Mouldable composition containing polyethylene for making films and method of preparing mouldable composition in presence of mixed catalyst

FIELD: chemistry.

SUBSTANCE: composition contains polyethylene and traditional additives, has density of 0.915-0.955 g/cm3, melt index MI from more than 0 to 3.5 g/10 min, flow-rate rating HLMI/MI of 5-50 and polydispersity Mw/Mn of 5-20. Z-average molecular weight Mz of the mouldable composition is less than 1 million g/mol. The mouldable composition is obtained in one reactor in the presence of a mixed catalyst which contains a pre-polymerised chromium compound and metallocene.

EFFECT: films containing disclosed mouldable compositions have very good mechanical properties, high impact resistance and high breaking strength coupled with very good optical properties, the films do not easily stick together and they can be transported in a car without adding lubricants and anti-adhesives or only in their small amount.

9 cl, 3 tbl, 6 ex

 

The present invention relates to moldable compositions containing polyethylene, and way of making a moldable composition in the presence of a mixed catalyst containing pre-polymerized a chromium compound and a metallocene compound. From moldable compositions based on polyethylene can be obtained film with a surprisingly high transparency and at the same time good mechanical properties.

Recently, to obtain films of all types began to use a mixture of polyethylene. In many applications, especially in the food industry, the desired film is not only good mechanical properties such as high tensile strength, but also with specific optical properties. Typically the luster and transparency of the films deteriorate with increasing density so that, in particular, it is difficult to obtain a film with an average density and good optical properties.

Known application of catalytic compositions containing two or more different polymerization catalysts ziperovich type or metallocene type. For example, to get from the reactor blends with a wide molecular weight distribution, you can use a combination of two catalysts, one of which provides polyethylene with an average molecular weight than the molecular weight poly is tilina, get on another catalyst (WO 95/11264). Copolymers of ethylene and higher α-olefins, such as propene, 1-butene, 1-penten, 1-hexene or 1-octene, known as LLDPE (linear low density polyethylene), which are formed in the presence of classical catalysts of the Ziegler-Natta titanium-based, differ from LLDPE, which are the presence of metallocene. The number of side chains formed during the implementation of the copolymer, and their distribution, known as the distribution of branched side chains (SCBD), varies when using different catalytic systems. The number and distribution of the side chains has a strong influence on the crystallization of ethylene copolymers. While the fluidity and, therefore, the processing of these copolymers of polyethylene depend primarily on their molecular mass and molecular mass distribution, mechanical properties, in particular, depend on the distribution of branched side chains. However, the distribution of branched side chains plays an important role in special ways of processing, for example during extrusion of films, where the crystallization of copolymers of ethylene during cooling, the extruded film is an important factor in determining how quickly and to what quality film can be obtained. In view of the many possible combinations, it is difficult to find the right is ombinatio catalysts for a balanced ratio of good mechanical properties and processing characteristics.

In EP-A-339571 described mixed catalysts comprising chromium catalysts and metallocene. Received moldable compositions based on polyethylene have a very broad molecular weight distribution and suitable for the manufacture of a molding with a blow.

In patent WO 97/08213 described mixed catalysts comprising chromium catalysts and metallocene on different media. Received moldable compositions based on polyethylene have a very wide molecular weight distribution and is particularly suitable for manufacturing articles by blow molding.

Therefore, the main object of the present invention to provide a moldable composition based on polyethylene only one way. Thus obtained molded composition must be processed to form films with high prozracnosti and gloss, possessing at the same time, good mechanical properties, especially for the manufacture of films by extrusion blow.

This problem is solved by using a moldable compositions based on polyethylene with a density in the range 0,915-0,955 g/cm3, MI in the range of 0-3,5 g/10 min, MRF in the range of 5-50, polydispersity Mw/Mnin the range of 5-20, and z-average molecular mass Mzless than 1 million g/mol.

The density of the moldable composition is in accordance with the present invention is 0,915-0,955 g/cm 3preferably 0,925-0.95 g/cm3and particularly preferably in the range of 0.93-0,945 g/cm3. MI moldable composition according to the present invention is in the range 0-3,5 g/10 min, preferably in the range of 0-3 g/10 min and more preferably 0.1 to 2.5 g/10 min. For the purposes of the present invention, the expression "MI" means, as usual, "melt index" and is determined at 190°C. and load of 2.16 kg 190°C/2,16 kg) according to ISO 1133. MFR moldable composition is in the range of 5-50, preferably in the range of 10-30, and more preferably 14 to 25. For the purposes of the present invention, the expression "MFR" means, as is known, the degree of fluidity of the melt and corresponds to the ratio of HLMI to MI, where "HLMI" means, for the purposes of the present invention the melt index under high load and is determined at 190°C. and a load of 21.6 kg 190°C/21,6 kg) according to ISO 1133. Moldable composition according to the present invention has a polydispersity Mw/Mnin the range of 5-20, preferably 5,01-10 and especially preferably a 5.1-8.

the z-Average molecular mass Mzmouldable composition is less than 1 million g/mol, preferably is in the range 150000-800000 g/mol and particularly preferably 200000-600000 g/mol. The definition of the z-average molecular weight can be found, for example, in High Polymers, vol. XX, Raff and Doak, Interscience Publishers, John Wiley & Son, 1965, p.443.

Moldable composition according to the present invention contains an amount less than 0.5 wt.%, preferably 0-3 wt.% and especially less than 0.1 wt.% calculated on the total mass of the moldable compositions of polyethylene with a molecular mass of more than 1 million g/mol, preferably more than 900 000 g/mol. The proportion of polyethylene with a molecular weight above 1 million g/mol determined here by the method of gel permeation chromatography, based on the determination of molecular masses.

For the purposes of the present invention, the term polyethylene includes ethylene polymers, such as homopolymers of ethylene and/or copolymers of ethylene. Possible comonomers which may be present along with ethylene in the copolymer of ethylene moldable compositions of the present invention either individually or in a mixture with one another, include all alkenes with 3-10 carbon atoms, e.g. propene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene and 1-mission. Preferably, the copolymer of ethylene included as units of the copolymer of 1-alkenes with 4-8 carbon atoms, for example, 1-butene, 1-penten, 1-hexene, 4-methylpentene or 1-octene in the form of the polymer. Particularly preferred 1-alkenes, which are selected from the group consisting of 1-butene, 1-hexene and 1-octene. Preferably the ethylene copolymer contains from 0.01 to 5 wt.% the co monomer, and particularly preferably 0.1 to 2 wt.% someone the A.

Preferably, the average mass molecular mass Mwmoldable compositions of the present invention were in the range 5000-700000 g/mol, preferably 30000-5500000 g/mol and particularly preferably 70000-450000 g/mol.

Molecular weight distribution according to the present invention can be modal, bimodal or polymodal. For the purposes of this patent application modal molecular weight distribution means that the molecular weight distribution has a single maximum. For the purposes of this patent application bimodal molecular weight distribution means that the molecular mass distribution, since the maximum is on the sides of the at least two points of inflection. Preferably, the molecular weight distribution was modal.

Preferably, the moldable composition according to the present invention contain from 0.01 to 20 branches/1000 carbon atoms, preferably 1-15 branches/1000 carbon atoms and particularly preferably 3 to 10 branches/1000 carbon atoms. Number of branches/1000 carbon atoms is determined by the method of13C-NMR as described by James C. Randall, JMS-REV. Macromol. Chem. Phys., C29(2&3), 201-317 (1989) and calculated on the total content of CH3groups/1000 carbon atoms.

Preferably, the moldable composition according to the present and the finding contained at least 0,05 vinyl groups/1000 carbon atoms, preferably 0.1 to 5 vinyl groups/1000 carbon atoms and particularly preferably 0.15 to 3 vinyl groups/1000 carbon atoms. The content of vinyl groups/1000 carbon atoms is determined by the method of IR, ASTM D 6248-98. For the purposes of this text the expression vinyl group refers to the group-CH=CH2. This expression does not include vinylidene group and internal olefinic groups. Vinyl group usually refers to the reaction of chain termination after the introduction of ethylene, while vinylidene end groups are usually formed by the reaction of breakage of the polymer after the introduction of the copolymer. Vinylidene and vinyl groups can be functionalized or cross stitched, and vinyl groups are more suitable for these subsequent reactions.

Preferably, the moldable composition according to the present invention contain at least 0,05 vinylidene groups/1000 carbon atoms, in particular 0.1 to 1 vinylidene groups/1000 carbon atoms and particularly preferably 0.12 to 0.5 to vinylidene groups/1000 carbon atoms. The determination performed in accordance with ASTM D 6248-98.

Preferably, the moldable composition according to the present invention had the mixing quality, measured according to ISO 13949, less than 3, in particular 0 to 2,5. This value refers to polyethylene, which is obtained directly from the reactor, namely the powder polite the Jena without prior melting in the extruder. It is preferable to obtain a powder of polyethylene by polymerization in a single reactor.

Preferably, the moldable composition according to the present invention have a degree of branching of long chains of λ (lambda) from 0 to 2 branches long chains/1000 carbon atoms and particularly preferably 0.1 to 1.5 branches long chains/1000 carbon atoms. The degree of branching of long chains of λ (lambda) was measured by the light scattering method, as described, for example, in ACS Series 521, 1993, Chromatography of Polymers, Ed. Theodore Provder, Simon Pang and Alfred Rudin: Size-Exclusion Chromatographic Assessment of Long-Chain Branch Frequency in Polyethylenes, page 254-269.

Moreover, the moldable composition according to the present invention may also contain 0-6 wt.%, preferably 0.1 to 1 wt.% in calculating the masses of polymers of ethylene, at least one additive, including traditional additives for thermoplastics, e.g. processing stabilizers, stabilizers against the effects of light and heat, conventional additives such as lubricants, antioxidants, antiadhesive and antistatics and, if necessary, dyes. Preference is given, among other things, lubricants (CA stearate); traditional stabilizers such as phenols, phosphites, benzophenone, benzothiazoles or thioethers; fillers, for example, Tio2, chalk or soot; traditional pigments such as Tio2, ultramarine blue. Supplements are generally consumed by mixing with the moldable composition is th traditional ways technology plastics, for example, by melt extrusion, rolling, compaction or mixing solutions. The preferred melt extrusion, for example, in a twin-screw extruder. The temperature of extrusion is usually 140-250°C.

Moreover, it was proposed to use moldable composition to obtain films. There had also been a film, which includes as a main component forming composition and the preferred options.

The present invention also relates to films in which the moldable composition according to the present invention is present as a major component, such as a film comprising a polymer including moldable composition, as described above, and preferably, the moldable composition is present in amount of 50-100 wt.%, more preferably 60-90 wt.% in the calculation on the entire polymer. In particular, the present invention relates to films with at least one layer containing 50 to 100 wt.% moldable compositions of the present invention.

The film is usually produced by plasticization moldable composition at the temperature of the melt in the range of 190-230°C, extrusion of plasticized moldable composition, for example, through a slot punch on the cooling roller, and cooling the extruded molded composition. In addition, if necessary, the film may contain the at least one additive, for example, conventional additives such as stabilizers, antioxidants, antistatics, lubricants, antiadhesive or pigments in an amount of 0-30 wt.%.

The film of the present invention is suitable for obtaining films with a thickness of from 5 μm to 2.5 mm Film can be obtained, for example, by extrusion blown film, and the thickness is from 10 μm to 2.5 mm In the extrusion of blown film forming composition is extruded in the form of melt through the annular punch. The tube with the melt is then blown off with air and is removed at a speed that is greater than the speed at which the melt flows from the punch. With intensive cooling, the melt is cooled below the melt point of the crystallite in the cooling lines. Here you can set the size of the bubbles in the film. Bubble film then stick together, it is cut, if necessary, and is wound with a suitable device for winding. Moldable compositions of the present invention can be obtained with short or long neck depending on the way to work. For the extrusion flat film, for example, films get at facilities with cold roller or plants timepressure films. Moreover, it is possible to obtain a composite film on the cladding installations or rolling. This applies, in particular, to a composite film, in which the composite structure is introduced thin SL and paper, aluminum or fiber media. The film of the present invention may include at least one layer, preferably at least many layers and preferably a single layer.

Moldable compositions of the present invention is very suitable, in particular, to obtain films on blown films and devices for cast films at high outputs. Films containing moldable compositions of the present invention have very good mechanical properties, high resistance to impact and high tensile strength combined with very good optical properties, in particular transparency and gloss. They are suitable in particular for the manufacture of packaging, for example, as thermovalve films as in bags for weights and food packaging. In addition, the film is very loosely stick together and can be transported in the car without adding grease and antiadhesive or in the presence of only small amounts.

The film of the present invention is suitable, in particular, as a protective film for the surface, stretch film, hygienic film office film, film for bags to carry loads, the composite film and the calendered film. Thanks to the very good optical properties of the film according to the present invention is particularly suitable for slurry the bags, because of possible high-quality printing, as calendered films for thermovalve layers in food packaging, because films have a weak smell and taste, and films for avtopapkovki, i.e. film suitable for processing in automatic machines, because they can be processed on a rapidly rotating devices.

