Polyethylene and catalyst composition for polyethylene synthesis

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

 

The present invention relates to a new type of polyethylene, to a catalytic composition and method of its production, as well as fibers, molded articles, films or polymer mixtures which contain the specified polyethylene.

To the mechanical strength of the films, including polyethylene, are constantly increasing requirements. In particular, the required product with high resistance to cracking under stress, impact strength and rigidity, which are particularly suitable for obtaining films for food packaging. A necessary condition for the existence of both good resistance to cracking under stress and strength to perform easy, since they are opposite to each other. While the hardness increases with increasing density polyethylene, resistance to cracking when the voltage decreases with increasing density.

The formation of cracks in the tension in plastics is a physical-chemical process that does not alter the molecules of the polymer. It is caused, inter alia, a gradual softening or Raspletina linking of molecular chains. The formation of cracks when the voltage flows less easily at higher average molecular weight, a broader molecular weight distribution and a higher grade is branching molecules, that is, smaller densities. It is more difficult in larger lengths of the side chains. Surface-active substances, in particular Soaps, and thermal loading speed up the cracking with the strain. On the other hand, with increasing density deteriorate the optical properties such as transparency.

Properties of bimodal polyethylene depend, first, on the properties of the components present. Secondly, a special influence on the mechanical properties of polyethylene has the quality of mixing high molecular weight component and a low molecular weight component. Low quality mixing results, inter alia, to the low resistance to cracking under stress and adverse effect on the slow change of the properties of pressure pipelines made of polyethylene blends.

It was found that for the manufacture of hollow bodies and penstocks advantageous to use a mixture of high molecular weight copolymer of ethylene low density and low molecular weight homopolymer ethylene high density, which have good resistance to cracking under stress, as described, for example, L. L. Böhm et al., Adv. Mater. 4, 234 - 238 (1992). Similar plastic mixture described in the publications EP-A-100843, EP-A533154, EP-A533155, EP-A533156, EP-A533160, as well as in U.S. Patent No. 5350807.

Such bimodal polyethylene is new mixes often done with the use of cascade reactors, i.e. two or more polymerizers connected, and the polymerization of low molecular weight component takes place in a single reactor, and the polymerization of high-molecular component occurs in the following (see, for example, the publication of M. Rätzsch, W. NeiBI "Bimodale Polymerwerkstoffe auf der Basis von PP und PE" in "Aufbereiten von Polymeren mit neuartigen Properties", pp. 3-25, VDI-Verlag, Düsseldorf 1995). The disadvantage of this method is that it is necessary to add relatively large amounts of hydrogen for the production of low molecular weight component. Therefore, the polymers obtained by this method have a low content of terminal vinyl groups, especially in the low molecular weight component. In addition, it is technically difficult to prevent comonomers added to the first reactor or hydrogen, is added as a growth regulator circuit, to the next reactor.

The application of catalytic compositions comprising two or more different catalysts for polymerization of olefins of the type of Ziegler or metallocene type, you know. For example, you can apply a combination of two catalysts, one of which catalyzes the receipt of polyethylene with an average molecular weight that is different from the average molecular weight of the polyethylene produced another catalyst, to obtain mixtures having a wide molecular weight distributions (WO 95/11264). polimery of ethylene with higher α-olefins, such as propene, 1-butene, 1-penten, 1-hexene or 1-octene, known as LLDPE (linear low density polyethylene), which is obtained using the classical catalysts of the Ziegler-Natta titanium-based, differ from LLDPE, which is obtained using metallocene. The number of side chains formed by introduction of co monomer, and their distribution, known as the distribution of short-chained branching (short chain branching distribution - SCBD), using different catalytic systems is different. The number and distribution of the side chains has a significant impact on the crystallization properties of ethylene copolymers. While the characteristics of fluidity and, therefore, the technological properties of these ethylene copolymers depend mainly on molecular mass and molecular mass distribution, mechanical properties largely depend on the distribution of short-chained structure. However, the distribution of short-chained structure also plays a role in technological processing, for example, in the extrusion of films, where crystallization properties of ethylene copolymers in the process of cooling film extrudate are an important factor in determining how quickly and in what quantity can ekstrudirovaniya film. The right combination katalysatorrolle optimum combination of good mechanical properties and good processability are difficult to determine due to the large number of possible combinations.

Adding components metals, including "late" (toward the end of the Periodic system of elements) transition metals in catalysts for the polymerization of olefins based on "early" (closer to the beginning of the Periodic system of elements) of transition metals to obtain the activity or stability of the latter catalysts described many times (Herrmann, C; Streck, R.; Angew. Makromol. Chem. 94 (1981) 91-104).

Synthesis of branched polymers and ethylene without the use of co monomer with the use of bimetallic catalysts in which the catalyst will oligomerize part of ethylene and another copolymerized with ethylene oligomers, thus obtained, was described (Beach, 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 Organometaliics 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 the publication WO 99/46302 describes a catalytic composition based on (a) iron-pyridinylamino component and (b) additional catalyst, such as zirconium or a Ziegler catalyst, and its use for the polymerization of ethylene with olefins.

Another important kind of technology gaining the films is the shape of the sleeve. Many properties of the film can be further enhanced by the transition from the so-called "standard" method, where the sleeve is intensively cooled immediately upon exit from the mouthpiece to the way the so-called "long sprue" ("long stalk"). In the latter method, the upper edge of the cooling ring is adjusted to obtain a large gap for air outlet. As a result, the speed of the cooling air is lower than in the standard way, even when the output power of the fan remains the same. Static pressure around the sleeve remains relatively high. It prevents the expansion and thus leads to the formation of the Central sprue. Due to the relatively small surface cooling temperature of the sprue remains high, and the orientation of the polymers formed from the flow in the mouthpiece, partially weakened. The height of the level of hardening (polymer) remains unchanged. The sleeve is blown uniformly and synchronously in the transverse direction of the intense cooling directly before it reaches the level of hardening. This usually leads to the improvement of the mechanical properties of the film. On the other hand, it is impossible at all extrusion lines to adjust the top edge of the cooling ring and, thus, to influence the properties of the film in the form of a sleeve.

Known mixture of ethylene copolymers yet who constitute much to be desired in terms of a combination of good mechanical properties, high melt fluidity and good optical properties. In addition, it is desirable to have films which have similar properties regardless of how they extrusion received "standard" or "long sprue".

Unexpectedly, it was found that this objective can be achieved by using a specific catalyst compositions, whereby the obtained polyethylene having good mechanical properties, good processability, and high optical quality.

The authors of the present invention obtained polyethylene, which includes homopolymers of ethylene and/or of a copolymer of ethylene with 1-alkenes with a wide molecular mass distribution Mw/Mnin the interval from 5 to 30, a density in the range from 0.92 to 0,955 g/cm3, srednevekovoi molecular mass Mwin the range of from 50000 g/mol to 500,000 g/mol and contains from 0.01 to 20 branches/1000 carbon atoms and z-average molecular mass Mzwhich is less than 1 Mio. g/mol.

The width of the molecular mass distribution of MW/Mnpolyethylene according to the present invention is in the range from 5 to 30, preferably in the range from 6 to 20 and particularly preferably in the range from 7 to 15. Density polyethylene according to the present invention is in the range from 0.92 to 0,955 fuel 3, preferably in the range from 0.93 to 0.95 g/cm3especially preferably in the range from 0,935 to 0,945 g/cm3. Srednevekovaja molecular mass Mwpolyethylene according to the invention is in the range of from 50000 g/mol to 500,000 g/mol, preferably in the range of from 100000 g/mol to 300,000 g/mol and particularly preferably in the range from 120000 g/mol to 250000 g/mol.

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

The polyethylene according to the present invention contains from 0.01 to 20 branches/1000 carbon atoms, preferably from 1 to 10 branches/1000 carbon atoms, particularly preferably from 3 to 8 branches/1000 carbon atoms. Number of branches/1000 carbon atoms specified by using the13WITH THE MR, as described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and means the total content of CH3groups/1000 carbon atoms.

the z-Average molecular mass Mzpolyethylene according to the invention is in the range from less than 1 Mio. g/mol, preferably in the range of from 250,000 g/mol to 700000 g/mol, particularly preferably in the range of 300,000 g/mol to 500,000 g/mol. The definition of the term "z-average molecular mass Mz" is, for example, High Polymers Vol. XX, Raff and Doak, Interscience Publishers, John Wiley & Sons, 1965, p. 443.

HLMI of polyethylene according to the present invention is in the range from 5 to 100 g/10 min, preferably in the range from 7 to 60 g/10 min and particularly preferably in the range from 9 to 50 g/10 min. In the description of the present invention, the term “HLMI” is used in its well-known meaning and refers to the index of the melt at high shear stress, which is defined at 190°c load of 21.6 kg 190°C/21,6 kg) according to ISO 1133.

The number of polyethylene according to the invention with a molecular mass below 1 Mio. g/mol, which is defined gel chromatography (GPC) according to the standard method for determining molecular weight distribution, is preferably more than the 95.5 wt.%, preferably more than 96 wt.% and particularly preferably more than 97 wt.%. This value is defined in soo is according to the conventional method for quantitative determination of molecular mass distribution using the software WIN GPC.

The polyethylene according to the present invention contains at least a 0.5 vinyl groups/1000 carbon atoms, preferably from 0.6 to 3 vinyl groups/1000 carbon atoms and particularly preferably from 0.7 to 2 vinyl groups/1000 carbon atoms. The content of vinyl groups/1000 carbon atoms is defined by using the infrared spectrum in accordance with ASTM D 6248-98. In the description of the present invention, the expression "vinyl group" refers to the groups-CH=CH2; vinylidene group and internal olefinic groups are not included in this term. The vinyl groups are usually the result of breakage of the polymer chain after the introduction of ethylene, while vinylidene end groups are usually formed after the reaction of breakage of the polymer chain after the introduction of the co monomer. Vinylidene and vinyl groups can be subsequently funktsionaliziruyutsya or crosslinked, and usually the vinyl group to a greater extent suited for such subsequent reactions. Preferably, at least 0.5 to proper groups/1000 carbon atoms, more preferably from 0.5 to 10 vinyl groups/1000 carbon atoms and particularly preferably from 0.7 to 5 vinyl groups/1000 carbon atoms is present in 20 wt.% polyethylene with low molecular masses. This characteristic can be defined solvent-resolvent fractionation (i.e. si is the subject of "solvent-non-solvent"), which was later called fractionation of Holtrop (Holtrup fractionation) and described in the publication W. Holtrup, Makromol. Chem. 178, 2335 (1977), in combination with IR-study of various fractions, and the number of vinyl groups is determined in accordance with ASTM D 6248-98. As solvents for fractionation was used xylene and etilenglikolevye ether at 130°C. the sample of polyethylene by weight of 5 g was divided into 8 fractions.

