(cycloalkyl)methylsiloxanes as external donors for catalysts used in synthesis of polyolefins

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic systems used in polymerization of alpha-olefins, methods for preparing catalytic systems for polymerization of alpha-olefins and methods for polymerization (and copolymerization) of alpha-olefins. Invention describes the catalytic system for polymerization of olefins comprising solid titanium component of catalyst, organoaluminum compound comprising at least one bond aluminum-carbon and organosilicon compound comprising at least one (cycloalkyl)-methyl group used as an external donor of electrons. Also, invention describes the catalytic system for polymerization of olefins comprising solid titanium component of the catalyst prepared by contacting titanium compound with magnesium compound and comprising from about 0.01 to about 500 moles of titanium compound per one mole of magnesium compound, organoaluminum compound comprising at least one bond aluminum-carbon wherein the mole ratio of aluminum to titanium in the catalytic system is in the range from about 5 to about 1000, and organosilicon compound comprising at least one (cycloalkyl)-methyl group and used a external donor of electrons wherein the mole ratio of organoaluminum compound and organosilicon compound in the catalytic system is in the range from about 2 to about 90. Also, invention describes methods for preparing catalyst used in polymerization of olefins and comprising interaction of Grignard reactive comprising (cycloalkyl)-methyl group with ortho-silicate to form organosilicon compound comprising a (cycloalkyl)-methyl link, mixing organosilicon compound with organoaluminum compound comprising at least one bond aluminum-carbon and solid titanium component of the catalyst to form the catalyst, and a method for polymerization of olefins. Invention provides preparing propylene block-copolymer showing good fluidity in the melt, capacity for molding, hardness, impact viscosity and impact strength in combination with high effectiveness of the catalyst and good technological effectiveness of the preparing process.

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

 

The technical field

The present invention in General relates to catalytic systems for polymerization of olefins. In particular, the present invention relates to catalytic systems to obtain olefin polymers and copolymers and to methods for catalytic systems and alpha-olefin polymers and copolymers.

Background of the invention

Polyolefins are a class of polymers derived from simple olefins, and they include polypropylene and polybutene. Known methods for producing polyolefins include the use of polymerization catalysts of the Ziegler-Natta. These catalysts lead to polymerization of the vinyl monomers using to get stereoregular polymer, the transition metal halide.

There are a large number of polymerization catalysts of the Ziegler-Natta. The catalysts have different characteristics and/or produce polyolefins having different properties. For example, some catalysts have high activity, while other catalysts have low activity, and similarly, some of the catalysts are characterized by long service life, whereas the life of other catalysts small. In addition, the polyolefins obtained with the use of polymerization catalysts Cigeratte, different stereoregularity, molecular weight distribution, impact strength, flowability in the melt, toughness, weldability, isotacticity and the like.

In the polymerization of alpha-olefins, in particular having 3 or more carbon atoms, the polymerization catalyst of the Ziegler-Natta type electron donor to facilitate increased stereospecificity. However, there is a tendency in which the use of an electron donor to facilitate the achievement of high stereospecificity the poly-alpha-olefins in the scheme of polymerization Ziegler-Natta leads to a large decrease in catalytic activity. While you can put up with lower levels for many of the characteristics associated with the polymerization catalysts of the Ziegler-Natta, in relation to the activity of the catalyst compromise is difficult to achieve. As a result, we have not seen the need for the polymerization catalysts of the Ziegler-Natta (and associated methods)that would have a high catalytic activity, in addition to other desirable characteristics.

U.S. patent 4784983 and U.S. patent 4861847 belong to a catalytic system for use in the polymerization and copolymerization of olefins, which consists of the following components: (A) the solid product is Ostoji, essentially of titanium, magnesium, halogen, esters of polybasic carboxylic acids and organo-phosphorus compounds, (C) alyuminiiorganicheskikh connection and (C) the organosilicon compound.

U.S. patent 4829038 relates to a catalytic system for the polymerization of olefins comprising a solid, insoluble in hydrocarbons, magnesium-containing, titanium containing component containing electron donor; derived alkylamine; and derived organosilane selected from the group consisting of diisobutyldimethoxysilane, diisobutyldimethoxysilane, tert-butyldimethylsilyl and di-tert-butyldimethylsiloxy and mixtures thereof.