Preferably, the film according to the present invention with a thickness of 50 μm had a haze of less than 40%, in particular in the range of 5-35% and especially preparedpattern 10-33%. Haze is measured according to ASTM D 1003-00 on a BYK Gardener Haze Guard Plus Device for at least 5 films 10x10 see Definition using the incident pointed cargo (DDI) impact strength of the films of the present invention with a thickness of 50 microns, preferably gives a value greater than 130 g, in particular in the range of 150-500 g and particularly preferably 170-400, the DDI Value measured according to ASTM D 1709, method A. Preferably, the film according to the present invention with a thickness of 50 μm had a transparency of more than 90%, preferably in the range of 91-100% and, in particular, in the range of 93-99%. Transparency was measured according to ASTM D 1746-03 on a BYK Gardener Haze Guard Plus Device, calibrated using calibration cells 77,5. Preferably, the gloss of the films of the present invention with a thickness of 50 μm at 60° was greater than 50, preferably in the range 52-90 and, particularly, 55-80. The gloss was determined according to ASTM D 2457-03 on glossmeter 60° C suction plate for fixing the film.

Waste materials generated during the production of films, can be reused and mixed with fresh moldable composition according to the present invention. Waste is usually shredded and served via a side extruder in the main extruder.

Moldable composition according to the present invention is very suitable, for example, to obtain high performance installations of blown films on the plates. Films containing moldable composition according to the present invention exhibit good mechanical and optical properties. It should be noted also high resistance to puncture the obtained films.

The authors have developed a catalytic system for receiving the moldable compositions of the present invention, a method of using a catalytic system for the polymerization of ethylene or copolymerization of ethylene with 1-alkenes with 3-10 carbon atoms and the method for forming the compositions of the present invention by polymerization of ethylene or copolymerization of ethylene with 1-alkenes with 3-10 carbon atoms in the presence of catalytic systems.

Moldable composition according to the present invention can be obtained using the catalytic system of the invention and, in particular, its preferred options

The invention also provides a method of obtaining a moldable composition according to the present invention by copolymerization of ethylene, optionally in the presence of 1-alkenes of the formula R1CH=CH2where R1is a hydrogen or alkyl radical with 1-10 carbon atoms, at a temperature of 20-200°C and a pressure of 0.5 to 100 bar, which corresponds to 0.05 to 1 MPa, in the presence of a mixed catalyst containing pre-polymerized compound of chromium and metallocene. Suitable 1-olefins are, for example, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-penten or 1-octene.

Preference is given to polymerization of one of ethylene or a mixture of at least 50 wt.% ethylene and not more than 50 wt.% other 1-alkene of the above formula. In particular, polimerizuet one ethylene or a mixture of at least 80 wt.% ethylene and not more than 20 wt.% other 1-alkene of the above formula.

Due to the high activity used mixed catalyst the method according to the present invention allows to obtain polymers with a very low content of transition metal and halogen-free and therefore extremely high settings of the color stability test and corrosion, but especially transparency.

A mixed catalyst containing pre-polymerized compound of chromium and metallocene. Preferably mobilitat connection of the group of chromium on a solid medium at the stage a), then immobilized chromium compound to activate the heating stage b), then the activated chromium compound pre-polymerizate on stage) and then pre-cured chromium compound to use on stage (d) as a carrier for immobilization of metallocene.

Further, the invention provides a mixed catalyst obtained by this method.

As media are preferred finely crushed carriers - organic or inorganic solids. In particular, the media can be porous, such as talc, scaly silicate type montmorillonite, mica, inorganic oxide or a finely divided powder of the polymer (e.g. polyolefin or a polymer with polar functional groups).

You can also use organic media, such as finely crushed powder of polyolefin (e.g. polyethylene, polypropylene or polystyrene), preferably purified before use from adhering moisture, residual solvent or other impurities by appropriate operations and drying. You can also use polymeric carriers, for example, on the basis of polystyrene, polyethylene, polypropylene or polybutene, functionalityand such groups as the ammonium or hydroxyl, and at least one of the components to which telesfora can be immobilized. You can also use a mixture of polymers.

Inorganic oxides suitable as media components, can be found among the oxides of elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of elements. Examples of oxides preferred as carriers include silica, aluminum oxide and mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium, as well as an appropriate mixture of oxides. Other inorganic oxides which can be used alone or in combination with the specified oxide carriers include, for example, MgO, CaO, ZrO2, TiO2B2O3or mixtures thereof.

Other preferred inorganic 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)3or phosphate type AlPO4.

Preferred inorganic carriers are the hydrotalcite and calcined hydrotalcite. In Mineralogy hydrotalcite is a natural mineral with the ideal formula

Mg6Al2(OH)16CO3·4 H2O,

the structure of which is derived from the structure of brucite g(OH) 2. Brucite crystallizes in the form of flakes with metal ions in octahedral voids between the two layers of close-Packed hydroxyl ions, and is busy only every second layer of octahedral voids. In hydrotalcite some magnesium ions replaced by aluminium ions, resulting layers acquire a positive charge. This charge is compensated by anions located together with crystallization water between layers.

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

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

which have scaly structure and in which M(II) is a divalent metal such as Mg, Zn, Cu, Ni, Co, Mn, Ca and/or Fe and M(III) is a trivalent metal such as Al, Fe, Co, Mn, La, Ce and/or Cr, x is 0.5 to 10 in increments of 0.5, And is Midwesterner anion, and n is the charge Midwesterner anion, which can be 1 to 8, usually 1 to 4, and z is an integer of 1-6, in particular 2-4. Mezhdouzliya anions may include organic anions such as alkoxide anions, sulphate simple alilovic esters, sulfates simple arolovich esters or sulfate esters of glycol, inorganic anions such as, in particular, carbonates, guide carbonate, nitrate, chloride, sulfate or B(OH)4-or polyoxoanion metals, such as Mo7O246-or V10O286-. However, it may be a mixture of several of such anions.

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

Calcined hydrotalcite can be obtained from hydrotalcite during annealing, i.e. heated, in which among other things establishes the desired content of hydroxyl groups. In addition, it also changes the crystal structure. Calcined hydrotalcite used according to the invention are usually obtained at temperatures above 180°C. the Preferred annealing for 3-24 h at temperatures 250-1000°C and, in particular 400-700°C. during this stage can be skipped over solid air or inert gas or to create a vacuum.

When heated natural or synthetic hydrotalcite first pays water, which is drying. With further heating - real annealing the metal hydroxides are converted into the metal oxide by removing hydroxyl groups and Midwesterner anions; the Oh-group or mezhdouzliya anions such as carbonates, may also be present in the calcined hydrotalcite. Measure the number is TBA is weight loss by burning. This is the weight loss of the sample when heated in two stages - first for 30 min at 200°C in a drying Cabinet and then for one hour at 950°C in a muffle furnace.

Thus, the calcined hydrotalcite used as carriers, are mixed oxides of divalent and trivalent metals M(II) and M(III) with a molar ratio of M(II) and M(III) in the range of 0.5 to 10, preferably 0.75 to 8 and, in particular, 1-4. In addition, there may be the regular amount of impurities, for example, Si, Fe, Na, Ca or Ti, as well as chlorides and sulfates.

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

Preference is also given to the calcined hydrotalcite in which the structural transition is completed or almost completed. Changing patterns in the calcination can be confirmed, for example, by x-ray diffraction.

Preferred are also melkorazdroblennuyu xerogels doped silicon oxide as a carrier, which can be obtained, for example, as described in DE-A 2540279. Melkorazdroblennuyu xerogels doped silicon oxide preferably receive the following way, which includes:

α) using part of the hydrogel of silica, which includes 10-25 wt.% solids (calculated as SiO2), and the particles are mostly spherical with a diameter of 1.8 mm and get them on stage:

α1) introduction of a solution of sodium or potassium soluble glass in a rotating stream of an aqueous mineral acid along and tangentially to the thread

α2) spraying the obtained Hydrosol of alumina in a gas environment with dripping,

α3) solidification of Hydrosol in a gaseous environment,

α4) allocation received mostly spherical particles of hydrogel salts by washing without prior aging,

β) extraction of at least 60% of water present in the hydrogel with an organic liquid,

χ) drying the obtained gel to stop the weight loss at 180°C and a reduced pressure of 30 mbar for 30 min (formation of a xerogel) and

δ) regulation of the diameter of the resulting xerogel particles in the range of 20-2000 microns.

In the first stage, α) preparation of media it is important to use mainly spherical hydrogel particles of silicon oxide with a relatively high solids content from 10 to 25 wt.% (based on SiO2), preferably 12-20 wt.%, particularly preferably 14-20 wt.%. Such a hydrogel of silica was prepared in a special way, as described in the stages α1)-α4). Stage α1)-α3) are described in more detail what about in DE-A 2103243. Stage α4), the washing of the hydrogel, can be different, for example, on the counterflow principle, using water at a temperature of 80°C and slightly podslashennoyi (pH up to about 10) with ammonia.

Extraction of water from the hydrogel (phase β)) is preferably conducted using an organic liquid which is selected from the group consisting of alcohols With1-C4and/or ketones With3-C5preferably miscible with water. Particularly preferred alcohols are tert-butanol, isopropyl alcohol, ethanol and methanol. Among the preferred ketones is acetone. The organic liquid may also consist of mixtures of the above organic liquids, and in any case, the organic liquid prior to extraction should contain less than 5 wt.%, preferably less than 3 wt.%, water. The extraction can be carried out in conventional apparatus for the extraction, for example in the column extractors.

Drying (stage χ)) is preferably carried out at temperatures 30-140°C, particularly preferably at 80-110°C and at pressures preferably from 1.3 mbar to atmospheric. Here, given the vapor pressure, the temperature rise should be combined with increasing pressure and Vice versa.

The regulation of the particle diameter of the obtained xerogel (stage δ)) can be performed in any way, nab the emer crushing and screening.

Further preferred media are prepared inter alia by spray drying the crushed and sifted hydrogels, which for this purpose is mixed with water or an aliphatic alcohol. Primary particles are porous, and granules suitably crushed and sieved hydrogel have an average diameter of 1-20 μm, preferably 1-5 μm. The preferred powdered and sifted the hydrogels SiO2.

As solid carriers for mixed catalysts according to this invention the preferred silica, because of these substances it is possible to obtain particles of such sizes and patterns, which make them particularly suitable as carriers for the polymerization of olefins. Preferred granular silica gels. It was found that particularly suitable silica gels after spray drying, which are spherical agglomerates of smaller granules, namely primary particles. Before using the silica gels can be dried and/or calcined.

Preferred carriers have a specific surface area in the range of 10-1000 m2/g, pore volume in the range of 0.1 to 5 ml/g and average particle diameter D50 in the range of 1-500 μm. Preference is given to media with a specific surface area in the range of 50-700 m2/g, pore volume in the range of 0.4-3.5 ml/g and an average particle diameter of 50 in the range of 5-350 μm. Particularly preferred carriers with a specific surface area in the range of 200-550 m2/g, pore volume in the range of 0.5 to 3.0 ml/g and an average particle diameter D50 in the range of 10-150 μm.

Inorganic carrier can be subjected to heat treatment, for example, to remove the adsorbed water. Such drying is usually carried out at temperatures in the range of 50-1000°C, preferably 100 to 600°C, and dried at 100-200°C, preferably at reduced pressure and/or in the atmosphere of inert gas (e.g. nitrogen), or inorganic carrier can be ignited at temperatures of 200 to 1,000°C. to obtain a desired structure of solids and/or establish the desired concentration of Oh-groups on the surface. The media can also be treated chemically using traditional moist collectors, such as metallicity, preferably alkali aluminum, CHLOROSILANES or SiCl4or even methylalumoxane. Appropriate processing methods are described, for example, in WO 00/31090.

Inorganic carrier can also be chemically modified. For example, treatment of silica gel with NH4SiF6or other fluorinating reagents leads to fluorination of the silica gel surface, and the treatment of silica gels with silanes containing nitrogen-, fluorine - or sulfur-containing groups leads to correspondingly modified surfaces Seeley is agela. Suitable carrier materials can also be obtained by modification of the pore surface, for example, using boron compounds (BE-A-861275), aluminum (USA 4284527), silicon (EP-A 0166157) or phosphorus (DE-A 35 36 710).

Chrome compounds may contain inorganic or organic group. Preference is given to inorganic chromium compounds. Examples of suitable chromium compounds are, in addition to chromium trioxide and chromium hydroxide, salts of trivalent chromium with an organic and inorganic acids, for example, chromium acetate, oxalate, sulfate, and nitrate, as well as chelates of trivalent chromium, such as chromium acetylacetonate. Among them, most preferred are 9-hydrate nitrate chromium (III) and chromium acetylacetonate.

