluene, added to 82.9 mg (0,158 mmol) dichloride 2,6-bis[1-(2,4,6-trimethylaniline)ethyl]peridiniales (II)and the mixture was stirred at room temperature for 1 castoridae substance was filtered, was washed with toluene and dried under reduced pressure to friable state. Obtained 4.6 g of catalyst.

Polymerization

15 ml of 1-hexene, 500 ml of hydrogen and 2 mmol of triisobutylaluminum loaded in a 10 l autoclave for the gas phase, containing the initial number (80 g) of polyethylene, in an atmosphere of inert gas (argon), and finally added 145 mg of the solid catalyst obtained in example C2. The polymerization was performed for 60 min at 80°C at a pressure of 18 bar ethylene. The polymerization was stopped by pressure relief. Received 191 g of polyethylene. Capacity: 1250 g of PE/g of solid catalyst. Properties of the obtained polymer are summarized in table 2.

Comparative example 3

The Ziegler catalyst prepared as described in EP-A-739937, and polymerization was carried out in a suspension cascade using ethylene/hydrogen in the first reactor and ethylene/1-butene in the second reactor. Product data are shown in table 2.

Example 12

a) Pre-processing of the media

XPO 2107, spray dried silica gel from Grace, was probalily at 600°C for 6 hours.

b) Preparation of the mixed catalyst system

The mixture 0,899 g (1,483 mmol) dichloride 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales (II), 6.25 g (12,707 mmol) dichloride bis(n-butylcyclopentadienyl)hafnium, 8,3 ml Tolu is La and 277,6 ml MAO (4,75M in toluene, 1,3186 mol) was stirred at room temperature for one hour and then added with stirring to 211,8 g of pre-treated media (a) ((Fe+Hf):Al=1:90). After 1 hour stirring, the catalyst was separated and not dried. The catalyst contained 39.5 wt.% solvent (based on the total weight of the assumption of the full introduction of all components on the carrier).

Polymerization

Polymerization was conducted in the fluidized bed reactor with a diameter of 0.5 m, the polymerization Temperature was 105°C. with a polymer yield of 5 kg/hour at a pressure of 20 bar and the concentration of ethylene 49% and the concentration of 1-hexene 0,16%vol.

The obtained polymer had a HLMI equal of 25.9 g/10 min, density 0,9504 g/cm3, Mw160424 g/mol, Mw/Mnto 12.52 and 3.8 CH3/1000 carbon atoms. Polyethylene analyzed by sieving through sieves with different hole sizes and determined the molecular weight of the different fractions by gel permeation chromatography. The fraction of particles with a diameter of 125 μm and below had Mw161450 g/mol and Mw/Mn12,87. The fraction of particles with a diameter of 125 μm to 250 μm had a value of Mw160584 g/mol and Mw/Mn13,44. The fraction of particles with a diameter of 250 μm to 500 μm had Mw151872 g/mol and Mw/Mn12,55. The fraction of particles with a diameter of 500 μm to 1000 μm had Mw155553 g/mol and Mw/Mn11,75. The fraction part is with a diameter above 1000 microns had M w176043 g/mol and Mw/Mn13,89. Molecular weight distribution was very similar for particles of different sizes. This shows that the catalyst particles are very uniform and the proportion of the polymer obtained at different catalysts does not change significantly over time.

1. Polyethylene, representing the homopolymers of ethylene and copolymers of ethylene with α-olefins and having a width of the molecular mass distribution of Mw/Mnfrom 6 to 100, a density of from 0.89 to 0.97 g/cm3, srednevekovoy molecular mass Mwfrom 5000 g/mol to 700000 g/mol and from 0.01 to 20 branches/1000 carbon atoms and at least a 0.5 vinyl groups/1000 carbon atoms, and the proportion of polyethylene with a molecular weight of less than 10000 g/mol has a degree of branching of from 0 to 1.5 branches of side chains longer than CH3/1000 carbon atoms.

2. The polyethylene according to claim 1, in which 5-50 wt.% polyethylene with the lowest molecular masses have a degree of branching less than 10 branches/1000 carbon atoms and 5-50 wt.% polyethylene with high molecular masses have a degree of branching of more than 2 branches/1000 carbon atoms.