U.S. patent 4990479 and U.S. patent 5438110 refer to the catalyst for polymerization of olefins comprising (A) a solid titanium catalyst component containing magnesium, titanium and halogen as essential ingredients, (B) alyuminiiorganicheskikh connection and (C) the organosilicon compound containing cyclopentyloxy group, cyclopentenyl group, cyclopentadienyls group or derived from any of these groups.

U.S. patent 5244989 relates to a method for producing a stereospecific polyolefin in the presence of a catalyst containing a transition metal compound and ORGANOMETALLIC compound, using a catalytic system, to ora contains (a) a solid component of catalyst, resulting from the reaction between (i) the homogeneous solution obtained by the reaction of (i-1) magnesium and organic gidrauxilirovannogo compounds (i-2) an organic oxygen-containing compounds of titanium and/or (i-3) organic oxygen-containing compounds of silicon with oxygen-containing organic compound of aluminum and/or boron compound, and (ii)at least one derivative of aluminum halide to obtain a solid product of the reaction with this solid product (iii) compounds, generouse electron, and (iv) a derivative of titanium halide with obtaining a solid component, and then the reaction with this solid component (v) of silicon tetrachloride and/or alkyl substituted product derived from silicon tetrachloride, (C)at least one member selected from the group consisting of ORGANOMETALLIC compounds of groups IA, IIA, IIB, IIIB and IVB of the Periodic table, and (C) connection, generouse electron.

U.S. patent 5773537 relates to catalytic systems related to the type of Ziegler-Natta containing as active ingredients (a) titanium containing solid component, upon receipt of which used a combination of titanium, magnesium compound, halogenation agent and electron-donating component b) a compound of aluminum and (C) in which the quality of an additional electron-donating component silicone compound, described by the formula, R1R2Si(OR3)2where R1represents a C1-C10-alkyl or C3-C8-cycloalkyl, excluding sec-butyl, R2represents sec-butyl, and R3represents a C1-C8-alkyl.

Brief description of the invention

The present invention provides a catalytic system for the polymerization of alpha-olefins, methods of obtaining catalytic systems for the polymerization of alpha-olefins and methods of polymerization (copolymerization) of alpha-olefins, including the use of external electron donors containing (cycloalkyl)methyl link. In catalytic systems for the polymerization of alpha-olefins external electron donors containing (cycloalkyl)methyl link, give their contribution in obtaining poly-alpha-olefins with a high solubility in xylene while maintaining high catalytic efficiency of the catalyst. The use of external electron donors containing (cycloalkyl)methyl link, makes a valid large error bounds on the number of the external electron donor without influencing the properties of the catalytic system or polymer, resulting in the result.

One aspect of the invention relates to a catalytic system for use in the olymerization olefins, containing solid titanium catalyst component; alyuminiiorganicheskikh connection with at least one link aluminum-carbon; and the organosilicon compound containing (cycloalkyl)methyl group.

Another aspect of the invention relates to a catalytic system for use in the polymerization of olefins containing solid titanium catalyst component obtained by introducing a compound of titanium in contact with the magnesium compound, and the solid titanium catalyst component contains from about 0.01 to about 500 moles of a compound of titanium on one mole of the compounds of magnesium; alyuminiiorganicheskikh connection with at least one link aluminum-carbon, where the catalytic system is different molar ratio of aluminum to titanium in the range from about 5 to about 1000; and the organosilicon compound containing (cycloalkyl)methyl group, where the catalytic the system has a molar ratio of alyuminiiorganicheskikh compound to the organosilicon compound being in the range from approximately 2 to approximately 90.

Another aspect of the invention relates to a method for producing a catalyst used for the polymerization of olefins, comprising the stage of interaction of the Grignard reagent, it is found (cycloalkyl)methyl group, with orthosilicate obtaining organosilicon compounds having (cycloalkyl)methyl link; and mixing the organosilicon compounds with alyuminiiorganicheskikh compound having at least one link aluminum-carbon, and solid titanium component of the catalyst to obtain a catalyst.

Another aspect of the invention relates to a method of polymerization comprising the polymerization or copolymerization of alpha-olefin in the presence of a catalytic system containing a solid titanium catalyst component; alyuminiiorganicheskikh connection with at least one link aluminum-carbon; and the organosilicon compound containing (cycloalkyl)methyl group.