The media is usually suspended in a solvent and adding a chromium compound in the form of a solution. It is also possible, for example, to dissolve the chromium compound in suspension and then add it to the media. Preferably muddle the media in suspension and, if necessary, in the acid, preferably a carboxylic acid With1-C6such as formic acid or acetic acid, and particularly preferably formic acid, for 10-120 min before adding a chromium compound.

Additives to the media usually make a mass ratio of carrier:the chromium compound is from 100:0.1 to 100:10, in particular from 100:0.3 to 100:3.

is Tadeu reaction (a) can be carried out at temperatures from 0 to 100°C. Cost considerations the preferred room temperature. The solvent and/or acid can be partially or completely overtake before the next stage b). The chrome-containing media from stage a) is preferably selected and the maximum release from the suspension medium and the acid before the subsequent reactions.

As solvents it is possible to use the proton and aprotic solvents depending on the type of connection chromium. At the stage a) preference is given to contacting the media with a chromium compound in water or methanol. Here, the chromium component is preferably dissolved in water or methanol and then mixed with suspended carrier. The reaction time is usually from 10 minutes to 5 hours

Then it is preferable to remove the solvent, preferably at a temperature of 20-150°C and a pressure of 10-1 mbar. The catalyst precursor thus obtained can be dried completely or to leave some amount of residual moisture. However, the content of volatile components shall be not more than 20 wt.%, in particular not more than 10 wt.% in the calculation of the not-yet-activated chromium precursor of the catalyst.

The catalyst precursor obtained in reaction stage a), you can immediately enter in stage b) or pre-calcined in stage a') in an atmosphere of dry inert what about the gas at temperatures above 280°C. The calcination is preferably carried out at temperatures 280-800°C in a fluidized bed within 10-1000 minutes

The intermediate compound thus obtained in stage a) or a'), then activate oxidative conditions, for example in oxygen-containing atmosphere, at temperatures of 400-1000°C in stage b). The intermediate compound obtained from step a) or a'), preferably activated in a fluidized bed, directly replacing the inert gas to the oxygen-containing gas and increasing the temperature to the activation temperature. In this case it is better to heat in a dry gas stream containing oxygen in a concentration greater than 10 vol.%, during 10-1000 rpm, in particular, 150-750 min at 400-1000°C., in particular between 500 and 800°C, and then cooled to room temperature. Preferably, the maximum activation temperature was below the sintering temperature of the intermediate stages (a) or (a') at 20-100°C. the Oxygen can be fed in the presence of suitable fluorinating reagents, such as ammonium fluorosilicate preparation.

Chromiferous the catalyst precursor thus obtained, contains 0.1 to 5 wt.% chromium, in particular 0.3 to 2 wt.%.

Thus obtained chromium precursor of the catalyst is characterized by a short induction period of the polymerization of 1-alkenes.

Thus obtained chromium p is electonic catalyst, used according to the invention can also be restored in suspension or in the gas phase, for example, with ethylene and/or α-olefins, carbon monoxide or triethylborane, or modify solirovanie before use on stage). The molar ratio of reductant and chromium is usually in the range from 0.05:1 to 500:1, preferably from 0.1:1 to 50:1, in particular from 0.5:1 to 5.0:1.

In suspension temperature recovery is usually in the range of 10-200°C., preferably in the range of 10-100°C., and the pressure is 0.1 to 500 bar, preferably 1-200 bar.

Temperature recovery processes using fluidized bed is typically in the range from 10 to 800°C., in particular from 10 to 600°C. in General, the recovery in the gas phase is carried out at a pressure of 0.1 to 500 bar, preferably in the range of 1-100 bar and in particular in the range of 5-20 bar.

When restoring in the gas phase of the recovered chromium catalyst is usually suspended in the fluidized bed reactor using a flow of inert carrier gas, such as nitrogen or argon. The flow of carrier gas is usually mixed with a reducing agent, and a liquid reducing agents typically have a vapor pressure at STD. T and P equal to at least 1 bar.

At the stage (C) chromiferous the catalyst precursor is first pre-polymerized with α-olefins, pre is respectfully linear 1-alkenes With 2-C10and, in particular, ethylene or mixtures of ethylene with 1-alkenes With2-C10. The mass ratio of the chromium catalyst precursor used in the preliminary polymerization, the polymerized monomer is usually from 1:0.1 to 1:1000, preferably from 1:1 to 1:200. The preliminary polymerization can be carried out in suspension, in solution or in the gas phase at a temperature of 20-200°C and a pressure of 0.5 to 50 bar, which corresponds to 0.05 to 0.5 MPa.

The preliminary polymerization in the presence of a chromium catalyst precursor can be carried out in the presence of ORGANOMETALLIC compounds of the first, second, third or fourth main group or of the second transition series of the Periodic Table of elements. Suitable compounds of this type include gomolepticheskimi1-C10-alkali lithium, boron, aluminum or zinc, for example, n-utility, criativo, trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylamine, tridecylamine, trioctylamine, diethylzinc. In addition, well-suited With1-C10-alkoxides dialkylamide, such as ataxic diethylaluminum. You can also use dimethylammoniumchloride, methylaluminoxane, methylaluminoxane or diethylaluminium. As the ORGANOMETALLIC compound is particularly Ave is pactically n-utility or tridecylamine. Usually as well as mixtures of the above ORGANOMETALLIC compounds. The molar ratio of ORGANOMETALLIC compound:chromium is typically in the range of from 0.1:1 to 50:1, preferably in the range from 1:1 to 50:1. However, since many activators, such as alkali aluminum, at the same time are used to remove catalytic poisons (called traps), the amount used depends on the contamination of other starting substances. However, experts in this field can determine the optimal number of trials. Particularly preferable to carry out the preliminary polymerization in the absence of other ORGANOMETALLIC compounds.

After completion of the preliminary polymerization of the pre-polymerized chromiferous the catalyst precursor thus obtained, it is preferable to select and fully or partially separate from the monomers and solvent.

Thus obtained pre-polymerized catalyst precursor can be dried completely or leave it some moisture. However, volatile components shall be not more than 20 wt.%, in particular not more than 10 wt.% in the calculation of the pre-polymerized chromiferous the catalyst precursor. Pre-polymerized chromiferous preaches is the owner of catalyst, thus obtained, contains 0.1 to 5 wt.% chromium, in particular 0.3 to 2 wt.%. Preferably, the pre-polymerized chromiferous the catalyst precursor contained 5-50 wt.% polymer in the calculation of the pre-polymerized chromiferous the catalyst precursor, in particular 10 to 30 wt.% and particularly preferably 15-25 wt.%.

Preferably, the pre-polymerized chromiferous the catalyst precursor was a calcined catalyst CrO3/SiO2that in the polymerization of ethylene or of ethylene with 1-alkenes With2-C10allows to obtain a polyethylene with a broad molecular weight distribution (Mw/Mnin the range of 7-50, preferably 8-30), and the addition of hydrogen does not affect the molecular weight polyethylene or affected only to a small extent. Preference is given only very small amounts of incorporated 1-alkenes With2-C10preferably less than 2 wt.%, in particular less than 1 wt.% in the calculation of the thus obtained polyethylene.

Pre-polymerized compound of chromium is then used as a carrier for metallocene.

Particularly preferred metallocene represent complexes of the General formula (I)

in which the substituents and in which Exi have the following meanings:

M1Arepresents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten or an element of group 3 of the Periodic Table and the lanthanides,

XArepresents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C10alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, -OR6Aor-NR6AR7Aor two radicals XAin substituted and unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals XAare the same or different or may be connected to each other or XAis a ligand of the following groups:

where

Q1A-Q2Aare each O, NR6A, CR6AR7Aor S, and Q1Aand Q2Aassociated with M1A,

YArepresents C or S and

ZAis a OR6A, SR6A, NR6AR7APR6AR7Ahydrogen, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C10alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR8A3,

E1A-E5Aeach represents the angle the rod and not more than one of the E 1A-E5Ais phosphorus or nitrogen, preferably carbon,

t is 1, 2 or 3, and t depends on the valency of M1Athus, to the complex of General formula (I) has not been charged,

where

R1A-R5Aeach independently represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which, in turn, can contain1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, NR8A2N(SiR8A3)2, OR8A, OSiR8A3, SiR8A3where the organic radicals R1A-R5Amay also be substituted by Halogens and/or two radicals R1A-R5Ain particular vicinal radicals, may also be connected with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R1A-R5Acan also be connected with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S,

R6Aand R7Aeach independently of one another represent C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C 22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R6Aand R7Acan also be substituted by Halogens and/or two radicals R6Aand R7Acan also be connected with the formation of five-, six - or semichasnoho cycle, or SiR8Aand

R8Amay be the same or different and each may represent a C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, C1-C10-alkoxy or C6-C10-aryloxy, where the organic radicals R8Amay also be substituted by Halogens and/or two radicals R8Acan also be connected with the formation of five-, six - or semichasnoho cycle, and

Z1Ais a XAor

where the radicals

R9A-R13Aeach independently of one another represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which can, in turn, contain a1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 the volume of carbon in the aryl radical, R14A-C(O)Oh, R14A-C(O)NR14A, NR14A2N(SiR14A3)2, OR14A, OSiR14A3, SiR14A3where the organic radicals R9A-R13Acan also be substituted by halogen atoms, and/or two radicals R9A-R13Ain particular vicinal radicals, may be combined to form a five-, six - or semiology cycle, and/or vicinal radicals R9A-R13Acan be connected with the formation of five-, six - or semichasnoho heterocycle, which contains at least one atom from the group consisting of N, P, O and S, where

R14Aare the same or different and each represents a C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, C1-C10-alkoxy or C6-C10-aryloxy, where the organic radicals R14Amay also be substituted by halogen atoms and/or two radicals R14Acan also be connected with the formation of five-, six - or semichasnoho cycle, and

E6A-E10Aeveryone is carbon and not more than one of the E6A-E10Ais phosphorus or nitrogen, preferably carbon,

or the radicals R4Aand Z1Atogether form the group-R 15Av-A1Awhere

R15Arepresents a

=BR16A, =BNR16AR17A, =AlR16A, -Ge-, -Sn-O-, -S-, =SO, =SO2, =NR16A, =CO, =PR16Aor =P(O)R16A,

where

R16A-R21Aare the same or different and each represents a hydrogen atom, halogen atom, trimethylsilyloxy group, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, C1-C10-alkoxy or C6-C10-aryloxy, where the organic radicals R16A-R21Amay also be substituted by Halogens and/or two radicals R16A-R21Acan also be combined, form a five-, six - or semiology cycle, and

M2A-M4Aeach are silicon, germanium or tin, preferably silicon,

-NR22A2, -PR22A2or unsubstituted, substituted or condensed heterocycle, where

R22Aeach independently of one another is C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22-alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in alkylene the radical and 6-20 carbon atoms in the aryl radical, or Si(R 23A)3where the organic radicals R22Amay also be substituted by halogen atoms and/or two radicals R22Acan also be combined with the formation of five-, six-or semichasnoho cycle

R23Arepresents hydrogen, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R23Amay also be substituted by halogen atoms and/or two radicals R23Acan also be combined with the formation of five-, six-or semichasnoho cycle

v is 1 or may be equal to 0 when A1Ais an unsubstituted, substituted or condensed heterocycle,

or the radicals R4Aand R12Atogether form a group-R15A-.

These metal complexes can be synthesized by known methods, and preferred are the reaction of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium or chromium.

For the purposes of the present invention, the term alkyl refers to a linear or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl Term of alkenyl refers to linear or branched alkenyl, in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, 1-butenyl, 1-pentenyl or 1-hexenyl. The term C6-C22aryl refers to an unsubstituted, substituted or condensed aryl system, and the aryl radical may be substituted by other alkyl groups, such as phenyl, naphthyl, biphenyl, antronio, 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. The term arylalkyl refers to the aryl-substituted alkyl, and arylalkyl can be replaced by other alkyl groups, such as benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl.

A1Atogether with the bridge R15Amay, for example, to form an amine, a simple ether, thioether or phosphine. However, A1Acan also be an unsubstituted, substituted or condensed heterocycle, which can contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus, together with the carbon atoms of the cycle. Examples of 5-membered heteroalkyl groups, which may contain one to four nitrogen atoms and/or sulfur or oxygen as the atoms of the cycle together with the carbon atoms include 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-about sasoli, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl and 1,2,4-triazole-3-yl. Examples of 6-membered heteroaryl groups which may contain one to four nitrogen atoms and/or phosphorus, include 2-pyridinyl, 2-phosphabensidi, 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. Five-membered and six-membered heteroaryl group can be substituted C1-C10-alkyl, C6-C10-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-10 carbon atoms in the aryl radical, trialkylsilyl or halogen, such as fluorine, chlorine or bromine, or may be condensed with one or more aromatic or heteroaromatic compounds. Examples benzododecinium five-membered heteroaryl groups include 2-indolyl, 7-indolyl, 2-coumaroyl, 7-coumarinyl, 2-tianeptine, 7-tianeptine, 3-indazole, 7-indazole, 2-benzimidazolyl and 7 benzimidazolyl. Examples benzododecinium six-membered heteroaryl groups include 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 was taken from L. Fieser and M. Fieser, Lehrbuch der organiscen Chemie, 3rd revised edition, Verlag Chemie, Weinheim 1957.