3. The polyethylene according to claim 1 or 2, which contains from 0.9 to 3 vinyl groups/1000 carbon atoms.

4. The polyethylene according to claim 1 or 2, characterized by at least bimodal raspredelennymi short circuits.

5. The polyethylene according to claim 1 or 2, which was obtained in the same reactor.

6. The polyethylene according to claim 1 or 2, which is a polymer powder.

7. Catalytic composition for obtaining polyethylene according to claim 1, comprising at least two different polymerization catalysts, of which (A) represents at least one polymerization catalyst based on monotsiklopentadienil complex of a metal of groups 4-6 of the Periodic table of elements, in which cyclopentadienyls system is substituted by an uncharged donor (A1)having the General formula
,
where the variables have the following meanings:
Cp-Zk-A is a

where the variables have the following meanings:
E1A-E5Aeach represents a carbon or from the E1Ato E5Anot more than phosphorus,
R1A-R4Aeach independently from each other represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR5A2N(SiR5A3)2, OR5A, OSiR5A3, SiR5A3, BR5A2in which the organic radicals R1A-R4Acan also be substituted by Halogens which two vicinal radicals R 1A-R4Acan also be connected with the formation of five-, six - and semichasnoho cycle, and/or two vicinal radicals R1A-R4Aassociated with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S,
the radicals R5Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two genialnyh radical R5Acan also be connected with the formation of five - or six-membered cycle,
Z is a divalent bridge between a and CP, which are selected from the following groups
,,,
,,,
,,,
-AlR6A-, -Sn-, -O-, -S-, -SO-, -SO2-, -NR6A-, -CO-, -PR6A- or-P(O)R6A-,
where L1A-L3Aeach independently from each other represents silicon or germanium,
R6A-R11Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C 20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR12Awhere the organic radicals R6A-R11Acan also be substituted by Halogens and two genialnyh or vicinal radicals R6A-R11Acan also be connected with the formation of five - or six-membered cycle, and
the radicals R12Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, C1-C10-alkoxyl or
With6-C10-aryloxy and two radicals R12Acan also be connected with the formation of five - or six-membered cycle, and a is an uncharged donor group containing one or more atoms 15 and/or 16 groups of the Periodic table of elements, MArepresents a metal chosen from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten, and k is 0 or 1,
or harricana (A2), and b represents at least one polymerization catalyst based on iron-containing component with a tridentate ligand containing at least two ortho, orthogonalising aryl radical ().

8. The catalytic composition p is 7, containing one or more activators, and/or one or more organic or inorganic carriers and/or one or more compounds of a metal of groups 1, 2 or 13 of the Periodic table.

9. The catalytic composition according to claim 7 or 8, in which the catalyst A1) has a General formula
,
where the variables have the following meanings:
Cp-Zk-A is a

where the variables have the following meanings:
E1A-E5Aeach represents a carbon or from the E1Ato E5Anot more than phosphorus,
R1A-R4Aeach independently from each other represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR5A2N(SiR5A3)2, OR5A, OSiR5A3, SiR5A3, BR5A2in which the organic radicals R1A-R4Acan also be substituted by Halogens and two vicinal radicals R1A-R4Acan also be connected with the formation of five-, six - and semichasnoho cycle, and/or two vicinal radicals R1A-R4Aassociated with the formation of five-, six - or semichasnoho heterocycle containing at least one atom of g is PI, consisting of N, P, O and S,
the radicals R5Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two genialnyh radical R5Acan also be connected with the formation of five - or six-membered cycle,
Z is a divalent bridge between a and CP, which are selected from the following groups
,,,
,,,
,,,
-AlR6A-, -Sn-, -O-, -S-, -SO-, -SO2-, -NR6A-, -CO-, -PR6A- or-P(O)R6A-where L1A-L3Aeach independently from each other represents silicon or germanium,
R6A-R11Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR12Awhere the organic radicals R6A-R11Acan also be substituted by Halogens and two genialnyh or vicinal radicals R6A- 11Acan also be connected with the formation of five - or six-membered cycle, and the radicals R12Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, With1-C10-alkoxyl or6-C10-aryloxy and two radicals R12Acan also be connected with the formation of five - or six-membered cycle, and a is an uncharged donor group containing one or more atoms 15 and/or 16 groups of the Periodic table of elements
MArepresents a metal chosen from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten, and k is 0 or 1.