The polyethylene according to the present invention contains at least 0,05 vinylidene groups/1000 carbon atoms, preferably from 0.1 to 1 vinylidene groups/1000 carbon atoms and particularly preferably from 0.14 to 0.4 vinylidene groups/1000 carbon atoms. The definition of this characteristic were conducted in accordance with ASTM D 6248-98.

Preferably 5-50 wt.% polyethylene according to the invention with the lowest molecular mass of preferably 10-40 wt.% and particularly preferably 15-30 wt.%, have a degree of branching less than 12 branches/1000 carbon atoms. The degree of branching part of the polyethylene having the lowest molecular weight, is preferably from 0.01 to 10 branches/1000 carbon atoms and particularly preferably from 0.1 to 6 branches/1000 carbon atoms. 5-50 wt.% polyethylene according to the present invention, having the largest molecular weight, preferred the additional 10-40 wt.% and particularly preferably 15-30 wt.%, have a degree of branching of more than 1 branch/1000 carbon atoms. The degree of branching in part of polyethylene with high molecular mass preferably is in the range from 2 to 40 branches/1000 carbon atoms and particularly preferably in the range from 5 to 20 branches/1000 carbon atoms. The proportion of polyethylene with the highest or lowest molecular weight determined by the method of solvent-nesolventnost fractionation, later called fractionation of Holtrop, as described in the publication W. Holtrup, Makromol. Chem. 178, 2335 (1977), in combination with IR or NMR study of the various factions. As solvents for fractionation was used xylene and etilenglikolevye ether at 130°C. the sample of polyethylene by weight of 5 g was divided into 8 fractions. Fractions were then studied using the13C-NMR spectroscopy. The branching of the different polymer fractions can be defined using the13C-NMR as described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and means the total content of CH3groups/1000 carbon atoms in the low-molecular and high-molecular fractions.

The polyethylene according to the present invention preferably contains from 0.1 to 20 branches of side chains larger than CH3/1000 carbon atoms, preferably b is the same circuits from 2-C6/1000 carbon atoms, more preferably from 1 to 10 branches larger than CH3/1000 carbon atoms, preferably side chains from C2-C6/1000 carbon atoms, and especially preferably from 2 to 6 branches of side chains larger than CH3/1000 carbon atoms, preferably side chains from C2-C6/1000 carbon atoms. The number of branches of side chains larger than CH3/1000 carbon atoms specified by using the13C-NMR as described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and means the total content of side chains larger than the group of CH3per 1000 carbon atoms (no limit). Particularly preferably polyethylene with 1-butene, 1-hexene or 1-octene as a 1-alkene content of from 0.01 to 20 ethyl, Budilnik or exiling side branches/1000 carbon atoms, preferably from 1 to 10 ethyl, Budilnik or exiling side branches/1000 carbon atoms, more preferably from 1 to 10 ethyl, Budilnik or exiling side branches/1000 carbon atoms and particularly preferably from 2 to 6 ethyl, Budilnik or exiling side branches/1000 carbon atoms. This characteristics means the content of ethyl, Budilnik or exiling side chains per 1000 carbon atoms without end is a Republican.

The ratio of Eta-variables polyethylene according to the present invention Eta(vis)/Eta(GPC) is preferably less than 0.95, more preferably less than 0,93, especially preferably less than about 0.90. Eta(vis) is a characteristic viscosity, which is determined according to ISO 1628-1 and -3 in decaline at 135°C. Eta(GPC) is a viscosity, which is defined GPC (gel chromatography) according to DIN 55672, where instead of the THF used 1,2,4-trichlorobenzene, and the determination is performed at 140°C but not at room temperature. The value of Eta(GPC) and calculated in accordance with the method of publication Arndt/Müller Polymer Charakterisierung, München 1996, Hanser Verlag, ISBN 3-446-17588-1 using equation coefficients Brand-Havinga (Mark-Houwing-equation) (page 147, the equation is 4.93) for polyethylene, equal To= 0,00033 DL/g and α=0,73, which adjusted for 1,2,4-trichlorobenzene at 140°C using a GPC curve M-eta (page 148, equation 4,94, bottom) to obtain the equation of Brand-Havinga (4,9) values the characteristic viscosity [eta] decline with E=0,00062 DL/g and α=0.7 for decalin at 135°C.

In the polyethylene according to the invention the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20,000, preferably has a degree of branching in the range from 0 to 1.5 branches of side chains larger than CH3/1000 ATU is s carbon preferably side chains from C2-C6/1000 carbon atoms. Especially preferably the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20,000, has a degree of branching of from 0.1 to 0.9 of the branches of side chains larger than CH3/1000 carbon atoms, preferably side chains from C2-C6/1000 carbon atoms. Preferably the polyethylene according to the present invention with 1-butene, 1-hexene or 1-octene as the α-olefin portion of the polyethylene with a molecular weight of less than 10000 g/mol, preferably less than 20,000, preferably has a degree of branching in the range from 0 to 1.5 ethyl, Budilnik or exiling branches of side chains per 1000 carbon atoms. Particularly preferably, the part of the polyethylene having a molecular weight of less than 10000 g/mol, preferably less than 20,000, has a degree of branching in the range from 0.1 to 0.9 ethyl, Budilnik or exiling branches of side chains per 1000 carbon atoms. This feature can also be determined using the above-mentioned method of Holtrop/13C-NMR. It shows the content of ethyl, Budilnik or exiling side chains or in whole branches of side chains larger than CH3/1000 carbon atoms without end groups.

In addition, preferably, at least 70% otvetvleniyami circuits larger than CH 3/1000 carbon atoms is present in 50 wt.% polyethylene with the highest molecular weights. It can also be determined using the above-mentioned method of Holtrop/13C-NMR.

The quality of mixing of the polyethylene according to the present invention, determined in accordance with ISO 13949, preferably less than three, especially in the interval from 0 to 2.5. This is the value defined for polyethylene at the exit of the reactor, i.e. for powdered polyethylene without prior melting in the extruder. Such powdered polyethylene may preferably be obtained by polymerization in a single reactor.

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

As 1-alkenes, representing the comonomers which may be present in the ethylene copolymers, alone or in mixture with one another, along with ethylene in the copolymers of ethylene to polyethylene is not according to the invention, you can apply all of 1-alkenes containing from 3 to 12 carbon atoms, e.g. propene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene and 1-mission. Ethylene copolymer preferably comprises 1-alkenes containing from 4 to 8 carbon atoms, for example, 1-butene, 1-penten, 1-hexene, 4-methylpentene or 1-octene, copolymerizable form as comonomers link. Particularly preferably, the application of 1-alkenes selected from the group comprising 1-butene, 1-hexene and 1-octene.

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

Further, it was found that the processing properties of the polyethylenes according to the present invention can be further enhanced by the addition of small amounts of forecasters or thermoplastic polyesters. Such forecaster known as additives that improve the technological t the VA, and are commercially available, e.g. under the trade names Viton® and Dynamar® (see also, for example, US-A-3125547). They are preferably added in quantities of from 10 to 1000 h/million, particularly preferably from 20 to 200 h/million based on the total weight of the polymer mixture according to the invention.

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

The authors of the present invention is provided the use of polyethylene for the production of films and foils, in which the polyethylene according to the present invention is present as a main component.

The film, in which the polyethylene according to the present invention is present as a main component, are films that contain from 50 to 100 wt.%, preferably from 60 to 90 wt.%, polyethylene according to the invention is based on the whole polymer material used for production. In particular, it also includes film, in kataraktis layer contains from 50 to 100 wt.% polyethylene according to the invention.

Usually the film is produced by plasticization of polyethylene according to the invention with a melting point in the range of from 190 to 230°C, forced pass the softened polyethylene through a mouthpiece with a ring nozzle and cooling. The film may optionally include from 0 to 30 wt.%, preferably from 0.1 to 3 wt.% auxiliary components and/or additives known in the art, such as stabilizers, processing stabilizers against the effects of light or high temperatures, conventional additives, for example, improve slip, antioxidants, antiadhesive and antistatics, and also, if appropriate, dyes.

The polyethylene according to the present invention can be applied to obtain films with a thickness in the range from 5 μm to 2.5 mm, for Example, extrusion blow can be obtained film thickness in the range from 5 μm to 250 μm, the film thickness in the range from 10 μm to 2.5 mm can be obtained using a flat-film extrusion process, such as extrusion casting film. During extrusion film blowing machinery melted polyethylene is forced passed through the mouthpiece with a ring nozzle. Thus formed, the sleeve is inflated with air and is pulled at a speed exceeding the speed of its exit from the nozzle. The sleeve is intensively cooled by the flow of air is so, that the temperature of the "frost line" below the melting temperature of the crystallite. At this stage, the fixed dimensions of the sleeve. Then the sleeve destroy (taper), cut if necessary, and rolled, using a suitable winding device. The polyethylene according to the present invention can ekstrudirovaniya "traditional" way or "long sprue". Flat film can be obtained, for example, on the lines of rolling with rapid cooling or line thermoforming films. In addition, a composite film of polyethylene according to the present invention can be obtained on the lines of production of coatings or laminates. Particularly preferred composite films, a complex structure which entered paper, aluminum or fibrous substrates. The film can be single-layer or multi-layer, obtained by joint extrusion, and preferably are single layer.

The polyethylene according to the present invention, for example, is very ideal to obtain films on the apparatus for the production of films with blowing and casting films of high performance. The films exhibit good mechanical properties, high impact strength and high tensile strength combined with very good optical properties, in particular transparency and g is anawim Shine. They are very suitable in particular for use in the manufacture of packaging, for example, heat-sealed films for bags used in heavy mode, and food packaging. In addition, the films show a low tendency to stick together (in a roll) and, therefore, can be used for automatic packaging with a small addition, if necessary, substances which improve the sliding or caking.

Films according to the invention are particularly suitable as tensile films, hygiene films, films for office use, sealing layers, composite and laminating films. Films are particularly suitable for those applications that require transparency and glossy luster, for example, for manufacturers of bags with handles, as it provides an opportunity to obtain a high-quality print, as laminating films for food packaging because of the film according to the invention have a very low odor and taste, and film for automatic packaging, because the film can be processed on high-speed lines.

Matte films according to the invention with a thickness of 50 μm, which is determined in accordance with ASTM D 1003-00 on the device BYK Gardener Haze Guard Plus Device, at least 5 pieces of film 10x10 cm, suppose the equipment is less than 22%, preferably is in the range from 5 to 21% and particularly preferably in the range from 7 to 20%. The impact strength of the film thickness of 50 μm when tested leaning pointed cargo, which is defined by method a ASTM D 1709, is preferably more than 80 g, preferably is in the range from 85 to 400 g, and particularly preferably is in the range from 90 to 350, Transparency film thickness of 50 μm, which is determined in accordance with ASTM D 1746-03 apparatus BYK Gardener Haze Guard Plus Device, calibrated using a calibration device 77,5 at least 5 pieces of film size 10 x 10 cm, preferably is at least 95%, preferably is in the range of from 96 to 100% and particularly preferably is in the range from 97 to 99%. Shine with the reflection of light at an angle of 45°With film thickness of 50 μm, which is determined in accordance with ASTM D 2457-03 on blastomere with the reflection of light at an angle of 45° and a vacuum plate for fixation of a film, at least 5 pieces of film, is preferably at least 46, preferably is in the range from 47 to 80 and particularly preferably is in the range from 49 to 70.

