Copolymers of ethylene with α olefins

FIELD: chemistry.

SUBSTANCE: invented here is a copolymer of ethylene with α-olefins, with molecular weight distribution Mw/Mn from 1 to 8, density from 0.85 to 0.94 g/cm3 , molecular weight Mn from 10000 g/mol to 4000000 g/mol, not less than 50% distribution width index of the composition, and at least, bimodal distribution of branching of side chains. Branching of side chains in maximums of separate peaks of distribution of branching of side chains in all cases is larger than 5 CH3/1000 carbon atoms. Ethylene copolymers are obtained in the presence of a catalyst system, comprising at least, one monocyclopentadienyl complex A) or A'), optionally an organic or inorganic substrate B), one ore more activating compounds C) and optionally one or more compounds, containing group 1, 2 or 13 metals of the periodic system D).

EFFECT: invented compounds have bimodal distribution of short-chain branching and narrow molecular weight distribution, as well as high impact property.

11 cl, 1 tbl, 3 ex, 2 dwg

 

The present invention relates to copolymers of ethylene with α-olefins, which have a molecular weight distribution Mw/Mn1 to 8, a density of from 0.85 to 0.94 g/cm3, molecular mass Mnfrom 10,000 g/mol to 4000000 g/mol, ISRC less than 50% and in which the branching of the side chains in the maxima of the individual peaks of the distribution of branching of the side chains in all cases more than 5 CH3/1000 carbon atoms, to the way they are received and to fibers, molded articles, films and blends of polymers containing these copolymers.

Copolymers of ethylene with higher α-olefins, such as propene, 1-butene, 1-penten, 1-hexene and 1-octene, known as LLDPE (linear low density polyethylene), can be obtained, for example, using the classical catalysts of the Ziegler-Natta based on titanium, or using metallocenes. Since these copolymers of ethylene does not contain a lot of chains of the same length, and have a molecular weight distribution including a relatively long and relatively short polymer chains, the inclusion of co monomer in the chain of different length may be the same or different. The number of side chains formed by the inclusion of co monomer, and their distribution, known as the distribution of short-chain branching (RCCR), when using asnyk systems catalysts is very different. The number and distribution of side chains critical impact on the characteristics of the crystallization of ethylene copolymers. While the characteristics of fluidity and thereby the machinability of these copolymers of ethylene mainly depend on the molecular mass and molecular mass distribution, mechanical properties strongly depend on the distribution of short-chain branching. The distribution of short-chain branching also plays a role in specific ways of processing, such as extrusion film, in which the characteristics of the crystallization of copolymers of ethylene during cooling, the extruded film is an important factor in determining the speed at which you can ekstradiroval film, and the quality of the films obtained.

There are many ways to determine the distribution of short-chain branching. One method is the "method of analysis with fractionated by elution with increasing temperature" (FAPT). In this case, the polymer slowly crystallized from a solution of the polymer on an inert substrate material by cooling and then elute at different temperatures. The concentration of polymer in the fractions obtained at different temperatures, measured by infrared spectroscopy. At low temperatures suiryudan molecules, obladaushi the large number of side chains. With increasing temperature also suiryudan fraction less branched polymers. Build the dependence of the concentrations of the obtained polymer solutions the temperature of the elution and receive a distribution of short-chain branching. Data obtained using FAPT, you can also calibrate using preparative selected fractions of polyethylene, with a certain amount of short chain branching. The number of side chains is usually expressed as the number of methyl groups per 1000 carbon atoms of the polymer chains (CH3/1000) and it includes end groups and all long-chain branching, formed during polymerization. The way FEPT described, for example, in the Wild, Advances in Polymer Science, 98, p.1-47, 57, 153, 1992. According to FAPT you can define, for example, ESRC (index width distribution of the composition), which is a measure of the width of the distribution of the composition. This is described, for example, in international application WO 93/03093. ISRC is defined as expressed in wt.% the percentage of copolymer molecules having a content of monomer equal to ±25% of the average full molecular content of co monomer.

Recently developed a new method of determining the distribution of short-chain branching, namely Crystaf®because the way FEPT is very long. In this case korotkotsepochechnye the first branching is determined by the one-step method during crystallization from a solution of the polymer. The polymer solution is stirred, cooled slowly and at certain temperatures selected sample solution. These samples contain a fraction of the polymer that have not yet secretaryshall, and their concentrations determined using infrared spectroscopy. Because the samples taken during crystallization, get the cumulative distribution of short-chain branching. Subtraction allows to obtain the distribution of short-chain branching, similar to those obtained using FAPT. In addition to fast data retrieval method Crystal® provides an additional advantage is that these funds can also be defined soluble or recrystallizes components polymer (Monrabal Century Crystallization analysis fractionation, a new technique for the analysis of branching distribution in polyolefines; J. Appl. Polym. Sci. 1994, 52, 491-9).

The catalysts of the Ziegler-Natta give LLDPE, having a wide or two-mode distribution of short-chain branching and a relatively wide average molecular weight distribution Mw/Mnthat is typically greater than 5, where Mn- Brednikova molar mass and Mw- srednevekovaja molecular weight. The branching of the side chains in the polymer chains having relatively low molecular weights, usually more pronounced than with bol is large molecular masses. In addition, these copolymers contain the fraction of polymer with high molecular weight, having an extremely low content of branching of the side chains constituting less than 4 SN3/1000 carbon atoms.

In contrast, the use in the polymerization metallocene catalysts usually gives copolymers of ethylene having a narrow molecular weight distribution and is ISRC constituting more than 50%. These LLDPE have particularly good mechanical properties. The distribution of short-chain branching is single-mode. Copolymerization with higher α-olefins often leads to reduced molecular weight. Usually at higher concentrations of co monomer chain termination becomes to a greater extent and therefore the molecular weight decreases (in US patent US 5625016 indicated that Mnis less than 50,000). Copolymers with low molecular weight can, firstly, be deposited in the reactor during the polymerization and, secondly, to provide the product with undesirable characteristics, for example, the stickiness of the surface. It is difficult to get LLDPE having a large molecular weight and a high content of co monomer.

In the international application WO 01/92346 disclosed cyclopentadienyls complexes elements 4-6 groups of the Periodic system, in which cyclopentadienyls is the system connected group dihydrocarvone-Y, in which Y is an element of group 14 of the Periodic system of elements, which are attached to some Foundation Lewis.

In the international application WO-A-98/44011 described copolymers of ethylene with at least one alpha-olefin containing at least 5 carbon atoms, which have a melt index IL equal to from 0.1 to 15, is ISRC equal to not less than 70%, a density equal to from 0.91 to 0.93 g/ml, a value of turbidity equivalent to less than 20%, the ratio of melt indexes FID equal to from 35 to 80, the average modulus equal from 20000 to 60000 pounds-force/inch2and a certain ratio of the module to the impact resistance, as measured by the incident pointed cargo. In addition, reported that the resulting polymers contain virtually no unsaturated end groups.

In the international application WO-A-93/12151 described copolymers of ethylene with alpha-olefins containing at least 10 carbon atoms, which have a density equal to from 0.85 to 0.95 g/cm3the average molecular mass Mwequal from 30000 to 1000000 Yes, and the molecular weight distribution in the range from 2 to 4.

Presently discovered that copolymers of ethylene with not less than two-mode distribution of short-chain branching and simultaneously narrow molecular weight distribution and high impact resistance, defined by p is giving a pointed cargo obtained if the polymerization is carried out using a special chrome catalysts.

Accordingly, we received copolymers of ethylene with α-olefins, which have a molecular weight distribution Mw/Mnequal to from 1 to 8, a density equal to from 0.85 to 0.94 g/cm3, molar mass Mnequal to 10,000 g/mol to 4000000 g/mol, is ISRC equal to less than 50%, and in which the branching of the side chains in the maxima of the individual peaks in the distribution of short-chain branching in all cases more than 5 CH3/1000 carbon atoms.

In addition, we have developed a method of producing copolymers of ethylene of the present invention, which involves the polymerization of ethylene with α-olefins in the presence of the following components:

A) at least one monotsiklopentadienil complex, with structural fragment of the formulain which the variables have the following meanings:

Cp-Z-A denotes a ligand of formula (II)

in which R1A-R4Aindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR11A  2N(SiR11A3)2, OR11A, OSiR11A3, SiR11A3, BR11A2where the organic radicals R1A-R4Amay also contain as substituents halogen, and where at least two of the end of the radicals R1A-R4Aconnected with the formation of five - or six-membered cycle, and/or two vicinal radicals R1A-R4Aconnected with the formation of the heterocycle, which contains at least one atom selected from the group comprising N, P, O and S,

Z means the bridge between a and CP, having the formula

in which L is carbon or silicon, preferably carbon,

R5A, R6Adenote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11A3where the organic radicals R5Aand R6Amay also contain as substituents halogen and R5Aand R6Acan also be connected with the formation of five - or six-membered cycle,

And means

where E1A-E4Amean carbon or nitrogen,

R7A-R10Aindependently from each other mean odor is d, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11A3where the organic radicals R7A-R10Aalso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11A3as deputies and two vicinal radicals R7A-R10Aor R7Aand Z can also be connected with the formation of five - or six-membered cycle,

R11Aindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, and two vicinal radicals R11Acan also be connected with the formation of five - or six-membered cycle and

R is 0, if E1A-E4Amean nitrogen and is 1 if E1A-E4Amean carbon

C) optionally an organic or inorganic substrate,

C) it is certainly one or more activating compounds and

D) optionally one or more compounds containing a metal of group 1, 2 or 13 of the Periodic system.

In addition, we received a mixture of polymers containing at least one copolymer of ethylene with α-olefins with 3 to 12 carbon atoms corresponding to the present invention, as well as fibers, films and molded articles, in which as a significant component contains copolymers of ethylene with α-olefins with 3 to 12 carbon atoms, corresponding to the present invention.

We also found the use of copolymers of ethylene with α-olefins with 3 to 12 carbon atoms, of the present invention, for the manufacture of fibers, films and molded articles.

Preferred copolymers of ethylene with α-olefins are those which have a molecular weight distribution Mw/Mnequal to from 1 to 8, a density equal to from 0.85 to 0.94 g/cm3, molar mass Mnequal to 10,000 g/mol to 4000000 g/mol, and at least two-mode distribution of short-chain branching and branching of the side chains in the maxima of the individual peaks in the distribution of short-chain branching in all cases more than 5 CH3/1000 carbon atoms.

Particular preference is given to copolymers of ethylene with α-olefins, which on the present molecular weight distribution M w/Mnequal to from 1 to 8, a density equal to from 0.85 to 0.94 g/cm3, molecular mass Mnequal to 10,000 g/mol to 4000000 g/mol, is ISRC equal to less than 50%, and not less than two-mode distribution of short-chain branching and branching of the side chains in the maxima of the individual peaks in the distribution of short-chain branching in all cases more than 5 CH3/1000 carbon atoms.

A copolymer of ethylene α-olefins with 3 to 12 carbon atoms corresponding to the present invention, has a molecular weight distribution Mw/Mnequal to from 1 to 8, preferably from 1.5 to 5 and particularly preferably from 2 to 3.5. Its density is in the range from 0.85 to 0.94 g/cm3preferably from 0.86 to 0.93 g/cm3and especially preferably of 0.87 to 0.91 g/cm3. The molecular mass Mnof ethylene copolymers of the present invention is in the range of from 10,000 g/mol to 4000000 g/mol, preferably from 50000 g/mol to 1,000,000 g/mol and particularly preferably from 100000 g/mol to 400,000 g/mol.

For tasks of this patent application singlemode distribution of short-chain branching means that the distribution of short-chain branching, as determined by Crystaf method®has one maximum. The two races is the definition of short-chain branching to the tasks of the present patent application means, the distribution of short-chain branching, as determined by Crystaf method®has not less than two points of inflection on the both sides of the maximum. For the tasks of the present patent application is not less than a two-mode distribution of short-chain branching distribution means, which may be two, tramadolum or multimode. Preferably, the distribution of short-chain branching was two or tramadolum, more preferably two.

The branching of the side chains in the maxima of the individual peaks in the distribution of short-chain branching in all cases more than 5 CH3/1000 carbon atoms, preferably more than 8 CH3/1000 carbon atoms and more preferably in the range of from 10 to 80 CH3/1000 carbon atoms, and especially preferably from 15 to 60 CH3/1000 carbon atoms.

In accordance with the present invention, the distribution of short-chain branching and the number of side chains is determined by Crystaf method®. Temperature elution installed in this way, by using the translation table is translated into the number of groups of CH3per 1000 carbon atoms.

Molecular mass distribution of short-chain branching is preferably such that when to the m fraction, which form a peak having the greatest number of CH3/1000 carbon atoms, have an average molecular weight of equal to or greater than the corresponding peak (peaks)with less number of CH3/1000 carbon atoms.

Preferably, the peak having the greatest number, had a quantity of at least 8, preferably at least 12, and particularly preferably at least 15 CH3/1000 carbon atoms more than the peak having the smallest number of CH3/1000 carbon atoms.

Preferably, the copolymer of ethylene corresponding to the present invention did not contain peaks in the spectrum of the Crystal® differential distribution above 80°C, preferably not higher than 75°C. Therefore, in the case of applications for films of copolymers of ethylene find values increased impact resistance, defined by the incident pointed cargo, and/or yield strength and/or resistance tear on Elemendorf. In the case of applications for heat-sealable films they has a low temperature bonding, but excellent mechanical bonding characteristics. In the case of application in the form of mixed compositions of the mixture have a higher transparency and permeability than the mixture with conventional copolymers of ethylene.

It is preferable that the copolymer of ethylene, corresponding to the present invention contain at least one peak in the spectrum Crystaf® differential distribution in the range from 5 to 40°and at least one additional peak in the spectrum Crystaf® differential distribution in the range from 25 to 80°C, preferably at least one peak in the spectrum Crystaf® differential distribution in the range from 8 to 30°and at least one additional peak in the spectrum Crystaf® differential distribution in the range from 28 to 60°C.

Is STRWN of ethylene copolymers of the present invention is in the range from 0.001 to 200 g/10 min, preferably from 0.1 to 50 g/10 min and particularly preferably from 2 to 40 g/10 minutes For the task of the present invention, the expression "STRUN" means the rate of flow of the melt under high load and is determined in accordance with ISO 1133 at 190°and a load equal to 21.6 kg (190°C/21,6 kg).

Preferably, copolymers of ethylene, corresponding to the present invention, had an index of long-chain branching (DCR) λ (lambda), is equal to from 0 to 0.1 DCR/1000 carbon atoms, preferably from 0.001 to 0.09 is DCR/1000 carbon atoms when measured by light scattering in accordance with the description given in the ACS Series 521, 1993, Chromatography of Polymers, Ed. Theodore Provder; Simon Pang and Alfrd Rudin: Size-Exclusion Chromatographic Assessment of Long-Chain Branch Frequency in Polyethylens, page 254-269. Therefore, the film made with the use of these copolymers of ethylene, possess high stability to the formation of bubbles during processing.