10. The catalytic composition according to claim 9, in which all E1A-E5Arepresent carbon.

11. The catalytic composition according to claim 9, in which a is an unsubstituted, substituted or condensed heteroaromatic cyclic system containing heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus in addition to carbon atoms of rings.

12. The catalytic composition according to claim 11, in which a represents a group of formula (IV)

where
E6A-E9Aeach independently from each other represents a carbon or nitrogen,
R16A-R19Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR20A3, and the organic radicals R16A-R19Acan also be substituted by halogen atoms or nitrogen and also With1-C20-alkyl, C2-C20-alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR20Aand two vicinal radicals R16A-R19Aor R16Aand Z can also be connected with the formation of five - or six-membered cycle and
the radicals R20Aeach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl or alkylaryl with 1-10 carbon atoms in the alkyl part 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-E9Arepresents nitrogen and is 1 when E6A-E9Ais the carbon.

13. The catalytic composition according to item 12, where 0 or 1 for E6A-E9Arepresents nitrogen.

14. Catalytic the song on PP-13, in which MArepresents chromium in the oxidation States 2, 3 and 4.

15. The catalytic composition according to 14, in which MArepresents chromium in the oxidation state 3.

16. The catalytic composition according to claim 7 or 8, in which Garrity (A2) represent the hafnium complexes of General formula (VI)

in which the substituents and indices have the following meanings:
XBrepresents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl,6-C15-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, -OR6Bor-NR6BR7Bor two radicals XBform a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand,
the radicals XBare the same or different and can be connected to each other,
E1B-E5Beach represents a carbon or not more than one of the E1B-E5Brepresents a phosphorus or nitrogen, preferably carbon,
t is 1, 2 or 3 depending on the valence Hf takes values such that the metallocene complex of General formula (VI) is uncharged,
and
R6Band R7Beach represents a C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, foralkyl or FPO is aryl, each of which has 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, and
R1B-R5Beach independently of one another represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which in turn can contain1-C10-alkyl groups as substituents, With2-C22alkenyl,
With6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR8B2N(SiR8B3)2, OR8B, OSiR8B3, SiR8B3, and the organic radicals R1B-R5Bcan also be substituted by halogen atoms and/or two radicals R1B-R5Bcan also be connected with the formation of five-, six-or semichasnoho cycle, and/or two vicinal radicals R1D-R5Dcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and
the radicals R8Bmay be the same or different and each of them can be a1-C10-alkyl, C3-C10-cycloalkyl,6-C15-aryl, C1-C4-alkoxyl or6-C10-aryloxy and
Z1Bis a XBor

moreover, the radicals
R9B-R13Beach independently from each other represents hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which in turn may contain as a substituent With1-C10-alkyl, C2-C22alkenyl,6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR14B2N(SiR14B3)2, OR14B, OSiR14B3, SiR14B3, and the organic radicals R9B-R13Bcan also be substituted by halogen atoms and/or two radicals R9B-R13Bin particular vicinal radicals, may also be connected with the formation of five-, six - or semichasnoho cycle and/or two vicinal radicals R9B-R13Bcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and
the radicals R14Bmay be the same or different and each represents a C1-C10-alkyl, C3-C10-cycloalkyl,6-C15-aryl, C1-C4-alkoxyl or6-C10-aryloxy,
E6B-E10Beach represents a carbon or not more than one of the E6B-E10Brepresents a phosphorus or as the from, preferably carbon, or the radicals R4Band Z1Btogether form the groupand
R15Brepresents a
,,,
,,,
,
=BR16B, =BNR16BR17B, =AlR16B, -Ge -, - Sn-, -O-, -S-, =SO, =SO2, =NR16B, =CO, =PR16Bor =P(O)R16B,
and
R16B-R21Bare the same or different and each represents a hydrogen atom, halogen atom, trimethylsilyloxy group, group C1-C10-alkyl, C1-C10-foralkyl,6-C10-ferril,6-C10-aryl, C1-C10-alkoxyl, and7-C15-alkylacrylate,2-C10alkenyl,7-C40-arylalkyl, C8-C40-arylalkyl or7-C40-alkylaryl or two adjacent radicals together with the atoms connecting them, form a saturated or unsaturated cycle with 4 to 15 carbon atoms and
M2B-M4Beach represents a silicon, germanium or tin, or preferably silicon,
A1Brepresents a
-O-, -S-,,, =O, =S, NR22B, -O-R22B,
or unsubstituted, substituted or condensed heterocyclic system, and
the radicals R22Beach independently from each other represents C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, C7-C18-alkylaryl Si(R23B)3,
R23Brepresents hydrogen, C1-C10-alkyl, C6-C15-aryl, which in turn can contain as substituents of group C1-C4-alkyl or C3-C10-cycloalkyl,
v is equal to 1 or can also be equal to 0 when A1Bis unsubstituted, substituted or condensed heterocyclic system,
or the radicals R4Band R12Btogether form a group-R15B-.