Detailed description of the invention

The present invention relates to catalytic systems and methods of producing poly-alpha-olefins, such as polypropylene, with the use of catalytic systems containing organosilicon compound containing (cycloalkyl)methyl group, and, in particular, the organosilicon compound containing (cycloheptyl)methyl group, (cyclohexyl)methyl group, (cyclopentyl)methyl group, (cyclobutyl)methyl group and/or (cyclopropyl)methyl group. Cycloalkyl group may be substituted (such as (cycloalkyl)methyl, substituted bottom is their alkyl) or unsubstituted. The lower alkyl groups contain about 4 carbon atoms or less. Poly-alpha-olefins include homopolymers and copolymers derived from alpha-olefins.

Speaking in General, the present invention relates to a catalytic system for polymerization of olefins formed from (A) a solid titanium catalyst component containing magnesium, titanium, halogen and optionally a phosphorus compound and/or an ester of polybasic carboxylic acid; (C) alyuminiiorganicheskikh connection; and (C) the organosilicon compound containing at least one (cycloalkyl)methyl group or a derivative thereof, derived from any of these groups; and to the method of polymerization, which involves the polymerization or copolymerization of olefins in the presence of the above-described catalytic system for polymerization.

The solid titanium catalyst component (A)used in this invention is a highly active catalyst component containing at least magnesium, titanium and halogen. In one embodiment, the implementation uses solid titanium catalyst component containing magnesium, titanium, halogen and an internal electron donor, because the activity is sometimes increased and the catalyst results in a polymer with a high stereoregularity.

TBE is every titanium catalyst component (A) can be obtained as a result of the introduction of compounds of magnesium in contact with the connection of titanium. The connection of titanium, used in the preparation of solid titanium catalyst component (A) in the present invention is, for example, derived tetravalent titanium, described by formula (I)

Ti(OR)gX4-g(I)

where R represents a hydrocarbon group, preferably alkyl group containing from 1 to about 4 carbon atoms, X represents a halogen atom, and 0≤g≤4. Specific examples of the titanium compounds include tetrachloride titanium, such as TiCl4, TiBr4and TiI4; trihalogen of alkoxysilane, such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-n-s4H9)Cl3, Ti(OC2H5)Br3and Ti(O-ISO-From4H9)Br3; dihalogenide of dialaction, such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-s4H9)2Cl2and Ti(OC2H5)2Br2; monofunctional of tralkoxydim, such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-s4H9)3Cl and Ti(OC2H5)3Br; and tetraalkoxysilane, such as Ti(OCH3)4, Ti(OC2H5)4and Ti(O-n-s4H9)4.

Among them, preferred halogen-containing compounds of titanium, in particular tetrachloride titanium. The data connection is of titanium can be used individually or in combination of two or more components. They can be used after dilution with hydrocarbon compounds or halogenated hydrocarbons.

The magnesium compounds used in the preparation of solid titanium catalyst component include, for example, a magnesium compound having reducing properties, and the connection of magnesium, not having reducing properties. The magnesium compound having reducing properties, is, for example, a compound of magnesium in relation magnesium-carbon or relationship magnesium-hydrogen. Specific examples of the magnesium compounds having reducing properties, include dialkylamines, such as dimethylamine, diethylamine, dipropylamine, dibutylamine, ethylbutylamine, diamylamine, vexillary and dodecylamine; monoalkylamines, such as ethylmagnesium, propylaniline, butylaniline, hexylaniline and nilmanifold; utilitarian; and butylaniline. These magnesium compounds can be used as such or in the form of a complex with alyuminiiorganicheskikh connection to be described. These magnesium compounds may be in liquid or solid state.

Specific examples of compounds of magnesium, not having reducing properties, include magnesium halides such as magnesium chloride magnesium bromide, the magnesium iodide and magnesium fluoride; alkoxysilylated, such as methoxymandelic, ethoxymethylene, isopropoxyaniline, butoxyaniline and Aktobemunaigaz; aryloxypropanolamine, such as proximinality and methylenebisacrylamide; alkoxyimino, such as ethoxyline, isopropoxide, butoxymethyl, n-octoxide and 2-ethylhexylamine; aryloxyalkanoic, such as enoximone and dimethylethanolamine; and magnesium salts of carboxylic acids, such as magnesium laurate and magnesium stearate.