Preferably, copolymers of ethylene, corresponding to the present invention, had a high content of vinyl groups. It is preferable that the content of the vinyl groups was more than 0,05 vinyl groups/1000 carbon atoms, preferably from 0.1 to 1 vinyl groups/1000 carbon atoms and more preferably from 0.15 to 0.5 vinyl groups/1000 carbon atoms. In the present invention the vinyl groups represent only the vinyl group and do not include, for example, vinylidene group. Preferably, copolymers of ethylene, corresponding to the present invention, had the content vinylidene groups/1000 carbon atoms, which is more than 0.1 vinylidene groups/1000 carbon atoms, preferably from 0.1 to 1.5 vinylidene groups/1000 carbon atoms and particularly preferably from 0.15 to 0.8 vinylidene groups/1000 carbon atoms. It is preferable that the total content of the vinyl and vinylidene groups had more than 0,2 groups/1000 carbon atoms, preferably from 0.2 to 2 groups/1000 carbon atoms and particularly preferably from 0.3 to 1 groups/1000 carbon atoms. The vinyl group is usually associated with the breakage of the polymer chain after turning ethylene, what about consider what vinylidene group formed when the polymer chain is terminated after the inclusion of the co monomer, such as enabling hexene. Vinylidene and the vinyl group can enter into a reaction with a reagent that introduces a functional group, or to use for knitting. Therefore, the copolymers of ethylene, corresponding to the present invention are highly suitable for grafting, crosslinking and introduction of functional groups.

In a preferred embodiment of the present invention, the copolymer has the measure of the width of the distribution of co monomer in the composition, less than or equal to 50%, preferably from 5 to 45%, and especially preferably from 20 to 30%.

As comonomers, which in addition to ethylene may be contained individually or in mixture with each other in the copolymer corresponding to the present invention, it is possible to use all α-olefins containing from 3 to 12 carbon atoms, for example propene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene and 1-mission. Preferably, the copolymer of ethylene as comonomer links included copolymerizable α-olefins containing from 3 to 9 carbon atoms, such as butene, Panten, hexene, 4-methylpentene or octene. Particular preference is given to using α-olefins selected from the group comprising propene, 1-butene, 1-hexene and 1-octene. Somone who measures typically contain copolymerizable form copolymers of ethylene, relevant to the present invention, in amounts of from 1 to 40 wt.%, preferably from 2 to 30 wt.% and most preferably from 2 to 20 wt.%, in all cases, based on the copolymer of ethylene.

Copolymers of ethylene preferably can be obtained using the above new method using manonmaniam complexes of formula I.

Monosyllabically complexes (A)used in the method corresponding to the present invention include a structural fragment of formulain which the variables are as defined above. Therefore, with the metal atom Cr may be associated with additional ligands. The number of additional ligands depends on the oxidation state of the metal atom. Possible additional ligands do not include additional cyclopentadienyls system. Suitable additional ligands are monoanionic and gianinni ligands are described, for example, for X. In addition to the metal center Cr can also be connected to the base of the Lewes, such as amines, ethers, ketones, aldehydes, esters, sulfides and phosphines.

On the behavior of metal complexes in the polymerization also can be influenced by changing the substituents R1A-R4A. The number and type of substituents can affect the and the ability to polymerize olefins to gain access to the metal atom M. This makes it possible to modify the activity and selectivity of the catalyst in relation to the various monomers, in particular to surround the monomers. Because deputies can also affect the reaction rate of breakage of the growing polymer chain, thus you can modify the molecular weight of the resulting polymer. Therefore, to achieve the desired results and receiving system of the catalysts with desired properties can widely change the chemical structure of the substituents from R1Ato R4Aprovided that at least two of the vicinal radicals R1A-R4Aconnected with the formation of five - or six-membered cycle and/or two vicinal radicals R1A-R4Aconnected with the formation of the heterocycle, which contains at least one atom selected from the group comprising N, P, and S. the Possible erbaorganics substituents R1A-R4Aare, for example, the following: alkyl with 1-20 carbon atoms which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent aryl group with 6-10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, CEC is heptyl, cyclooctyl, cyclonona or cyclododecyl, alkenyl with 2-20 carbon atoms 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, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil or arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1-or 2-ethylphenyl, where the organic radicals R1A-R4Amay also contain as substituents halogen, such as fluorine, chlorine or bromine. In addition, R1A-R4Acan also mean an amino group or alkoxyl, such as dimethylaminopropyl, n-pyrrolidinyl, picoline, methoxyl, ethoxyl or isopropoxy. In organosilicon substituents SiR11A3R11Amay be the same erbaorganics radicals, which are described in more detail in this paragraph for R1A-R4Aand two R11Acan also be connected with the formation of 5 - or 6-membered cycle, for example three utilily, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These radicals SiR11A3can also be associated with cyclopentadienyls the skeleton via an oxygen atom or nitrogen, such as trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylcyclohexyl. Preferred radicals R1A-R4Aare hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl - and ortho-dichlorsilane family, trialkyl and trichlorsilane family, naphthyl, biphenyl and anthranol. As organosilicon substituents particular preference is given trialkylsilyl groups containing from 1 to 10 carbon atoms in the alkyl radical, for example trimethylsilyl groups.

At least two of the vicinal radicals R1A-R4Aconnected with the formation of five - or six-membered cycle and/or two vicinal radicals R1A-R4Aconnected with the formation of heterocampa, which contains at least one atom selected from the group comprising N, P, and S. the Two vicinal radicals R1A-R4Ayou can, for example, in each case together with the carbon atoms to which they are linked, form gets recycl, preferably the heteroaromatic cycle that contains at least one atom selected from the group comprising nitrogen, phosphorus, oxygen and sulfur, particularly preferably nitrogen and/or sulfur. Preference is given to compounds and heteroaromatic cycles, including the loop containing 5 or 6 cyclic atoms. Examples of 5-membered heterocycles, which can contain from 1 to 3 nitrogen atoms and/or sulfur atom or oxygen as cyclic atoms in addition to carbon atoms, are 1,2-dihydrofuran, furan, thiophene, isoxazol, 3-isothiazol, pyrazole, oxazole, thiazole, imidazole. Examples of 6-membered heteroaryl groups which may contain from 1 to 4 nitrogen atoms and/or phosphorus atom, are pyridine, postabortal, pyridazine, pyrimidine, pyrazin, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine. 5 - and 6-Membered heterocycles may also contain as substituents alkyl with 1-10 carbon atoms, aryl with 6-10 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogen, such as fluorine, chlorine or bromine, dialkylamide, arylalkylamine, diarylamino, alkoxyl or aryloxy, or may be condensed with one or more aromatic or heteroaromatic systems. Examples of condensed with benzene, 5-membered gets reallyh groups are indole, indazol, benzofuran, benzothiophene, benzothiazole, benzoxazole and benzimidazole. Examples of condensed with benzene 6-membered heteroaryl groups are Roman, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, hinzelin, cinoxacin, 1,10-phenanthrolin and hemolysin. Names and numbering heterocycles taken from Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim, 1979. Preferably, they have been condensed with cyclopentadienyls skeleton double bond C=C heterocyclic/heteroaromatic system. Preferably, heterocyclic/heteroaromatic compounds containing heteroatom, were 2,3 - or b-condensed.

Examples cyclopentadienyls systems, Cf containing condensed heterocycle are tiefenthaler, 2-methylthiophenol, 2-ethylthiophene, 2-isopropylthioxanthone, 2-n-butylthioethyl, 2-tert-butylthiophenol, 2-trimethylsilylmethyl, 2-phenylthiophene, 2-aftercapture, 3-methylthiophenol, 4-phenyl-2,6-dimethyl-1-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, 2-methylisophthalic, 2-atlasapollo, 2-isopropylnaphthalene, 2-n-butylacetate, 2-trimethylsilylacetamide, 2-phenylazophenyl, 2-naphthylacetate, 1-phenyl-2,5-dimethyl-1-asapa talen, 1-phenyl-2,5-diethyl-1-isopentane, 1-phenyl-2,5-di-n-butyl-1-isopentane, 1-phenyl-2,5-di-tert-butyl-1-isopentane, 1-phenyl-2,5-di(trimethylsilyl)-1-isopentane, 1-tert-butyl-2,5-dimethyl-1-aspendale, oxapentane, phosphopentose, 1-phenyl-2,5-dimethyl-1-phosphopentose, 1-phenyl-2,5-diethyl-1-phosphopentose, 1-phenyl-2,5-di-n-butyl-1-phosphopentose, 1-phenyl-2,5-di-tert-butyl-1-phosphopentose, 1-phenyl-2,5-di-(trimethylsilyl)-1-phosphopentose, 1-methyl-2,5-dimethyl-1-phosphopentose, 1-tert-butyl-2,5-dimethyl-1-phosphopentose, 7-cyclopent[1,2]thieno[3,4]cyclopentadiene and 7-cyclopent[1,2]pyrrolo[3,4]cyclopentadiene.

In other preferred cyclopentadienyls systems, Wed, 4 radical R1A-R4Ai.e. 2 pairs of vicinal radicals, form 2 of the heterocycle, preferably 2 heteroaromatic cycle. Heterocyclic systems are the same as described in more detail above. Examples cyclopentadienyls systems, Cf containing 2 condensed heterocycle are 7-cyclopentadien, 7-cyclopentadienyl and 7-cyclopentadien.

The synthesis of such cyclopentadienyls systems containing condensed heterocycle described, for example, in the above-mentioned international application WO 98/22486. In "Metalorganic catalysts for synthesis and polymerization", Springer Verlag 1999, p.150 ff, Ewen et al., described other syntheses of these cyclopentadienyls systems.

Preference is also given to connect the changes, in which two vicinal radicals R1A-R4Apreferably R1Atogether with R2Aand/or R3Atogether with R4Aform a condensed cyclic system, preferably6the cyclic system, particularly preferably aromatic With6cyclic system, i.e. together with cyclopentadienyls C5the loop is formed, for example, unsubstituted or substituted, benzinger, phenanthrene, fluorene or tetrahydroindene, for example indenyl, 2-methylindenyl, 2-ethylidene, 2-isopropylphenyl, 3-methylindenyl, bensinger or 2-methylbenzhydryl, preferably, if R1Aand R2Atogether with cyclopentadienyls system form a substituted or unsubstituted indenolol system.

Condensed cyclic system may contain additional alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR11A2N(SiR11A3)2, OR11A, OSiR11A3or SiR11A3for example , 4-methylindenyl, 4-ethylidene, 4-isopropylphenyl, 5-methylindenyl, 4-phenylindane, 5-methyl-4-phenylindane, 2-methyl-4-phenylindane or naphthylidine.

As in the case of metallocenes, monosyllabically complexes And can be chiral. So, one of the substituents R1A-R4Acyclopentadienyls frame can contain one or more chiral centers or herself cyclopentadienyls system Cf may be a while, so the chirality occurs only if cyclopentadienyls system is associated with a transition metal M (for a description of chirality in cyclopentadienyls connections, see R. Halterman, Chem. Rev.92 (1992), 965-994).

Possible erbaorganics substituents R5A-R6Athe bridge Z are, for example, the following: hydrogen, alkyl with 1-20 carbon atoms which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent aryl group with 6-10 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, alkenyl with 2-20 carbon atoms 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, cyclopenten is l, cyclohexenyl, nikookar or cyclooctadiene, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil or arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where the organic radicals R5Aand R6Acan also be connected with the formation of 5 - or 6-membered cycle, or may contain as substituents halogen, for example fluorine, chlorine or bromine, or alkyl or aryl.

In organosilicon substituents SiR11A3possible radicals R11Aare the same as those radicals, which are described in more detail above, and it is also possible that two R11Awere connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane.

The radicals R5Aand R6Amay be the same or different. Preferred radicals R5Aand R6Aare hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, PR is o-dialkyl - and ortho-dichlorsilane family, trialkyl and tryparsamide family, naphthyl, biphenyl and anthranol.

The bridge Z between cyclopentadienyls system Cf and heteroaromatic system And is organic, preferably divalent bridge. Preferably, if Z stands for a group of CR5AR6A. Particularly preferably, if Z is connected and condensed with a heterocycle or a condensed aromatic cycle and cyclopentadienyls skeleton. So, if a heterocycle or aromatic cycle condensed in position 2,3 cyclopentadienyls of the skeleton, it is preferable that Z is at position 1 or 4 cyclopentadienyls of the skeleton.

And is unsubstituted, substituted or condensed heteroaromatic 6-membered cyclic system containing heteroaromatic part 1, 2, 3, 4 or 5 nitrogen atoms, which is linked to Z, preferably 2-pyridyl or 2-chinolin. Examples of 6-membered heteroaryl groups which may contain from 1 to 5 nitrogen atoms are 2-pyridinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazine-2-yl and 1,2,4-triazine-3-yl, 1,2,4-triazine-6-yl and 1,2,4-triazine-6-yl. 6-Membered heteroaryl group may also contain alkyl groups with 1-10 carbon atoms, aryl groups with 6-10 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-10 carbon atoms is kind of in the aryl part, trialkylsilyl group or halogen, such as fluorine, chlorine or bromine as substituents or may be condensed with one or more aromatic or heteroaromatic systems. Examples of condensed with benzene 6-membered heteroaryl groups are 2-chinolin, 3-cinnamyl, 2-chinadoll, 4-chinadoll, 2-minoxadil, 1-phenanthridine and 1-fedasil.

And may contact the metal M intermolecular or intramolecular. Preferably, And was associated with M intramolecular. Synthesis for linking And cyclopentadienyls ring can be performed, for example, by the method similar to that shown in the work .Enders et al. in Chem. Ber. (1996), 129, 459-463, or .Jutzi and U.Siemeling in J. Orgmet. Chem. (1995), 500, 175-185.

Examples of possible erbaorganics substituents R7A-R10AAnd are the following: hydrogen, alkyl with 1-20 carbon atoms which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent With6-C10-aryl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, alkenyl with 2-20 carbon atoms, which can the 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, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil or arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, in which two vicinal radicals R7Ato R10Acan also be connected with the formation of 5 - or 6-membered cycle, or may contain as substituents halogen, for example fluorine, chlorine or bromine, or alkyl or aryl. R7A-R10Apreferably signify hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl or phenyl. In organosilicon substituents SiR11A3possible radicals R11Aare the same as those radicals, which are described in more detail above, and two R11Acan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl,tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane.

Preferably, if 0 or 1 group E1A-E4AAnd means nitrogen, and other means of carbon. Particularly preferably, when a represents 2-pyridyl, 6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl, 3-pyridil, 4 pirimidil, 6-methyl-4-pyrimidyl, 2-pyrazinyl, 6-methyl-2-pyrazinyl, 5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethyl-2-pyrazinyl, 3,5,6-trimethyl-2-pyrazinyl, 2-chinolin, 4-methyl-2-chinolin, 6-methyl-2-chinolin, 7-methyl-2-chinolin, 2-Minoxidil or 3-methyl-2-Minoxidil.

Particularly preferably, the chromium was in one of the oxidation States 2, 3 and 4, preferably 3. The chromium complexes can be obtained by simple injection in the reaction of the appropriate metal salts, for example chlorides of chromium, with the anion of the ligand (for example, using techniques similar to those shown in the examples in German application DE 19710615).

In the method corresponding to the present invention, preference is given monosyllabically complexes (A) formulawhere the variables Cf, Z and a are as defined above and their preferred embodiments of which are preferred and in this case, and

X independently of one another denote fluorine, chlorine, bromine, iodine, hydrogen, alkyl with 1-10 ATO the AMI carbon alkenyl with 2-10 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing 1-10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR1R2, OR1, SR1, SO3R1, OC(O)R1, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion,

R1-R2independently of one another denote hydrogen, alkyl with 1-10 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR33where the organic radicals R1-R2may also contain as substituents, Halogens or nitrogen - and oxygen-containing groups and two radicals R1-R2can also be connected with the formation of five - or six-membered cycle,

R3independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 5-20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl portion and two radicals R3can also be connected with the formation of five - or six-membered cycle and

k = 1, 2, or 3.