17. The catalytic composition according to claim 7 or 8, in which the polymerization catalyst) is a complex of the metal with at least one ligand of General formula

in which the variables have the following meanings:
E1Crepresents nitrogen or phosphorus,
E2C-E4Ceach independently of one another represents a carbon, nitrogen or phosphorus,
R1C-R3Ceach independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl with 1-10 atoms ug is erode in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R1C-R3Cmay be substituted by halogen atoms 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 N, P, O and S,
R4C-R7Ceach independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, SiR19C3, and the organic radicals R4C-R7Ccan also be substituted by halogen atoms and/or two genialnyh or vicinal radicals R4C-R7Ccan also be connected with the formation of five-, six - or semichasnoho cycle and/or two genialnyh or vicinal radicals R4C-R9Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, and when v is 0, R6Cis the relationship with L1Cand/or R7Cis the relationship with L2Cand L 1Cforms a double bond with the carbon atom associated with R4Cand/or L2Cforms a double bond with the carbon atom connected with
R5C,
u = 0 when E2C-E4Crepresents a nitrogen or phosphorus and is 1 when
E2C-E4Cis carbon
L1C-L2Ceach independently of one another represents nitrogen or phosphorus,
R8C-R11Ceach independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R8C-R11Ccan also be substituted by halogen atoms 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 N, P, O and S and/or R8Cand R10Cand/or R9Cand R11Ceach represents a halogen atom such as fluorine, chlorine or bromine,
R12C-R17Ceach independently of one another represents hydrogen, C 1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R12C-R17Ccan also be substituted by halogen atoms 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 N, P, O and S,
the indices v are each independently of one another are 0 or 1,
the radicals XCeach independently of one another represent fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl,8-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SR18C, SO3R18C, OC(O)R18C, CN, SCN, β-diketonate, CO, BF4-,
PF6-or surround coordinatewise anion and the radicals XCcan connect to each other,
the radicals R18Ceach independently of one another represents hydrogen, C1-C20-alkyl,C 2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3, and the organic radicals R18Ccan also be substituted by halogen atoms 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 represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, and the organic radicals R19Ccan also be substituted by halogen atoms or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - or six-membered cycle,
s is equal to 1, 2, 3,or 4
D is an uncharged donor and
t is from 0 to 4.

18. The catalytic composition according to 17, in which the polymerization catalyst) is a complex of the metal with at least one ligand of General formula