Compound of magnesium, not having reducing properties, there may be a connection obtained from the magnesium compounds having reducing properties, separately or during retrieval component of the catalyst. This can be accomplished, for example, due to the introduction of the magnesium compounds having reducing properties, is in contact with such a connection, as derived polysiloxane derived halogenated silane, halogen-containing compound of aluminum, ester or alcohol. In addition to the above-mentioned magnesium compounds having reducing properties, and connections, not having reducing properties, the magnesium compound used in this invention may be a compound or double the connection with another metal or a mixture with the compound of another metal.

In one aspect of the present invention preferred compounds of magnesium, not having reducing properties. In another aspect of the present invention, the preferred halogen-containing compounds of magnesium, such as magnesium chloride, alkoxysilane and aryloxyalkanoic.

In one embodiment, the implementation method of producing a solid titanium catalyst component (A) preferably using an external electron donor, for example, oxygen-containing electron donor, such as alcohols, certain organosilicon compounds, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides and anhydrides of the acids, and nitrogen-containing electron donor, such as ammonia, amines, NITRILES and isocyanates. Specific examples include alcohols having from 1 to about 18 carbon atoms, which may have an alkyl group, such as methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecylamine alcohol, benzyl alcohol, phenethyl alcohol, tomilovy alcohol and isopropylbenzyl alcohol; phenols having from 6 to about 25 carbon atoms, such as phenol, audio record, Xylenol, ethylphenol, propylene, cumylphenol, Nonylphenol and naphthol; ketones having from about 3 doprinosilo 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, Propionaldehyde, octillery, benzaldehyde, tolualdehyde and naphthaldehyde; esters of organic acids having from 2 to about 30 carbon atoms, such as methylformate, ethyl acetate, vinyl acetate, propyl, octylated, cyclohexylacetate, ethylpropane, methylbutyrate, Etisalat, telstart, methylchloride, ethyldichlorosilane, methyl methacrylate, etildronat, dibutylated, diethylmalonate, diatribution, ethylcyclohexylamine, diethyl-1,2-cyclohexanedicarboxylate, di-2-ethylhexyl-1,2-cyclohexanedicarboxylate, methylbenzoate, ethylbenzoic, propylbenzoate, butylbenzoate, octylbenzoic, cyclohexylbenzene, phenylbenzoate, benzyl benzoate, methylfolate, atilola, amitola, utilitybased, methylenethf, ationist, utilitariansim, dimethylphthalate, diethylphthalate, dibutyl phthalate, dioctylphthalate, gamma-butyrolactone, Delta-valerolactone, coumarin, phtalic and ethylene carbonate resulting; esters of inorganic acids, such as ethyl silicate, butylsilane, vinyltriethoxysilane, phenyltriethoxysilane and diphenyldichlorosilane; acid halides having from 2 to about 15 carbon atoms, such as acetylchloride, benzoyl is lurid, taillored, Antillid and tuloldalarol; ethers having from 2 to about 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as ndimethylacetamide, benzamide, toluene; acid anhydrides such as benzoic anhydride and phthalic anhydride, amines, such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine; and NITRILES, such as acetonitrile, benzonitrile and tolunitrile.

As an internal electron donor can also be used and the organosilicon compound described by formula (II)

RnSi(OCR')4-n(II)

where R and R' represent a hydrocarbon group, and n is enclosed within 0≤n<4. Specific examples of organosilicon compounds described by formula (II)include trimethyloxonium, trimethylaluminium, dimethyldiethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, tert-butylmethylether, tert-butylmethylether, tert-amiloridesensitive, diphenylmethylsilane, FemaleCircumcision, diphenyldichlorosilane, bis-o-tridimensional, bis-m-tridimensional, bis-p-tridimensional, bis-p-cardiotoxicity, bisa alpenlitetrailer, dicyclohexylammonium, cyclohexanedimethanol, cyclohexyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, VINYLTRIMETHOXYSILANE, gamma chloropropionitrile, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tert-butyltrichlorosilane, n-butyltrichlorosilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, gamma aminopropyltriethoxysilane, chlorotriethylsilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, cyclohexyltrichlorosilane, cyclohexyltrichlorosilane, 2-norbornenedicarboxylic, 2-norbornadiene, 2-norbornenedicarboxylic, ethyl silicate, butylsilane, tributyltinoxide, methyltriethoxysilane, vinyltris(beta methoxyethoxy), vinyltriethoxysilane and dimethylhydrogensiloxane.