Scrap obtained during the production of such films can be recycled. Crop of films can pressoffice or fragmentation and fed in the auxiliary extruder, where the melt them and then return to the main extruder. Residual film again should be reduced to the size of the grains that can be fed into the feed section of the technological device with a primary polyethylene. Films prepared with the addition of chopped films according to the invention in a single layer, do not show any significant deterioration in properties compared to films without adding crushed films.

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

The applicants of the present invention provided a catalytic system for producing polyethylenes according to the invention and a method of producing polyethylene according to the invention the polymerization of ethylene or copolymerization of ethylene with 1-alkenes, comprising from 3 to 12 carbon atoms in the presence of catalytic systems. The preferred method of producing polyethylene according to the invention the polymerization of ethylene or copolymerization of ethylene with one or more 1-alkenes of the formula R1CH=CH2where R1represents a hydrogen or alkyl radical containing from 1 to 10 carbon atoms, in the presence of the catalyst system at a temperature in the range from 20 to 200°C. and a pressure in the range from 0.5 to 100 bar, equivalent to the pressure in intervallet 0.05 to 1 MPa. 1-Alkenes are, for example, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-penten or 1-octene.

Preferably the ethylene used in the method as the sole monomer or as a mixture, at from 50 wt.% ethylene and 50 wt.% or less 1-alkenes of the formula R1CH=CH2preferably one 1-alkene of the formula R1CH=CH2. Preferably, ethylene is polymerized in a mixture of at least 80 wt.% ethylene and 20 wt.% or less 1-alkenes of the formula R1CH=CH2.

The method according to the invention leads to the production of polyethylene at low concentrations of transition metal and halogen-free due to the high activity of the catalyst. Thus, the polyethylene exhibit high color stability, corrosion resistance and transparency.

The present invention also provides a catalytic composition comprising at least two different polymerization catalyst, of which (A) represents at least one polymerization catalyst based garretsen (a) and (B) represents at least one catalyst polymerizatio-based component of iron, including tridentate ligand that contains at least two aryl radical, each of which contains a halogen or tert-alkyl substituent in the ortho-position (In).

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

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

Especially preferred hipnotizame (A) are complexes of hafnium General formula (I)

where the substituents and indices have the following meanings:

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

E1B-E5Beach represents a carbon atom or one of the E1B- E5Bis an atom of phosphorus or nitrogen, preferably represents a carbon atom,

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

where

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

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

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

Z1Bis a XBor

where the radicals

R9B- R13Beach independently represents hydrogen, C1-C22-alkyl, 5 - to 7-membered cycloalkyl or cycloalkenyl, which may in turn contain C1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl containing from 1 to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR14B2N(SiR14B3)2, OR14B, OSiR14B3, SiR14B3where the organic radicals R9B-R13Bcan also be substituted by Halogens and/or two radicals of R9B-R13Bin particular vicinal the f radicals, can also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R9B-R13Bcan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms of N, P, O and S, where

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

each of the E6B-E10Brepresents a carbon atom or one of the E6B-E10Brepresents a phosphorus atom or a nitrogen atom, and preferably represents a carbon atom,

or where the radicals R4Band Z1Btogether form-R15B-A1Bgroup

where

R15Brepresents a

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

where

R16B-R21Bare the same or different and each represents a hydrogen atom, halogen atom, trimethylsilyloxy group, C1-C10is an alkyl group, a C1-C10-alkyl fluoride group, a C6-C10-porarily group, C6-C10-aryl group, a C1-C10and Consilina group, C7-C15-alkylresorcinol group, C2-C10-alkenylphenol group, C7-C40-arylalkyl group, C8-C40-arylalkyl group or a C7-C40-alcylaryl group, or two adjacent radicals together with the atoms connecting them form a saturated or unsaturated cycle containing from 4 to 15 carbon atoms,

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

A1Brepresents-O-, -S-,

-NR22B2, -PR22B2or unsubstituted, substituted or condensed heterocyclic system, where

the radicals R22Beach independently represents a C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, C7-C18-alkylaryl or Si(R23B)3,

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

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

or where the radicals R4Band R12Btogether form-R15Bgroup.

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

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

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

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

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

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

Among guarracino General formula (I) preferred are the compounds of formula (II)

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

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

t is 1 or 2, preferably 2,

each of R1B-R5Brepresents hydrogen, C1-C8-alkyl, C6-C8-aryl, NR8B2, OSiR8B3or Si(R8B)3and

each of R9B-R13Brepresents hydrogen, C1-C8-alkyl or C6-C8-aryl, NR14B2, OSiR14B3or Si(R14B)3

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

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

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

dichloride, bis(cyclopentadienyl)hafnium, dichloride, bis(indenyl)hafnium, dichloro the d bis(fluorenyl)hafnium, dichloride, bis(tetrahydroindene)hafnium, dichloride, bis(pentamethylcyclopentadienyl)hafnium, dichloride, bis(trimethylsilylethynyl)hafnium, dichloride, bis(trimethoxysilylmethyl)hafnium, dichloride, bis(ethylcyclopentadienyl)hafnium, dichloride, bis(isobutyrylacetate)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, 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 appropriate connections dimethylamine.

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

Suitable ka is listorama B) are complexes of transition metals, at least one ligand of the General formula (III)

where the variables have the following meanings:

E1Crepresents a nitrogen atom or phosphorus, in particular nitrogen,

E2C-E4Ceach independently represents a carbon atom, nitrogen or phosphorus, in particular carbon,

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

R4C-R7Ceach independently represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C , SiR19C3where the organic radicals R4C-R7Ccan also be substituted by Halogens and/or two pairs or vicinal radicals of R4C-R7Ccan also be connected with the formation of five-, six-or semichasnoho cycle, and/or two pairs or vicinal radicals of R4C-R9Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom selected from the group comprising atoms of N, P, O and S, and when v is 0, R6Crepresents the relationship with L1Cand/or R7Crepresents the relationship with L2Cso that L1Cforms a double bond with the carbon atom that is attached to R4Cand/or L2Cforms a double bond with the carbon atom that is attached to R5C,

u is 0 when E2C-E4Crepresents a nitrogen atom or a phosphorus atom, and is 1 when E2C-E4Crepresents a carbon atom,

L1C-L2Ceach independently represents a nitrogen atom or a phosphorus atom, in particular nitrogen,

R8C-R11Ceach independently represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C , SiR19C3where the organic radicals R8C-R11Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of five-, six-or semichasnoho cycle and/or two vicinal radicals of R8C-R17Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom from the group comprising atoms of N, P, O and S, provided that at least R8Cand R10Crepresents a halogen or tert-C1-C22is an alkyl group,

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

the indices v, each independently, PR is astavliaut a 0 or 1,

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

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

the radicals R19Ceach independently represents hydrogen, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R19Ccan also be substituted by Halogens or nitrogen - and coloreds is holding groups and two radicals R 19Ccan also be connected with the formation of five - or six-membered cycle,

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

D represents an electrically neutral donor and

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

Three atoms of E2C- E4Cin the molecule may be the same or different. If E1Crepresents a phosphorus atom, then each of the E2C-E4Cpreferably represents a carbon atom. If E1Crepresents a nitrogen atom, then each of the E2C-E4Cpreferably represents a nitrogen atom or carbon, in particular carbon.

The substituents R1C-R3Cand R8C-R17Ccan vary within wide limits. Possible operatingincome substituents R1C-R3Cand R8C-R17Care, for example, the following: C1-C22-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as substituents, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or CEC shall dodecyl, C2-C22alkenyl, which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example, phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R1C- R3Cand/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle and/or two vicinal radicals of R1C-R3Cand/or two vicinal radicals of R8C-R17Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms of N, P, O and S, and/or the organic radicals R1C-R3Cand/or R8C-R17Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R1C-R3Cand R8C-R17Ccan also be an amino group NR18C2and the and N(SiR 19C3)2, alkoxy or aryloxy group OR18Cfor example dimethylamino, N-pyrrolidinyl, picoline, methoxy, ethoxy or isopropoxy or halogen, such as fluorine, chlorine or bromine. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals, which have been described above for R1C-R3Cwhere two R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example, trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These SiR19C3radicals can also join the E2C-E4Cthrough an oxygen atom or nitrogen, and represent, for example, trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylsilane.

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

Preferred radicals R12C-R17Care hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen. In particular, R13Cand R16Ceach represents a methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine or bromine, and R12C, R14C, R15Cand R17Ceach represents hydrogen.

Preferred radicals R8C-R11Care hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine. In particular, R8Cand R10Ceach preferably a halogen, such as fluorine, chlorine or bromine, especially chlorine, and R9Cand R11Ceach represents C1-C22-alkyl, which can also be substituted by Halogens, in particular C1-C22-n-alkyl, which can also be substituted by Halogens, such as methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen, such as fluorine, chlorine or bromine. In another preferred combination of R8C and R 10Crepresent tert-C1-C22is an alkyl radical, in particular tert-butyl, and R9Cand R11Ceach represents hydrogen or halogen, such as fluorine, chlorine or bromine.

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

The substituents R4C-R7Ccan also vary within wide limits. Possible operatingincome substituents R4C-R7Care, for example, the following: C1-C22-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as substituent, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example, phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl where arylalkyl can be substituted for more alkyl groups, and represent, for example, benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl where two radicals of R4C-R7Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle and/or two pairs radical of R4C-R7Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms of N, P, O and S, and/or the organic radicals R4C-R7Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R4C-R7Cmay be an amino group of the formula NR18C2or N(SiR19C3)2for example dimethylamino, N-pyrrolidinyl or picolinic. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals described above for R1C-R3Cwhere two R19Ccan also be connected by the research 5 - or 6-membered cycle, for example, trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These radicals SiR19C3can also join in carrying them to the carbon atom through the nitrogen atom. When v is 0, R6Crepresents the relationship with L1Cand/or R7Crepresents the relationship with L2Cso L1Cforms a double bond with the carbon atom that is attached to R4Cand/or L2Cforms a double bond with the carbon atom that is attached to R5C.

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

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

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

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

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

D represents an electrically neutral donor, in particular electrically neutral Lewis base or Lewis acid, such as amines, alcohols, ethers, ketones, aldehydes, esters, sulfides or phosphines which can be connected to the Central iron atom or present as solvent remaining after obtaining complexes of iron.

The number t of ligands D may be on the 0 to 4 and often depends on the solvent, which had received the iron complex, and the time during which dried the resulting complexes, and therefore it can be represented by a non-integer number, such as 0.5 or 1.5. In particular, t is 0, 1 and 2.