Options for implementation and preferred options implemented the program Wed, Z and A, described above, also apply separately and in combination to these preferred monosyllabically complexes (A).

The ligands X may be determined, for example, by selecting the appropriate source of chromium compounds used in the synthesis monosyllabically complexes, but can be changed afterwards. Suitable ligands X are preferably halogen - fluorine, chlorine, bromine and iodine, preferably chlorine. Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl and benzyl, are also suitable ligands X. Other possible ligands X are, for example and without imposing any restrictions, triptorelin, BF4-PF6-and weakly coordinating and coordinarussia anions (see, for example, Strauss in Chem. Rev. 1993, 93, 927942), such as B(C6F5)4-.

Amides, alkoxides, sulfonates, carboxylates and β-diketonates are also particularly suitable ligands X. changing the radicals R1and R2you can, for example, finely adjust the physical characteristics, such as solubility. Possible erbaorganics substituents R1-R2are, for example, the following: alkyl with 1-20 carbon atoms which may be linear or branched, for example methyl, ethyl, n-prop is l, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent aryl group with 6-10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, alkenyl with 2-20 carbon atoms which may be linear, cyclic or branched and contain internal or terminal double bond, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, 2-methoxyphenyl, 2-N,N-dimethylaminophenyl and arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where R1can also be connected to R2with the formation of 5 - or 6-membered cycle and organic radicals R1-R2may also contain as substituents halogen, for example fluorine, chlorine or bromine. In silicon the organic substituents SiR 33, R3can be the same radicals that described above for R1-R2and two R3can also be connected with the formation of 5 - or 6-membered cycle. Examples of the substituents SiR33are trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, trialkylsilyl, triphenylsilanol and dimethylphenylsilane. Preference is given to alkyl with 1-10 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, as well as vinyl, allyl, benzyl and phenyl as radicals R1and R2. Some of these substituted ligands X apply particularly preferable, because they are cheap and readily available starting materials. In a particularly preferred embodiment, X means dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluensulfonate, acetate or acetylacetonate.

The number k of ligands X depends on the oxidation state of chromium. Therefore, the number k can be defined in General terms. The oxidation state of the transition metal M in catalytically active complexes is typically known to a person skilled in the art. Most likely, the chromium is in the oxidation state +3. However, you can use and complexes, the oxidation state which does not correspond comprising the s in the active catalyst. Such complexes can then respectively be restored or oxidize with suitable activators. Preference is given to the use of complexes of chromium in the oxidation state +3.

In addition, we received a catalytic system for the polymerization of olefins, including

A') at least one monosyllabically complex A')comprising a structural fragment of formulain which the variables have the following meanings:

Cp-CR5BR6B- A means

in which R1B-R4Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR11B2N(SiR11B3)2, OR11B, OSiR11B3, SiR11B3, BR11B2where the organic radicals R1B-R4Bmay also contain as substituents, Halogens and two vicinal radicals R1B-R4Bcan also be connected with the formation of five - or six-membered cycle,

R5V, R6Bmean hydrogen or methyl,

And means

in which E1B-E4Bmean ug is erod or nitrogen,R 7B-R10Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3where the organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle,

R11Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms or arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, and two radicals R11Bcan also be connected with the formation of five - or six-membered cycle,

R is 0, if E1B-E4Bmean nitrogen and is 1 if E1B-E4Bmean carbon

where at least one radical R7B -R10Bmeans alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3and organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle, or not less than one E1B-E4Bmeans nitrogen,

B) optionally an organic or inorganic substrate,

C) optionally one or more activating compounds and

D) optionally one or more compounds containing a metal of group 1, 2 or 13 of the Periodic system.

Monosyllabically a')corresponding to the present invention include a structural fragment of formulain which the variables are as defined above. Therefore, an atom is atalla M may be associated with additional ligands. The number of additional ligands depends on the oxidation state of the metal atom. Possible additional ligands do not include additional cyclopentadienyls system. Suitable additional ligands are monoanionic and gianinni ligands are described, for example, for X. In addition to the metal center M can also be connected to the base of the Lewes, such as amines, ethers, ketones, aldehydes, esters, sulfides and phosphines.

On the behavior of metal complexes in the polymerization also can be influenced by changing the substituents R1B-R4B. The number and type of substituents can influence the ability of polymerizing olefins to gain access to the metal atom M. This makes it possible to modify the activity and selectivity of the catalyst in relation to the various monomers, in particular to surround the monomers. Because deputies can also affect the reaction rate of breakage of the growing polymer chain, thus you can modify the molecular weight of the resulting polymer. Therefore, to achieve the desired results and receiving system of the catalysts with desired properties can widely change the chemical structure of the substituents from R1Bto R4B. Possible erbaorganics substituents R1B-R4Bablauts is, for example, the following: alkyl with 1-20 carbon atoms which may be linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent aryl group with 6-10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, alkenyl with 2-20 carbon atoms 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, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil or arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1-or 2-ethylphenyl, where two of R1B-R4Bcan also be connected with the formation of 5-or 6-membered cycle and organic radicals R1B-R4Balso may include the step as substituents halogen, such as fluorine, chlorine or bromine. In addition, R1B-R4Bcan also mean an amino group or alkoxyl, such as dimethylaminopropyl n-pyrrolidinyl, picoline, methoxyl, ethoxyl or isopropoxy. In organosilicon substituents SiR11B3, R11Bcan be the same radicals that described above for erbaorganics radicals R1B-R4Band two R11Bcan also be connected with the formation of 5 - or 6-membered cycle, for example, trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane. These radicals SiR11B3can also be associated with cyclopentadienyls the skeleton via an oxygen atom or nitrogen, such as trimethylsilyloxy, triethylsilane, butyldimethylsilyloxy, tributyltinoxide or three-tert-butylcyclohexyl. Preferred radicals R1B-R4Bare hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl - and ortho-dichlorsilane family, trialkyl and trichlorsilane family, naphthyl, biphenyl and anthranol. As organosilicon substituents particular preference is given trialkylsilyl groups containing from 1 to 10 carbon atoms, the alkyl radical, for example trimethylsilyl groups.

Examples cyclopentadienyls systems (without group-CR5BR6B-A, which is preferably located in position 1, are 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3-isopropylcyclopentadienyl, 3-tert-butylcyclopentadienyl, dialkylanilines, such as tetrahydroindene, 2,4-dimethylcyclopentane and 3-methyl-5-tert-butylcyclopentadienyl, trialkylsilanes, such as 2,3,5-trimethylcyclopentanone and tetraalkyllead, such as 2,3,4,5-tetramethyl-cyclopentadienyl.

Preferably, if at least two of the vicinal radicals R1B-R4Bconnected with the formation of five - or six-membered cycle, and/or two vicinal radicals R1B-R4Bconnected with the formation of the heterocycle, which contains at least one atom selected from the group comprising nitrogen, phosphorus, oxygen and sulfur.

Preference is also given to compounds in which two vicinal radicals R1B-R4Bpreferably R1Btogether with R2Band/or R3Btogether with R4Bform a 5 - or 6-membered ring, preferably a condensed cyclic system, preferably6the cyclic system, particularly preferably aromatic cyclic system with 6 carbon atoms, i.e. form together with the cycle of pentadienyl ring with 5 carbon atoms, and/or two vicinal radicals R1B-R4Bconnected with the formation of the heterocycle, which contains at least one atom selected from the group comprising nitrogen, phosphorus, oxygen and sulfur. Examples of such systems are unsubstituted or substituted indenyl, benzinger, phenanthrene, fluorene or tetrahydroindene, for example indenyl, 2-methylindenyl, 2-ethylidene, 2-isopropylphenyl, 3-methylindenyl, bensinger or 2-methylbenzhydryl. Preferably, if R1Band R2Btogether with cyclopentadienyls system form a substituted or unsubstituted indenolol system.

Condensed cyclic system may contain additional alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR11B2N(SiR11B3)2, OR11B, OSiR11B3or SiR11B3for example , 4-methylindenyl, 4-ethylidene, 4-isopropylphenyl, 5-methylindenyl, 4-phenylindane, 5-methyl-4-phenylindane, 2-methyl-4-phenylindane or 4-naphthylidine.

As in the case of metallocenes, monosyllabically a)corresponding to the present invention, there may be chiral is passed. So, one of the substituents R1B-R4Bcyclopentadienyls frame can contain one or more chiral centers or herself cyclopentadienyls system Cf may be a while, so the chirality occurs only if cyclopentadienyls system is associated with a transition metal M (for a description of chirality in cyclopentadienyls connections see R.Halterman, Chem. Rev.92 (1992), 965-994).

Bridge-CR5BR6Bbetween cipointernet system Cf and heteroaromatic system And is a divalent organic bridge. -OR5BR6B- this could mean-CH2-, -SSN3- or- (CH3)2-. -CR5BR6B- preferably denotes-CH2or SSN3-, more preferably-CH2-. Most preferably, if CR5VR6V- connected and condensed with a heterocycle or a condensed aromatic cycle and cyclopentadienyls frame. So, if a heterocycle or aromatic cycle condensed in position 2,3 cyclopentadienyls frame, preferably,- CR5VR6B- was in position 1 or 4 cyclopentadienyls frame.

Examples of possible erbaorganics substituents R7B-R10BAnd are the following: hydrogen, alkyl with 1-20 carbon atoms which may be linear the output or branched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent aryl group with 6-20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl, alkenyl with 2-20 carbon atoms, which may to 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, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups, for example phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, and arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, in which two vicinal radicals R7Bto R10Bcan also be connected with the formation of 5 - or 6-membered cycle, or may also contain as substituents halogen, for example fluorine, chlorine or bromine, or alkyl or aryl. R7B-R10Bpredpochtitelno mean hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl or phenyl. In organosilicon substituents SiR11B3possible radicals R11Bare the same as those radicals, which are described in more detail above for R11Aand two R11Bcan also be connected with the formation of 5 - or 6-membered cycle, for example trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, three-tert-Boticelli, trialkylsilyl, triphenylene or dimethylphenylsilane.

A is a substituted or condensed heteroaromatic 6-membered cyclic system containing heteroaromatic part 1, 2, 3, 4 or 5 nitrogen atoms, which is linked with the-CR5BR6Bor unsubstituted, substituted or condensed heteroaromatic 6-membered cyclic system containing heteroaromatic parts 2, 3, 4 or 5 nitrogen atoms, which is linked with the-CR5BR6B-preferably 2-chinolin or substituted 2-pyridyl. Examples of 6-membered heteroa ilen groups, which can contain from 2 to 5 nitrogen atoms are 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. 6-Membered heteroaryl group may also contain alkyl groups with 1-10 carbon atoms, aryl groups with 6-10 carbon atoms, kilrenny group, containing from 1 to 10 carbon atoms in the alkyl fragment and 6-10 carbon atoms in the aryl part, trialkylsilyl group or halogen, such as fluorine, chlorine or bromine as substituents or may be condensed with one or more aromatic or heteroaromatic systems. Examples of condensed with benzene 6-membered heteroaryl groups are 2-chinolin, 3-cinnamyl, 2-chinadoll, 4-chinadoll, 2-minoxadil, 1-phenanthridine and 1-fedasil.

And can communicate with chromium intermolecular or intramolecular. Preferably, And was associated with intramolecular Cr. Synthesis for linking And cyclopentadienyls ring can be performed, for example, by the method similar to that shown in the work .Jutzi and U.Siemeling in J. Orgmet. Chem. (1995), 500, 175-185.

Preferably, if one of the groups E1B-E4Bmeans nitrogen, and other means of carbon. Particularly preferably, if a represents 3-pyridil, 4 pirimidil, 6-methyl-4-pyrimidyl, 2-pyrazinyl, 6-methyl-2-pyrazinyl, 5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethyl-2-pyrazinyl, 3,5,6-trimethyl-2-pyrazinyl, 2-chinolin, 4-methyl-2-chinolin, 6-methyl-2-chinolin, 7-methyl-2-chinolin, 2-Minoxidil or 3 methyl-2-Minoxidil.

In addition, preference is given monosyllabically complexes in which all E1B-E4Bmean carbon and not less than the Dean, preferably one radical R7B-R10Bmeans alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3. Particularly preferably, if a represents 6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl or 6-benzyl-2-pyridyl.

Particularly preferably, the chromium was in one of the oxidation States 2, 3 and 4, preferably 3. The chromium complexes can be obtained by simple injection in the reaction of the appropriate metal salts, for example chlorides of chromium, with the anion of the ligand (for example, using techniques similar to those shown in the examples in German application DE 19710615).

Monosyllabically complex And') can be in the form of Monomeric, dimeric or trimeric compounds. For example, one or more ligands X may form a bridge between two metal centers M

In the method corresponding to the present invention, preference is given monosyllabically complexes And') formulain which the variable Cp-CR5BR6B-A is the same as defined above, and preferred embodiments of are alleged the equipment and in this case, and

X independently from each other, means fluorine, chlorine, bromine, iodine, hydrogen, alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing 1-10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR1R2, OR1, SR1, SO3R1, OC(O)R1, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion,

R1-R2independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR33where the organic radicals R1-R2may also contain as substituents, Halogens or nitrogen - and oxygen-containing groups and two radicals R1-R2can also be connected with the formation of five - or six-membered cycle,

R3independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, and two radicals R3can also be connected with the formation of five - or chesticles the th cycle and

k is 1, 2 or 3.

Options for implementation and preferred embodiments of the above for Cp-CR5BR6B-A also apply separately and in combination to these preferred monosyllabically complexes And').

The ligands X may be determined, for example, by selecting the appropriate source of chromium compounds used in the synthesis monosyllabically complexes And'), but can be changed afterwards. Suitable ligands X are preferably the Halogens fluorine, chlorine, bromine and iodine, preferably chlorine. Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl and benzyl, are also suitable ligands X. Other possible ligands X are, for example and without imposing any restrictions, triptorelin, BF4-PF6-and weakly coordinating and coordinarussia anions (see, for example, Strauss in Chem. Rev. 1993, 93, 927-942), such as In(C6F5)4-.

Amides, alkoxides, sulfonates, carboxylates and β-diketonates are also particularly suitable ligands X. changing the radicals R1and R2you can, for example, finely adjust the physical characteristics, such as solubility. Possible erbaorganics substituents R1-R2are, for example, is the following: alkyl with 1-20 carbon atoms, which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5 - to 7-membered cycloalkyl, which, in turn, may contain as a substituent aryl group with 6-10 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclododecyl alkenyl with 2-20 carbon atoms which may be linear, cyclic or branched and contain an internal or terminal double bond, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctyl or cyclooctadiene, aryl with 6 to 20 carbon atoms, which may contain as substituents for more alkyl groups and/or N - or O-containing radicals, such as phenyl, naphthyl, biphenyl, anthranol, o-, m-, p-were, 2,3-, 2,4-, 2,5 - or 2,6-dimetilfenil, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimetilfenil, 2-methoxyphenyl, 2-N,N-dimethylaminophenyl and arylalkyl, which may contain as substituents for more alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1 - or 2-ethylphenyl, where R1can also be connected to R2with the formation of 5 - or 6-membered cycle and organic radicals R1-R2also with erati as substituents halogen, for example fluorine, chlorine or bromine. In organosilicon substituents SiR33, R3can be the same radicals that described above for R1-R2and two R3can also be connected with the formation of 5 - or 6-membered cycle. Examples of the substituents SiR33are trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributyrin, trialkylsilyl, triphenylsilanol and dimethylphenylsilane. Preference is given to using alkyl with 1-10 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, as well as vinyl, allyl, benzyl and phenyl as radicals R1and R2. Some of these substituted ligands X apply particularly preferable, because they are cheap and readily available starting materials. In a particularly preferred embodiment, X means dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluensulfonate, acetate or acetylacetonate.