Preferably, the radicals XAin the General formula (I) were identical and consisted of fluorine, chlorine, bromine, C1-C7is alkyl or aralkyl, in particular chlorine, methyl or benzyl.

For the purposes of the present invention, this type of complexes of formula (I) also include compounds with at least one ligand derived from cyclopentadienyl or heterocyclizations condensed with a heterocycle, preferably aromatic heterocycles containing nitrogen and/or sulfur. Such compounds are described, for example, in WO 98/22486. In particular, it can be dimethylsilanol(2-methyl-4-phenylindane)(2,5-dimethyl-N-phenyl-4-isopetasin)zirconiated, dimethylsilane(2-methyl-4-phenyl-4-gidrousilenny)zirconiated, dimethylsilane(2-ethyl-4-phenyl-4-gidrousilenny)zirconiated, bis(2,5-dimethyl-N-phenyl-4-isopetasin)zirconiated or (indenyl)(2,5-dimethyl-N-phenyl-4-isopetasin)zirconiated.

Among the complexes of the General formula (I), preferred are the following:

where the substituents and indices have the following meanings:

M1Arepresents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten or an element of group 3 of the Periodic Table and the lanthanides,

XArepresents fluorine, chlorine, bromine,iodine, hydrogen, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C10alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, -OR6Aor-NR6AR7Aor two radicals in substituted and unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals XAare the same or different and may be connected to each other or XAis a ligand of the following groups:

where

Q1A-Q2Aare each O, NR6A, CR6AR7Aor S, and Q1Aand Q2Aassociated with M1A,

YArepresents C or S and

ZAis a OR6A, SR6A, NR6AR7APR6AR7Ahydrogen, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C10alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR8A3,

E1A-E5Aeach represents a carbon, and not more than one of the E1A-E5Ais phosphorus or nitrogen, preferably carbon,

t is 1, 2 or 3, and t depends on the valency of M1Ato the complex of General formula (I) has not been charged,

where

R 1A-R5Aeach independently represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which, in turn, can contain1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, NR8A2N(SiR8A3)2, OR8A, OSiR8A3, SiR8A3where the organic radicals R1A-R5Amay also be substituted by halogen atoms and/or two radicals R1A-R5Ain particular vicinal radicals, may also be combined with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R1A-R5Acan also be combined with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S,

R6Aand R7Aeach independently of one another represent C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R6Aand R7Acan also be substituted by atoms of Galaga the a and/or two radicals R 6Aand R7Acan also be combined with the formation of five-, six - or semichasnoho cycle, or SiR8Aand

R8Amay be the same or different and each may represent a C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, C1-C10-alkoxy or C6-C10-aryloxy, where the organic radicals R8Amay also be substituted by halogen atoms and/or two radicals R8Acan also be combined with the formation of five-, six - or semichasnoho cycle, and

R9A-R13Aeach independently of one another represent hydrogen, C1-C22-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, which can, in turn, contain a1-C10-alkyl groups as substituents, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, R14A-C(O)Oh, R14A-C(O)NR14A, NR14A2N(SiR14A3)2, OR14A, OSiR14A3, SiR14A3where the organic radicals R9A-R13Acan also be substituted by halogen atoms, and/or two radicals R9 -R13Ain particular, two vicinal radicals, may be combined with the formation of five-, six - or semichasnoho cycle, and/or two vicinal radicals R9A-R13Acan be combined with the formation of five-, six - or semichasnoho heterocycle, which contains at least one atom from the group consisting of N, P, O and S, where

R14Aare the same or different, and each represents a C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, C1-C10-alkoxy or C6-C10-aryloxy, where the organic radicals R14Amay also be substituted by halogen atoms and/or two radicals R14Acan also be combined with the formation of five-, six - or semichasnoho cycle, and

E6A-E10Aeveryone is carbon and not more than one of the E6A-E10Ais phosphorus or nitrogen, preferably carbon,

=BR16A, =BNR16AR17A, =AlR16A, -Ge-, -Sn-, -O-, -S-, =SO, =SO2,

=NR16A, =CO, =PR16Aor =P(O)R16A,

where

R16A-R21Aare the same or different, and each represents a hydrogen atom, halogen atom, trimetals lilou group, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, C1-C10-alkoxy or C6-C10-aryloxy, where the organic radicals R16A-R21Amay also be substituted by halogen atoms and/or two radicals R16A-R21Acan also be combined with the formation of five-, six - or semichasnoho cycle, and

M2A-M4Aeveryone is silicon, germanium or tin, preferably silicon,

A1Arepresents - O -, - S -, >NR22A, >PR22A, =O, =S, =NR22A, -O-R22A, -NR22A2, -PR22A2or unsubstituted, substituted or condensed heterocycle, where

R22Aeach independently of one another represents a C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, or Si(R23A)3where the organic radicals R22Acan also be substituted by halogen atoms and/or two radicals R22Acan also be combined with the formation of five-, six - or semichasnoho cycle

R23Arepresents in the location, C1-C10-alkyl, 5-7-membered cycloalkyl or cycloalkenyl, C2-C22alkenyl, C6-C22-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R23Acan also be substituted by halogen atoms and/or two radicals R23Acan also be combined with the formation of five-, six - or semichasnoho cycle

v is equal to 1 and may also be equal to 0 when A1Ais unsubstituted, substituted or condensed heterocycle.

Particularly suitable complexes are not associated bridging groups metallocene complexes (B) of General formula (II)

where the substituents and indices have the following meanings:

M1Bis a metal of the 4th group of the periodic Table of elements, in particular, Zr,

E1BE4Beach independently of one another represents a nitrogen, phosphorus, oxygen or sulfur,

m is 0 when E1Bor E4Bare oxygen or sulfur, and is 1 when E1Bor E4Bis nitrogen or phosphorus,

E2BE3BE5VE6Veach independently of one another represents a carbon, nitrogen or phosphorus,

n is 0 when E2BE3BE5Bor E6Bare and the Otomi or phosphorus, and equal to 1 when E1Bor E4Bare carbon

R1B-R14Beach independently of one another represents hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, NR15V2N(SiR15V3)2, OR15V, OSiR15V3, SiR15V3where the organic radicals R1B-R14Vmay also be substituted by halogen atoms and/or two adjacent radicals R1B-R14Vcan also be combined with the formation of five-, six - or semichasnoho cycle, and/or two adjacent radicals R1B-R14Vcan be combined with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, where

R15Bare the same or different, and each represents a C1-C20-alkyl, C6-C15-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, and

XBrepresents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl, C6-C15-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical,

-OR16B or-NR16BR17V, -OC(O)R16AAbout3SR16B, R16BC(O)-CH-CO-R17B, CO, or two radicals XBform substituted and unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals XBare the same or different or may be connected to each other,

s is equal to 1 or 2 depending on the valency of M1Bto metallocene complex of General formula (II) has not been charged,

where

R16Band R17Beach represents a C1-C10-alkyl, C6-C15-aryl, arylalkyl, foralkyl or ferril each with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical.

The chemical structure of the substituents R1B-R14Bmay vary within wide limits. Possible organic substituents can be, for example, the following: hydrogen, C1-C22-alkyl which may be linear, cyclic 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, 3-12-membered cycloalkyl, which can, in turn, contain a C1-C10is an alkyl group as substituent, e.g. cyclopropane, CYCLOBUTANE, cyclopentane, cyclohexane, Cycloheptane, cyclooctane, cyclonona or cyclododecane, C2-C22-alkene is, which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, C6-C22-aryl which can be substituted by other alkyl groups, 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 aryl-substituted alkyl radical arylalkyl, which can be substituted by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where two adjacent radicals R1B-R14Bcan also be combined with the formation of 5-, 6 - or 7-membered cycle and/or two adjacent radicals R1B-R14Bcan be combined with the formation of five-, six - or semichasnoho heterocycle, which contains at least one atom from the group consisting of N, P, O and S, and/or the organic radicals R1B-R14Bcan also be substituted by halogen atoms such as fluorine, chlorine or bromine. Moreover, R1B-R14Bcan be an amino group NR15B2or N(SiR15B3)2, alkoxyl or aryloxides OR15Bfor example dimethylamino-N-ethylmethylamino, diethylamino-, N-methylpropylamine-, N-methylisobutyl the Mino-, N-ethylisopropylamine, dipropylamino, diisopropylamino-, N-methylbutylamine-, N-ethylbutylamine-, N-tert-butylamino, dibutylamino, di-sec-butylamino, diisobutylamine-, N-methylpentylamino, digoxigenin-, N-methylcyclohexylamine-, N-ethylcyclohexylamine-, N-isopropylcyclohexane, dicyclohexylamine, N-pyrrolidinyl, piperidinyl, decahydroquinoline, diphenylamine, N-methyl-aniline production or N-ethylaniline, metaxylem, ataxia or isopropoxide. Possible radicals R15Vin organosilicon substituents SiR15B3is the same organic radicals listed above for R1B-R14Band the radicals R15Bcan be combined with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. Radicals SiR15B3can also be combined in cyclopentadienyls cycle through the atoms of oxygen or nitrogen, such as trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylcyclohexyl.

Two adjacent radicals R1B-R14Bmay in each case together with the carbon atoms to which they are linked, form a heteroaromatic compounds containing at least one atom from the GRU is dust, consisting of nitrogen, phosphorus, oxygen and sulfur, particularly preferably nitrogen and/or sulfur. Preferred heterocyclic compounds and heteroaromatic compounds with 5-6-membered cycles. Examples of 5-membered heterocycles which can contain one to four nitrogen atoms and/or sulfur, or oxygen in the loop along with the carbon atoms include 1,2-dihydrofuran, furan, thiophene, pyrrole, isoxazol, 3-isothiazol, pyrazole, oxazole, thiazole, imidazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-triazole and 1,2,4-triazole. Examples of 6-membered heteroaryl groups which may contain one to four nitrogen atoms and/or phosphorus, include pyridine, postabortal, pyridazine, pyrimidine, pyrazin, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine. 5-Membered and 6-membered heterocycles can be substituted C1-C10-alkyl, C6-C10-aryl, alkylaryl with 1-10 carbon atoms in the alkyl radical and 6-10 carbon atoms in the aryl radical, trialkylsilyl or halogen atoms such as fluorine, chlorine or bromine, dialkylamino, alkylolamides, diarylamino, alkoxyl or aryloxides or be condensed with one or more aromatic or heteroaromatic compounds. Examples benzododecinium five-membered heteroaryl groups are indole, indazole, benzofuran, benzothiophene, benzothiazole, benzoxazole, gasoline is Idasa. Examples benzododecinium 6-membered heteroaryl groups are Roman, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, hinzelin, cinoxacin, 1,10-phenanthrolin and hemolysin. The nomenclature and numbering of the compounds was taken from Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979. Preferably, heterocycles/heteroaromatic compounds were condensed to the double bond C-C heterocycles/heteroaromatic compounds with the formation of cyclopentadienyls cycle. Heterocycles/heteroaromatic compounds with heteroatoms are preferably 2,3 -, or b-condensed.

T1Band T2Beach form together with cyclopentadienyls system condensed heteroaromatic 5-membered cycle or condensed aromatic 6-membered cycle. E1Bcan be localized on the carbon atom adjacent to the carbon atom connected with R3Bor R1B. E4Bcan be localized on the carbon atom adjacent to the carbon atom connected with R8Bor R10B. Preferably, E1Band E4Brepresented sulfur or nitrogen. Preferably, E2BE3BE5Band E6Brepresented the carbon. Preferred systems (along with cyclopentadienyls system) are, for example, thiopental, 2-methylthiophenol, 2-ethylthiophene the flax, 2-isopropylthioxanthone, 2-n-butylthioethyl, 2-tert-butylthiophenol, 2-trimethylsilylmethyl, 2-phenylthiophene, 2-aftercapture, 3-methylthiophenol, 4-phenyl-2,6-dimethyl-1-tiefenthaler, 4-phenyl-2,6-diethyl-1-tiefenthaler, 4-phenyl-2,6-aminobutiramida 1-tiefenthaler, 4-phenyl-2,6-di-n-butyl-1-tiefenthaler, 4-phenyl-2,6-di(trimethylsilyl)-1-tiefenthaler, isopentane, 1-methylacetylene, 1-atlasapollo, 1-isopropylnaphthalene, 1-n-butylacetate, 1-trimethylsilylacetamide, 1-phenylazophenol, 1-naphthylacetate, 1-phenyl-2,5-dimethyl-1-isopentane, 1-phenyl-2,5-diethyl-1-isopentane, 1-phenyl-2,5-di-n-butyl-1-isopentane, 1-phenyl-2,5-di(tert-butyl)-1-isopentane, 1-phenyl-2,5-ditrimethylol-1-aspendale, 1-tert-butyl-2,5-dimethyl-1-aspendale, oxapentane, phosphopentose, 1-phenyl-2,5-dimethyl-1-phosphopentose, 1-phenyl-2,5-diethyl-1-phosphopentose, 1-phenyl-2,5-di(n-butyl)-1-phosphopentose, 1-phenyl-2,5-di(tert-butyl)-1-phosphopentose, 1-phenyl-2,5-di(trimethylsilyl)-1-phosphopentose, 1-methyl-2,5-dimethyl-1-phosphopentose, 1-tert-butyl-2,5-dimethyl-1-phosphopentose, 7-cyclopent[1,2]thiophene[3,4]cyclopentadiene or 7-cyclopent[1,2]pyrrole[3,4]cyclopentadiene. The synthesis of such cyclopentadienyls systems with condensed heterocycle described, for example, in WO 98/22486. In the book "Metalorganic catalysts for synthesis and polymerisation", Springer Verlag 1999, p. 150 ff, Ewen et al., also described the synthesis of such cyclopentadienyls systems.