In a preferred embodiment, the complexes of (B) correspond to formula (IV)

where

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

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

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

u is 0 when E2C-E4Crepresents a nitrogen atom or phosphorus and is 1 when E2C-E4Crepresents a carbon atom,

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

R8C-R11Ceach independently represents a C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R8C-R11Ccan also be substituted by Halogens and/or two vicinal radicals R8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R8C-R17Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom from the group comprising atoms of N, P, O and S, provided that at least R8Cand R10Crepresents a halogen or tert-C1-C22is an alkyl group,

R12C-R17Ceach independently represent hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R12C-R17Ccan also be substituted by Halogens and/or two vicinal radicals 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 comprising atoms of N, P, O or S,

the indices v, each independently, represent 0 or 1,

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

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

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

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

D represents an electrically neutral donor and

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

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

The substituents R4C-R5Ccan vary in a wide area. Possible operatingincome substituents R4C-R are, for example, the following: hydrogen, C1-C22-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, can contain C1-C10is an alkyl group and/or C6-C10-aryl group as substituent, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example, phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where the organic radicals R4C-R5Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R4C-R5C can be an amino group NR18C2or N(SiR19C3)2for example, dimethylamino, N-pyrrolidinyl or picolinic. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals described above for R1C-R3Cwhere two radicals R19Ccan also be connected with the formation of 5 - or 6-membered cycle, for example, trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. Such SiR19C3radicals can join the carbon atom on which they are located, through the nitrogen atom.

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

The substituents R8C-R17Ccan vary in a wide area. Possible operatingincome substituents R8C-R17Care, for example, the following: C1-C22-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5-7-membered cycloalkyl, which, in turn, may contain the substance, C 1-C10is an alkyl group and/or C6-C10-aryl group as substituent, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, C2-C22alkenyl, which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted for more alkyl groups, for example, phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, or arylalkyl, which can be substituted for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two radicals of R8C- R17Ccan also be connected with the formation of 5-, 6 - or 7-membered cycle and/or two vicinal radicals of R8C-R17Ccan be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms of N, P, O and S, and/or the organic radicals R8C-R17Ccan also be substituted by Halogens such as fluorine, chlorine or bromine. In addition, R8C-R17Ccould the t to represent halogen, such as fluorine, chlorine, bromine, amino group NR18C2or N(SiR19C3)2, alkoxy or aryloxy OR18Cfor example dimethylamino, N-pyrrolidinyl, picoline, methoxy, ethoxy or isopropoxy. Possible radicals R19Cin organosilicon substituents SiR19C3are uglerodosoderzhaschie radicals, which have been indicated above for R1C-R3Cwhere two 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 SiR19C3can also join via an oxygen atom or nitrogen, and represent, for example, trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylsilane.

Preferred radicals R12C-R17Care hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen. In particular, R13Cand R16Ceach represents a methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, f the Nile, fluorine, chlorine or bromine, and R12C, R14C, R15Cand R17Ceach represents hydrogen.

Preferred radicals R8C-R11Care hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine. In particular, R8Cand R10Ceach preferably represents halogen, such as fluorine, chlorine or bromine, especially chlorine, and R9Cand R11Ceach represents a n-C1-C22-alkyl, which can also be substituted by Halogens, for example, methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen, such as fluorine, chlorine or bromine. In another preferred combination of R8Cand R10represent tertiary1-C22is an alkyl radical, in particular, tert-butyl, and R9Cand R11Ceach represents hydrogen or halogen, such as fluorine, chlorine or bromine.

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

Obtaining the compounds (B) are described, for example, J Am. Chem.-Soc. 120, p. 4049 ff. (1998), J. Chem. Soc., Chem. Commun. 1998, 849, and in WO 98/27124. Preferred complexes (B) are dichloride, 2,6-bis[1-(2-tert-butylaniline)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2-tert-butyl-6-chlorpheniramine)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2-chloro-6-methyl-phenylimino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,4-dichlorophenylamino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,6-dichlorophenylamino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,4-dichlorophenylamino)methyl]peridiniales(II)dichloride, 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,4-diftorhinolonom)ethyl]peridiniales(II)dichloride, 2,6-bis[1-(2,4-dibromopyridine)ethyl]peridiniales(II) or a corresponding trichloride, dibromide or tribromide.

Further, the reference to the complex of the transition metal (A) or catalyst (A) means garretsen (A). The molar ratio of the complex transition metal (A) to the polymerization catalyst (B) is usually in the range from 1:100 to 100:1, preferably in the range from 1:10 to 10:1 and particularly preferably in the range from 1:1 to 5:1. When the complex of the transition metal (A) is used as the sole catalyst in the same reaction conditions of homopolymerization or copolymerization is preferably results in a higher Mwthan in the application of complex (B) as the sole whom the Lex in the same reaction conditions. Preferred variants of the complexes (A) and (B) are also preferred in the combination of these two complexes.

The catalytic composition according to the invention can be used by itself or together with additional components as catalytic systems for polymerization of olefins. In addition, the applicants of the present invention offers the catalytic system polymerization of olefins, including

A) at least one polymerization catalyst based garretsen (A)

C) at least one polymerization catalyst based on iron component containing tridentate ligand which comprises at least two aryl radical, each of which contains a halogen or tert-alkyl substituent in the ortho-position,

C) optionally one or more activating compounds,

D) optionally one or more organic or inorganic carriers,

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

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

The activator or activators (C) can in each case be used in any amount is based on the complexes (A) and (B) a catalytic composition according to the invention. Preferably they are used in excess or in stoichiometric amounts, in each case based on the complex (A) or (B)that they activate. The number of trigger(s) connection(s)intended for use depends on the type of activator (C). Usually the molar ratio of the complex transition metal (A) to the activating compound (C) may be in the range from 1:0.1 to 1:10000, preferably from 1:1 to 1:2000. The molar ratio of the iron complex (B) activating the compound (C) is also usually náchod is conducted 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) to turn it into a catalytically active or more catalytically active compound are, for example, such compounds as alumoxane, strong electrically neutral Lewis acid, an ionic compound containing a cation of a Lewis acid or anionic compound containing the acid Bronsted as cation.

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

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

Especially applicable alumoxanes connection is methylalumoxane.

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

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

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

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

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

M2DX1DX2DX3D(XII),

where

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 of which contains from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or fluorine, chlorine, bromine or iodine, in particular galogenidy, preferred is entrusted pentafluorophenyl.

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

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

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

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

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

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

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

where

M3Dis an element 1 - 16 groups of the Periodic table of elements

QA-Qsub> zare simply negatively charged radicals, such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, halogenated, halogenared, each of which contains from 6 to 20 carbon atoms in the aryl part and from 1 to 28 carbon atoms in the alkyl part, C3-C10-cycloalkyl, which may contain C1-C10-alkyl groups as substituents, halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptal,

a represents an integer of 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.

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

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

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

Compounds containing anionic boron heterocycles, which are described in the publication WO 97/36937, are also suitable as component (C), in particular, bratabandha dimethylaniline (dimethylanilinium boratabenzenes) or trietilborazina (trityl boratabenzenes).

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

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

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

The number of strong electroneutral of Lewis acids, ionic compounds containing cations of Lewis acids or ionic compounds containing acid Bronsted as cations is preferably from 0.1 to 20 equivalents, more preferably from 1 to 10 equivalents, and particularly preferably from 1 to 2 equivalents based on the complex of the transition metal (A) or the iron complex (B).

Suitable activating compounds(C) include boron-aluminievye compounds such as di[bis(pentafluorobenzylbromide)]matellan (di[bis(penta-fluorophenylboroxy)]methylalane). Examples of such bioluminogenic compounds described in the publication WO 99/06414.

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

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

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

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

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

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

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

The person is but the preferred catalytic system, comprising at least one complex of a transition metal (A)at least one iron complex (B)at least one activating compound (C) and at least one component carrier (D).

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

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

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

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

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

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

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

Applied materials carrier preferably have a specific surface area in the range from 10 to 1000 m2/g, pore volume in the range from 0.1 to 5 ml/g and average particle size in the range from 1 to 500 μm. Preferred carriers 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 which intervale from 5 to 350 μm. Particularly preferred carriers with a specific surface area in the range from 200 to 550 m2/g, pore volume in the range from 0.5 to 3.0 ml/g and an average particle size in the range from 10 to 150 microns.

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

The inorganic carrier may be subjected to heat treatment, for example to remove the absorbed water. Such processing for drying is usually conducted at temperatures in the range from 50 to 1000°C, preferably from 100 to 600°C, and drying at temperatures in the range from 100 to 200°C, preferably at reduced pressure and/or inert gas (e.g. nitrogen), or inorganic carrier may be subjected to calcination at temperatures in the range from 200 to 1000°C for the floor is placed the desired structure of solids and/or achieve the desired OH concentration on the surface. The media may also be treated chemically using conventional driers such as alkali metals, preferably of Akilov aluminum, CHLOROSILANES or SiCl4or methylalumoxane. Suitable processing methods are described, for example, in WO 00/31090.

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

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

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

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

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

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

Mg6Al2(OH)16CO3·4H2O,

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

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

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

which have a sheet structure and in which M(II) represents the t of 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 in the range of 0.5 to 10 in increments of 0.5, A is an embedded anion, n represents the charge introduced anion, which can take values in the interval from 1 to 8, usually from 1 to 4, and z is an integer in the range from 1 to 6, especially from 2 to 4. Possible embedded anions are organic anions such as alkoxide anions, sulphate simple alilovic esters, sulfates simple arolovich esters or sulfates simple glycol ethers, inorganic anions such as, in particular, carbonate, bicarbonate, nitrate, chloride, sulfate or B(OH)4-or anions polyoxides metals, such as Mo7O246-or V10O286-. However, you can also use many of these anions.

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

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

When heated, the natural or synthetic hydrotalcite first is the removal of water, i.e. drying. Upon further heating, full annealing, the metal hydroxides are converted to metal oxides in the removal of hydroxyl groups and internal anions; OH group or internal anions, such as carbonate, may still be present in calcinatory hydrotalcite. Measure the calcination is the loss on ignition. It represents the mass loss occurred in the sample, which was subjected to two-stage heat - first for 30 minutes at 200°C in a drying oven and then for 1 hour at 950°C in a muffle furnace.

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

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

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

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

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

MG(R1G)rG(R2G)sG(R3G)tG (XX),

where

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

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

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

rGis an integer from 1 to 3

and

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

where component (E) is usually not identical to the component (C). You can also use mixtures of different compounds which deposits of metals of the formula (XX).

Among the metal compounds of General formula (XX) are preferred compounds in which

MGrepresents 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, especially n-butyl-n-octylamine, tri-n-hexylamine, triisobutylaluminum, tri-n-butylamine, triethylamine, dimethylammoniumchloride, dimethylaminophenyl, methylaluminoxane, methylaluminoxane, diethylaluminium and trimethylaluminum and mixtures thereof. Can also be applied to the products of partial hydrolysis of Akilov aluminum with alcohols.