The number k of ligands X depends on the oxidation state of chromium. Therefore, the number k can be defined in General terms. The oxidation state of the transition metal M in catalytically active complexes is typically known to a person skilled in the art. Most likely, the chromium is in the oxidation state +3. However, can the use and complexes, the oxidation state which does not meet the condition in the active catalyst. Such complexes can then respectively be restored or oxidize with suitable activators. Preference is given to the use of complexes of chromium in the oxidation state +3.

In addition, we have developed a method of producing anions cyclopentadienyls system of the formula (VIIa)

where the variables have the following meanings:

R1B-R4Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR11B2,N(SiR11B3)2, OR11B, OSiR11B3, SiR11B3, BR11B2where the organic radicals R1B-R4Bmay also contain as substituents, Halogens and two vicinal radicals R1B-R4Bcan also be connected with the formation of five - or six-membered cycle,

R5V, R6Bmean hydrogen or methyl,

And means

where E1B-E4Bmean carbon or nitrogen,

R7B-R10Bindependently of one another denote hydrogen, alkyl with 1-20 the volumes of carbon alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3where the organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle,

R11Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms or arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl portion and two radicals R11Bcan also be connected with the formation of five - or six-membered cycle,

R is 0, if E1B-E4Bmean nitrogen and is 1 if E1B-E4Bmean carbon

where at least one radical R7B-R10Bmeans alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6-2 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3and organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle, or not less than one E1B-E4Bmeans nitrogen,

which includes a step (a), where on stage and fulvin formula (VIIIa)

is introduced into the reaction with the anion And-formula (VIIIa)

where all variables are as defined above.

Variables and their preferred embodiments of the above.

Fulvene known for a long time and they can be obtained, for example, as described in the work Freiesleben, Angew. Chem. 75 (1963), R.

Protivoatomnom for anion cyclopentadienyls system (VIIa) is cation anion And-. Usually a metal of group 1 or 2 of the Periodic system the volumes of the elements, which may have additional ligands. Particular preference is given to cations of lithium, sodium and potassium, which can be uncharged ligands, such as amines and ethers, and the cations of magnesium chloride and magnesium bromide, which can also have additional uncharged ligands, preferably cations of lithium, of magnesium chloride and magnesium bromide.

Anion And-get in exchange reactions of metal - halogen of the halide And alkyl derivatives of metal containing a metal of group 1 or 2, preferably a cation of lithium, of magnesium chloride or magnesium bromide. Suitable metal alkyl derivatives are, for example, alkyl derivatives of lithium, alkyl derivatives of magnesium, (alkyl)magnesium halides and their mixtures. The molar ratio of alkyl derivatives of metal to halide And is typically in the range from 0.4:1 to 100:1, preferably in the range from 0.9:1 to 10:1 and particularly preferably from 0.95:1 to 1.1:1. Examples of such reactions are described, in particular, Furukawa et al. in Tet. Lett. 28 (1987), 5845. As solvents it is possible to use all aprotic solvents, preferably aliphatic and aromatic hydrocarbons, such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene or ethers such as diethyl ether, disutility ether, tetrahydrofuran, dimethoxyethane and dimethyl the new ether diethylene glycol and mixtures thereof. The exchange of the halogen - metal you can spend at a temperature of from -100 to +160°C, preferably from -80 to 100°C. At temperatures above 40°preference is given to using aromatic or aliphatic solvents which do not contain ethers or have a very low content of ethers. Particularly preferred systems And-are 2-pyridinyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 2-chinolin, 3-cinnamyl, 2-chinadoll and 4-chinadoll.

Anion And-received by the exchange of the metal - halogen, can be distinguished, but it is preferable to introduce it into the reaction fulvene (VIIIa) without selection. As solvents for subsequent reactions you can use all aprotic solvents, preferably aliphatic and aromatic hydrocarbons, such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene, or ethers, such as diethyl ether, disutility ether, tetrahydrofuran, dimethoxyethane and dimethyl ether of diethylene glycol, and mixtures thereof. The deprotonation can be carried out when a temperature of from -100 to +160°C, preferably from -80 to 100°C and particularly preferably from 0 to 60°C. At temperatures above 40°preference is given to using aromatic or aliphatic solvents which do not contain simple is Firov or have a very low content of ethers.

Anion cyclopentadienyls system (VIIIa), thus obtained, can then be input in a reaction with a suitable compound of a transition metal, such as grantrichland-Tris(tetrahydrofuran), and to obtain the appropriate monosyllabically complex (A).

In addition, we have developed a method of obtaining cyclopentadiene systems of the formula (VIIb)

where the variables have the following values:

E1C-E5Cmean carbon, where the four neighboring E1C-E5Cform a conjugated diene system, and the rest of the E1C-E5Cadditionally contain a hydrogen atom,

R1B-R4Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR11B2N(SiR11B3)2, OR11B, OSiR11B3, SiR11B2, BR11B2where the organic radicals R1B-R4Bmay also contain as substituents, Halogens and two vicinal radicals R1B-R4Bcan also be connected with the formation of five - or six-membered cycle,

R5B, R6Bmean ogorodili methyl,

And means

where E1B-E4Bmean carbon or nitrogen,

R7B-R10Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3where the organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle,

R11Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms or arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl portion and two radicals R11Bcan also be connected with the formation of five - or six-membered cycle,

R is 0, if E1B-E4B1B-E4Bmean carbon

where at least one R7B-R10Bmeans alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, arylalkyl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3and organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle, or not less than one E1B-E4Bmeans nitrogen, which includes the next stage:

a') the interaction of the anion A-CR5BR6B-with cyclopentenone system of the formula (IX)

in which the variables are as defined above.

Variables and their preferred embodiments of the above and these definitions are applicable to this method.

Cation anion A-CR5BR6B-usually t is aetsa metal of group 1 or 2 of the Periodic system of elements, which may contain additional ligands. Particular preference is given to cations of lithium, sodium and potassium, which can be uncharged ligands, such as amines and ethers, and the cations of magnesium chloride and magnesium bromide, which can also have additional uncharged ligands.

The anion A-CR5BR6B-usually obtained by deprotonation of A-CR5BR6BH. This can be done with the use of strong bases, such as alkyl derivatives of lithium, sodium hydride, amides of sodium, sodium alkoxides, alkyl derivatives of sodium, potassium hydride, amides potassium, potassium alkoxides, potassium alkyl derivatives, alkyl derivatives of magnesium, (alkyl)magnesium halides or mixtures thereof. The molar ratio of the base and A-CR5BR6BH is typically in the range from 0.4:1 to 100:1, preferably in the range from 0.9:1 to 10:1 and particularly preferably from 0.95:1 to 1.1:1. Examples of such deprotonation described in L.Brandsma, Preparative polar organometallic chemistry 2, pp.133-142.

As solvents under deprotonation you can use all aprotic solvents, preferably aliphatic and aromatic hydrocarbons, such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene, or ethers, such as diethyl ether, disutility ether, tetrahydrofuran, dimethoxy the Academy of Sciences and the dimethyl ether of diethylene glycol, and mixtures thereof. The deprotonation can be carried out when a temperature of from 100 to +160°C, preferably from 80 to 100°C. At temperatures above 40°, preference is given to using as solvent an aromatic or aliphatic solvents which do not contain ethers or have a very small content of ethers.

Particularly preferably, if A-CR5BR6BH means a group of the formula (VIIIb)

in which the variables are as defined above.

Preferably, the group of CR5BR6BH was located in the ortho-position relative to the nitrogen atom of the group A. ACR5BR6BH means preferably 2,6-lutidine, 2,4-lutidine, 2,5-lutidine, 2,3-cycloheptatrien, 5-ethyl-2-methylpyridine, 2,4,6-kallidin, 3-methylpyridazine, 4-methylpyrimidine, 4,6-dimethylpyrimidine, 2-methylpyrazine, 2-ethylpyrazine, 2,6-dimethylpyrazine, 2.5-dimethylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine, tetrahydroquinoxalin, tetramethylpyrazine, giraldin, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,7-dimethylphenol, 2-methylphenoxy, 2,3-dimethylquinoxaline or neocuproine.

The anion A-CR5BR6B-obtained after deprotonation, it is possible to allocate, but it is preferable to introduce it into the reaction cyclopentenone (IX) without selection. As solvents for the subsequent reaction of mo is but to use all aprotic solvents, preferably aliphatic and aromatic hydrocarbons, such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene, or ethers, such as diethyl ether, disutility ether, tetrahydrofuran, dimethoxyethane and dimethyl ether of diethylene glycol, and mixtures thereof. Reaction with cyclopentenone (IX) can be used at temperatures from -100 to +160°C, preferably from -80 to 100°and especially preferably from 0 to 60°C. At temperatures above 40°preference is given to using aromatic or aliphatic solvents which do not contain ethers or have a very small content of ethers as solvent.

Cyclopentenone obtained by the reaction of the anion A-CR5BR6B-with cyclopentenone (IX)before dehydration usually protonium. This can be accomplished, for example, using small amounts of acid, such as HCl, or by treatment with water. Thus obtained intermediate product, i.e. Cyclopentanol, then dehydration. This is often accomplished by the addition of catalytic amounts of acid, for example HCl or p-toluensulfonate acid, or iodine. The dehydration can be carried out when a temperature of from -10 to +160°C, preferably from 0 to 100°and particularly preferably from 20 to 80°C. as solvents which can be used aprotic solvents, preferably aliphatic and aromatic hydrocarbons, such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene, or ethers, such as diethyl ether, disutility ether, tetrahydrofuran, dimethoxyethane and dimethyl ether of diethylene glycol, and mixtures thereof. Especially preferred solvents are toluene and heptane. For dehydration often use water separators.

This method of obtaining cyclopentadiene systems (VIIb) is especially preferred because it is carried out using simple starting compounds and leads to good yields. The resulting by-products (dehydration in the Exo-position), you can easily separate with subsequent reactions with the formation of monotsiklopentadienil complex. Thus obtained cyclopentadienyl system (VIIb) can be deprotonate conventional methods, for example using potassium hydride or n-utility followed by reaction with a suitable compound of a transition metal, such as grantrichland-Tris(tetrahydrofuran) and get the appropriate monosyllabically complex (A'). By-products do not come in any of these reactions. In addition, cyclopentadienyl system (VIIb) can also be introduced into the reaction directly, for example, the inorganic salts of chromium and get monosyllabically complex (A'), similar to that described in European patent application EP AND 742046. Monosyllabically complexes corresponding to the present invention, can be used separately or in conjunction with other components as catalytic systems for polymerization of olefin.

To mononitrobenzene complexes (a) or (A') can be used in the polymerization in the gas phase or in suspension, it is often useful to use metallocene in the form of solids, i.e. to apply them on a solid substrate). In addition, monosyllabically complexes on the substrate provide high performance. So if you need monosyllabically complexes (a) or (A') can also be mobilitat organic or inorganic substrate) and used in the polymerization together with the substrate. This allows, in particular, to avoid sludge formation in the reactor and to control the morphology of the polymer. As materials of the substrate preference is given to using silica gel, magnesium chloride, aluminum oxide, mesoporous materials, aluminosilicates, hydrotalcites and organic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene or polar polymers having functional groups, for example, copolymers of Athena and acrylic acid, acrolein or finilize the ATA.

Particular preference is given to a catalyst system comprising monosyllabically complex (a) or (A') and at least one activating compound (C), and component-substrate).

To obtain such catalytic systems on the catalytic substrate without substrate (a) or (A') can be introduced into the reaction with the component-substrate). The order in which the combined component-substrate), monosyllabically complex (a) or (A') and the activating compound (C), is in principle immaterial. Monosyllabically complex (a) or (A') and the activating compound (C) can be immobilized independently of one another, for example, sequentially or simultaneously. Thus, the component-substrate) can first be brought into contact with the activating compound or compounds With or component, the substrate can first be brought into contact with monosyllabically complex (a) or (A'). It is also possible pre-activation monotsiklopentadienil complex (a) or (A') using one or more activating compounds C) before mixing with the substrate). In one possible embodiment, the complex of the metal (A) can also be obtained in the presence of the substrate material. Another method of immobilization is preliminary polymerization ka is aliciously system prior to application to the substrate or without application.

Immobilization is usually carried out in an inert solvent, which can be removed by filtration or by evaporation after performing immobilization. After the individual stages of the method, the solid can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons, and dried. However, you can also use the more humid catalyst on the substrate.

In the preferred method for the catalytic systems on the substrate at least one monosyllabically complex (a) or (A') is brought into contact with at least one activating compound (C) in a suitable solvent, preferably forming a soluble reaction product, an adduct or a mixture. Thus obtained composition is then mixed with digidrirovanny or passivated material of the substrate, the solvent is removed and the resulting monotsiklopentadienil complex catalytic system on the substrate is dried to the entire solvent or most of it has been removed from the pores of the substrate material. The catalyst on the substrate is obtained in the form of loose powder. Examples of industrial applications of the above method is described in international applications WO 96/00243, WO 98/40419 and WO 00/05277. Another preferred implementation includes applying an activating with the Union With) the component-substrate) and then bringing into contact of this compound on the substrate with monosyllabically complex (a) or (A').

As a component of the substrate In) preference is given to using finely ground substrates, which can be any organic or inorganic solids. In particular, component-substrate) can be a porous substrate, such as talc, layered silicate such as montmorillonite, mica, inorganic oxide or a finely ground powder polymer (e.g. polyolefin or a polymer having polar functional groups).

Preferably used substrate material had a specific surface area in the range from 10 to 1000 m2/g with a pore volume in the range from 0.1 to 5 ml/g and an average particle size equal to from 1 to 500 μm. Preferred substrates having a specific surface area in the range from 50 to 700 m2/g with a pore volume in the range from 0.4 to 3.5 ml/g and an average particle size in the range from 5 to 350 μm. Particular preference is given to substrates having a specific surface area in the range from 200 to 550 m2/g with a pore volume in the range from 0.5 to 3.0 ml/g and an average particle size equal to from 10 to 150 microns.

The inorganic substrate can be subjected to heat treatment, for example, to remove the adsorbed water. Such a drying treatment is usually carried out at a temperature of from 80 to 300°C, preferably from 100 to 200°C. Drying when the fact is the temperature value from 100 to 200° With preferably carried out at reduced pressure and/or in the atmosphere of inert gas (e.g. nitrogen) or inorganic substrate can be calcined at a temperature of from 200 to 1000°to provide the necessary structure of solids and/or required concentration groups IT on the surface. The substrate can also be subjected to chemical treatment using conventional drying agent such as alkyl derivatives of metals, preferably alkyl derivatives of aluminum, CHLOROSILANES or SiCl4or methylaluminoxane. Suitable processing methods are described, for example, in international application WO 00/31090.