in which
E2C-E4Ceach independently from each other represents a carbon, nitrogen or phosphorus,
R1C-R3Ceach independently from each other represents hydrogen, C 1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R1C-R3Ccan also be substituted by halogen atoms 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 N, P, O and S,
R4C-R5Ceach independently from each other represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, SiR19C3, and the organic radicals R4C-R5Ccan also be substituted by halogen,
u = 0 when E2C-E4Cis nitrogen or phosphorus and is 1 when E2C-E4Cis carbon
R8C-R11Ceach independently from each other represents C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, arylalkyl with 1-10 atoms the carbon in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3, and the organic radicals R8C-R11Ccan also be substituted by halogen atoms 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 N, P, O and S, and/or each of R9Cand R11Cis a halogen like fluorine, chlorine or bromine,
R12C-R17Ceach independently from each other represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18CSiR19C3, and the organic radicals R12C-R17Ccan also be substituted by halogen atoms 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 N, P, O or S,
the indices v are each independently researched the Simo from each other 0 or 1,
the radicals XCeach independently of one another represent fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl,6-C20-aryl, arylalkyl with 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 coordinatewise anion and the radicals XCcan connect to each other,
the radicals R18Ceach independently from each other represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3, and the organic radicals R18Ccan also be substituted by halogen atoms and the 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 from each other represents hydrogen,
With1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, arylalkyl with 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, and the organic radicals R19Ccan also be substituted atoms is of alogena or nitrogen - and oxygen-containing groups and two radicals R 19Ccan also be connected with the formation of five - or six-membered cycle,
s is equal to 1, 2, 3,or 4
D is an uncharged donor and
t is from 0 to 4.

19. Catalytic composition for p, in which each E2C-E4Crepresent carbon.

20. Catalytic composition for PP-19, in which each R8Cand R10Crepresents a C1-C22-alkyl which may be substituted by a halogen atom such as fluorine, chlorine or bromine.

21. Pre-polymerized catalyst system to obtain a polyethylene according to claim 1, containing the catalytic system according to any one of claims 7 to 20, and linear C2-C10-1-alkenes, polymerized therein in a weight ratio of from 1:0.1 to 1:200.

22. The use of a catalytic system according to any one of claims 7 to 20, for the polymerization or copolymerization of ethylene with α-olefins.

23. A method of producing copolymers of ethylene according to any one of claims 1 to 6, in which the ethylene will polimerizuet together with α-olefins in the presence of a catalytic composition according to any one of claims 7 to 20.

24. The method according to item 23, in which the ethylene will polimerizuet with3-C12-l-alkenes.

25. The method according to item 23, in which the monomer mixture of ethylene and/or C3-C12-l-alkene containing at least 50 mol.% ethylene is used as a monomer for polymerization.

26. The mixture of the polymer is in for extruding, contains
(P1) from 20 to 99 wt.% one or more new types of polyethylene according to any one of claims 1 to 5, and
(P2) from 1 to 80 wt.% polymer different from (P1), and the mass percentage calculated on the total weight of the mixture of polymers.

27. Fiber, film or extruded product of a copolymer of ethylene according to any one of claims 1 to 6 or 26.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to high-strength bimodal polyethylene compositions which are meant for preparing compositions for pipes, particularly high-strength compositions for pipes. The composition has density equal to or greater than 0.940 g/cm3, overall polydispersity index equal to or greater than 25 and contains a high-molecular polyethylene component and a low-molecular polyethylene component. The ratio of weight-average molecular weight of the high-molecular component to the weight-average molecular weight of the low-molecular component of the composition is equal to or greater than 30. The weight-average molecular weight of the low-molecular polyethylene component ranges from 5000 to 30000. The composition is classified as PE 100 material, has proper balance of properties such as strength and hardness, as well as good processing properties. A pipe made from the composition which has undergone internal strength tests has extrapolated stress equal to or greater than 10 MPa when the internal strength curve of the pipe is extrapolated to 50 or 100 years in accordance with ISO 9080:2003(E).

EFFECT: increased strength of products.