As an internal electron donor for use with titanium component of the catalyst can also be used and esters. Examples of these esters are compounds described by the following formulas:

where R1represents a substituted or unsubstituted hydrocarbon group, and R2, R5and R6represent the atom in Dorada or a substituted or unsubstituted hydrocarbon group, R3and R4represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and at least one representative of them, preferably represents a substituted or unsubstituted hydrocarbon group, and R3and R4can be connected to each other. In one embodiment, the implementation of the substituted or unsubstituted hydrocarbon groups contain from 1 to about 30 carbon atoms.

Examples of substituted hydrocarbon groups for R1-R5represent a hydrocarbon group having a group containing heteroatoms, such as N, O and S, such as C-O-C, COOR, COOH, OH, SO3H-C-N-C - NH2. Particularly preferred complex diesters dibasic carboxylic acids, in which at least one representative from R1and R2represents an alkyl group having at least about 2 carbon atom.

Specific examples of esters of polybasic carboxylic acids include esters of aliphatic polybasic carboxylic acids, such as diethylamine, dibutylamine, diethylpyrazine, Diisobutyl-alpha methylglutaric, dibutylamine, diethylmalonate, diethylethylene, diethylethanolamine, diethylmalonate, diethylformamide, diethylmalonate, diethylaniline, ethyldiethanolamine, diatide-n-butylmalonate, dimethylmaleic, monoacrylate, dioctylmaleate, dibutylated, dibutylphthalate, diethylphthalate, aminobutiramida-beta-methylglutaryl, diallylmethylamine, di-2-ethylhexylphthalate, diethylmalonate, debutylation, dioctylsebacate and dimethylcarbonate; esters of alicyclic polybasic carboxylic acids, such as diethyl-1,2-cyclohexanecarboxylate, Diisobutyl-1,2-cyclohexanecarboxylate, diethylacrylamide and diethyl ether endeavou acid; esters of aromatic polybasic carboxylic acids, such as monoethylfumarate, dimethylphthalate, mutilateral, monoisobutyrate, mono-n-butylphthalate, diethylphthalate, utilizability, ethyl-n-butylphthalate di-n-propietat, Diisopropylamine, di-n-butylphthalate, diisobutylphthalate, di-n-heptylphenol, di-2-ethylhexylphthalate, di-n-octylphthalate, dineopentyl, dodecylphenol, benzylbutylphthalate, definiltely, diethyldithiocarbamate, dibutyldithiocarbamate, trietiltsitratom and dibutylthiourea; and esters of heterocyclic polybasic carboxylic acids, such as esters of 3,4-furandicarboxylic acid. Specific examples of esters of polyhydroxystearic may include 1,2-diacetoxybenzoic, 1-methyl-2,3-diacetoxybenzoic, 2-methyl-2,3-diacetoxybenzoic, 2,8-diacetoxynaphthalene is, etilenglikolevye and batandjieva. Specific examples of esters replacement of carboxylic acids are benzoylacetonitrile, acetylsalicylate, acetylsalicylic.

As esters of polybasic carboxylic acids that may be included in the titanium component of the catalyst, it is also possible to use long-chain esters of dibasic carboxylic acids, such as diethylacetal, diisobutylamine, Diisopropylamine, di-n-butylbenzene, di-n-octylsilane and di-2-ethylhexylamine. Among these polyfunctional esters preferred connection configuration which describes the above General formula. Preferred esters are formed by the interaction between phthalic acid, maleic acid or substituted malonic acid and alcohols having at least about 2 carbon atoms, particularly preferred complex diesters formed by the interaction between phthalic acid and alcohols having at least about 2 carbon atom.