Inorganic substrate material can also be subjected to chemical modification. For example, treatment of silica gel with NH4SiF6or other fluorinating reagents leads to fluorination of the silica gel surface, or treatment of silica gels with silanes containing nitrogen-, fluorine - or sulfur-containing groups leads to correspondingly modified surfaces of silica gel.

You can also use an organic substrate materials, such as finely powdered polyolefins (e.g. polyethylene, polypropylene or polystyrene), and before using them preferably likewise be exempt from accumulated moisture, residual solvent and dragapella using the appropriate cleansing and drying. You can also use a substrate of polymers with functional groups, for example the substrate on the basis of polystyrene, polyethylene or polypropylene, with functional groups, for example ammonium or hydroxy groups, you can assign at least one component of the catalyst.

To inorganic oxides suitable for use as a component of the substrate)may include oxides of elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic system of elements. Examples of oxides preferred as substrates include silicon dioxide, 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 above preferred oxide substrates are, for example, MgO, CaO, AlPO4, ZrO2, TiO2In2About3or mixtures thereof.

As a solid substrate material) catalysts for polymerization of olefin preference is given to using silica because of this substance can be obtained particle size and structure which makes it suitable for use as substrates for polymerization of olefins. Dried by spraying the silica containing spherical agglomerates slightly the x granular particles, i.e. primary particles, have proved particularly suitable. Before using the silica gels can be dried and/or calcined.

Other preferred substrates) are hydrotalcite and calcined hydrotalcite. In Mineralogy hydrotalcite is a natural mineral having theoretical formula

Mg6Al2(OH)16CO3·4H2O,

the structure of which is derived from the structure of brucite Mg(OH)2. Brucet crystallizes in a plate structure with the metal ions in the octahedral voids between the two layers of close-Packed hydroxyl ions, and is populated only every second layer of octahedral voids. In hydrotalcite part of magnesium is replaced by aluminium ions and as a result, the packaging layer acquires a positive charge. He is compensated by anions, which together with crystallization water are placed in the intermediate layers.

Such lamellar structures are found not only at the hydroxides of magnesium - -of aluminium, but is usually mixed metal hydroxides of the formula

M(II)2x2+M(III)23+(OH)4x+4·A2/nn·zH2O,

which have a lamellar 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 what Etalon, such as Al, Fe, Co, Mn, La, CE and/or Cr, x is from 0.5 to 10 in increments of 0.5, And the mean interstitial anion and n means the charge interstitial anion, which may be from 1 to 8, usually from 1 to 4, and z is an integer equal to from 1 to 6, preferably from 2 to 4. Possible interstitial anions are organic anions such as alkoxide anions, sulphate simple alkylation, sulfates simple arylation or sulfates ethers of glycols, inorganic anions, such as preferably a carbonate, bicarbonate, chloride, sulfate, and IN(OH)4-or polyoxoanion metals, such as Mo7O246-and V10O286-. However, it can also contain a mixture of such anions.

Accordingly, for the objectives of the present invention all such mixed metal hydroxides having a lamellar structure, should be considered as hydrotalcite.

Calcined hydrotalcite can be obtained from hydrotalcites by calcination, i.e. heat, which can provide the necessary content of hydroxyl groups. Obtaining calcined hydrotalcites used in accordance with the present invention is usually carried out at temperatures above 180°C. the Preferred calcination for 3 to 24 hours at a temperature of from 250 to 1000°C, site is preferably from 400 to 700° C. At this stage the above solid matter can pass air or inert gas or to use the vacuum.

When heated natural and synthetic hydrotalcite first lose water, which is drying. With further heating, in fact annealing, the metal hydroxides are converted to metal oxides due to the removal of hydroxyl groups and interstitial anions; in the calcined hydrotalcite can still contain the group HE or interstitial anions, such as carbonate. The measure of this is the loss during drying. It represents the mass loss of a sample is heated in two stages, first for 20 minutes at 200°in a drying Cabinet and then for 1 hour at 950°in a muffle furnace.

Thus, the calcined hydrotalcite, used as component B)are mixed oxides of divalent and trivalent metals M(II) and M(III) molar ratio of M(II) M(III), typically in the range from 0.5 to 10, preferably from 0.75 to 8 and more preferably from 1 to 4. In addition, can also contain conventional amounts of impurities, such as Si, Fe, Na, Ca or Ti, as well as chlorides and sulfates.

The preferred calcined hydrotalcite) are mixed oxides, in which M(II) means magnesium and M(III) means aluminum. Such mixed oxides of al the MINIA-magnesium produced by the company Condea Chemie GmbH (currently Sasol Chemie), Hamburg, under the trade name Puralox Mg.

Preference is also given to the calcined hydrotalcites, in which the conversion structure is full or almost full. The calcination, i.e. transformation patterns can be confirmed, for example, by x-ray.

Applying hydrotalcite, calcined hydrotalcite or silica gels are usually used in the form of fine powders having an average particle diameter of d50equal to from 5 to 200 μm, preferably from 10 to 150 μm, particularly preferably from 15 to 100 μm and most preferably from 20 to 70 μm, and typically having a pore volume equal to from 0.1 to 10 cm3/g, preferably from 0.2 to 5 cm3/g and a specific surface area equal to from 30 to 1000 m2/g, preferably from 50 to 800 m2/g and more preferably from 100 to 600 m2/, Monosyllabically complexes corresponding to the present invention is preferably used in an amount such that the concentration monotsiklopentadienil complex in the finished catalyst system ranged from 5 to 200 μmol, preferably from 20 to 100 μmol and particularly preferably from 25 to 70 mmol per 1 g of substrate).

Some of monosyllabically complexes (a) or (A') themselves have activity in the polymerization and that they could is reality good activity during polymerization, they are brought into contact with the activator, namely component (C). For this reason, the catalyst system additionally contains, as component (C) one or more activating compounds, preferably at least one activating compound (C).

Suitable compounds C)which are able to react with monosyllabically complex (a) or (A') into catalytically active or more active compound are, for example, such compounds as aluminosis, a strong uncharged Lewis acid, an ionic compound having a cation of a Lewis acid or an ionic compound containing the acid Bronsted as the cation.

The amount subject to use activating compounds depends on the type of activator. Usually the molar ratio of the content of the complex of the metal (a) or (A') to the content of the activating compounds C) may be from 1:0.1 to 1:10000, preferably from 1:1 to 1:2000.

As iluminacao can be used, for example, compounds described in international application WO 00/31090. Particularly suitable luminokaya are having an open chain or cyclic luminokaya the compounds of formula (X) or (XI)

where R1D-R4Dindependently of one another denote an alkyl group with -6 carbon atoms, preferably methyl, ethyl, boutelou or isobutylene group and I is an integer equal to from 1 to 40, preferably from 4 to 25.

Particularly suitable aluminoxamine connection is methylaluminoxane.

These oligomeric luminokaya connections usually get adjustable recovery solution trialkylamine, preferably trimethylaluminum and water. Usually oligomeric luminokaya compounds, thus obtained, is a mixture of linear and cyclic chain molecules of various lengths, so that the value of I should be considered as average. Luminokaya compounds can also be mixed with other alkyl derivatives of metals, typically alkyl derivatives of aluminum. Luminokaya composition suitable for use as component C), are commercially available.

In addition, as the component (C) instead aluminating compounds of the formula (X) or (XI) it is also possible to use modified iluminacin, in which some of the hydrocarbon radicals substituted with hydrogen atoms or CNS, azlocillin, siloxane or amide radicals.

It was found that it is advisable to use monosyllabically complexes (a) or (A') and laminarinase compounds in such amounts that the atomic is the rate of the aluminum content in aluminating connections including still contained alkyl derivatives of aluminum, the content of transition metal in mononitrobenzene complex (a) or (A'), was in the range of from 1:1 to 2000:1, preferably from 10:1 to 500:1 and particularly preferably in the range from 20:1 to 400:1.

Another class of suitable activating components) are hydroxyalkyloxy. They can be obtained, for example, the addition to alkylamino connection from 0.5 to 1.2 equivalents of water, preferably from 0.8 to 1.2 equivalents of water per 1 equivalent of aluminum, for example to triisobutylaluminum, at low temperatures, usually below 0°C. Such compounds and their use in the polymerization of olefins is described, for example, in international application WO 00/24787. The atomic ratio of aluminum content in gidroksilaminooksimov connection and content of transition metal in mononitrobenzene complex (a) or (A'), is usually in the range from 1:1 to 100:1, preferably from 10:1 to 50:1 and particularly preferably in the range from 20:1 to 40:1. Preference is given to using monotsiklopentadienil dealkiller compounds of the metal (a) or (A').

As strong, uncharged acids of Luisa preference is given to compounds of the formula (XII)

where M2Dis an element of group 13 of the Periodic system of elements, in the example, Al or Ga, preferably B, X1DX2Dand X3Ddenote hydrogen, alkyl with 1-10 carbon atoms, aryl with 6 to 15 carbon atoms, alkylaryl, arylalkyl, halogenated or halogenared, each of which contains from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or fluorine, chlorine, bromine or iodine, preferably galogenidy, preferably pentafluorophenyl.

Other examples of strong, uncharged acids of Luisa described in international application WO 00/31090.

Compounds of this type, particularly suitable for use as component C)are boron and braccini, such as trialkylborane, trainborn or trimethylboroxine. Particular preference is given to using Baranov that contain at least two perfluorinated aryl radicals. Particular preference is given to compounds of the formula (XII)in which X1DX2Dand X3Dare the same, preferred is Tris(pentafluorophenyl)borane.

Suitable compounds C) are preferably obtained by reaction of compounds of aluminum or boron formula (XII) with water, alcohols, phenol derivatives, thiophenolate derivatives or aniline derivatives, and particularly preferably halogenated and more preferably perfluorinated alcohols and phenols. Examples OS is especially suitable compounds are pentafluorophenol, 1,1-bis(pentafluorophenyl)methanol and 4-hydroxy-2,2',3,3',4,4',5,5',6,6'-nonaboriginal. Examples of combinations of compounds of the formula (XII) with acids of Bronsted are, in particular, trimethylaluminum/pentafluorophenol, trimethylaluminum/1-bis(pentafluorophenyl)methanol, trimethylaluminum/4-hydroxy-2,2',3,3',4,4',5,5',6,6'-nonaboriginal, triethylaluminium/pentafluorophenol and triisobutylaluminum/pentafluorophenol and triethylaluminum/4,4'-dihydroxy-2,2'-,3,3',5,5',6,6'-octafluoropentyl.

Other suitable compounds of aluminum and boron of the formula (XII) R1Dmeans the group HE. Examples of compounds of this type are boranova acid, preferably boranova acid containing perfluorinated aryl radicals, for example (C6F5)2OUT.

Strong uncharged acid of Luisa suitable for use as the activating compounds (C)include reaction products Bronevoy acid with two equivalents of trialkylamine and the reaction products trialkylamine with two equivalents of an acidic fluorinated, preferably perforated hydrocarbon compounds, such as pentafluorophenol and bis(pentafluorophenyl)Barinova acid.

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

where M3D is an element of groups 1 to 16 of the Periodic system of elements

Q1-Qzare groups with a single negative charge, such as alkyl with 1-28 carbon atoms, aryl with 6 to 15 carbon atoms, alkylaryl, arylalkyl, halogenated, halogenared, each of which contains from 6 to 20 carbon atoms in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, cycloalkyl with 3-10 carbon atoms, which may contain as substituents alkyl groups with 1-10 carbon atoms, halogen, alkoxy with 1-28 carbon atoms, aryloxy from 6-15 carbon atoms, silyl or mercaptopropyl,

and is an integer equal to from 1 to 6, and

z is a whole number equal to from 0 to 5,

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

Particularly suitable cations are carbonium cations, oxonium cations and sulfonamide cations, and cationic complexes of transition metals. It should be particularly noted triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocene cation. Preferably, they contain a disorderly counterions, in particular boron compounds, designated in the international application WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.

Salt containing uncoordinated anions, can also be obtained by combining the boron compounds Il is aluminum, for example alkylamine, with a second compound which can react with the linking of two or more atoms of boron or aluminum, for example, with water, and a third compound which forms an ionizing ionic compound with a boron compound or aluminum, for example triphenylmethane, or optional with base, preferably an organic nitrogen-containing base, for example an amine, an aniline derivative or a nitrogen-containing heterocycle. In addition to this you can add a fourth connection, which is similarly reacted with a compound of boron or aluminum, for example pentafluorophenol.

Likewise preferably, ionic compounds containing acid Bronsted as cations, also contained coordinarussia counterions. As acids Branstad particular preference is given protonated derivatives of amines or aniline. The preferred cations are N,N-dimethylaniline, N,N-dimethylcyclohexylamine and N,N-dimethylbenzylamine, and derivatives of the latter two compounds.

For use as component (C) are also suitable compounds containing anionic boron-containing heterocycles, such as described in international application WO 97/36937, preferably dimethylaniline - bortleson and tritovores.

predpochtitelnye ionic compounds (C) include borates, which contain at least two perforated aryl radical. Particular preference is given to N,N-dimethylanilinium-tetrakis-(pentafluorophenyl)borate, and preferably N,N-dimethylcyclohexylamine-tetrakis-(pentafluorophenyl)borate, N,N-dimethylbenzylamine-tetrakis-(pentafluorophenyl)borate, trityl-tetrakis-pentafluorobenzoate.

You can also link two or more borate anions with each other, as in dianion [(C6F5)2B-C6F4In(C6F5)2]2-or the borate anion can contact in the form of a bridge with a suitable functional group of the substrate surface.

Other suitable activating compounds C) are listed in the international application WO 00/31090.

The content of a strong uncharged Lewis acids, ionic compounds containing cations of Lewis acids or ionic compounds as cations acid Branstad, is preferably from 0.1 to 20 equivalents, more preferably from 1 to 10 equivalents, and particularly preferably from 1 to 2 equivalents per monosyllabically complex (a) or (A').

Suitable activating compounds (C) include compounds of boron-aluminum, such as di[bis(pentafluorophenyl)barocci]meillan. Examples of such compounds of boron-aluminum connections are disclosed in the international application WO 99/06414.

It is also possible to use mixtures of the above-activating compounds C). Preferred mixtures include iluminacin, preferably methylaluminoxane, and ionic compounds, preferably containing tetrakis-(pentafluorophenyl)borate anion and/or strong the uncharged Lewis acid, preferably Tris(pentafluorophenyl)borane or noroxin.

And monosyllabically complexes (a) or (A')and the activating compound (C) preferably used in a solvent, preferably in an aromatic hydrocarbon containing from 6 to 20 carbon atoms, such as xylenes, toluene, pentane, hexane, heptane or mixtures.

Another possibility is to use the activating compound C), which can simultaneously be used as a substrate). Such systems are, for example, of the inorganic oxide by treatment with zirconium alkoxide followed by chlorination, for example, using carbon tetrachloride. The receipt of such systems are described, for example, in international application WO 01/41920.