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

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

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

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

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

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

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

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

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

To obtain a polyethylene according to the invention ethylene is subjected to polymerization, as described above, with α-olefins containing from 3 to 10 carbon atoms.

In the method of copolymerization according to the invention ethylene is subjected to polymerization with α-olefins containing from 3 to 12 carbon atoms. Preferred α-olefins are linear or branched C2-C10-1-alkenes, in particular linear C2-C8-1-alkenes, such as Eten, propene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene, or branched C2-C10-1-alkenes such as 4-methyl-1-penten. Particularly preferred α-olefins are C4-C10-1-alkenes, in particular linear C6-C10-1-alkenes. You can also polymerizate mixture of different α-olefins. Preferably will polimerizuet at least one α-olefin, you the early group, including Aten, propene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene and 1-mission. Preferably the use of mixtures of monomers containing at least 50 mol.% Athena.

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

Polymerization is usually conducted at temperatures in the range from -60 to 350°C, preferably in the range from 20 to 300°C and pressures in the range is from 0.5 to 4000 bar. The average values of the residence time of the feedstock in the reactor is typically in the range from 0.5 to 5 hours, preferably from 0.5 to 3 hours. Preferred pressure range and temperature for carrying out the polymerization is usually dependent on the method of polymerization. In the case of polymerization at high pressure process pressure in the range from 1000 to 4000 bar, in particular in the range from 2000 to 3500 bar, it also supports high temperature polymerization. Preferred temperature ranges for methods of polymerization at high pressures comprise a temperature from 200 to 320°C, in particular from 220 to 290°C. In the case of methods of polymerization at low pressure is normally maintained temperature that at least a few degrees below the softening temperature of the polymer. In particular, these methods of polymerization are set temperature in the range from 50 to 180°C, preferably from 70 to 120°C. In the case of application of the method of suspension polymerization, the polymerization is usually carried out in a suspension medium, preferably in an inert hydrocarbon, such as isobutane, or mixtures of hydrocarbons, as well as among monomers. The polymerization temperature is usually in the range from -20 to 115°C, and the pressure is usually in the range from 1 to 100 bar. The content of solids in which spezie is usually in the range from 10 to 80%. The polymerization can be conducted either periodic manner, for example, under stirring autoclaves or continuous manner, for example, in a tubular reactor, preferably the reactor with circulation. Particularly preferred application of the method of Phillips PF, which is described in the publication US-A 3242150 and US-A 3248179. Gas-phase polymerization is usually carried out at temperatures in the range from 30 to 125°C and pressures in the range from 1 to 50 bar.

Among the above-mentioned methods of polymerization are particularly preferred gas-phase polymerization, in particular in gas-phase fluidized bed reactor catalyst, polymerization in solution and suspension polymerization, in particular in the reactor circulation and capacitive reactors with agitators. Gas-phase polymerization can also be carried out in the condensed or overcondensation mode, in which part of the circulating gas is cooled to a temperature below the dew point and is returned as a two-phase mixture in the reactor. In addition, it is possible to apply multi-zone reactor, in which two zones polymerization is connected, and the polymer is passed through these two zones several times. Two zones can also vary the conditions of polymerization. Such a reactor is described, for example, in WO 97/04015. Different or identical methods of polymerization may also need coodinates is consistent with the formation of a polymerization cascade, for example, as in the way Hostalen®. It is also possible parallel arrangement when using two or more identical or different methods of polymerization. In addition, the polymerization can also be applied molecular weight regulators, for example hydrogen, or conventional additives such as antistatics. Hydrogen is specially used to improve the activity of garretsen (A). Hydrogen and fever usually result in a lower z-average molecular weight.

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

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

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

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

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

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

The content of the vinyl groups was determined by IR in accordance with ASTM D 6248-98. Number of branches/1000 carbon atoms was determined by using13C-NMR in accordance with the method described in the publication of James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and based on the total content of group CH3/1000 carbon atoms, including end groups. The number of side chains longer than CH3and , in particular, ethyl, Budilnik and exiling side branches/1000 carbon atoms, including end groups, are also determined by this method.

The branching of the individual polymer fractions were determined by the method of Holtrop (W. Holtrup, Makromol. Chem. 178, 2335 (1977)) in combination with13C-NMR.

Determination of molecular mass distributions, mean values of Mn, Mw, Mzand their derived values of Mw/Mnconduct high-temperature gel chromatography apparatus WATERS 150 C using a method based on DIN 55672, using series-connected columns: 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, volume of 500 ál injection temperature 140oC. Calibration is performed using PE standards with molecular masses of from 100 to 107g/the ol. The calculation is performed using WIN-GPC Fa. HS-Entwicklungsgesellschaft für wissenschaftliche Hard - und Software mbH, Ober-Hilbersheim.

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

Matte is determined in accordance with ASTM D 1003-00 on the device BYK Gardener Haze Guard Plus Device using at least 5 pieces of film of size 10x10 cm and a thickness of 50 μm. The impact strength of the film thickness of 50 μm define test incident pointed cargo in accordance with method A of ASTM D 1709. The transparency of the film is determined in accordance with ASTM D 1746-03 apparatus BYK Gardener Haze Guard Plus Device, calibrated using a calibration device 77,5 at least 5 pieces of film size 10 x 10 cm and a thickness of 50 μm. Shine with the reflection of light at an angle of 45°With determined according to ASTM D 2457-03 on blastomere with the reflection of light at an angle of 45° and a vacuum plate for fixation of a film, using at least 5 pieces of film thickness of 50 microns.

Abbreviations in the tables below:

Cat.Catalyst
TPolym)The temperature of polymerization
MwSrednevekovaja molecular weight
MnSrednekislye molecular weight
Mzthe z-Average molecular weight
Tight.The density of the polymer
Production.The performance of the catalyst in g of polymer obtained in g of used catalyst per hour
Just CH3The number of CH3 groups at 1000C, including end groups
-HC=CH2The number of vinyl groups
>C=CH2The number vinylidene groups
GPC % at 1 mm Mio.wt.%. according to GPC molecular weight less than 1 Mio. g/mol.

Getting separate components

2,6-Bis[1-(2-tert-butylaniline)ethyl]pyridine receive in accordance with example 6 publication WO 98/27124, dichloride, 2,6-bis[1-(2-tert-butylaniline)ethyl]peridiniales(II) receive, in accordance with the method of example 15 publication WO 98/27124.

2,6-bis[1-(2,4,6-trimethylaniline)ethyl]pyridine get in according to the according to the method of example 1 publication WO 98/27124 and similarly subjected to interaction with chloride of iron (II) obtaining dichloride 2,6-bis[1-(2,4,6-trimethylaniline)ethyl]peridiniales(II), as described in WO 98/27124.

Dichloride, 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II) receive, in accordance with the method described in Qian et al., Organometallics 2003, 22, 4312-4321.

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 (4 Å) was stirred in 1500 ml of toluene at 80°C for 5 hours, then add 32 g of silica gel type 135 and 160 g of molecular sieves (4 Å). The mixture is stirred at 80°C for an additional 8 hours, the insoluble solid precipitate is filtered off and washed twice with toluene. The solvent is distilled off from the filtrate thus obtained, the residue is mixed with 200 ml of methanol and successively stirred at 55°C for 1 hour. Thus obtained suspension is filtered and the obtained solid product is washed with methanol and removing the solvent. The result is 95 g of 2,6-bis[1-(2,4,6-trimethylaniline)ethyl]pyridine to yield 47%. Interaction with iron chloride (II) is carried out in accordance with the method of publication Qian et al., Organometallics 2003, 22, 43,12-4321.

Getting mixed catalytic systems

Example 1

a) Pre-processing of the media

Silica XPO 2107, dried by spray drying, Grace, calcined at 600°C for 6 hours, after which 252,2 g of dried silica gel is mixed with 164,5 ml MAO (OF 4.75 M in toluene,0.78 mol). The mixture is stirred for one hour, filtered, the solids washed with toluene and then dried under reduced pressure.

b) obtaining a mixed catalyst systems

A mixture of 1.48 g (2.45 mmol) of dichloride of 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]peridiniales(II), 3,61 g (7,34 mmol) dichloride bis(n-butylcyclopentadienyl)hafnium and 159,6 ml MAO (OF 4.75 M in toluene, from 0.76 mol) was stirred at room temperature for 1 hour and, while continuing the stirring, is added to the suspension 237,1 g of pre-treated material of the carrier (a) in 800 ml of toluene. The mixture is stirred at room temperature for additional 3 hours, the resulting solid product is filtered and washed with toluene. The solid product is dried under reduced pressure to a fluid state. Get 256,7 g of catalyst.

Example 2

a) Pre-processing of the media.

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

b) obtaining a combined catalytic systems

A mixture of 5.35 g (RS 9.69 mmol) dichloride 2,6-bis[1-(2-tert-butylaniline)ethyl]peridiniales(II), 7,49 g (15,22 mol) dichloride bis(n-butylcyclopentadienyl)hafnium and 472 ml MAO (OF 4.75 M in toluene, of 2.24 mol) was stirred at room temperature for 30 minutes and then was added with stirring to a suspension 276,8 g pretreated is the material of the carrier within 45 minutes ((Fe+Hf):Al=1:90). The solid product is dried under reduced pressure to a fluid state. Receive 609 g of the catalyst, which still contain 31.5 wt.% solvent (based on the total weight, calculated taking into account the full application of all components on the carrier).

Example 3

A) Pre-processing of the media

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

b) obtaining a mixed catalyst systems

A mixture of 1.6 g (2.89 mmol) of dichloride of 2,6-bis[1-(2-tert-butylaniline)ethyl]peridiniales(II)of 2.05 g (3,71 mmol) dichloride bis(n-butylcyclopentadienyl)hafnium and 194,5 ml MAO (OF 4.75 M in toluene, 0,924 mmol) was stirred at room temperature for 15 minutes and then added with stirring to the suspension with 95.5 g of the pretreated material carrier a) ((Fe+Hf):Al=1:140). After 2 hours the suspension is filtered and washed with 500 ml of toluene. The obtained solid product is dried under reduced pressure to obtain a flowable powder. The catalyst still contains of 25.2 wt.% solvent (based on the total weight, calculated taking into account the full application of all components on the carrier).

Comparative example C1

a) Pre-processing of the media

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

b) obtaining a mixed catalyst from the system

A mixture of 0.99 g (1,755 mmol) dichloride 2,6-bis[1-(2,4,6-trichloranisole)ethyl]peridiniales (II)of 3.69 g (7.5 mmol) dichloride bis(n-butylcyclopentadienyl)hafnium and 203,8 ml MAO (OF 4.75 M in toluene, 0,968 mol) was stirred at room temperature for one hour and then, while continuing the stirring, is added to a suspension of 125 g of the pretreated material carrier a) ((Fe+Hf):Al=1:105). The mixture is stirred for additional 2 hours, then the solvent is removed under reduced pressure and the solid product is dried under reduced pressure to a fluid state. The resulting catalyst contains 38,9 wt.% solvent (based on the total weight, calculated taking into account the full application of all components on the carrier).