Another group internal electron donor, which can be included in the titanium component of the catalyst, are esters of monobasic carboxylic acids described by the formula RCOOR', where R and R' represent hydrocarbone group which may have a Deputy, and at least one representative of them is a branched (including alicyclic) or containing aliphatic ring group. Specifically, at least one representative from R and R' can be (CH3)2CH-, C2H5CH(CH3)-, (CH3)2SNSN2-, (CH3)3C-, C2H5CH-, (CH3)CH2-, cyclohexyl, methylbenzyl, para-xilion, acrylic link and carbonylation. If any member of R and R' will be any of the groups described above, the second representative of R and R' may be the above-described group or another group such as a linear or a cyclic group. Specific examples of esters monobasic carboxylic acids include complex monetary dimethyloxazole acid, trimethylhexanoic acid, alpha-methylmalonic acid, beta-methylmalonic acid, methacrylic acid and benzoyloxy acid; and esters of monobasic carboxylic acids formed using alcohols such as isopropanol, Isobutanol and tert-butanol.

As the internal electron donor is also possible to use esters of carbonic acid. Specific examples are diethylcarbamyl, ethylene carbonate resulting in Diisopropylamine, phenylethylamine and diphenylcarbonate.

Optional internal electron donors can be used individually or in combination. When using the internal electron donor it is not necessarily be used directly as an initial matter, and as starting substances can also be used compounds into the electron donors in the course of obtaining titanium catalyst components.

In the present invention, the solid titanium catalyst component (A) can be obtained as a result of the introduction of compounds of magnesium (or magnesium metal in contact with the connection of titanium and optional internal electron donor, using known methods used to obtain highly active titanium catalyst component of the magnesium compounds, titanium compounds and optionally an electron donor. The above compounds can enter into contact in the presence of another participant reactions, such as silicon, phosphorus or aluminum.

Some examples of the method of producing a solid titanium catalyst component (A) are briefly described below.

(1) a magnesium Compound or a complex compound of magnesium with optional internal electron donor is introduced into reaction with a compound of titanium in the liquid phase. This reaction can be carried out in Pris is accordance agent, facilitate grinding. Compounds that are solid, before carrying out the reaction can be subjected to grinding.

(2) a Compound of magnesium, not having reducing properties, and compounds of titanium, both are in liquid state, is introduced into reaction with each other in the presence of the optional internal electron donor to precipitate a solid complex titanium.

(3) the reaction Product obtained in stage (2), then injected into reaction with a compound of titanium.

(4) the reaction Product obtained in stage (1) or (2), then injected into the reaction with the internal electron donor and a compound of titanium.

(5) the magnesium Compound or a complex compound of magnesium and optional internal electron donor is crushed in the presence of compounds of titanium, and the resulting solid product is treated with a halogen, a halogen compound or an aromatic hydrocarbon. In this method, the magnesium compound or a complex with an electron donor can be crushed in the presence of an agent promoting the grinding, and the like. In an alternative embodiment, the magnesium compound or a complex compound of magnesium and optional internal electron donor is crushed in the presence of compounds of titanium, pre-treated substance, contributing to the reaction, and after this is processed by halogen and the like. A substance that promotes the reaction may be alyuminiiorganicheskikh compound or halogen-containing silicon compound.

(6) the Product obtained in stage (1) through (4), is treated with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) the Product resulting from the introduction of metal oxide in contact with dihydroquinine and halogenated alcohol, is introduced into contact with the optional internal electron donor and a compound of titanium.

(8) a Compound of magnesium, such as magnesium salt of organic acid, alkoxyamine or aryloxyalkyl enter into reaction with the optional internal electron donor, a compound of titanium and/or halogenated hydrocarbon.

In embodiments of the method of obtaining the catalyst component (A), corresponding to the examples(2), (3), (4) and (6), the solution of the magnesium halide is mixed with the liquid tetrachloride titanium in the presence of an auxiliary precipitant to obtain a solid residue. An ester of polybasic carboxylic acid can be added before, during or after the deposition of the solid phase, or you can spend dosage on a solid phase.

The process of deposition of a solid phase can be done in one of two ways. One method involves mixing liquid tetrachloride titanium halide magni is at a temperature in the range of from approximately -40 aboutWith up to approximately 0aboutAnd planting a solid phase when the temperature is slowly raised to a range from approximately 30aboutWith up to approximately 120aboutC, preferably from approximately 60aboutC to about 100aboutC. Another method includes Pocatello adding at room temperature liquid tetrachloride titanium to a homogeneous solution of magnesium halide for immediate planting of the solid phase. In both ways in the reaction system, preferably in the presence of an internal electron donor. Optional internal electron donor can be added either after the resulting solution of magnesium halide, or a halide of magnesium in stage 1. Alternatively, you can add two or more auxiliary precipitant.