The catalytic system may further comprise, as additional component D) a compound of the metal of the formula (XX)

where MGmeans Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gallium, indium, thallium, zinc, preferably Li, Na, K, Mg, boron, aluminum is or Zn,

R1Gdenotes hydrogen, alkyl with 1-10 carbon atoms, aryl with 6 to 15 carbon atoms, alkylaryl or arylalkyl, each of which contains from 1 to 10 carbon atoms in the alkyl portion and from 6 to 20 carbon atoms in the aryl part,

R2Gand R3Gmean hydrogen, halogen, alkyl with 1-10 carbon atoms, C6-C15aryl with 6 to 15 carbon atoms, alkylaryl, arylalkyl or alkoxy, each of which contains from 1 to 20 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or alkoxy containing alkyl with 1-10 carbon atoms or aryl with 6 to 15 carbon atoms,

rGis an integer equal to from 1 to 3, and

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

where component D) is usually not identical to the component). It is also possible to use mixtures of various metal compounds of the formula (XX).

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

MGmeans lithium, magnesium, boron or aluminum, and

R1Gmeans alkyl with 1-20 carbon atoms.

Especially preferred compounds of metals of the formula (XX) are motility, utility, n-utility, methylaniline, methylacrylamide, ethylaniline, ethylaniline, butila ichorid, dimethylamine, diethylamine, dibutylamine, n-butyl-n-octylamine, n-butyl-n-heptylamine, preferably 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 alkyl derivatives of aluminum.

If you are using a compound of the metal (D), preferably, it is contained in the catalyst system in an amount such that the molar ratio of the content of MGin the compound of formula (XX) to the content of transition metal in mononitrobenzene compound A) or A'), ranged from 2000:1 to 0.1:1, preferably from 800:1 to 0.2:1 and particularly preferably from 100:1 to 1:1.

Typically, the compound of the metal (D) of the formula (XX) is used as a component of a catalytic system for the polymerization or copolymerization of olefins. In this case, the connection metal D) can be used, for example, to obtain a solid catalyst comprising a substrate), and/or may be added during or shortly before the polymerization. Used metal link (D) may be the same or different. It is also possible, especially if the solid catalyst does not contain kiviruusu component C), in the catalytic system in addition to the solid catalyst to add one or more compounds (C), which coincide with any of the compounds (D)contained in the solid catalyst, or differ from them.

To obtain the catalytic systems according to the present invention the preferred immobilization of at least one of the components (a) or (A') and/or (C) on the substrate by physical adsorption or by chemical reaction, i.e. covalent binding components with reactive groups of the substrate surface. The order in which combine component-substrate), the component (a) or (A') and any component (C)is not significant. Components (a) or A') and (C) can be added to C) independently of each other or simultaneously, or sequentially, or in the form of a previously prepared mixture. After execution of individual stages of the method, the solid can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons.

In a preferred embodiment, monosyllabically complex (a) or (A') is brought into contact with the activating compound C) in a suitable solvent, preferably forming a soluble reaction product, an adduct or a mixture. Thus obtained composition then privodjat contact with the substrate), which may be subjected to preliminary treatment and the solvent is completely or partially removed. Preferably, there was obtained a solid substance in the form of loose powder. Examples of industrial applications of the above method is described in international applications WO 96/00243, WO 98/40419 and WO 00/05277. Another preferred implementation includes applying an activating compound (C) on the substrate) and then bringing into contact of this compound on the substrate with monosyllabically complex (a) or (A').

Similarly, the component (D) in any order, you can enter into reaction with components (a) or (A') and, if necessary, with b) and C). For example, monosyllabically complex And can be brought into contact with component (components) and/or (D) before or after bringing it in contact with the underlying polymerization of olefins. It is also possible pre-activation of one or more components (C) prior to mixing with the olefin and further addition of the same or other components) and/or (D) after bringing the mixture into contact with the olefin. Pre-activation is usually carried out at a temperature of 10-100°C, preferably 20-80°C.

Preferably D) first brought into contact with component (C), and then use the use of components (a) or A') and b) and the additional amount), as is described above. In another preferred embodiment, the solid catalyst was prepared from components (a) or (A'), b) and C)as described above, and it is brought into contact with the component (D) during, at the beginning or shortly before the polymerization. Preferably D) first brought into contact with the subject of polymerization α-olefin and then add the solid catalyst containing components (a) or A'), b) and C)as described above.

The catalytic system can first be subjected to a preliminary polymerization with α-olefins, preferably linear 1-alkenes with 2 to 10 carbon atoms, particularly preferably ethylene or propylene, and the resulting pre-polymerized solid catalyst is then used in the subsequent polymerization. The mass ratio of the content of the solid catalyst used in the preliminary polymerization, and the content of polymerized therein 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 receipt of a catalytic system as an additive you can add a small amount of olefin, preferably α-olefin, such as vinylcyclohexane, styrene or phenyldimethylsilane, as modifying component in small amounts, the creation of antistatic or a suitable inert compound, such as wax or oil. The molar ratio of the content of additives and content of the transition metal compounds (a) or (A') is usually from 1:1000 to 1000:1, preferably from 1:5 to 20:1.

In the method corresponding to the present invention, copolymerization of ethylene with α-olefins α-olefins are hydrocarbons containing terminal double bond, and hydrocarbons may also include a functional group containing atoms of groups 14 to 17 of the periodic system of elements. Suitable monomers include containing functional group refinancinn compounds such as acrolein, esters and amines acrylic and methacrylic acid, for example acrylates, methacrylates and Acrylonitrile, and vinyl esters such as vinyl acetate. Preferred non-polar olefinic compounds that contain only carbon atoms including aryl-substituted α-olefins. Especially preferred α-olefins are linear or branched 1-alkenes with 2 to 12 carbon atoms, preferably a linear 1-alkenes with 2-10 carbon atoms, such as Eten, propene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene, 1-mission and branched 1-alkenes with 2-10 carbon atoms, such as 4-methyl-1-penten, paired and unpaired diene, such as 1,3-butadiene, 1,5-hexadiene and 1.7-octadiene and blame the aromatic compounds, such as styrene and substituted styrene. You can also polimerizuet mixtures of different α-olefins. Preference is given to polymerization of at least one α-olefin selected from the group comprising Aten, propene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene and 1-of the mission.

A mixture of two or more α-olefins can also be copolymerisate with Atena. Preference is given to using mixtures of monomers containing at least 50 mol.% Athena.

The method of polymerization of ethylene with α-olefins according to the present invention can be combined with all known industry methods carried out at temperatures from -60 to 350°and pressure, equal to from 0.5 to 4000 bar. The polymerization can be conducted in a known manner in the block, in suspension, in gas phase or supercritical medium in the conventional reactors used for the polymerization of olefins. It can be done in batch or preferably in a continuous mode in one or more stages. How polymerization at high pressure tubular reactors or autoclaves, in solution, in suspension, in gas phase under stirring or in the gas phase in the fluidized bed.

The polymerization is usually carried out at temperatures of from 60 to 350°C, at pressures equal to from 0.5 to 4000 bar, with the average time of stay is, equal to from 0.5 to 5 hours, preferably from 0.5 to 3 hours. Preferred to conduct the polymerization temperature ranges and pressure usually depend on the method of polymerization. In the case of polymerization at high pressures, which is usually carried out at pressures equal to from 1000 to 4000 bar, preferably from 2000 to 3500 bar, usually set and high temperature. Preferred temperature ranges for this polymerization at high pressures range from 200 to 320°C, preferably from 220 to 290°C. In the case of polymerization at low pressures usually set the temperature that at least a few degrees below the softening temperature of the polymer. These methods of polymerization preferably takes place at temperatures of from 50 to 180°S, more preferably from 70 to 120°C. In the case of suspension polymerization, the polymerization is usually carried out in a suspension medium, preferably in an inert hydrocarbon, such as isobutane, or a mixture of hydrocarbons, or even in the monomers. The polymerization temperature is usually in the range from 20 to 115°and the pressure is typically in the range from 1 to 100 bar. The solids content of the suspension is typically in the range from 10 to 80%. The polymerization can be carried out in periodic mode, for example, in autoclaves at first is mesheanii or in continuous mode, for example, in a tubular reactor, preferably in loop reactors. Particular preference is given to the application of the method of Phillips PF described in the claims USA USA 3242150 and USA 3248179. Gas-phase polymerization is usually carried out at temperatures from 30 to 125°and at pressures from 1 to 50 bar.

Of the above methods of polymerization particular preference is given to gas-phase polymerization, preferably in a gas-phase fluidized bed reactor, polymerization in solution and polymerization in suspension, preferably in loop reactors and housing the reactor with stirring. Gas-phase polymerization can also be carried out in the condensed or sverhorganizovanny phase, in which part of the circulating gas is cooled below the dew point temperature and in the form of a two-phase mixture of recycle to the reactor. You can also use the multi-zone reactor, in which two zones polymerization are connected to each other and the polymer several times alternately passes through these two zones. In these zones, the conditions of polymerization can be different. Such a reactor is described, for example, in international application WO 97/04015. Different or the same reactor for polymerization, if necessary, can be connected in series so as to form a sequence of polymerization, for example, in the way Hostalen. It is also possible parallel is the location of the reactors using two or more different ways. In addition, when the polymerization is also possible to use molecular weight regulators, for example hydrogen, or conventional additives such as antistatics.

Ethylene copolymer of the present invention may also be a mixture of polymers. So, for example, can be mixed with each other two or three different copolymer of ethylene according to the present invention, which may vary, for example, its density and/or its molecular weight distribution and/or distribution of short-chain branching. They can also be obtained by using a sequential polymerization.

Others used a mixture of polymers include:

(E) from 1 to 99 wt.% one or more of ethylene copolymers of the present invention and

(F) from 1 to 99 wt.% polymer, which is different from (E)with values in wt.% given the total weight of the mixture of polymers.

A mixture of polymers, including:

(E) from 1 to 99 wt.% one of ethylene copolymers of the present invention, preferably from 30 to 95 wt.% and particularly preferably from 50 to 85 wt.%, and

(F) from 1 to 99 wt.% polyolefin which is different from (E), preferably from 5 to 70 wt.% and particularly preferably from 15 to 50 wt.%, where values in wt.% given the total weight of the mixture of polymers, are particularly preferred.

The type of addition is sustained fashion polymer component (F) in the mixture depends on the purpose of the mixture. The mixture can be obtained, for example, by mixing with one or more additional LLDPE, or HDPE (high density polyethylene)or LDPE (low density polyethylene)or PP (polypropylene), or polyamides, or polyesters. An alternative mixture of polymers can be obtained by simultaneous polymerization using monotsiklopentadienil complex and one or more catalyst systems, which are also active in the polymerization of olefins. Suitable catalysts for production of mixtures of polymers or for the simultaneous polymerization are preferably classical catalysts of the Ziegler-Natta titanium-based, classical Phillips catalysts based on chromium oxides, metallocene, preferably complexes of metals of groups 3 to 6 of the Periodic system of the elements, containing one, two or three cyclopentadienyls, indanilnykh and/or fluoroaniline systems, namely systems with bounded geometry (see, for example, European patent application EPA 0416815 or EPA 0420436), bis-minovia system Nickel or palladium (receive, see international application WO 9803559 A1) and pyridine bis-imine compounds of iron or cobalt (receive, see international application WO 9827124 A1). However, in the case of mixtures containing different polymers of the present invention, also m is tenderly to use another set of chrome). Additional polymerization catalysts can also be applied to the same substrate or on different substrates.

Ethylene copolymer of the present invention can also form a mixture having a wide or two-mode molecular weight distribution, with other olefin polymers, preferably homopolymers and copolymers of ethylene. These compounds can be obtained, or when the above-described simultaneous maintenance of additional catalysts suitable for the polymerization of olefins or by the subsequent mixing obtained separately polymers or copolymers.

Mixtures containing other olefin copolymers of the present invention can also optionally include two or three other olefinic polymer or copolymer. They may include, for example, LDPE (their mixtures are described, for example, in German patent application DE-A1-19745047) or polyethylene homopolymers (a mixture thereof are described, for example, in European patent application EP-IN-100843), LLDPE (as described, for example, in European patent application EUA 728160 or international application WO-A-90/03414), LLDPE/LDPE (in the international application WO 95/27005 or European patent application EP-B1-662989). The share of the copolymers of the present invention is at least 40-99 wt.%, preferably 50-90 wt.%, the total weight of the mixture of polymers.

The copolymers e is Elena, mixtures and compositions of the polymers may additionally include known excipients and/or additives, such as processing stabilizers, stabilizers against the effects of light and heat, customary additives such as lubricants, antioxidants, substances that prevent adhesion and antistatic agents, and optionally dyes. The type and amount of these additives known to specialists in this field of technology.

In addition, it is found that the adulteration of small amounts of forecasters or thermoplastic polyesters may lead to additional improvement of the machinability characteristics of the polymers of the present invention. Such forecaster themselves known as technological additives and are commercially available, e.g. under the trade names Viton® and Dynamar® (see, for example, an application USA USA-3125547). They are preferably added in quantities of from 10 to 1000 parts per million, particularly preferably from 20 to 200 parts per million based on total weight of the mixture of polymers of the present invention.

The polymers of the present invention also can be modified later via grafting, crosslinking, hydrogenation, introduction of functional groups or other modification reactions, known to specialists in this field of technology.

The production of polymer blends is by mixing can be performed by all the known methods. This can be accomplished, for example, by loading the powder components in the apparatus for granulating, for example in a twin-screw kneading machine (ZSK), kneading machine Farrel or kneading machine Kobe. You can also process the granulated mixture directly on the fabrication of the film.

Polymers and mixtures of polymers of the present invention are highly suitable, for example, for the manufacture of films on plants blowing and casting films great performance. Films made from mixtures of polymers, have very good mechanical properties, high impact resistance and high wear resistance combined with very good optical properties, in particular transparency and luster. They are particularly suitable for the packaging industry, for example, as termoskleivaniya films, and for labels and bags, and in the food industry. In addition, these films have only a weak tendency to stick together and therefore can pass through the machine without the addition of lubricants and chemicals, caking, or with the addition of very small quantities of these substances.

Due to their very good mechanical properties of copolymers of ethylene according to the present invention is also suitable for the manufacture of fibers and molded is of steli, in particular pipes and welded pipes. They are also suitable for blow molding, rotational molding and injection molding. They are also suitable for use as compendiously components, bonding agents and as kucukodabasi components in polypropylene, in particular in polypropylene compounds having high impact strength.

The following examples illustrate the present invention.

Examples

Samples for NMR taken in an atmosphere of inert gas and, if it is appropriate, then melted. The solvent signals act as internal standard in the spectra of1H and13C-NMR and chemical shifts are then converted to chemical shifts relative to tetramethylsilane.

Indicate in NMR spectra: s - singlet, d - doublet, t - triplet, br - broad.

Density [g/cm3] determined in accordance with ISO 1183.

Determination of molecular mass distributions and derived average values of Mn, Mwand Mw/Mnperformed using high temperature gel permeation chromatography according to the method based on DIN 55672 under the following conditions: solvent is 1,2,4-trichlorobenzene, flow rate 1 ml/min, temperature 140°With calibration using standards of polyethylene.

And what Aliza FEPT carried out under the following conditions: solvent - 1,2,4-trichlorobenzene, flow rate 1 ml/min, heating rate 1°C/min, the amount of polymer 5-10 mg, substrate - diatomaceous earth (kieselguhr).

ISRC determined as described in the international application WO-A-93/03093.