Comparative example C2

A) Pre-processing of the media

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

b) obtaining a mixed catalyst systems

A mixture of 5.6 g (is 11.39 mmol) dichloride bis(n-butylcyclopentadienyl)hafnium and 297 ml of MAO (OF 4.75 M in toluene, of 1.41 mol) was stirred at room temperature for one hour and then, while continuing the stirring, add to 228 g of the pretreated material carrier as) (Hf:Al-1:120). The mixture is stirred for additional 20 minutes and dried under reduced pressure to a fluid state. Received catalysis is the PR contains 33.3% solvent based on the total weight taking into account the full application of all components on the carrier). Get 460 g of a fluid catalyst.

Polymerization catalysts

The polymerization is carried out in a reactor with a fluidized bed with a diameter of 0.5 M. the reaction Temperature, performance and composition of the gas in the reactor are shown in table 1, the reactor pressure is 20 bars. In each case, the dose of 0.1 g of triisobutylaluminum per hour. As catalysts using the catalysts obtained in the examples described above. Properties of the obtained polymers are shown in table 2.

Table 1
The results of polymerization
Cat. from approx.T(poly)
[°C]
Production.
[kg/h]
Ethylene
[kg/h]
1-Hexene
[g/h]
H2
[l/h]
1
2
3
C1
C2
105
94
100
94
100
3,2
3,8
3,1
4,4
4,8
4
5
3,4
5,2
of 5.4
52
100
85
147
136
1,47
0,57
0,67
4,15
4.09 to

Table 2
Cat. example123C1C2
Density [g/cm3]0,94340,94390,9380,94130,935
Etaviz/EtaGPC0,8950,8850,8950,988Do not use
Mw[g/mol]141769126115161781240628151049
Mw/Mn8,1213,23to 12.449,073,7
Mz3966963801774859411339939279249
GPC % at 1 mm Mio.99,39299,52998,948 95,40699,896
-HC=CH2 [1/1000C]0,751,911,20,340,07
>C=CH2 [1/1000C]0,15,0,20,20,170,09
Just CH3 [1/1000C]4,36,56,45a 4.9
Butilka [1/1000C]to 2.673,834,674,172,7
HLMI [g/10 min]2243161125

Obtained polymers homogenized and granularit on a ZSK 30 by set screws 8A. Temperature processing 220°C., screw rotation speed of 250 rpm, the maximum throughput of 20 kg/hour. For the stabilization of polymers add 1500 h/million Irganox B215.

The polymer ekstragiruyut in film extrusion blown on the extruder Weber, where the nom device collapse of the bubble with a flat wooden plates.

Ring diameter of the mouthpiece is 50 mm, the width of the gap 2/50 and the angle at which the cooling air is blown on the extruded film is 45°. Filters are not used. Use the extruder 25D with a screw diameter of 30 mm and a speed of rotation of the auger 50./min, which is equivalent to the performance of 5.1 kg/hour. The blowing ratio is 1:2, the speed of removal of the extruder is 4.9 m/10 min. Elevation pour point equal to 160 mm. Receive a film thickness of 50 μm. Technology, optical and mechanical properties of films presented in table 3.

Table 3
Technology, optical and mechanical properties of films
The film of when.123C1C2
So plvl. [°C]240225230241228
Haze [%]13,9to 19.910to 75.222,7
Transparency [%]98,8to 97.19913,994,6
The gloss 45°60,449,6Not ODA.745
DDI (g)124162330<60Not ODA.

1. Polyethylene, which is formed by copolymers of ethylene with 1-alkenes and has a width of molecular weight distribution Mw/Mn in the range from 5 to 30, a density in the range from 0.92 to 0,955 g/cm3, srednevekovoy molecular weight Mw in the range of from 50000 g/mol to 500,000 g/mol, contains from 0.01 to 20 branches/1000 carbon atoms and z-average molecular weight is less than 1 Mio g/mol, where 5-50 wt.% polyethylene with the lowest molecular masses has a degree of branching less than 12 branches/1000 carbon atoms, and 5-50 wt.% polyethylene with the highest molecular masses has a degree of branching of more than 1 branch/1000 carbon atoms.

2. The polyethylene according to claim 1, which has a bimodal molecular weight distribution is.

3. The polyethylene according to claim 1 or 2, in which the value of Eta(vis)/Eta(GPC) is less than 0.95, where Eta(vis) is a characteristic viscosity, which is determined according to ISO 1628-1 and -3, and Eta(GPC) is a viscosity, which is defined GPC (gel chromatography) according to DIN 55672 using 1,2,4-trichlorobenzene at 140°C.

4. The polyethylene according to claim 1 or 2, where the number of polyethylene according to the invention with a molecular mass below 1 Mio g/mol as determined by GPC, is preferably more than the 95.5 wt.%.

5. The polyethylene according to claim 3, where the number of polyethylene according to the invention with a molecular mass below 1 Mio g/mol as determined by GPC, is preferably more than the 95.5 wt.%.

6. The polyethylene according to any one of claims 1, 2 or 5, which is obtained in a single reactor.

7. The polyethylene according to claim 3, which is obtained in a single reactor.

8. The polyethylene according to claim 4, which is obtained in a single reactor.

9. A method of producing copolymers of ethylene according to any one of claims 1 to 8, wherein the ethylene is polymerized optionally in the presence of 1-alkenes containing from 3 to 12 carbon atoms, in the presence of a catalytic system, which includes a catalytic composition comprising at least two different polymerization catalyst, of which (A) represents at least one polymerization catalyst based on garrote is a (A), those having the formula :
,
in which 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,
each of R1B-R5Brepresents hydrogen, C1-C8-alkyl, C6-C8-aryl, NR8B2, OSiR8B3or Si(R8b)3and
each of R9B-R13Brepresents hydrogen, C1-C8-alkyl or C6-C8-aryl,
NR14B2, OSiR14B3or Si(R14V)3
or in each case two radicals of R1B-R5Band/or R9B-R13Btogether with C5cycle form indenyl, fluorenyl or substituted indenolol or fluorenyl system;
B) represents at least one polymerization catalyst based on iron component containing at least one ligand of General formula (III)

where
E1Crepresents a nitrogen atom or phosphorus, in particular nitrogen,
E2C-E4Ceach independently represents a carbon atom, nitrogen or phosphorus, in particular carbon,
R1C-R3C,each independently represents hydrogen, C1-C22-alkyl,
With2-C22and canil, With6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C,
SiR19C3where the organic radicals R1C-R3Ccan also be substituted by Halogens and/or two vicinal radicals of R1C-R3Ccan also be connected with the formation of five-, six - or semichasnoho cycle and/or two vicinal radicals of R1C-R3Ctogether with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms N, P, O and S,
R4C-R7Ceach independently represents hydrogen, C1-C22-alkyl,
With2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, SiR19C3where the organic radicals R4C-R7Ccan also be substituted by Halogens and/or two genialnyh or vicinal radicals of R4C-R7Ccan also be connected with the formation of five-, six-or semichasnoho cycle, and/or two genialnyh or vicinal radicals of R4C-R9Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom, in the last of the group, including the atoms N, P, O and S, and when v is 0, R6Crepresents the relationship with L1Cand/or R7Crepresents the relationship with L2Cso L1Cforms a double bond with the carbon atom that is attached to R4Cand/or L2Cforms a double bond with the carbon atom that is attached to R5C,
u is 0 when E2C-E4Srepresents a nitrogen atom or a phosphorus atom,
and is equal to 1 when E2C-E4Srepresents a carbon atom,
L1C-L2Ceach independently represents a nitrogen atom or a phosphorus atom, in particular nitrogen,
R8C-R11Ceach independently represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C,
SiR19C3where the organic radicals R8C-R11Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms N, P, and S, provided that at least R8Cand R10Crepresent halogen or tert-C1-C22is an alkyl group,
R12C-R17Ceach independently represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C,
SiR19C3where the organic radicals R12C-R17Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of five-, six-or semichasnoho cycle, and/or two vicinal radicals of R8C-R17C
connected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom from the group comprising atoms N, P, O and S,
the indices v, each independently represents 0 or 1,
the radicals XCeach independently represents a fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl,6-C20-aryl, arylaryl containing 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, OR18C, SR18CSO3R18C, OC(O)R18C, CN, SCN, β-diketonate, CO, BF4-PF6-or the lines gecoordineerde anion, the radicals XCcan be connected to each other,
the radicals R18Ceach independently represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3where the organic radicals R18Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R18Ccan also be connected with the formation of five - or six-membered cycle,
the radicals R19Ceach independently represents hydrogen, C1-C20-alkyl,
With2-C20alkenyl,6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R19Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - or six-membered cycle,
s is 1, 2, 3 or 4, in particular 2 or 3,
D represents an electrically neutral donor and
t is an integer from 0 to 4, in particular 0, 1 or 2,
moreover, the molar ratio of the complex transition metal And a catalyst of polymerization) is usually in the range from 1:100 to 100:1.

10. The method according to claim 9, the de lightly copolymerized ethylene with one or more alkenes of formula R 1CH=CH2where R1represents a hydrogen or alkyl radical containing from 1 to 10 carbon atoms, at a temperature in the range from 20 to 200°C. and a pressure in the range from 0.05 to 1 MPa.

11. The method according to claim 9 or 10, where the catalytic system used for the copolymerization of ethylene, contains a catalytic composition comprising at least two different polymerization catalyst (a) and (b)determined as specified in claim 9, and further comprises at least one of the following components:
C) one or more activating compounds representing alumoxane, strong electroneutral a Lewis acid, an ionic compound containing a cation of a Lewis acid or an ionic compound containing the acid Bronsted as cation and the molar ratio of the complex transition metal (A) to the activating compound (C) is in the range from 1:0.1 to 1:10000, and the molar ratio of the iron complex (B) to the activating compound (C) is in the range from 1:0.1 to 1:10000,
D) one or more organic or inorganic carriers selected from silica gel, magnesium chloride, aluminum oxide, mesoporous materials, aluminosilicates, hydrotalcites and organic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, or polymers containing NGF the national group, for example, copolymers of Athena and esters of acrylic acid, acrolein or vinyl acetate, (E) one or more compounds of metals of groups 1A, 2A or 3A of the Periodic table, having the General formula (XX)

where
MGrepresents Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum,
gallium, indium, thallium, zinc, particularly Li, Na, K, Mg, boron, aluminum or Zn,
R1Grepresents hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl, each of which contains from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part,
R2Gand R3Geach represent hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy, each of which contains from 1 to 20 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or alkoxy with C1-C10-alkyl or C6-C15-aryl,
rGis an integer from 1 to 3, and
sGand tGrepresent integers from 0 to 2, where the sum rG+sG+tG
corresponds to the valency of MG,
moreover, the component (E) is usually not identical to the component (C), and when the component (E) is present in the catalytic system, it is in such a quantity that the molar ratio of MGof the four who uly (XX) to the amount of transition metal complex of the transition metal (a) and the iron complex (B) is in the range from 3000:1 to 0.1:1.