<> T1Band T2Bare preferably the above diene structure and together with cyclopentadienyls skeleton to which they are attached, preferably form a substituted or unsubstituted indenolol system such as indenyl, 2-methylindenyl, 2-ethylidene, 2-isopropylphenyl, 3-methylindenyl, bensinger or 2-methylbenzhydryl. Condensed cyclic system may contain, in addition, C1-C20-alkyl, C2-C20alkenyl, C6-C20-aryl, arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, group, NR15B2N(SiR15B3)2, OR15B, OSiR15B3or SiR15B3for example , 4-methylindenyl, 4-ethylidene, 4-isopropylphenyl, 5-methylindenyl, 4-phenylindane, 5-methyl-4-phenylindane, 2-methyl-4-phenylindane or 4-naphthylidine.

The choice of ligands XBis determined, for example, the nature of the source compounds of the respective metals, which are used for the synthesis of metallocene complexes (B), but can also be varied. Possible ligands XBinclude, in particular, halogen atoms such as fluorine, chlorine, bromine or iodine, in particular chlorine. As the ligand XBalso suitable alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or bentilee as ligands X Byou can mention just for example, but without claiming to be complete, triptorelin, BF4-PF6-and poorly coordinated or uncoordinated anions (see, for example, S. Strauss in Chem. Rev. 1993, 93, 927-942), for example, B(C6F5)4-.

As the ligand XBalso widely used amides, alkoxides, sulfonates, carboxylates and β-diketonates. The variation of the radicals R16Band R17Byou can, for example, fine-tune the physical properties such as solubility. Possible organic substituents R16Band R17Binclude the following, for example: C1-C20-alkyl which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 3-12-membered cycloalkyl, which can, in turn, contain a C6-C10-aryl group as substituent, e.g. cyclopropane, CYCLOBUTANE, cyclopentane, cyclohexane, Cycloheptane, cyclooctane, cyclonona or cyclododecane, 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 is whether cyclooctadiene, C6-C20-aryl which can be substituted by other alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl, biphenyl, antoanela, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, 2-methoxyphenyl, 2-N,N-dimethylaminophenyl or arylalkyl, which can be substituted by other alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where R16Bcan also be combined with R17Bwith the formation of 5 - or 6-membered cycle, and organic radicals R16Band R17Vcan also be substituted by halogen atoms such as fluorine, chlorine or bromine. Particularly preferable to use some substituted ligands XBbecause you can get them from cheap and readily available starting materials. Thus, particularly preferred is one in which XBrepresents diethylamid, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluensulfonate, acetate or acetylacetonate.

The number s of the ligands XBdepends on the oxidation state of the transition metal MB. The index s can be represented in General form. The oxidation state of the transition metal MBin catalytically active complexes is usually well-known experts in this field. It is highly likely that the circus is, and hafnium present in the oxidation state +4. However, you can also use complexes, in which the oxidation state does not correspond to the oxidation state of the active catalyst. Such complexes can then oxidize with suitable activators. Preference is given to complexes of zirconium in oxidation state +4.

The radicals XBpreferably represent fluorine, chlorine, bromine, C1-C7-alkyl or benzyl, in particular chlorine.

Metallocene complexes can also be chiral. Thus, it is possible to use meso or racemic form, or a mixture of two forms (relative signs of chirality cyclopentadienyls connections, see R. Halterman, Chem. Rev. 92, (1992), 965-994). Preference is given to metallocene in racemic form or in the form of enriched racemate.

Such complexes can be synthesized by known methods by the reaction of the appropriately substituted, cyclic hydrocarbon anions with a particularly preferred halides of zirconium. Examples of appropriate preparative methods are described, inter alia, in Journal of Organometallic Chemistry, 369 (1989), 359-370.

Especially suitable zirconocene formula (II) with the same cyclopentadienyls radicals.

The following examples of particularly suitable catalysts include, among others, bis(indenyl)tiandihui, bis(fluorenyl)tiandihui, bis(indenyl)zirconiated, b is(2-methylindenyl)zirconiated, bis(2-ethylidene)zirconiated, bis(2-isopropylphenyl)zirconiated, bis(2-tert-butylidene)zirconiated, bis(2-methylindenyl)zirconiabased, bis(2-methyl-4,5-benzinger)zirconiated, bis(2-methyl-4-phenylindane)zirconiated, bis(2-methyl-4-(1-naphthyl)indenyl)zirconiated, bis(2-ethyl-4-(1-naphthyl)indenyl)zirconiated, bis(2-propyl-4-(1-naphthyl)indenyl)zirconiated, bis(2-isobutyl-4-(1-naphthyl)indenyl)zirconiated, bis(2-propyl-4-(9-phenanthrol)indenyl)zirconiated, bis(2-methyl-4-isopropylidene)zirconiated, bis(2,7-dimethyl-4-isopropylidene)zirconiated, bis(2-methyl-4,6-diisopropylphenol)zirconiated, bis(2-methyl-4[p-triptoreline]indenyl)zirconiated, bis(2-methyl-4-[3',5'-dimetilfenil]indenyl)zirconiated, bis(2-methyl-4-[4'-tert-butylphenyl]indenyl)zirconiated, bis(2-ethyl-4-[4'-tert-butylphenyl]indenyl)zirconiated, bis(2-propyl-4-[4'-tert-butylphenyl]indenyl)zirconiated, bis(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)zirconiated, bis(2-n-butyl-4-[4'-tert-butylphenyl]indenyl)zirconiated, bis(2-hexyl-4-[4'-tert-butylphenyl]indenyl)zirconiated, (2-isopropyl-4-phenylindane)(2-methyl-4-phenylindane)zirconiated, (2-isopropyl-4-(1-naphthyl)indenyl)(2-methyl-4-(1-naphthyl)indenyl)zirconiated, (2-isopropyl-[4'-tert-butylphenyl]indenyl)(2-methyl-4-[1-naphthyl]in enyl)zirconiated, and is also appropriate dimethylzirconium, monochromon(alkylacrylate)zirconium and di(alkylacrylate)zirconium compounds. Other examples include the relevant zirconocene, in which one or both chloride ligands are replaced by bromine or iodine.

The mass ratio of the transition metal in metallocene and chromium in the chromium compound in the pre-depolimerization the catalyst precursor in the mixed catalyst is usually in the range from 1:1 to 1:10, preferably from 1:1.1 to 1:5 and particularly preferably from 1:1.2 to 1:2.

Mixed catalyst may be completely dry or contain residual moisture. However, volatile components shall be not more than 30 wt.%, in particular not more than 10 wt.% in the calculation of the mixed catalyst. Pre-polymerized chromiferous the catalyst precursor preferably contains 5-50 wt.% polymer in the calculation of the mixed catalyst, in particular 10 to 30 wt.% and particularly preferably 15-25 wt.%.

When using metallocene as the sole catalyst in the same reaction conditions of homopolymerization ethylene preferably receive increased Mwcompared with the pre-polymerized precursor of the catalyst when used as the sole catalyst in the same conditions is s response.

Some metallocene themselves have low activity in the polymerization, and then process them one or more activators, in particular component (C), to obtain a good polymerization activity. Therefore, the mixed catalyst system optionally contains one or more activators (C). Depending on the combination of the preferred catalysts is one or more activators (C). Preferably, the mixed catalyst of the present invention contain one activator (C).

The activator or activators (C) can in each case be used in any quantity in the calculation of metallocene in the composition of the mixed catalyst of the present invention, but preferably in each case to take them in excess or stoichiometric amount based on metallocene that they activate. The number of activators depends on the type of activator (C). In General, the molar ratio of metallocene and activator (C) may be from 1:0.1 to 1:10000, preferably from 1:1 to 1:2000.

Suitable compounds (C), which can react with metallocenes to turn it into a catalytically active or more active compound are, for example, connection type alumoxane, a strong uncharged Lewis acid, an ionic compound with the cation Lewis acid or ion is the first connection, contains as cation Pentecostal acid.

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

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

Particularly suitable alumoxanes is methylalumoxane.

Such oligomeric alumoxane usually get with adjustable reaction solution trialkylamine, in particular trimethylaluminum with water. In the General case thus obtained oligomeric alumoxane compounds are mixtures of molecules with linear and cyclic chain of different length, so I should be considered as an average value. Alumoxane can be mixed with other metallacycle, usually aluminiumalloy. Drugs alumoxanes, suitable as component (C), available in the industry.

In addition, as the component (C) instead of alumoxanes General formulas (X) and (XI) it is possible to use modified alumoxane, in which some of the hydrocarbon radicals substituted by atoms of water is entering or CNS, azlocillin, siloxane or amide radicals.

It was found that it is advantageous to use metallocene and alumoxane in such quantities, in which the atomic ratio of aluminum in alumoxane, including any aluminiuim, and the transition metal in the metallocene complex is in the range from 1:1 to 2000:1, preferably from 10:1 to 500:1 and in particular in the range from 20:1 to 400:1.

Another class of suitable activators (C) represent hydroxyalkoxy. They can be obtained by adding 0.5 to 1.2 equivalents of water per equivalent of aluminum in aluminiumgie, in particular triisobutylaluminum, at low temperatures, usually below 0°C. Such compounds and their use in polymerization of olefins is described, for example, in WO 00/24787. The atomic ratio of aluminum in hydroxyadamantane and transition metal metallocene is usually in the range from 1:1 to 100:1, preferably from 10:1 to 50:1 and in particular in the range from 20:1 to 40:1. Preference is given dialkyldithiocarbamato connection.

As strong, uncharged Lewis sites acids, preference is given to compounds of the 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 X3Dit is jdy represent hydrogen, With1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloacyl each with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine, in particular, galarry, preferably pentafluorophenyl.

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

Compounds of this type which are particularly suitable as component (C)are boron and braccini, such as trialkylborane, trainborn or trimethylboroxine. Particularly preferred boron containing at least two perfluorinated aryl radical. Especially preferred compounds of General formula (XII)in which X1DX2Dand X3Dthe same, for example, triphenylboron, Tris(4-forfinal)borane, Tris(3,5-differenl)borane, Tris(4-formationl)borane, Tris(pentafluorophenyl)borane, Tris(tolyl)borane, Tris(3, 5dimethylphenyl)borane, Tris(3,5-differenl)borane or Tris(3,4,5-tryptophanyl)borane. Preference is given to Tris(pentafluorophenyl)borane.

Suitable compounds (C) preferably receives the reaction of the aluminum or boron compounds of the formula (XII) with water, alcohols, derivatives of phenol, derivatives thiophenol or aniline, and especially important halogenated and especially perfluorinated alcohols and phenols. Examples of particularly prigodnyh compounds include pentafluorophenol, 1,1-bis(pantpthenic)methanol and 4-hydroxy-2,2',3,3',4',5,5',6,6'-nonaboriginal. Examples of combinations of compounds of the formula (XII) and pentecosta acids include, 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 hydrate.

Other suitable compounds of aluminum and boron of the formula (XII) R1Drepresents an OH group, such as, for example, in Borno and Borisovich acids, and in a sense Barinova acid with perfluorinated aryl radicals, for example (C6F5)2BOH, less suitable.

Strong uncharged, lisowska acid, are suitable as activators (C)also include the reaction products of boric acid with two equivalents of trialkylamine or reaction products trialkylamine with two equivalents of an acidic fluorinated, in particular perfluorinated, carbon compounds, such as pentafluorophenol or bis(pentafluorophenyl)Barinova acid.