Measurements by the method of Crystaf® performed on the device manufacturing company Polymer Char, P.O. Box 176, E-46980 Paterna, Spain, using 1,2-dichlorobenzene as solvent and the data processed using the included software. Obtained by the method of Crystaf® curve temperature - time is shown in figure 1. Differential Crystaf curve® shows modulesthe distribution of short-chain branching. To convert the obtained curves Crystaf® depending on the number of groups of CH3per 1000 carbon atoms using the curve presented in figure 2, depending on the type of co monomer. On this curve T-w is defined as the sum of all mass fractions of m-i, multiplied by the temperature T-i, divided by the sum of all mass fractions of m-i:

The degree of short chain branching (CH3/1000) you can then simply be calculated by the following equation:

(CH3/1000)=as·T-w+b (see figure 2),

in which the following notation is used:

weighted average t is mperature T-w (°)
tiltand: -0,582 (CH3/1000)/(°)
crossingb: 60,46 (CH3/1000)

The content of the vinyl and vinylidene groups is determined using1H-NMR.

The degree of long chain branching λ determined using light scattering in accordance with the description in the work of the 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.

In the table below, the following notation is used:

Cat.catalyst
t(poly)the duration of polymerization
Polymerthe amount of the formed polymer
Mwsrednevekovaja molecular weight
MnBrednikova molecular weight
Densitythe density of the polymer
Production.the performance of the catalyst in grams of polymer per 1 mmol of the used catalyst (complex chromium) per hour

Example 1

1.1. Obtaining [2-(1H-inden-3-yl)methyl]-3,5,6-trimethylpyrazine

A mixture of 13.6 ml (0.1 mol) of 2,3,5,6-tetramethylpyrazine in 50 ml then it is carbonated is rufuran cooled to -20° And then, while stirring add 62.5 ml n-utility (1.6 M in hexane, 0.1 mol). Mixture is allowed to warm to room temperature with stirring. After stirring for a further 1 hour the solution is cooled to -60°and stirring for 15 minutes, add a solution of 15 g (0.11 mol) of 1-indanone in 20 ml of tetrahydrofuran. Mixture is allowed to warm to room temperature with stirring and stirred for another 12 hours. The mixture is then hydrolized with 250 ml of diluted hydrochloric acid and left to stand. After 24 hours the precipitate is filtered off 2-[(2,3-dihydro-1H-inden-1-ylidenemethyl]-3,5,6-trimethylenetrinitramine (by-product). The organic phase is separated from the liquid phase and the aqueous phase is extracted twice with ethyl acetate. Then the aqueous phase is an aqueous solution of ammonia and shaken out three times with portions of methylene chloride in 60 ml the combined Organic phases, dried over magnesium sulfate, the magnesium sulfate and the solvent is distilled off. This gives 17.3 g of a mixture of 2-(1H-inden-3-ylmethyl)pyridine and 2-[(S)-2,3-dihydro-1H-inden-1-ylidenemethyl]-3,5,6-trimethylpyrazine (yield 55%) and unreacted tetramethylpyrazine in the ratio of 10:3 (NMR). The mixture is used directly in the next stage. NMR1H (CDCl3): rate of 7.54 (d, 1H); of 7.48 (d, 1H); to 7.35 (t, 1H); to 7.25 (t, 9H); of 5.92 (br.s, 1H); 4,07 (br.s, 2H); 3,54 (br.s, 2H); of 2.56 (s, 3H); to 2.54 (s, 3H); 2,52 (s, 3H).

1.2. Receiving the s (1-(2-(3,5,6-trimethylpyrazine)methyl)indenyl)grandiflora

A solution of 7.25 g of the mixture obtained above in 80 ml of tetrahydrofuran is cooled to -100°C. While stirring slowly added dropwise 16 ml of 15% solution of n-utility in hexane (0,0256 mol). After completion of addition, the reaction mixture is stirred for a further 1 hour at -100°C. the mixture is allowed to warm to room temperature. After stirring for a further 2 hours the solution is cooled to -60°and with stirring was added 10.2 g (0,0272 mol) Tris(tetrahydrofuran)-fratricide. Mixture is allowed to slowly warm to room temperature and then stirred for a further 10 hours at room temperature. The solid is in the form of precipitate is filtered off, washed twice with diethyl ether and dried under reduced pressure. This gives 5.2 g of green powder, 4,2 g of which is recrystallized from a mixture of CH2Cl2-Et2O. Obtain 3.1 g (1-(2-(3,5,6-trimethylpyrazine)methyl)indenyl)grandiflora (43%).

Example 2

2.1. Obtaining [2-(1H-inden-3-yl)-1-methylethyl]pyridine

A solution of 7.25 g (0.046 mol) of 2-bromopyridine in 20 ml of diethyl ether cooled to -60°and then, with stirring, was added a mixture of 28.7 ml of n-utility (1.6 M in hexane, 0.046 mol) and 70 ml of diethyl ether. The mixture is stirred for another 15 minutes and then add the solution 7,16 g (0.046 mol) 1-(1-methylethylidene)-1-and the dena in 10 ml of ether. Mixture is allowed to warm to room temperature and hydrolyzing with 100 ml of diluted hydrochloric acid. The organic phase is separated and the aqueous phase is once extracted with diethyl ether, then the aqueous phase is neutralized with an aqueous solution of ammonia and shaken out three times with portions of chloroform, 50 ml the combined Organic phases, dried over magnesium sulfate, the magnesium sulfate and the solvent is distilled off. Gain of 0.54 g (5%) [2-(1H-inden-3-yl)-1-methylethyl]pyridine.

2.2. Receive (3-(2-pyridyl-1-methylethyl)indenyl)grandiflora

A solution of 0.54 g (0,0023 mol) of [2-(1H-inden-3-yl)-1-methylethyl]pyridine in 20 ml of tetrahydrofuran is cooled to -100°C. slowly added dropwise 1,72 ml of 15% solution of n-utility in hexane (0,0027 mol). After completion of addition, the reaction mixture was stirred at -100°C for another 30 minutes. The mixture is allowed to warm to room temperature. After stirring for a further 1 h the solution is cooled to -60°and with stirring was added 1.1 g (0,0029 mol) Tris(tetrahydrofuran)fratricide. Mixture is allowed to slowly warm to room temperature and then stirred for a further 10 hours at room temperature. Then the reaction mixture is refluxed for 20 minutes and then cooled to room is based temperature. The solid is in the form of precipitate is filtered off, washed with diethyl ether and dried under reduced pressure. This gives 0.3 g (3-(2-pyridyl-1-methylethyl)indenyl)grandiflora (37%).

Comparative example 1

5-[(2-Pyridyl)methyl]-1,2,3,4-tetramethylcyclopentadienyl receive, as described in international application WO 01/92346.

Polymerization

The polymerization is carried out at a temperature of 40°in argon atmosphere in chetyrehkolkoy flask of 1 l, which is attached with contact thermometer, stirrer with Teflon blade, the heating jacket and the pipe for gas supply. Appropriate amount of MAO (methylaluminoxane) (10% solution in toluene, Cr:Al=1:500) was added to the solution in amounts indicated in the table, the corresponding complex in 250 ml of toluene and the mixture is heated to 40°With water bath.

Shortly before the introduction of ethylene into the flask, 3 ml of hexene and through bootstrapping at atmospheric pressure then let ethylene at a rate equal to about 20-40 l/h the Remaining number of hexene (7 ml) was injected via the dropping funnel within 15 minutes. After the date specified in the time table with the constant stream of ethylene polymerization is stopped by addition of HCl solution in methanol (15 ml of concentrated hydrochloric acid in 50 ml of methanol). the ATEM add 250 ml of methanol and the resulting white polymer was filtered off, washed with methanol and dried at 70°C.

Data on the polymerization
The catalyst of example No.The amount of catalyst [mg]t (poly) [min]Polymer [g]Prod. [g/mmol Cr·h]Mw[g/mol]Mw/MnDensity [g/cm3]ISRCThe distribution of short-chained branching
17,425the 3.84591067432,940,934<50%two-mode
29,82011,512602520116,24no data<50%two-mode
C17,72012,8169228067br4.610,94>50%singlemode

Example 3

(3-(2-(4-Methylpyridyl)methyl)indenyl)chromdioxid get by the method similar to the one used in example 1, but using the appropriate quantities of 2,4-dimethylpyridine instead of tetramethylpyrazine.

Polim is the document, thereby carried out so, as described above, at 40°in argon atmosphere using hexene as co monomer and the duration of polymerization is 60 minutes. The activity of the complex (Cr : MAO=1:500) is 1730 g/mmol Cr in 1 hour. Mwthe copolymer is equal to 283910 g/mol, Mw/Mnequal to 2.57. The copolymer has a value of ESRC equal to less than 50%, and two-mode distribution of short-chain branching (differential Crystaf curve®). The Crystaf peak maxima® on the differential curve Crystaf® located at 12°33°C. the Content of the vinyl groups is 0,19 vinyl groups/1000 carbon atoms. Content vinylidene groups is 0.52 vinylidene groups/1000 carbon atoms. Indicator of long-chain branching λ is less than 0.1 DCR/1000 carbon atoms.

1. A copolymer of ethylene α-olefin, which has a molecular weight distribution Mw/Mn1 to 8, a density of from 0.85 to 0.94 g/cm3, the molecular mass Mnfrom 10,000 to 4000000 g/mol, the index value of the width distribution for the composition (ESRC) less than 50%, and at least a bimodal distribution of branching of the side chains, and in which the branching of the side chains in the maxima of the individual peaks of the distribution of branching of the side chains in all cases more than 5 CH3/1000 carbon atoms.

<> 2. A copolymer of ethylene α-olefins according to claim 1, characterized in that it has a content of vinyl groups is from 0.1-1 vinyl groups/1000 carbon atoms.

3. A copolymer of ethylene α-olefins according to claim 1, characterized in that it has a molecular mass Mnequal 150,000 to 1,000,000 g/mol.

4. A copolymer of ethylene α-olefins according to claim 1, characterized in that it contains at least one peak in the spectrum Crystaf® differential distribution in the range from 15 to 40°and at least one additional peak in the spectrum Crystaf® differential distribution in the range from 25 to 80°C.

5. A copolymer of ethylene α-olefins according to any one of claim 2 to 4, characterized in that the distribution of branching of the side chains is tri-modal.

6. A method of producing copolymers of ethylene according to any one of claims 1 to 5, namely, that includes the polymerization of ethylene with α-olefins in the presence of the following components:

A) at least one monosyllabically complex comprising a structural fragment of formulain which the variables have the following meanings:

Cp-Z-A denotes a ligand of formula (II)

where R1A-R4Aindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl from 2 to 20 atoms in the of Lerida, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR11A2N(SiR11A3)2, OR11A, OSiR11A3, SiR11A3, BR11A2where the organic radicals R1A-R4Amay also contain as substituents halogen, and where at least two of the vicinal radicals R1A-R4Aconnected with the formation of five - or six-membered cycle, and/or two vicinal radicals R1A-R4Aconnected with the formation of the heterocycle, which contains at least one atom selected from the group comprising nitrogen (N), phosphorus (P), oxygen (O) and sulphur (S)

Z means the bridge between a and CP, having the formula

where L is carbon or silicon, preferably carbon,

R5A, R6Adenote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11A3where the organic radicals R5Aand R6Amay also contain as substituents halogen and R5Aand R6Acan also be combined with education is the Finance five - or six-membered cycle,

And means

where E1A-E4Amean carbon or 1-2 nitrogen atom,

R7A-R10Aindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11A3where the organic radicals R7A-R10Aalso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11A3as deputies and two vicinal radicals R7A-R10Aor R7Aand Z can also be connected with the formation of five - or six-membered cycle,

R11Aindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, C6-C20-aryl, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl portion and two genialnyh radical R11Acan also be connected with the formation of five - or W is stilnovo cycle, and

R is 0, if E1A-E4Amean nitrogen and is 1 if E1A-E4Amean carbon

X independently of one another denote fluorine, chlorine, bromine, iodine, hydrogen, alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing 1-10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR1R2, OR1, SR1, SO3R1, OC(O)R1, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion,

R1-R2independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR33where the organic radicals R1-R2may also contain as substituents, Halogens or nitrogen - and oxygen-containing groups and two radicals R1-R2can also be connected with the formation of five - or six-membered cycle,

R3independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 20 carbon atoms in the aryl portion and two radicals R 3can also be connected with the formation of five - or six-membered cycle and k is 1, 2 or 3,

B) optionally an organic or inorganic substrate,

C) one or more activating compounds, and

D) optionally one or more compounds containing a metal of group 1, 2 or 13 of the Periodic system.

7. Catalytic system for the (co)polymerization of olefins, comprising A') at least one monosyllabically complex A')comprising a structural fragment of formulain which the variables have the following meanings:

Cp-CR5BR6B- A means

where R1B-R4Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR11B2N(SiR11B3)2, OR11B, OSiR11B3, SiR11B3, BR11B2where the organic radicals R1B-R4Bmay also contain as substituents halogen, and where at least two vicinal radicals R1B-R4Bconnected with the formation of five - or six-ichinohe cycle, and/or two vicinal radicals R1B-R4Bconnected with the formation of the heterocycle, which contains at least one atom selected from the group comprising nitrogen (N), phosphorus (P), oxygen (O) and sulphur (S)

R5B, R6Bmean hydrogen or methyl,

And means

where E1B-E4Bmean carbon or 1-2 nitrogen atom,

R7B-R10Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3where the organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle,

R11Bindependently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkene is from 2-20 carbon atoms, aryl with 6 to 20 carbon atoms or alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl portion and two radicals R11Bcan also be connected with the formation of five - or six-membered cycle,

R is 0, if E1B-E4Bmean nitrogen and is 1 if E1B-E4Bmean carbon

where at least one radical R7B-R10Bmeans alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3and organic radicals R7B-R10Balso may contain Halogens or nitrogen, or more alkyl groups with 1-20 carbon atoms, alkeline group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alcylaryl group containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR11B3as deputies and two vicinal radicals R7B-R10Bcan also be connected with the formation of five - or six-membered cycle or at least one E1B-E4Bmeans nitrogen,

X independently of one another denote fluorine, chlorine, bromine, iodine, hydrogen, alkyl with 1-1 carbon atoms, alkenyl with 2-10 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing 1-10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, NR1R2, OR1, SR1, SO3R1, OC(O)R1, CN, SCN, β-diketonate, CO, BF4-PF6-or surround gecoordineerde anion,

R1-R2independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl part, or SiR33where the organic radicals R1-R2may also contain as substituents, Halogens or nitrogen - and oxygen-containing groups and two radicals R1-R2can also be connected with the formation of five - or six-membered cycle,

R3independently of one another denote hydrogen, alkyl with 1-20 carbon atoms, alkenyl with 2-20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl containing from 1 to 10 carbon atoms in the alkyl fragment and 6-20 carbon atoms in the aryl portion and two radicals R3can also be connected with the formation of five - or six-membered cycle, and

k is 1, 2 or 3,

B) optional organic or reorga the practical substrate,

C) one or more activating compounds, and

D) optionally one or more compounds containing a metal of group 1, 2 or 13 of the Periodic system.

8. Catalytic system for the (co)polymerization of olefin according to claim 7, in which two vicinal radicals R1B-R4Bin mononitrobenzene complex And') form a condensed cyclic system.

9. A method of producing copolymers of ethylene according to any one of claims 1 to 5, namely, that includes the copolymerization of ethylene with α-olefins in the presence of a catalytic system according to any of claims 7 and-8.