12. Catalytic composition for use in the method according to any of PP-11, including at least two different polymerization catalyst, of which (A) represents at least one polymerization catalyst based garretsen (A)having the formula
,
in which 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,
each of R1B-R5Brepresents hydrogen, C1-C8-alkyl, C6-C8-aryl, NR8B2, OSiR8B3or Si(R8B)3and
each of R9B-R13Brepresents hydrogen, C1-C8-alkyl or C6-C8-aryl,
NR14B2, OSiR14B3or Si(R14B)3
or in each case two radicals of R1B-R5Band/or R9B-Rl3Btogether with C5cycle form indenyl, fluorenyl or substituted indenolol or fluorenyl system,
and b represents at least one polymerization catalyst based on iron component containing at least one ligand of General formula (III)

where
E1Crepresents a nitrogen atom or a phosphor is a, in particular nitrogen,
E2C-E4Seach independently represents a carbon atom, nitrogen or phosphorus, in particular carbon,
R1C-R3Ceach independently represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C,
SiR19C3where the organic radicals R1C-R3Ccan also be substituted by Halogens and/or two vicinal radicals of R1C-R3Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R1C-R3Ctogether with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms N, P, O and S,
R4C-R7Ceach independently represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, SiR19C3where the organic radicals R4C-R7Ccan also be substituted by Halogens and/or two genialnyh or vicinal radicals of R4C-RC can also be connected with the formation of five-, six - or semichasnoho cycle, and/or two genialnyh or vicinal radicals of R4C-R9Cconnected with the formation of five-, six-or semichasnoho heterocycle containing at least one atom selected from the group comprising atoms N, P, O and S, and when v is 0, R6Crepresents the relationship with L1Cand/or R7Crepresents the relationship with L2Cso L1Cforms a double bond with the carbon atom that is attached to R4Cand/or L2Cforms a double bond with the carbon atom that is attached to R5C,
u is 0 when E2C-E4Crepresents a nitrogen atom or a phosphorus atom,
and is equal to 1 when E2C-E4Crepresents a carbon atom,
L1C-L2Ceach independently represents a nitrogen atom or atom
phosphorus, in particular nitrogen,
R8C-R11Ceach independently represents hydrogen, C1-C22-alkyl,
With2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C, SiR19C3where the organic radicals R8C-R11Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17C can also be connected with the formation of five-, six - or
semichasnoho cycle, and/or two vicinal radicals of R8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms N, P, O and S, provided that at least R8Cand R10Crepresents a halogen or tert-C1-C22is an alkyl group,
R12C-R17Ceach independently represents hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR18C2, OR18C,
SiR19C3where the organic radicals R12C-R17Ccan also be substituted by Halogens and/or two vicinal radicals of R8C-R17Ccan also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals of R8C-R17Cconnected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group comprising atoms N, P, O and S,
indexes v each independently represent 0 or 1,
the radicals XWitheach independently represents a fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C 10alkenyl,6-C20-aryl, alkylaryl containing 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR18C2, OR18C, SR18C, SO3R18C, OC(O)R18C, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion and the radicals XWithcan be connected to each other, the radicals R18Ceach independently represents hydrogen, C1-C20-alkyl, C2-C20alkenyl,6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR19C3where the organic radicals R18Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R18Ccan also be connected with the formation of five - or six-membered cycle,
the radicals R19Ceach independently represents hydrogen, C1-C20-alkyl,
With2-C20alkenyl,6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R19Ccan also be substituted by Halogens or nitrogen - and oxygen-containing groups and two radicals R19Ccan also be connected with the formation of five - or six-membered cycle,
's Rav is about 1, 2, 3 or 4, in particular 2 or 3,
D represents an electrically neutral donor and
t is an integer from 0 to 4, in particular 0, 1 or 2,
moreover, the molar ratio of the complex transition metal And a catalyst of polymerization) is usually in the range from 1:100 to 100:1.

13. Catalytic system for use in the method according to any of PP-11, containing the catalytic composition according to item 12, and optionally containing at least one of the following components:
C) one or more activating compounds representing alumoxane, strong electroneutral a Lewis acid, an ionic compound containing a cation of a Lewis acid or an ionic compound containing the acid Bronsted as cation and the molar ratio of the complex transition metal (A) to the activating compound (C) is in the range from 1:0.1 to 1:10000, and the molar ratio of the iron complex (B) to the activating compound (C) is in the range from 1:0.1 to 1:10000,
D) one or more organic or inorganic carriers selected from silica gel, magnesium chloride, aluminum oxide, mesoporous materials, aluminosilicates, hydrotalcites and organic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, or polymers containing functional groups, e.g. the measures copolymers of Athena and esters of acrylic acid, acrolein or vinyl acetate,
E) one or more compounds of metals of groups 1A, 2A or 3A of the Periodic table, having the General formula (XX):

where
MGrepresents Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gallium, indium, thallium, zinc, particularly Li, Na, K, Mg, boron, aluminum or Zn,
R1Grepresents hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl, each of which contains from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part,
R2Gand R3Geach represents hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy, each of which contains from 1 to 20 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or alkoxy with C1-C10-alkyl or C6-C15-aryl,
rGis an integer from 1 to 3, and
sGand tGrepresent integers from 0 to 2, where the sum rG+sG+tGcorresponds to the valency of MG,
moreover, the component (E) is usually not identical to the component (C), and when the component (E) is present in the catalytic system, it is in such a quantity that the molar ratio of MGfrom the formula (XX) with the Miu transition metal complex of the transition metal (a) and the iron complex (B) is in the range from 3000:1 to 0.1:1.

14. Film made of polyethylene according to any one of claims 1 to 8.

15. The film 14, selected from the group including stretch film, hygienic tapes for office use, sealing layers of film for automatic packaging, composite and laminating film.

16. Bags with handles, made of film 14.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to moulding composition for making films from vinyl chloride polymer or polyvinyl chloride in amount of 5-94 wt % and with coefficient K ranging from 50 to 90, an additive in amount of 2-25 wt % and a polymer based on polycrystalline or amorphous polyester with crystallisation half-time in molten state at least equal/longer than 5 minutes, where weight percentages are calculated per total weight of the moulding material, and the moulding material is a mixture of vinyl chloride polymer or polyvinyl chloride and polyester as a drawing capacity modifier and amount of polyester ranges from 5 to 90 wt % of the moulding material. The film is made from the moulding material, which is plasticised, molten and rolled or extruded into a film with thickness ranging from 100 mcm to 1 mm and, if necessary, drawn using a flow line method and/or independently. Drawing ratio ranges from 1.3 to 7, particularly from 3 to 4.

EFFECT: obtained film has improved light transmission, light- and thermal stability, is capable of stretching.

31 cl, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to the technology of making films for coating outer surfaces and can be used in decorating surfaces of plastic structural components in motor-car construction. The film consists of one or more layers. The top layer of the film consists of a moulding compound containing a) from 3 to 50 wt % polyamide, selected from group PA11 and PA12, b) from 50 to 97 wt % polyamide selected from group PA1012 and PA1212 c) up to 30 wt % target additives. The sum of components a) and b) or a)-c) is 100 wt %.

EFFECT: moulded components decorated this way retain their luster for the entire operation period.

13 cl, 5 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a composition based on methacrylic resin, as well as films made from methacrylic resin. Described is a composition based on methacrylic resin which is resistant to atmospheric effects and shields from ultraviolet rays and contains a composition based on methacrylic resin (C), containing methacrylate polymer (A) and acrylic cross linked elastic particles (B). The said composition based on methacrylic resin (C) is obtained through polymerisation of a mixture of monomers (a) in the presence of said acrylic cross linked elastic particles (B). The said methacrylate polymer (A) is obtained through polymerisation of a mixture of monomers (a) containing 50-100 wt % alkylmethacrylate and 0-50 wt % alkylacrylate. The said acrylic cross linked elastic particles (B) are obtained through copolymerisation of a mixture of monomers (b) containing 50-100 wt % alkylacrylate and 0-50 wt % alkylmethacrylate and a polyfunctional monomer containing two or more non-conjugated double bonds per molecule, where from 0.01 to 30 pts. wt per 100 pts. wt of the composition based on methacrylic resin (C) for ultraviolet light absorber with formula (1), where X is H or halogen; R1 represents H, methyl or a t-alkyl group with 4-6 carbon atoms; R2 represents a linear or branched alkylene group with 2-10 carbon atoms, and R3 represents H or methyl. The said ultraviolet light absorber is copolymerised with the said methacrylate polymer (A) and with the said acrylic cross linked elastic particles (B), in the said composition based on methacrylic resin (C). Also described is a film made from the said composition. A laminate is described, containing a metal or plastic coated with the said film. The film is laminated.

EFFECT: obtaining films with excellent transparency, capable of withstanding atmospheric effects, with excellent hardness, impact resistance, bending and tearing resistance, as well as moulding capacity.

8 cl, 3 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: method involves uniaxial drawing of a polymer article with an elongated shape in a medium with subsequent removal of the medium from the volume of the article while holding the article in a pulled state in the drawing direction. The polymer used is a partially crystalline polymer with degree of crystallinity over 10%. The medium used is a gas in a supercritical state, and the medium is removed from the volume of the article by lowering pressure to a value below the critical value. The polymer article with elongated shape used can be any object selected from a film, fibre, tape, pipe or rod.

EFFECT: invention simplifies the method of producing nanoporous polymers with open pores, reduces fire hazard and improves ecological indices of the method while retaining high parametre values of volume porosity and permeability of obtained polymers.

6 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a resin composition containing polyvinyl acetal resin, a dye and an agent which screens infrared beams. The resin composition contains an ester compound of phosphoric acid in ratio of 5 weight parts or less than 100 weight parts of polyvinyl acetal resin.

EFFECT: design of a film for laminating glass with excellent properties of screening infrared beams and resistant to bleaching even in case of moisture absorption, retaining basic properties as an interlayer film for laminated glass.

5 cl, 3 tbl

FIELD: process engineering.

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

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

2 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: film is featured with para-orentation of at least 95% polymer bonds. The method for film making includes polymerisation of para-oriented aromatic diamine and para-oriented aromatic dicarbon acid haloid in the mixture of solvents consisting of N-methylpyrrolidone or dimethylacetamyde and calcium chloride or lithium with obtaining of aramide polymer containing only para-oriented bounds. Then the spinning solution is obtained by solution of the polymer in solvent mixture up to concentration 2 - 6 wt %. The spinning solution is transformed to para-aramide fibrid film with usual known methods used for meta-aramide fibrids production.

EFFECT: enhancing of paper properties, durability, porosity; high heat stability and high content of moisture.