Suitable ionic compounds containing cations of Lewis sites acids include compounds of the type of salts of a cation of the General formula (XIII)

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

where

M3Dis an element of groups 1 to 16 of the Periodic Table of elements

Q1-Qzrepresent the negative of the singly charged group, such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl, haloacyl, each with 6-20 carbon atoms in the aryl radical and 1-28 carbon atoms in the alkyl radical, C3-C10-cycloalkyl, which may contain C1-C10-alkyl groups as substituents, halogen, C1-C28alkoxyl, C6-C15-aryloxy, silyl or mercaptamine group,

a is an integer from 1 to 6, and

z is an integer from 0 to 5,

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

Particularly suitable carbonium, oxonium and sulfonamide cations and cationic transition metal complexes, in particular triphenylmethyl-cation, the silver cation and the cation 1,1'-dimethylferrocene. Preferably, they have been associated with uncoordinated counterions, in particular, boron compounds, as also mentioned in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.

Salt with uncoordinated anions also obtained by reaction of compounds of boron or aluminum, for example aluminiumgie, with a second compound which can react with the formation of a link between two atoms is boron or aluminum, for example, water, and a third compound which forms an ionized ionic compound with a boron compound or aluminum, for example, triphenylmethane, or optional base, preferably an organic nitrogen-containing base, for example an amine, an aniline derivative or a nitrogen-containing heterocycle. In addition, you can add a fourth connection, which is similarly reacted with a compound of boron or aluminum, for example pentafluorophenol.

Preferably, ionic compounds with cations - Pentecoste acids were also associated with uncoordinated counterions. As Pentecostal acid is particularly preferred protonated amine or aniline derivatives. The preferred cations are N,N-dimethylaniline, N,N-dimethylcyclohexylamine, as well as derivatives of the last two.

As component C) are also suitable compounds containing anionic boron-containing heterocycles, such as described in WO 9736937, in particular dimethylaminoethanol or trietilborazina.

Preferred ionic compounds (C) include borates, which contain at least two perfluorinated aryl radical. Particular preference is given tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline and, in particular, tetrakis(pentafluorophenyl)borate, N,N-di is ethylcyclohexylamine, tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylamine or tricityregionalchamber.

There is a possibility of connection of two or more borate anions with each other, as in dianion [(C6F5)2B-C6F4-B(C6F5)2]2-or the borate anion can be bound via a bridge with a suitable functional group on the surface of the media.

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

The number of strong uncharged Lewis acids, ionic compounds with cations of Lewis acids or ionic compounds with cationic acids Branstad is preferably from 0.1 to 20 equivalents, preferably 1 to 10 equivalents, and particularly preferably from 1 to 2 equivalents per metallocen.

Suitable activators (C) also include compounds of boron-aluminum, such as di[bis(pentafluorophenyl)barocci]meillan. Examples of such compounds of boron-aluminum described in WO 99/06414.

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

Metallocen preferable to dissolve the e, preferably in an aromatic hydrocarbon from 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or mixtures thereof.

Particularly preferred combinations of preferred options (C) preferred options metallocene and pre-polymerized chromium catalyst precursor.

The preferred activator (C) for metallocene is alumoxane. Preference as activator is also preferred combinations of compounds of the type of salts of a cation of the General formula (XIII) (C), in particular tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline, tetrakis(pentafluorophenyl)borate, N,N-dimethyl-cyclohexylamine or trityl tetracosapentaenoic. In addition, as activator (C) is particularly suitable reaction products of aluminum compounds of the formula (XII) with perfluorinated alcohols and phenols.

Metallocen usually added to the pre-polymerized chromiferous the catalyst precursor in an amount of from 0.1 to 100 mol, preferably 1-20 mol and particularly preferably 2-10 mol. When using metallocene as the sole catalyst in the same reaction conditions of homopolymerization or copolymerization of ethylene preferably formed polymer with a higher Mw than in the presence of pre-polymerized chrome is terasawa catalyst precursor as the only complex in the same reaction conditions.

Preference is given to mixed catalyst containing at least one metallocene at least one pre-polymerized chromiferous the catalyst precursor and at least one activator (C). You can, for example, to add two different metallocene to one or two different pre-polymerized chromium catalyst precursor. Preferred is the introduction of at least one metallocene, preferably one metallocene, one pre-polymerized chromiferous the catalyst precursor to achieve a relative spatial proximity of different centers of the catalyst, and a good mixture of different of the resulting polymers.

For the preparation of the mixed catalyst according to the present invention metallocene and/or activator (S) preferably immobilized on pre-polymerized chromiferous the catalyst precursor by physical adsorption or by chemical reaction, i.e. covalent binding components with reactive groups on the carrier surface.

The order in which the unite pre-polymerized chromiferous the catalyst precursor, metallocene and the activator (C)is not significant. After the individual stages of the process is and the various intermediate products can be washed with suitable inert solvents, such as aliphatic or aromatic hydrocarbons. Metallocene and activator (s) can be mobilitat independently from each other, for example, sequentially or simultaneously. Thus, the pre-polymerized chromiferous the catalyst precursor can first be brought into contact with the activator or activators (C) or first metallocene or metallocene. It is also possible pre-activation of metallocene with one or more activators (C) before mixing with the pre-polymerized chromiferous the catalyst precursor. Pre-activation is usually carried out at temperatures of 10-100°C, preferably 20-80°C.

Applying metallocene and activator (S) on a substrate is typically carried out in an inert solvent, which can be removed by filtration or by evaporation after application is completed. After separate stages, the solid can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons, and dried. However, you can use another damp caused mixed catalyst.

In a preferred variant of the preparation caused a mixed catalyst system metallocen lead in contact with the activator (S) and then mixed with a pre-polymerized chromiferous p is electonica catalyst. Received caused a mixed catalyst system, it is preferable to dry, to make sure that all of the solvent or its main part is removed from the pores of the carrier. The mixed catalyst is preferably obtained in the form of loose powder. Examples of industrial implementation of these methods are described in WO 96/00243, WO 98/40419 or WO 00/05277.

Mixed catalyst may also contain as an additional 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, in particular Li, Na, K, Mg, boron, aluminum or Zn,

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

R2Gand R3Geach represent hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, or alkoxy that contains1-C10-alkyl or C6-C15-aryl,

rGis an integer from 1 to 3, and

sGand tGare integers from 0 to 2, the amount of rG+sG+tGcorresponds to the valency of MG,

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

Among the metal compounds of the formula (XX) are preferred so that

MGrepresents lithium, magnesium, boron or aluminum, and

R1Gis1-C20-alkyl.

Especially preferred compounds of metals of the formula (XX) are motility, utility, n-utility, methylaniline, methylacrylamide, ethylaniline, ethylaniline, butylaniline, dimethylamine, diethylamine, dibutylamine, n-butyl-n-octylamine, n-butyl-n-heptylamine, in particular n-butyl-n-octylamine, tri-n-hexylamine, triisobutylaluminum, tri-n-butylamine, triethylamine, dimethylammoniumchloride, dimethylaminophenyl, methylaluminoxane, methylaluminoxane, diethylaluminium and trimethylaluminum and mixtures thereof. You can also use the products of partial hydrolysis of aluminiumraw in spirits.

The compound (E) preferably used in the catalyst system in an amount such that the molar ratio of MGfrom the formula (XX) and the transition metal in metallocene ranged from 3000:1 to 0.1:1, preferably from 800:1 to 0.2:1 and particularly prefer the Ino from 100:1 to 1:1.

In General, the compound of the metal (E) of General formula (XX) is used as a component of a catalytic system for the polymerization or copolymerization of olefins. You can use the metal connection (E), for example, for the preparation of the mixed catalyst and/or it can be added during or immediately prior to polymerization. Metal link (E) may be the same or different.

Component (E) can be introduced into the reaction in any other way. For example, metallocene can be brought into contact with components (C) and/or (E) or before or after contact with the polymerized olefins.

In another preferred embodiment, the mixed catalyst was prepared as described above from metallocene, activator (C) and pre-polymerized chromium catalyst precursor and lead in contact with the component (E) during the polymerization, at the beginning or directly in front of her. A preferred such method, when the first (E) is brought into contact with an α-olefin, which will polimerizuet, and then add the mixed catalyst.

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

In addition, during, or after preparation of the mixed catalyst can be entered as a modifying additive component a small amount of olefin, preferably α-olefin, such as vinylcyclohexane, styrene or phenyldimethylsilane, an antistatic or a suitable inert compound such as a wax or oil. The molar ratio of additives and metallocene is usually from 1:1000 to 1000:1, preferably from 1:5 to 20:1.

A mixed catalyst of the present invention can be used to obtain the polyethylene of the present invention, which has good properties in operation and processing.

To obtain a polyethylene according to the present invention will polimerizuet ethylene or ethylene with α-olefins with 3 to 10 carbon atoms, as described above.

In the method of polymerization according to this invention will polimerizuet ethylene or ethylene with α-olefins with 3 to 10 carbon atoms. Preferred α-olefins are linear or branched C2-Cl0-1-alkenes, in particular linear C2-C10-1-alkenes, such as Eten, propene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-OK, the Yong, 1-the mission 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-C8-1-alkenes. You can also polymerizate mixture of different α-olefins. The preferred polymerizati at least one α-olefin chosen from the group consisting of Athena, propene, 1-butene, 1-pentene, 1-hexene, 1-Heptene and 1-octene. Preference is given to mixtures of monomers containing at least 50 mol.% of ethylene.

The method of polymerization of ethylene with α-olefins according to the present invention can be realized by all in the industry known methods of polymerization at temperatures from -60 to 350°C, preferably from 0 to 200°C and particularly preferably from 25 to 150°C, and pressures of from 0.5 to 4000 bar, preferably from 3 to 40 bar. The polymerization can be conducted in a known manner in the volume, in suspension, in gas phase or in a supercritical medium in the conventional reactors used for the polymerization of olefins. It can be done in periodic mode or preferably continuously in one or more stages. All possible methods of polymerization at higher pressures in tube reactors or autoclaves, in solution, in suspension, in gas phase under stirring or in a gas phase fluidized bed.

Polimeri what the situation is usually carried out at temperatures in the range from -60 to 350°C, preferably in the range from 20 to 300°C, and at pressures from 0.5 to 4000 bar. The average contact time is usually from 0.5 to 5 h, preferably from 0.5 to 3 hours Optimum temperature and pressure for carrying out the polymerization is usually dependent on the method of polymerization. In the case of polymerization at high pressure, typically at pressures from 1000 to 4000 bar, in particular from 2000 to 3500 bar, typically use high temperature polymerization. Optimal temperature ranges for these methods of polymerization at high pressure constitute 200-320°C, in particular 220-290°C. In the case of polymerization at low pressure usually set the temperature at least a few degrees below the softening temperature of the polymer. In particular, in such ways polymerization set the temperature from 50 to 180°C, preferably from 70 to 120°C. In the case of polymerization in suspension polymerization is usually conducted in the environment of the suspension, preferably in an inert hydrocarbon, for example in an aliphatic or cycloaliphatic hydrocarbon, such as butane, isobutane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane or mixture of hydrocarbons, or in the monomers. You can also use white spirit or fractions hydrogenated diesel oil, which are carefully freed from oxygen, sulfur compounds and moisture. Temperature is RA polymerization is usually in the range from -20 to 115°C, and the pressure is usually in the range of 1-100 bar. Solids in suspension are usually 10-80%. The polymerization can be conducted or in periodic mode, for example, in an autoclave under stirring, or continuously, for example in tubular reactors, preferably circulation reactors. Special preference is given to application of the method of Phillips PF, as described in US-A 3242150 and US-A 3248179. The polymerization in the gas phase is usually carried out at 30-125°C and a pressure of 1-50 bar. Gas-phase polymerization is preferably carried out in a fluidized bed using a carrier gas containing nitrogen and/or propane, at a concentration of ethylene 15-25 vol.%. The reactor temperature set in the range of 80-130°C and kept constant by a corresponding reduction in the amount of ethylene. At higher temperatures the activity of the chromium catalyst (A) is reduced, and, consequently, reduced z-average molar mass.

Among these methods, the polymerization is particularly preferred gas-phase polymerization, in particular in the reactor gas-phase polymerization in a fluidized bed polymerization in solution and polymerization in suspension, in particular in water reactors and in the reaction apparatus with stirrer. Gas-phase polymerization can also be carried out in the condensed or sverhorganizovannym condition, if this is part of the circulating gas is cooled below the dew point and re-fed into the reactor in the form of a two-phase mixture. You can also use multiple reactor in which two sections of polymerization are connected to each other, and the polymer repeatedly passes alternately through these two sections. The conditions of polymerization in two sections may be different. Such a reactor is described, for example, in WO 97/04015. Different or identical methods of polymerization can optionally be connected in series with the formation of the cascade polymerization, for example, in the process Hostalen®. It is also possible parallel arrangement of reactors using two or more identical or different ways. Furthermore, the polymerization can also use molecular weight regulators, for example hydrogen, or traditional additive type antistatic agent.