10. The method according to claim 9, characterized in that the copolymerization is carried out with the use of the monomers of the mixture of monomers, which includes ethylene and/or 1-alkenes with 3-12 carbon atoms and contains at least 50 mol.% of ethylene.

11. The mixture of polymers, including

(E) from 1 to 99 wt.% one or more copolymers of ethylene according to any one of claims 1 to 5, and

(F) from 1 to 99 wt.% polymer, which is different from (E)with values in wt.% given the total weight of the mixture of polymers.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: present invention pertains to a method of obtaining a resin composition. Description is given of the method of obtaining a resin composition through mixture in a molten mass of 100 weight parts of cyclic olefin polymer (A), whose glass transition temperature ranges from 60 and 200°C, and 1-150 weight parts of elastic polymer (B), with glass transition temperature 0°C or lower. Part of the cyclic olefin polymer (A) is first mixed in a molten mass with elastic polymer (B) and 0.001-1 weight parts of radical polymerisation initiator (C). The remaining cyclic olefin polymer (A) is then added and mixed in the molten mass. The ratio of the quantity of cyclic olefin polymer (A), initially added, to the quantity of the same polymer added later (initially added/added later) ranges from 1:99 to 70:30. Cyclic olefin polymer (A) is divided into two parts and added separately twice, such that, the mixture with a cross-linked structure can be diluted with cyclic olefin polymer (A), without a cross-linked structure. As a result, increase in the viscosity of the molten resin composition can be prevented.

EFFECT: good abrasion resistance and good moulding properties of the molten mass.

15 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: film is made from polymer mixture, which contains (wt %): 50-90% composition of the ethylene polymer and 10-50% polymer component on ethylene basis, having a density in the range from 0.9 to 0.930 g/ml and molten flow-rate till 4 g/10 min. Composition of the ethylene polymer contains a recurring unit, obtained from an ester, selected from (1) ethylene-unsaturated organic monomer in the form of esters unsaturated C3-C20 monobasic carboxylic acids and C1-C24 univalent aliphatic or alicyclic alcohols, (2) vinyl esters saturated C2-C18 carboxylic acids, where the content of esters is in the range from 2.5-8 wt %. Composition of the ethylene polymer has a density in the range from 0.920 to 0.94 g/ml. Stretchable packing film has a relation between the value of tear resistance longitudinally and the vale of tear resistance transversely, which exceeds 0.3 and the value of ultimate tensile strength lengthwise 30% in the range from 6.5 to 15 N.

EFFECT: effective application in the capacity of stretching adhesive covers in various operations in linking packing and wrapping.

6 cl, 3 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: polymer composition contains low- and high-molecular polyethylene components, the composition basically having a single peak of lamella width percentile curve and PENT greater than 1000 hours at 80°C and 2.4 MPa according to ASTM F1473. The process has several variants allowing production of tubes with enough viscosity to resist shock during laying or afterward; and with extra long working life under gas or water pressure, especially resistant to environmental stress cracking and to creep under internal pressure.

EFFECT: higher impact elasticity and longer working life of tubes.

37 cl, 5 dwg, 3 tbl, 7 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to soft polymer compositions containing large amount of inorganic fillers. Composition according to invention contains 20-60% heterophase polyolefin composition (I) and 40-80% inorganic filler (II) selected from fire-retardant inorganic fillers and inorganic oxides or salts. Moreover, heterophase polyolefin composition I includes 8 to 25% crystalline polymer component (A) selected from propylene homopolymer, propylene copolymers, and mixtures thereof, and 75 to 92% elastomer fraction (B) composed of at least elastomeric propylene 04 ethylene copolymer with 15-45% of at least one α-olefin. Heterophase polyolefin composition I is characterized by solubility in xylene at room temperature above 50%, while intrinsic viscosity of xylene-soluble fraction ranges between 3.0 and 6.5 dL/g. Polyolefin compositions of invention find their use as substitute of plasticized polyvinylchloride.

EFFECT: increased plasticity of materials at the same good thermoplastic properties.

15 cl, 1 dwg, 2 tbl, 10 ex

FIELD: biopolymers.

SUBSTANCE: invention relates to production of plastic masses based on ethylene and vinylacetate copolymer for mould products useful in food processing industry and agriculture. Claimed composition contains 50-68.7 mass % of ethylene and vinylacetate copolymer, biologically degradable filler containing rye flour in amount of 30-48,7 mass % and additives such as surfactant in amount of 0.1 mass %, maize amylacetate in amount of 1 mass %, and 0.2 mass % of methylcellulose.

EFFECT: new biologically degradable composition.

2 tbl

FIELD: polymeric materials.

SUBSTANCE: invention relates to polymeric composition materials, namely, to composition of polymeric composition of multifunctional modifying agent. Proposed multifunctional modifying agent comprises the following components, wt.-%: copolymer of ethylene with vinyl acetate, 2-20; calcium carbonate, 2-25; oleic acid amide, 2-20, and high pressure polyethylene, up to 100. Invention provides expanding functional properties of modifying agent and enhancing technological tasks in processing polymers. Invention can be used in making articles by extrusion or under pressure in casting machines of auger type and nontoxic materials using for package of foodstuffs an/or medicinal preparations.

EFFECT: valuable properties of modifying agent.

6 tbl, 6 ex

FIELD: chemical industry; metal working industry; methods of production of the adhesive composition used for deposition of the coatings on the metal surfaces.

SUBSTANCE: the invention is pertaining to the methods of production of the adhesive composition intended for deposition on the steel surface as the primer of the adhesive intermediate layer deposited on the steel surfaces under the polyolefin protecting coatings. The technical problem of the invention is the reduced duration of the contact of the adhesive composition melt with the surface of the metal at conservation of the high adhesive strength. The technical problem is being solved by that the method provides for the combined mixing of the ethylene copolymer and vinyl acetate or the combination of the copolymers of the ethylene and vinyl acetate differing in the contents of the vinyl acetate groups with polyisocyanate, caoutchouc and the filling agent. Premix the polyisocyanate containing of no less than two isocyanate groups with the filling agent consisting of the talcum or the mica in the conditions, when the polyisocyanate is in the liquid state, with the subsequent joint mixing of all the components. At that select the copolymer of ethylene and vinyl acetate with the contents of the vinyl acetate groups from 10 up to 45 %.

EFFECT: the invention ensures the reduced duration of the contact of the adhesive composition melt with the surface of the metal at conservation of the high adhesive strength.

1 tbl, 10 ex

Medical container // 2311165

FIELD: medical facilities.

SUBSTANCE: invention provides medical container, which is used to fill with blood, drug, and the like. Container is manufactured from film or sheet having at least one high-density polyethylene layer and polymer layer containing polyolefin composition, wherein said polyolefin composition comprises (A) at least one propylene-containing polymer selected from group consisting of (A1) propylene-containing polymer composition in the form of mixture of (A11) propylene polymer and (Q12) elastomeric ethylene-propylene copolymer and (A12) propylene-containing block-copolymer; and (B) ethylene-containing copolymer containing ethylene and at least one α-olefin having 4 or more carbon atoms and characterized by refractory index of xylene-soluble fraction of this polyolefin composition equal to 1.480-1.495; said high-density polyethylene containing 70% or more high-density polyethylene having density 0.950 g/cc or higher, while high-density polyethylene layer being disposed on at least one (inner or outer) side of container.

EFFECT: achieved temperature resistance high enough to enable sterilization at 121°C or higher and manifested excellent clearness, shock strength, elasticity, and resistance to conglomeration.

5 cl, 3 tbl, 14 ex

FIELD: rubber industry, in particular polymer composition.

SUBSTANCE: claimed composition contains (mass %): rubber 100; sulfur vulcanizating agent 2.5-3.5; promoter group 0.8-2.0; vulcanization activator 10-20; filler such as carbon black 50-70; plasticizer 2-3; anti-aging agent 3-6; ethylene/vinyl acetate copolymer containing 26-30 % of vinyl acetate 3-5.

EFFECT: copolymer with increased tear resistance.

2 tbl

FIELD: adhesives.

SUBSTANCE: invention relates to ethylene copolymers-based adhesive compositions used as adhesives when depositing polymeric protective coating on metallic surface utilizing extrusion and co-extrusion techniques and winding thermosetting multiple-layer adhesive tape. Using composition containing ethylene/vinyl acetate copolymer, silicate filler, and modifying agent (resin OSR-100) results in providing preservation of high adhesion and strength characteristics and resistance to cathode peeling when lowering metal temperature heating to 100-130°C in double-layer coating structure and also ensuring high values of adhesion strength for ground epoxide layer in triple-layer coating structure.

EFFECT: enhanced adhesive properties in multiple-layer coating applications.

3 tbl

The invention relates to a continuous method of gas-phase fluidized to obtain homopolymerization and copolymerizate ethylene with density d from 0.89 to 0.97 g/cm3

The invention relates to a method for ultracytochemical polyethylene and method of activating the catalyst carrier

FIELD: chemistry.

SUBSTANCE: invention relates to method of polymerisation and regulation of rheological characteristics of polymeric compositions. Method includes introduction of polymer with high molecular weight into polymer with low molecular weight. Polymeric compositions are obtained by polymerisation of monomers in gas-phase polymerisation reactor with the use of bimetal catalytic composition and at least one regulating agent. Regulating agent such as alcohol, simple ether, oxygen or amin, is added or removed in amount necessary to regulate the level of introduction of polymer with high molecular weight, level of polymer with low molecular weight or both of them. Polymerisation takes place in pseudoliquefied layer with fluidising medium, which includes alkan, selected from group including C4-C20 alkans. With increase of alkan content in reactor, amount of regulating agent is increased for supporting polymeric composition at target value of flow-behaviour index I21.

EFFECT: improvement of regulation of rheological characteristics.

20 cl, 2 dwg, 2 tbl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to butene-1 (co)polymers and a method of their synthesis. Except for, invention relates to articles made of butene-1 (co)polymers. Homopolymers of butene-1 are characterized by the following properties: (i) value of molecular-mass partition expressed as the ratio Mw/Mn based on measurement with using analysis carried out by gel-permeation chromatography method is less 6, and (ii) strength value of melt is above 2.8 g. These homopolymers are used for making tubes. Method for synthesis of butene-1 homopolymers is carried out in the presence of a stereospecific catalyst comprising (A) a solid component containing Ti compound and internal electron-donor compounds chosen from phthalates and applied on a carrier MgCl2; (B) alkylaluminum compound, and (C) tert.-hexyltrimethoxysilane as an external electron-donor compound. Butene-1 homopolymers possess a set of mechanical properties providing the presence both barostability after prolonged period time and their easy processing for making tubes.

EFFECT: valuable properties of (co)polymers, improved method of synthesis.

12 cl, 1 tbl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention describes process of producing propylene-based polymer via polymerization of monomer in hydrocarbon solvent at 20-80°C and excessive pressure 1 to 30 atm in presence of catalyst and hydrogen as polymer molecular mass regulator, said catalyst being a product obtained by preliminary treatment of titanium trichloride and diethylaluminum chloride with propylene carried out at weight ratio Et2AlCl/TiCl3 = 1 to 10 determined by density of layer of initial TiCl3 particles within the following limits: 1-2 at density below 0.46 g/cc, 3-5 at density 0.46-0.50 g/cc, 6-10 density above 0.50 g/cc. When polypropylene is obtained, preliminary treatment of titanium trichloride and diethylaluminum chloride with propylene is carried out to achieve conversion 2.0-3.0 g polymer per 1 g TiCl3 and, when propylene/ethylene copolymer is obtained, treatment is carried out to achieve conversion 3.0-4.0 g polymer per 1 g TiCl3. After termination of pretreatment of titanium trichloride and diethylaluminum chloride with propylene and before measuring out pretreatment product into principal polymerization reactor, weight ratio Et2AlCl/TiCl3 is adjusted to fall into range 6-10 through additionally dosing calculated quantity of diethylaluminum chloride.

EFFECT: prevented breaking of catalyst particles, preserved high activity and stereospecifity thereof, and increased productivity of process.

2 cl, 2 tbl, 18 ex

FIELD: organic chemistry, polymers, in particular method for olefin polymerization.

SUBSTANCE: invention relates to method for CH2=CHR olefin polymerization wherein R represents hydrogen or C1-C12-hydrocarbon group to produce polymer with increased bulk density; catalytic component and catalyst useful in said method. Catalytic component contains at least two fraction (A) and (B), wherein both contain Mg, Ti and halogen as essential elements. Said catalytic component contains 1-60 mass % of (B) fraction whish has less mean diameter than (A) component by 75 % or less. Catalyst of olefin polymerization is obtained by interaction of abovementioned catalytic component organometal compounds of metals from 1-3 groups of Periodical system, optionally in presence of electron-attractive compound. Method for olefin polymerization is carried out in presence of catalytic component (A), containing Mg, Ti and halogen as essential elements and catalytic component (B), also containing Mg, Ti and halogen as essential elements which makes it possible to produce polymer with less mean particle size than mean particle size of polymer obtained with catalytic component (A) at the same polymerization conditions.

EFFECT: method of high productivity; polymer of high bulk density.

25 cl, 6 ex, 1 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of olefins, namely, 1-butene of polymerization purity by a method of catalytic dimerization of ethylene. Invention describes the catalytic system for dimerization of ethylene to 1-butene based on titanium alcoholate of the general formula: Ti(OR)4 wherein R means (C2-C6), aluminum trialkyl of the general formula: AlR3 wherein R means (C2-C6) and ester chosen from group comprising tetrahydrofuran, dioxane or their mixture and wherein the mole ratio of ester to titanium alcoholate = (0.1-0.49):1 and that of aluminum trialkyl to tetraalkoxy-titanium = (2.6-6):1. Also, invention describes a method for dimerization of ethylene to 1-butene in hydrocarbon solvent medium at temperature 50-95°C and under ethylene pressure 0.3-0.4.0 MPa in the presence of the catalytic system. Invention provides enhancing selectivity of process, increasing yield of 1-butene as measured per unit of catalyst, reducing possibility for carrying out by-side reactions, such as polymer synthesis, isomerization of 1-butene to 2-butene and formation of butanes.

EFFECT: improved method of dimerization, valuable properties of catalytic system.

6 cl, 3 tbl, 12 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of polydienes on titanium-magnesium catalysts and can be used in synthesis of synthetic gutta-percha. Synthetic gutta-percha is synthesized by polymerization of isoprene in aliphatic solvent medium in the presence of catalytic system consisting of titanium-magnesium catalyst and co-catalyst representing trialkylaluminum. Titanium trichloride co-crystallized with magnesium dichloride is used as titanium-magnesium catalyst. Catalyst is prepared by interaction of magnesium with titanium tetrachloride in the presence of n-butyl chloride at 60-100°C, in the volume ratio titanium tetrachloride : n-butyl chloride = 1:(53-80) and in the content of magnesium 3.5-5.5 g per 1 ml of titanium tetrachloride. The polymerization process of isoprene is carried out at temperature 30-65°C, at the isoprene concentration in polymerization medium 1.0-2.0 mole/l and at the mole ratio co-catalyst : catalyst = 10-20, inclusively. Method provides carrying out the process for a single step and without washing out that simplified a method for synthesis of polymer that represents highly dispersed crumbs and reduces consumptions. Invention can be used in synthesis of synthetic gutta-percha.

EFFECT: improved method of synthesis.

4 cl, 2 tbl, 8 ex

Up!