10 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to technology of obtaining films based on hydroxyl-containing polymers of increased fire resistance, particularly, to composition for obtaining films and can be applied in different areas of industry and agriculture for fireproof modification of materials based on them. Composition includes in weight fraction: 1.0-5.0 polyvinyl alcohol, 95.0-99.0 water, 0.5 methhylphosphate borate and 2.0 plasticiser. As plasticiser applied is glycerin, ethylene glycol or diethylene glycol.

EFFECT: invention ensures obtaining from said composition fire resistance films with increased durability.

2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production technology of films having increased fire-resistance, particularly to films based on polyvinyl alcohol and can be used in various industries and economics for fireproof modification of the materials based on them. According to the method methylphosphite borate is preliminary mixed with plasticiser at the ratio 1:4 and 1-5% of aqueous solution of polyvinyl alcohol is added. Thereafter, films are moulded and dried at the ambient temperature. Glycerin, glycol alcohol or diethylene glycol is used as a plasticiser.

EFFECT: invention allows simplifying modification, increasing reliability and fire resistance of films.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: composition for film coating application includes polyvinyl alcohol as basic component, water and functional components such as polyatomic alcohol as plasticiser, carbamide-based inhibitor of air corrosion, and thixotropic component, and additionally contains structure forming agent based on oxyethylated alcohol and isopropyl alcohol, and can be applied in protection of various surfaces, such as facility walls and technological equipment, and of finished product surfaces during transportation. Antipyrene additive added to the composition allows for obtaining non-combustible fireproof coatings.

EFFECT: improved film quality due to enhanced film strength and drying rate.

1 tbl

FIELD: chemistry.

SUBSTANCE: there is described method for making a catalyst component for copolymerisation of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, on a MgCl2 carrier, involving use of a Mg compound selected from a Lewis adduct from adducts with formula MgX2(R"OH)m, in which R" represents C1-C20 hydrocarbon groups, X is chlorine, and m ranges from 0.1 to 6, Ti compound and electron-donor compound (ED), selected from alcohol, alkyl ester C1-C20 of aliphatic carboxylic acids, ketones, amines, amides, nitriles, alkoxysilanes and aliphatic ethers as basic compounds. The said method includes two or more reaction steps involving use of at least one of the said basic compounds themselves as a fresh reagent or in a mixture in which they are the main component. The method is distinguished by that, at the last two or more reaction steps, the basic compound which is used as the fresh reagent is an ED compound. Also described is a solid catalyst component for copolymerisation of olefins CH2=CHR, in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, including a Ti compound and an electron donor (ED), selected from alcohol, alkyl ester C1-C20 of aliphatic carboxylic acids, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers and esters of aliphatic carboxylic acids on a magnesium chloride carrier, in which molar ratio ED/Ti varies from 1.5 to 3.5, and molar ratio Mg/Ti exceeds 5.5. A catalyst is described for copolymerisation of olefins, for polymerisation of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, including a product obtained after contacting: (a) a solid catalyst component described above; (b) one or more compounds of alkyl aluminium and, optionally, (c) copolymerisation of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, carried out in the presence of the said catalyst.

EFFECT: increased stereospecificity of the catalyst.

22 cl, 4 tbl, 30 ex

FIELD: chemistry.

SUBSTANCE: invention relates to silicon ethers, of general formula (I) , a method of producing said ethers and use as a catalyst component for polymerisation of olefins. Silicon ethers of general formula (I) are proposed, where R1-R10 assume values given in the description.

EFFECT: obtaining silicon ethers which can be used as an external electron-donor component for producing polymers, which have high isotacticity, with high output.

14 cl, 2 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical industry, in particular, to creation of highly active homogenous catalysts. Described is catalyst based on binary bridge bis(phenoximine) complex of titanium, in which as bridge between phenyl substituents of imine nitrogen it contains n - phenylene group, and corresponds to the following formula: . Described is method of preparing described above catalyst by interaction of tetradentate diimine ligand with compound of transitive metal, in which as components for ligand preparation used is 4,4"-diamino-l-terphenyl and 3,5-dicumylsalicilic aldehyde, and as compound of transitive metal used is titanium diisopropoxydichloride TiCl2(OPr)2. Described is process of ethylene polymerisation in medium of hydrocarbon solvent in presence of catalyst obtained by claimed method with co-catalyst.

EFFECT: increase of polymerisation process economy due to lower catalyst consumption; obtaining of linear polyethylene with high and extra-high molecular mass, with temperature of melting 140-142°C, improved morphology of polymer powder and absence of its adhering on reactors wall.

4 cl, 2 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to metal-organic compounds of transitive metal of formula (I) where M1, X, n, Z, R1 -R8 and A are such as they are determined in invention formula, to biscyclopentadienyl ligand systems, which have such substitution model, to catalyst systems, containing at least one of metal-organic compounds of transitive metal of claimed invention, to method of obtaining polyolefins by polymerisation or co-polymerisation of, at least, one olefin in presence of one of catalyst systems of claimed invention, to application of biscyclopentadienyl ligand systems of claimed invention for obtaining metal-organic compounds of transitive metal and to method of obtaining metal-organic compounds of transitive method using biscyclopentadienyl ligand systems.

EFFECT: obtaining ethylene-propylene co-polymers, which have high molecular weights, increase of impact resistance of propylene polymers.

10 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method involves making a catalyst system, containing one or several components, chosen from a group containing metallocenes, non-metallocenes and activators, addition of mineral oil to the catalytic system, obtaining a suspension and addition of one or several liquid alkanes, containing three or more carbon atoms, to this suspension in an amount sufficient for reducing foaming and viscosity of the suspension. More mineral oil is added to the system, obtaining a suspension, containing a catalytic system and one or several liquid alkanes, containing three or more carbon atoms, in amount sufficient for reducing foaming and viscosity of the suspension. The invention also describes a method of polymerising olefins using such a system.

EFFECT: suspension has high content of solid particles, low viscosity and limited amount of foam.

11 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: catalyst systems according to claimed invention first of all relate to metallocene catalyst, characterised by optimized load on metal and activator concentration, as well as demonstrating improved efficiency and productivity. In one typical version of claimed invention realisation improved metallocene catalyst system according to claimed invention includes metallocene catalyst, activated with methylaluminoxane, and base material, amount of methylaluminoxane being in range from 3 to 9 mmoles of methylaluminoxane per g of base material, and metallocene is present in amount ranging from 0.01 to 1.0 mmole of metallocene per g of base material.

EFFECT: improved catalyst productivity and reactor efficiency.

11 cl, 6 tbl, 2 dwg, 27 ex

FIELD: chemistry.

SUBSTANCE: proposed is a polymerisation method for producing (co)polymer of one or more monomers from which at least 50 wt % is vinyl chloride, an in which one or several organic peroxides, chosen from a group consisting of diacyl peroxides, peroxy esters, peroxydicarbonates and their mixtures, are used together with control agents, chosen from a group consisting of organic hydroperoxides, organic compounds with ethylene saturation, which cannot be homo-polymerised, compounds with unstable carbon-hydrogen bonds, oximes and their mixture, under the condition that, solubility of peroxydicarbonate (peroxydicarbonates) in water at 0°C is not less than 5 pts/mln. The method is a standard polymerisation method in an aqueous dispersion or a polymerisation method in an aqueous dispersion in which at least part of one or several organic peroxides, used as the initiator, is added to the reaction mixture at polymerisation temperature. The invention also relates to formulations, containing organic peroxide and sufficient amount of additive, stabilising the organic peroxide, suitable for use in the given polymerisation method and (co)polymers, obtained using method of polymerisation in an aqueous dispersion.

EFFECT: wider field of using the compounds.

14 cl, 1 dwg, 3 tbl

FIELD: technological processes, chemistry.

SUBSTANCE: invention is related to methods of polymerisation, which provide for control of composition distribution and viscosity of polymer melts. Methods are described for control of polyolefin melt viscosity, control of distribution of comonomer units of polyolefin, achievement of target viscosity of polyolefin melt and film made of such polyolefins. These methods include contact of olefin monomer and at least one comonomer with catalytic system in presence of fluid medium that is able to condense and includes saturated hydrocarbon, which contains from 2 to 8 carbon atoms. In one version catalytic system includes hafnium metallocene catalytic component.

EFFECT: possibility to control distribution of comonomer units by variation of condensable fluid medium concentration in polymerisation reactor.

13 cl, 7 tbl, 3 dwg, 13 ex

FIELD: technological processes.

SUBSTANCE: invention is related to method for gas-cycle polymerisation realised at the temperature that is below critical. Method is described for continuous gas-cycle polymerisation, which includes polymerisation of one or several carbohydrate monomers in reactor with fluidised layer in the presence of catalytic system or catalyst of polymerisation and fluid medium able to condense for the period of at least 12 hours, in which temperature of layer is less than critical temperature, and dew point of gas composition in reactor stays within the limits of 25°C relative to layer temperature.

EFFECT: increase of efficiency maximum values with simultaneous elimination of resin stickiness problems.

55 cl, 2 dwg, 4 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention concerns methods of obtaining high-molecular compounds by method of 'live' radical polymerisation. Invention claims application of complex ruthenium compound with carborane fragment as catalyst, tert-butylamine as activation agent, and carbon tetrachloride as activation agent. Process speed is accelerated by 10-20 times in comparison to the prototype.

EFFECT: accelerated process of obtaining fine-dispersion polymethylmethacrylate by the method of controlled radical polymerisation.

2 cl, 1 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: there is described method for making a catalyst component for copolymerisation of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, on a MgCl2 carrier, involving use of a Mg compound selected from a Lewis adduct from adducts with formula MgX2(R"OH)m, in which R" represents C1-C20 hydrocarbon groups, X is chlorine, and m ranges from 0.1 to 6, Ti compound and electron-donor compound (ED), selected from alcohol, alkyl ester C1-C20 of aliphatic carboxylic acids, ketones, amines, amides, nitriles, alkoxysilanes and aliphatic ethers as basic compounds. The said method includes two or more reaction steps involving use of at least one of the said basic compounds themselves as a fresh reagent or in a mixture in which they are the main component. The method is distinguished by that, at the last two or more reaction steps, the basic compound which is used as the fresh reagent is an ED compound. Also described is a solid catalyst component for copolymerisation of olefins CH2=CHR, in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, including a Ti compound and an electron donor (ED), selected from alcohol, alkyl ester C1-C20 of aliphatic carboxylic acids, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers and esters of aliphatic carboxylic acids on a magnesium chloride carrier, in which molar ratio ED/Ti varies from 1.5 to 3.5, and molar ratio Mg/Ti exceeds 5.5. A catalyst is described for copolymerisation of olefins, for polymerisation of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, including a product obtained after contacting: (a) a solid catalyst component described above; (b) one or more compounds of alkyl aluminium and, optionally, (c) copolymerisation of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical containing 2-12 carbon atoms, carried out in the presence of the said catalyst.

EFFECT: increased stereospecificity of the catalyst.

22 cl, 4 tbl, 30 ex

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