It is preferable to conduct the polymerization in a single reactor, in particular in gas-phase reactor. The polyethylene according to the present invention is produced by polymerization of ethylene with α-olefins containing 3 to 10 carbon atoms, in the presence of a mixed catalyst of the present invention. The resulting polyethylene powder from the reactor is very smooth, so unlike cascading ways subsequent extrusion, typically used to obtain a uniform product is not needed.

Obtaining mixtures of polymers by thorough mixing of the individual components or by extrusion of the melt in the extruder is or kneading machine (see, for example, "Polymer Blends" in Ullmann''s Encyclopedia of Industrial Chemistry, 6th Edition, 1998 Electronic Release) are often fraught with some difficulties. The melt viscosity of the components with high and low molecular weight in a bimodal mixture of polyethylene vary enormously. While the low molecular weight component becomes liquid at conventional temperatures of obtaining mixtures of about 190-210°C, high-molecular component only softens ("lentil soup"). Therefore, homogeneous mixing of the two components is difficult. In addition, it is known that in the extruder of high molecular weight component can be destroyed as a result of thermal stress under the action of shear forces, so that the mixture properties deteriorate. Therefore, the quality of mixing in such polyethylene mixtures is often unsatisfactory.

The quality of mixing of polyethylene powder are obtained directly from the reactor, can be tested using thin slices ("microtome slices") of the sample in the optical microscope. Heterogeneity is manifested in the form of discontinuities or "white spots". Such heterogeneity and "white spots" are mainly represent particles with high molecular weight, high viscosity in the matrix with a low viscosity (see, for example, U. Burkhardt et al. in Aufbereiten von Polymeren mit neuartigen Properties", VDI-Verlag, Dusseldorf 1995, p. 71). These enabled, which can reach a size up to 300 μm, to cause cracking in tension and lead to brittle fracture of the components. The higher the quality of mixing of the polymer, the smaller the inclusions, the rarer they are. The quality of mixing of the polymer determined quantitatively according to ISO 13949. The method of determining includes obtaining microtome slice of a polymer sample, the calculation/measurement number and size of these inclusions and the assessment of the quality of mixing of the polymer according to the established pattern.

Getting polyethylene according to the present invention directly in the reactor reduces energy cost, does not require subsequent stages of mixing and facilitates the regulation of the molecular mass distribution and fractions of molecular weight for different polymers. In addition, achieves a good mixing of the polyethylene.

The following examples illustrate the invention without limiting its scope.

The results of the determination were obtained as follows.

Samples for NMR were dispersible in inert gas and, if necessary, sealed. The signals from the solvent in the NMR spectrum1H and13C served as internal standard, and chemical shifts were then converted to chemical shifts relative to tetramethylsilane.

The content of vinyl groups was determined using the X in accordance with ASTM D 6248-98. IR spectra were taken on a thick square is Russia a thickness of 0.1 mm, obtained by pressing at 180°C for 15 minutes the Content of 1-hexene in the polymer samples was determined by the method of X with chemical calibration of the IR spectrum, NMR spectra.

Number of branches/1000 carbon atoms was determined by NMR13C, as described by James C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and expected General content of CH3groups/1000 carbon atoms. Similarly define a longer side chain than CH3/1000 carbon atoms, but the ends of the chains not included.

The density of the samples of the polymers were determined using X using chemical calibration of the IR spectrum density determined by the immersion method in accordance with ISO 1183-1.

Molecular mass distribution and the values of Mn, Mw, Mzand Mw/Mnwas determined by the method of high-temperature gel permeation chromatography according to the method of DIN 55672 on a WATERS 150 C with the following columns connected in series: 3x SHODEX AT 806 MS, 1x SHODEX UT 807 and 1x SHODEX AT-G under the following conditions: solvent: 1,2,4-trichlorobenzene (stabilized of 0.025 wt.% 2,6-di-tert-butyl-4-METHYLPHENOL), flow rate: 1 ml/min, the volume of the sample to 500 ál temperature: 140°C. the Column was calibrated using standards of polyethylene with a molecular mass of from 100 to 107g/mol. The evaluation was performed using the program Win-GPC from HS-Entwicklungsgesellschaft fur wisseschaftliche Hard - und Software mbH, Ober-Hilbersheim.

For the purposes of the present invention, the expression "HLMI" means, as is known, the flow rate under high load, and it is always determined at 190°C under a load of 21.6 kg 190°C/21,6 kg) in accordance with ISO 1133.

The limiting viscosity of this, which corresponds to the limiting value of the viscosity when the concentration of the polymer tends to zero, was determined on an automatic Ubbelohde viscometer (Lauda PVS 1) at a concentration of 0.001 g/ml in a solution of decalin at 135°C in accordance with ISO 1628.

Bulk density was determined in accordance with DIN 53468, the polymer powder.

Tensile strength was determined in accordance with ISO 527.

The content of the element chromium was determined photometrically using peroxide complexes. The content of zirconium and chloride was determined by titration.

The transparency of the samples was determined in accordance with ASTM D 1746-03 on films with a thickness of 50 μm on the device BYK Gardener Haze Guard Plus Device, calibrated using calibration cells 77,5 at least 5 films of size 10×10 cm

Haze was determined in accordance with ASTM D 1003-00 on films with a thickness of 50 μm on a BYK Gardener Haze Guard Plus Device for at least 5 films of size 10×10 cm

Gloss at 20° and 60° was determined in accordance with STM D 2457-03 for films with a thickness of 50 μm on glossmeter with vacuum plate for fastening the film.

Abbreviations in sleduyushei table:

cat. - catalyst

T(poly) - temperature polymerization

Mw- mass-average molecular mass

Mn- srednekislye molecular mass

Mzz-average molecular weight

density - density polymer

Production. - the performance of the catalyst in g of the obtained polymer in g of used catalyst.

Beendelivered and methylalumoxane available in the industry from the company Crompton.

Example 1

Stage a) applying a chromium component on a substrate

1550 g deposited chromium component (nitrate chromium(III) 9-hydrate) with a chromium content of 1 wt.% in the chrome-containing solid substance was prepared as described in example 1 (without activation) EP-A-0589350.

Stage b) activation of the chromium component

1550 g of the catalyst precursor obtained in stage a), activated air in the fluidized bed in the activator at a temperature of 520°C for 10 hours To activate the catalyst precursor was heated to 350°C for 1 h, held at this temperature for 1 h, then heated to a temperature of calcination, held at this temperature for 2 h and then cooled below the temperature of 350°C in nitrogen.

Output 1200

Stage c) Preliminary polymerization

900 g of activated deposited chromium component, obtained in stage b), suspended in 20 the heptane with stirring. The suspension is heated to a temperature of 65°C in argon atmosphere and then filed ethylene at 80 l/h

After 60 min, the supply of ethylene was stopped and ethylene dissolved in the heptane was removed with argon for 2 hours and Then the slurry was removed residues of monomer and moved it to a ceramic filter, purged with argon. Pre-polymerized chromium precursor of the catalyst was filtered, washed 10 l of heptane and again filtered. Thus obtained pre-polymerized chromiferous the catalyst precursor was dried at 40°C and reduced pressure. Got 1050 g pre-polymerized chromium catalyst precursor with the content of 0.8 wt.% Cr and 0.95 wt.% ostatochnogo solvent.

Stage d) Applying metallocene on a substrate

of 3.54 g (9,02 mmol) beendelivered dissolved in 450 ml of toluene, mixed with 189,9 ml methylalumoxane (902 mmol, 4,75 M solution in toluene) (Zr:AI =1:100) and the resulting mixture was stirred at room temperature for 15 minutes 150 g of preliminarily polymerized chromium catalyst precursor obtained in stage c), was added to the solution over 10 minutes

After stirring at room temperature for 1 h, the resulting suspension was filtered, the precipitate washed twice with 400 ml of Tolu is La and twice with 400 ml of heptane. The obtained solid substance was dried at room temperature under reduced pressure. Got 204,5 g of a mixed catalyst with a content of residual solvent of 5.5 wt.%, chromium content of 0.57 wt.% and zirconium content of 0.29 wt.% in each case, in the calculation of the mixed catalyst.

Examples 2-5

Ethylene was polymerizable in the presence of a prepared in example 1, the mixed catalyst in the fluidized bed reactor with a diameter of 0.5 m using nitrogen as the gas supporting the fluidized bed, at a total pressure of 20 bar. The reaction temperature, performance and composition of the gas reactor are shown in table 1. The selection was 5 kg/h In each case were injected 0.1 g of triisobutylaluminum per hour. Properties of the obtained polymers are summarized in table 2. To offset molecular weight towards lower values of Mwand reducing the proportion of high-molecular polyethylene or increased the proportion of hydrogen in the reactor, or was the temperature of polymerization.

Table 1
Example2345
The reactor temperature [°C]100 10510094
The ethylene concentration [vol.%]54,354,954,452,6
The hexene concentration [vol.%]-0,010,041,0
The concentration of H2[l/h]--0,50,4
Performance
[g polyethylene/g]
2200280040003000

22
Table 2
Example2345
MI of 2.16 kg [g/10min]1,111,32,8
HLMI of 21.6 kg [g/10min]17,218,248
Bulk density [g/l]356378391315
Density [g/cm3]0,94910,94980,94250,9207
ETA [DL/g]2,412,142,152,28
Mw[g/mol]142310129850122038113023
Mw/Mn5,165,965,416,29
Mz[g/mol]322460282398255935673327
-HC=CH- [1/1000C]0,450,460,320,19
-HC=CH2 [1/1000C]0,13 0,170,170,27
>C=CH2 [1/1000C]0,060,070,160,38
Just CH3[1/1000C]1,0011,612,6
1-Hexene [%]<0,80<0,801,16,9

Example 6

Granulation and processing films

Powder polymer homogenized and compoundable on the extruder ZSK 30 firm Werner &Pfleiderer with a combination of screws 8A. Treatment temperature was 220°C, and the screw rotation speed was 250 rpm with a maximum capacity of 20 kg/h To stabilize the polymer powder was mixed with 1500 ppm Irganox B215.

The resulting material was processed at the facility blowing films Weber using compression plates.

The diameter of the mouthpiece with a ring nozzle was 50 mm, the width of the gap 2/50 and the angle of the cooling air stream was equal to 45°. The screens are not used. Screw extruder 25D diameter of 30 mm at a speed of rotation of 50 rpm./min, which provides the performance of 5.1 kg/who. To obtain films were selected blowing ratio equal to 1:2, and the removal rate of 4.9 m/10 min. Height of the cooling line was 160 mm Got a film thickness of 50 microns.

Table 3
Data processing and operational
the film properties
Moldable composition of example2345C1
Density [g/cm3]0,94980,94910,94250,92070,918
MI of 2.16 kg [g/10min]1,111,32,43,5
Capacity [kg/h]55555
The speed of rotation
(rpm)
53535353 53
Templar. [°C]222223224217218
Transparency [%]95,194,995,797,325,4
Haze [%]28,230,926,517,142,6
Gloss 20°13,314,516,622,91,5
Gloss 60°56,860,66377,115,5
DDI [g]--180510412
Tensile strength Wabout/a5,6the 5.76,9 15,225,4

Films prepared from moldable composition according to the present invention (examples 2-5)have significantly higher transparency even at a higher density.

Comparative example 1

Exxon m-LLDPE 18TFA is a copolymer of ethylene-1-hexene, prepared using metallocene.

1. Moldable composition comprising polyethylene and conventional additives and having a density in the range 0,915-0,955 g/cm3with melt index MI in the range of from more than 0 to 3.5 g/10 min, determined at 190°C/2,16 kg according to ISO 1133, the degree of fluidity of the melt HLMI/MI in the range of 5-50, polydispersity Mw/Mnin the range of 5-20, z-average molecular mass Mzless than 1 million g/mol and containing at least 0,05 vinyl groups/1000 carbon atoms.

2. The composition according to claim 1, containing a polyethylene with a molecular mass of more than 1 million g/mol in an amount less than 0.5 wt.% calculated on the total mass of the moldable composition.

3. The composition according to claim 1 or 2, in which the molecular weight distribution is modal.

4. The composition according to claim 1 or 2, where the moldable composition was prepared in the same reactor, a polymerization of ethylene in the presence of 1-alkenes of the formula R1CH=CH2where R1is a hydrogen or alkyl radical with 1-10 tomanipulate, at a temperature of 20-200°C and a pressure of from 0.05 to 1 MPa in the presence of a mixed catalyst containing pre-polymerized compound of chromium and metallocene.

5. The composition according to claim 4, where the mixed catalyst was prepared using the following steps:
a) immobilization of chromium compounds on a solid medium
b) activation of the immobilized compounds of chromium by heating,
c) pre-activated polymerization of compounds of chromium and
d) using the pre-polymerized compounds of chromium as a carrier for immobilization of metallocene.