15 cl, 6 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of preparing an ethylene polymer composition. Described is a method of preparing an ethylene polymer composition in a multistage process. The said method involves polymerisation of only one of ethylene or ethylene with a comonomer to obtain ethylene polymer at the first stage, supply of the polymer obtained at the first stage to the second stage, where at the second stage only one of ethylene or ethylene with a comonomer is polymerised in the presence of the polymer obtained at the first stage, and where the first stage is a suspension polymerisation stage, and polymerisation at the first stage is carried out in the presence of a catalyst system containing: (a) a precursor solid catalyst containing a transition metal selected from titanium and vanadium; magnesium, haloid, electron donor and solid dispersion material containing inorganic oxide, and (b) organoaluminium compound; and where the average diametre of particles of the precursor solid catalyst obtained per total volume of the precursor solid catalyst, D50, ranges from 1 to 13 micrometres. Also described is an ethylene polymer composition obtained using the said method, having density in the range 0.915-0.970 g/cm3 and MI5 in the range 0.02-3.5 dg/min and less than 6 regions of gel per m2 with size greater than 800 micrometres, and less than 100 regions of gel per m2 with size ranging from 400 to 800 micrometres, where the amount and size of gel is determined for a 5 m2 cast film sample with thickness of 50 micrometres, obtained from the ethylene polymer composition; also described is an industrial product made from the said composition. Described is an ethylene polymer composition obtained using the said method, having density in the range 0.915-0.970 g/cm3 and MI5 in the range 0.02-3.5 dg/min, where the composition has Young's modulus during bending, measured using an Instron device in accordance with ISO 178, exceeding 1340*{1-exp[-235*(density-0.9451)]}; ethylene polymer composition having density in the range 0.915-0.970 g/cm3 and MI5 in the range 0.02-3.5 dg/min, where the composition has Young's modulus during bending which exceeds 1355*{1-exp[-235*(density-0.9448)]}. Described is a composition obtained using the said method and containing bimodal polyethylene resin, and where the bimodal polyethylene resin contains high-molecular ethylene polymer and low-molecular ethylene polymer, and where the low-molecular ethylene polymer has MI2 ranging from 10 g/10 min to 1000 g/10 min and density of at least 0.920 g/cm3, and where the composition has density ranging from 0.915 g/cm3 to 0.970 g/cm3.

EFFECT: improved mechanical properties of products made from the compositions, reduced amount of gel in the compositions.

20 cl, 38 ex, 1 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: thermoplastic elastomer material contains: (a) from 10 to 100 wt % of at least one thermoplastic elastomer based on styrene; (b) from 0 to 90 wt % of at least one thermoplastic homopolymer or copolymer of α-olefin, different from (a); where amount of (a)+(b) equals 100; (c) from 2 to 90 pts. wt of vulcanised rubber in crushed state; (d) from 0.01 to 10 pts. wt of at least one coupling agent which contains at least one unsaturated ethylene; where amounts (c) and (d) are expressed in ratio to 100 pts. wt of (a)+(b).

EFFECT: improved mechanical properties, specifically breaking stress and breaking elongation, increased wear resistance.

60 cl, 6 tbl, 6 ex

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: polyethylene composition is intended for formation with blowing of barrels with 2 discharge holes with volume ranging from 50 to 250 dm3(l). Composition has density within the range from 0.950 to 0.956 g/cm3 at 23°C, value of index of melt flow rate MFR190/21.6 within the range from 1.5 to 3.5 dg/min and multimodal molecular-weight distribution. It includes from 35 to 45 wt % of homopolymer of ethylene A with low molecular weight, from 34 to 44 wt % of copolymer B with high molecular weight, representing copolymer of ethylene and 1-olefin, containing from 4 to 8 carbon atoms, and from 18 to 26 wt % of copolymer of ethylene C with superhigh molecular weight. Copolymer B contains less than 0.1 wt % of comonomer calculating on copolymer B weight, and copolymer C contains comonomers in amount from 0.1 to 0.6 wt % calculating on copolymer C weight.

EFFECT: polyethylene composition possesses increased impact viscosity and has high degree of blowing 180-220%.

9 cl, 1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a polyethylene composition with multimodal molecular weight distribution, which is specially suitable for blow moulding large containers with volume ranging from 10 to 150 dm3 (l). The composition has density which ranges from 0.949 to 0.955 g/cm3 at 23°C and melt flow rate (MFR190/5) from 0.1 to 0,3 dg/min. The composition contains from 38 to 45 wt % homopolymer of ethylene A with low molecular weight, from 30-40 wt %, copolymer B with high molecular weight, obtained from ethylene and another 1-olefin, containing 4 to 8 carbon atoms, and from 18 to 26 wt % copolymer C with ultra-high molecular weight. The composition has Izod impact strength with notch (from ISO) from 30 to 60 kJ/m2 and resistance to bursting under stress (FNCT) from 60 to 110 hours.

EFFECT: large blow moulded objects made from the composition have high mechanical strength.