6. The composition according to claim 4 or 5, in which metallocene is remotecomm metallocene complex (B) of General formula (II):

where the substituents and indices have the following meanings:
M1Bis a metal of the 4th group of the Periodic table of elements, in particular Zr,

E1BE4Beach independently of one another are nitrogen, phosphorus, oxygen or sulfur,
m is 0 when E1Bor E4Bare oxygen or sulfur, and is 1 when E1Bor E4Bis nitrogen or phosphorus,
E2BE3BE5BE6Beach independently of one another are carbon, nitrogen or phosphorus,
n is 0 when E2BE3BE5Bor E is nitrogen or phosphorus and is 1 when E1Bor E4Brepresent carbon,
R1B-R14Beach independently of one another represent hydrogen, C1-C22-alkyl, C2-C22alkenyl,6-C22-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, NR15B2N(SiR15B3)2, OR15B, OSiR15B3, SiR15B3where the organic radicals R1B-R14Bmay also be substituted by halogen atoms and/or two adjacent radicals R1B-R14BBcan also be combined with the formation of five-, six - or semichasnoho cycle, and/or two adjacent radicals R1B-R14Bcan also be combined with the formation of five-, six - or semichasnoho heterocycle containing at least one atom from the group consisting of N, P, O and S, where
R15Bare the same or different and represent each With a1-C20-alkyl, C6-C15-aryl, arylalkyl with 1-16 carbon atoms in the alkyl radical and from 6 to 21 carbon atoms in the aryl radical, and
XBrepresents fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10alkenyl,6-C15-aryl, arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 atoms in which laroda in the aryl radical,
-OR16Bor-NR16BR17B, -OC(O)R16A, -O3SR16B, R16BC(O)-CH-CO-R17B, CO, or two radicals XBform a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand, and the radicals XBare the same or different and can be connected to each other,
s is equal to 1 or 2, and s depends on the valency of M1Bto metallocene complex of General formula (II) was uncharged,
where R16Band R17Beach represents a C1-C10-alkyl, C6-C15-aryl, arylalkyl, foralkyl or ferril each with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical.

7. Film made of a polymer material containing a moldable composition according to any one of claims 1 to 6, with the specified moldable composition is present in amount of 50-100 wt.% in the calculation on the entire polymer, and optionally at least one additive.

8. The use of a film according to claim 7 for the manufacture of bags.

9. The use of a film according to claim 7 for the manufacture of thermovalve layers in food packaging.



 

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12 cl, 11 dwg, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing composite nanomaterials for antifrictional purposes. The materials can be used in systems working under high deformation loads and in friction assemblies. The method involves mechanical activation of powder filler in form of sheet silicate in a ball mill in high-speed mode. Further, the powder filler is then mixed with powdered ultra-high molecular weight polyethylene for 10-60 minutes in a high-energy mill combined with mechanical activation.

EFFECT: obtained mixture is starting material from which articles with improved tribological characteristics, high mechanical strength and elasticity are moulded.

2 cl, 9 dwg, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: composition contains a mixture of polyamide, where the ratio of terminal amino groups in the terminal carboxyl groups of the polyamide polymer is less than 0.2, polyester which is capable of crystallising and an interfacial tension reducing agent.

EFFECT: composition enables to obtain dispersed particles with average size of less than 200 nm when stretched, good colour composition which will not exhibit high increase in turbidity with increase in the amount of dispersed material, or has acceptable turbidity during production, and has good colour, especially in the absence of cobalt.

7 cl, 3 tbl, 18 ex, 8 dwg

FIELD: chemistry.

SUBSTANCE: invention describes multimodal polyethylene which is suitable for use as a film, as well as a pipe. The polyethylene is characterised by density between 0.940 and 0.965 g/cm3, flow melt index l21 between 4 and 20 dg/min. The polyethylene contains a low-molecular ethylene copolymer, having weight-average molecular weight between 5000 and 50000 amu, characterised by short-chain branching index between 2.5 and 4.5; and high-molecular ethylene copolymer, having weight-average molecular weight between 60000 and 800000 amu, characterised by short-chain branching index between 2 and 2.5. The invention also describes multimodal polyethylene, where the weight ratio of the high-molecular ethylene copolymer in terms of the overall multimodal composition is between 0.3 and 0.7. The ratio of branching indices of the low- and high-molecular ethylene copolymers is between 1.2 and 6.0.

EFFECT: balance of short-chain branches makes multimodal polyethylene suitable for use in making films, pipes, in fields using centrifugal moulding and blow moulding.

23 cl, 5 dwg, 6 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: air-permeable material contains a woven layer on which there is a polymer film layer. The polymer film layer contains a polymer composition and filler, where the air-permeable material was exposed to physical action in order to make the polymer layer mircroporous, so that SPVP of the air-permeable material is greater than 50 g/m2·24 h, and where the air-permeable material has primary dimension on the length and primary dimension on the width before the said physical action and secondary dimension on the length and secondary dimension on the width after the said physical action, where the secondary dimension on the length is not more than 2% greater than the primary dimension on the length and the secondary dimension on the width is not more than 2% greater than the primary dimension on the width. The invention also discloses methods of producing air-permeable material with said properties.

EFFECT: design of air-permeable material with improved properties.

49 cl, 11 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of modifying a biodegradable polymer or copolymer. Described is a method of modifying a polymer or copolymer, having the structure of one or more repeating units (1), where n is an integer, m is an integer between 0 and 6, and R is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, where said groups may include straight or branched alkyl fragments; optionally one or more substitutes are selected from a group comprising hydroxyl groups, alkoxy groups, straight or branched alk(en)yl, aryloxy, halogen, carboxylic acid, ester, carboxy, nitrile and amido, involving bringing the polymer or copolymer into contact with a cyclic organic peroxide under conditions where at least a certain amount of the said peroxide decomposes. The invention also describes a modified polymer or copolymer obtained using said method.

EFFECT: obtaining a (co)polymer characterised by high degree of branching without formation of gel.

7 cl, 4 ex, 8 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: method involves drawing an polyethylene terephthalate article in an adsorption-active liquid medium containing modifying additives, and drying the article in air until complete removal of the solvent. The modifying additive is a biocidal preparation or antipyrene. The polymer article with an extended shape used can be a fibre, a film, a tape, a tube or a rod.

EFFECT: invention simplifies the technology of making polyethylene terephthalate articles with good biocidal properties and low combustibility compared to existing articles.

20 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: article has a fluorescent coloured sublayer film and a fluorescent coloured film of an overlay layer on top of the fluorescent coloured sublayer film. The fluorescent coloured sublayer film has a first fluorescent dye in the polymer matrix of the sublayer. The fluorescent coloured film of the overlay layer has a second fluorescent dye in the polymer matrix of the overlay layer. The second fluorescent dye in the film of the overlay layer at least partially blocks light in a first wavelength range, while passing light in a second wavelength range in amount which is sufficient for fluorescence of the first fluorescent dye.

EFFECT: invention ensures design of a fluorescent article with improved operational characteristics.

25 cl, 8 dwg, 3 tbl, 3 ex

FIELD: process engineering.

SUBSTANCE: this invention relates to porous films used as filtration membranes. Proposed film comprise poly(vinylidene fluoride) as the main component and polyethylene glycol as hydrophilic component. Degree of crystallinity of poly(vinylidene fluoride) polymer makes 50% or higher, but not exceeds 90%, while product of degree of crystallinity of poly(vinylidene fluoride) polymer by specific area of film surface makes 300 (%·m2/g) or higher, but not exceeds 2000 (%·m2/g). Porous film is produced by extruding film-forming solution from injection orifice. Said solution comprises hydrophobic and hydrophilic components and common solvent. Film-forming solution is hardened.

EFFECT: improved water permeability and resistance to effects caused by porous poly(vinylidene fluoride) film reagents.

12 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of shrinkable polymer labels, particularly to preparation of a film composition. The composition contains (a) a high-impact polystyrene component (HIPS) with a block-copolymer grafted to the polystyrene, (b) 10-50 wt % general purpose polystyrene (GPPS) and (c) approximately 2-80 wt % styrene block-copolymer. Component (a) contains a grafted rubber component which is a styrene block-copolymer and a rubber-like diene with conjugated double bonds from 1 to 7 wt % of the weight of the HIPS; less than 10 wt % concentration of gel, defined by extraction of the methylethylketone/methanol mixture. The average particle size of the rubber is less than 1 mcm and 0.01 mcm or more. Approximately 40-90 vol % of the rubber particles have diametre approximately less than 0.4 mcm and approximately 10-60 vol % of the rubber particles have diametre of approximately 0.4-2.5 mcm. Most of the rubber particles have a nucleus-shell morphology and said particles are in concentration of 10-70 wt % of the total weight of the polymer composition, and 1-5 wt % of the rubber-like diene of the total weight of the polymer composition.

EFFECT: film made from said composition has ratio of directed length to non-directed length in the direction of the greatest drawing at least equal to 3:1 and enable increase in size by 20% in the direction of less stretching at 110°C.

10 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing electroconductive gas-sensitive material for a nitrogen dioxide sensor. The method of producing gas-sensitive material involves preparation of a film-forming solution from polyacrylonitrile and copper (II) chloride CuCl in dimethylformamide, which is deposited through centrifuging onto a substrate made from quartz glass and undergoes drying and infrared annealing successively in two steps: on air at temperature 150°C for 15 minutes and at 200°C for 15 minutes; and in an argon atmosphere at T=150°C, 200°C for 15 minutes; and then at T=500-800°C for 5 minutes.

EFFECT: obtaining gas-sensitive material which is sensitive to nitrogen dioxide with semiconductor properties from material which has dielectric properties using infrared annealing.

3 tbl, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer metallised biaxially-oriented polypropylene films used for food packing and to method of their production. Said film comprises main layer A made from crystalline home- or copolymers of propylene comprising bonds C2-C10 of alpha-olefine, one top layer B made from propylene copolymer containing 3 to 6 wt % of the bonds of linear C4-C10-1-alkene, and metal layer M applied on the surface of top layer B. Propylene copolymer of layer B has fraction soluble in xylene at 23°C, less than 4.0 wt %, Vick softening point above 135°C indenter depth in Vick test smaller than or equal to 0.05 mm at 120°C. Method of film production comprises co-extrusion of layers A and B, biaxial orienting of co-extruded layer A and B, treatment of top layer B surface and metal deposition on said layer.

EFFECT: multilayer metallised biaxially-oriented polypropylene films with high oxygen and steam barrier properties.

FIELD: chemistry.

SUBSTANCE: present invention relates to methods of polymerising olefins in the presence of hybrid catalysts, as well as methods of regulating relative activity of active centres of such hybrid catalysts. Described is a method of producing olefin polymers, involving polymerisation of at least one α-olefin in the presence of a catalyst system to obtain a polymer containing at least a high molecular weight polymer component and a low molecular weight polymer component, in the presence of water in amount of 2-100 pts. mol per mln or carbon dioxide in amount of 2-100 pts. mol per mln, in each case in terms of the entire reaction mixture, where the catalyst system includes at least two different catalyst components and at least one catalyst component which is a transition metal complex selected from Fe, Co, Ni, Pd and Pt, and at least one ligand of general formula (IVe): where each E1D atom denotes nitrogen, each E2D atom denotes carbon, R19D and R25D each independently denotes arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where organic radicals R19D and R25D may also be substituted with halogens or a group containing O, R20D-R24D each independently denotes hydrogen, C1-C10-alkyl, 5-7-member cycloalkyl or cycloalkenyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, -NR26D2> -SiR26D3, where organic radicals R20D-R25D may also be substituted with halogens and/or two geminal or vinyl radicals, R20D-R25D may also bond to form a 5-, 6- or 7-member ring, radicals R26D each independently denotes hydrogen, C1-C20-alkyl, a 5-7-member cycloalkyl or cycloalkenyl, , C2-C20-alkenyl, C6-C40-aryl or arylalkyl with 1-10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, and two R26D radicals may also bond to form a 5- or 6-member ring, u equals 1, each index v equals 1, where the bond between the carbon, which is bonded with one radical, and the neighbouring element E1D is a double bond. The invention also describes a method of regulating the ratio of the high molecular weight polymer component to the low molecular weight polymer component in the said method, which involves polymerisation of at least one α-olefin at temperature 50-130°Cand pressure 0.1-150 MPa in the presence of a catalyst system which includes at least two different catalyst components, in which carbon dioxide is used in amount of 2-100 pts. mol per mln, in order to reduce the amount of the high molecular weight polymer component or water in amount of 2-100 pts. mol per million in order to reduce the amount the low molecular weight polymer component, where the amount in pts. mol per mln is calculated based on the entire reaction mixture in each case. The invention describes use of carbon dioxide in the said method in order to reduce the ratio of the high molecular weight component to the low molecular weight component in the olefin polymer during polymerisation. The invention also describes use of water in the said method in order to increase the ratio of the high molecular weight component to the low molecular weight component in the olefin polymer during polymerisation.

EFFECT: regulation of the ratio of polymer components formed on active centres of catalyst components.

17 cl, 2 tbl, 7 ex

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