9 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to the technology of obtaining rubber, particularly to hydrogenated or non-hydrogenated nitrile rubber, to the method of obtaining it, to a polymer composite material, to the method of obtaining it and method of making moulded objects. Hydrogenated or non-hydrogenated rubber is obtained, with molecular weight Mw between 20000 and 250000, Mooney viscosity -ML 1+4 at 100°C between 1 and 50 and polydispersity index of not more than 2.5. The polymer composite material contains not less than one hydrogenated or non-hydrogenated nitrile rubber, not less than one filler and not less than one crosslinking agent. Without adding coolefin, the nitrile rubber is subjected to metathesis in the presence of Grubbs's catalyst in an inert solvent.

EFFECT: obtaining hydrogenated or non-hydrogenated nitrile rubber with low molecular weight and narrower molecular weight distribution.

13 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining compositions for production of pressure pipes. Composition is obtained from mixture of (a) polyethylene resin, containing fractions which have large molecular weight and fractions which have low molecular weight, and (b) ionomer. As ionomer, copolymer, which represents copolymer of alpha-olefin and ethylene-unsaturated carboxylic acid and/or anhydride, partly neutralised by metal ions or amines.

EFFECT: obtaining resins which have high resistance to creep at low temperature preserving high resistance to slow growth of cracks and shock resistance.

8 cl, 6 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to field of processing plastics, in particular to additive for processing polyolefins, which represents monoepoxyester of diane resin with molecular weight from 4000-4500 units and carboxylic acid - abietene, benzoic or salicylic. Obtained additive can be used as 100% product or in form of concentrate of said monoepoxyester in polyethylene with content of basic substance 10-20%.

EFFECT: increase of polyolefin melt index and 20-25°C reduction of processing temperature per each per cent of additive.

3 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: proposed thermoplastic composition contains a copolymer of ethylene and vinylacetate, biodegradable filler-coco husks - wastes from processing cocoa beans and a surface active substance from a range of monoesters of dicarboxylic acids.

EFFECT: design of a thermo moulded composition, products of which are biologically degradable under the effect of the sun, moisture and soil microbial flora.

2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of preparing a catalyst for metathesis polymerisation of dicyclopentadiene -[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N,N-dimethylaminomethylphenyl methylene)ruthenium. The method involves reacting a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran while boiling in an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The indenylidene ruthenium complex formed is separated and successively reacted in a single reactor with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere.

EFFECT: method increases output of product.

3 ex

FIELD: chemistry.

SUBSTANCE: catalysts for metathesis polymerisation of dicyclopentadiene are described, which are represented by [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N,N-diethylaminomethylphenylmethylene)ruthenium of formula (1) or [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N-pyrrolidinylmethylphenylmethylene)ruthenium of formula (2) . A method is described for producing a catalyst of formula (1), involving successively reacting a first generation Grubb catalyst with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and N,N-diethyl-(2-vinylbenzyl)amine in an inert atmosphere at temperature between 40 and 70°C in the presence of a solvent. In another version of the said method, a second generation Grubb catalyst is reacted with N,N-diethyl-(2-vinylbenzyl)amine in an inert atmosphere at temperature between 40 and 70°C in the presence of a solvent. A method is described for producing a catalyst of formula (2), involving successively reacting a first generation Grubb catalyst with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 1-(2-vinylbenzyl)pyrrolidine in an inert atmosphere at temperature between 40 and 70°C in the presence of a solvent. In another version of the method, a second generation Grubb catalyst is reacted with 1-(2-vinylbenzyl)pyrrolidine in an inert atmosphere at temperature between 40 and 70°C in the presence of a solvent. A method is described for metathesis polymerisation of dicyclopentadiene, involving polymerisation using catalysts of formulae (1) or (2) in molar ratio monomer:catalyst ranging from 70000:1 to 100000:1.

EFFECT: increased output of catalyst and simpler synthesis due to less number of stages, obtaining polydicyclopentadiene with good application properties with low catalyst consumption.

7 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of producing ruthenium carbene complex and a method of metathesis polymerisation of dicyclopentadiene. The catalyst for metathesis polymerisation of dicyclopentadiene is(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-N,N-dimethylamino-methylphenylmethylene)ruthenium of formula The method of producing the said catalyst involves reacting a second generation Grubbs catalyst with 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere. In another version of the said method, a first generation Grubbs catalyst is successively reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in a single reactor in toluene while heating in an inert atmosphere. The method of metathesis polymerisation of dicyclopentadiene is characterised by that, polymerisation is carried out using the proposed catalyst with ratio monomer: catalyst ranging from 75000:1 to 100000:1.

EFFECT: invention allows for obtaining a polymer with good mechanical properties at low expenses due to reduced catalyst consumption.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: method is described for producing electrocatalytic composition based on polypyrrole, involving polymerisation of pyrrole in the presence of platinised soot and surface-active additive, wherein the process is carried out under the effect of a radical initiator in an organic solvent at temperature of approximately 0°C, where the radical initiator is dicyclohexylperoxy dicarbonate, the surface-active additive is a product from reacting tertiary amine (CH3)2NR (R - aliphatic residue C12-14) and propylene oxide in ethyl cellosolve, containing an ionic component - quaternary ammonium base (CH3)2RN+R1(OH)-, where R1- propylene oxide oligomers and a nonionic component - propylene oligomers, and the organic solvent is ethyl cellosolve. After mixing, the components the mixture undergo vacuum treatment at 10-2 mm Hg, and during the initiation process, the system is exposed to an acoustic field with frequency 20 to 22 kHz. Polymerisation process of pyrrole is carried out until obtaining an electrocatalytic composition system which is soluble in organic solvents. In this process electrocatalytic composition is obtained, with the following ratio of said components, wt %: pyrrole 15 to 17; platinised soot 6 to 8; surface-active additive 8-10; dicyclohexylperoxy dicarbonate 5-7; ethyl cellosolve - the rest.

EFFECT: design of an efficient method of producing electrocatalytic composition based on polypyrrole.

2 cl, 2 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing styrene polymers by emulsion polymerization reaction in the presence of emulsifying agent and cobalt-organic initiating agent with tridentate ligands alkyl-{2-[(2-aminoethyl)imino]pent-3-ene-4-olate}(1,2-ethanediamine)cobalt (III) halides. As an initiating agent methods involves using a mixture consisting of initiating agent with alkyl ligand of normal structure and initiating agent with alkyl ligand of branched structure wherein their the sum concentration is 0.05-0.2 mas. p. per 100 p. p. of monomer and their ratio is from 2:1 to 9:1. The process is carried out at temperature 10-80°C and pH 4-10. Invention provides reducing the inductive period and possibility for using monomers with industrial treatment degree, i. e. stabilizing agent-containing monomers.

EFFECT: improved method for preparing.

5 cl, 1 tbl, 9 ex

The invention relates to the field of chemical industry, in particular to the creation of more efficient new homogeneous catalysts based on the same-olefin to obtain a wide range of branched polyolefins from high molecular weight (hard) to elastomers of various molecular weights

The invention relates to a technology for obtaining low molecular weight CIS-1,4-polybutadiene and can be used in the synthetic rubber industry, and the resulting polymer is used for the plasticizing of elastomers in the paint industry, for the manufacture of protective coatings and for other purposes

The invention relates to the production of CIS-butadiene rubber, which can be used in the manufacture of tires, rubber products, high impact polystyrene and ABS-plastics

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin synthesis method and more specifically to a polyethylene synthesis method. Polyethylene is a copolymer of ethylene with 1-alkenes. The invention also relates to polyethylene synthesis catalyst systems. The catalyst system is a mixture of metallocenes: hafnocene and an iron-based complex, an activating compound and a support. The invention also relates to films made from polyethylene and packets made from the said films.

EFFECT: disclosed catalyst system enables production of polyethylene with given molecular weight distribution in a single reactor.

16 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin synthesis method and more specifically to a polyethylene synthesis method. Polyethylene is a copolymer of ethylene with 1-alkenes. The invention also relates to polyethylene synthesis catalyst systems. The catalyst system is a mixture of metallocenes: hafnocene and an iron-based complex, an activating compound and a support. The invention also relates to films made from polyethylene and packets made from the said films.

EFFECT: disclosed catalyst system enables production of polyethylene with given molecular weight distribution in a single reactor.

16 cl, 3 tbl, 3 ex

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