The solid phase is treated by the system after the deposition process is an ester of polybasic carboxylic acid. Alternatively, an ester of polybasic carboxylic acid can be added during the deposition process. You can use a mixture of two or more esters of polybasic carboxylic acids.

In order to obtain a uniform solid particles, the deposition process can be slow. When using the second method with parabalym adding Gal who genid titanium at room temperature, the process is preferably carried out during the period of time in the range of from about 1 hour to about 6 hours. When using the first method with a slow temperature increase, the rate of increase of the temperature preferably is in the range from about 4aboutC to about 100aboutWith in the hour.

First, a mixture is separated solid precipitate. In this way the resulting solid precipitate can be captured by a wide range of complexes and impurities, so in some cases it may be necessary additional processing.

The solid residue is washed with an inert diluent and then treated with tetrachloride titanium or a mixture of tetrachloride titanium and an inert diluent. Tetravalent titanium, used at this stage is the same as tetravalent titanium, used in stage 2, or differs from it, however the most preferred titanium tetrachloride. The number of used tetrachloride titanium is in the range from about 1 to about 20 moles, preferably from about 2 to about 15 moles per one mole of magnesium halide. Treatment temperature is in the range of 50aboutWith up to approximately 150aboutC, preferably from approximately 60aboutwhat to approximately 100 aboutC. If a solid residue, use a mixture of tetrachloride titanium and inert diluent, the volume % of tetrachloride titanium in the solution used for processing, will be in the range from approximately 10% to approximately 100%, while the rest is inert diluent.

The treated solid phase, optionally washed with an inert diluent to remove inefficient titanium compounds and other impurities. The inert diluent used in this case may be hexane, heptane, octane, 1,2-dichloroethane, benzene, toluene, and other hydrocarbons. 1,2-dichloroethane is one of the preferred diluents for the final stage of washing.

In one implementation, particularly in implementations carried out in accordance with example (2)described above, the solid catalyst component (A) has the following chemical composition: titanium from about 1.5 to about 6.0% (wt.); magnesium is from about 10 to about 20% (wt.); the halogen from about 40 to about 70% (wt.); an ester of polybasic carboxylic acid is from about 5 to about 25% (wt.); optional organophosphorus compounds from about 0.1 to about 2.5% (wt.); and optional inert diluent from about 0 to the roughly 15% (wt.).

The number of ingredients used in the preparation of solid titanium catalyst component (A)can vary depending on the method of obtaining. In one embodiment, the implementation of one mol of the magnesium compounds used from about 0.01 to about 5 moles of an internal electron donor and from about 0.01 to about 500 moles of a compound of titanium. In another embodiment, the implementation of one mol of the magnesium compounds used from about 0.05 to about 2 moles of an internal electron donor and from about 0.05 to about 300 moles of a compound of titanium.

In one embodiment, the implementation in the solid titanium catalyst component (A) ratio of the number of atoms of halogen/titanium is in the range from about 4 to about 200; the molar ratio of internal electron donor/titanium is in the range from about 0.01 to about 10; and the ratio of numbers of atoms of magnesium/titanium is in the range from about 1 to about 100. In yet another variant implementation in the solid titanium catalyst component (A) ratio of the number of atoms of halogen/titanium is in the range from about 5 to about 100; the molar ratio of internal electron donor/titanium is in the range from about 0.2 to priblizitelen is 6; and the ratio of numbers of atoms of magnesium/titanium is in the range from about 2 to about 50.

The resulting solid titanium catalyst component (A) in General contains a magnesium halide crystals of smaller size compared to commercially purchased halides of magnesium, and it's usually different specific surface area at least equal to approximately 50 m2/g, preferably in the range from about 60 to 1000 m2/g, more preferably from about 100 to 800 m2/, As mentioned above, the ingredients combine to obtain the whole structure of the solid titanium catalyst component (A), the composition of the solid titanium catalyst component (A) is not materially altered by washing with hexane.

The solid titanium catalyst component (A) can be used individually. If desired, it can be used after dilution inorganic or organic compound such as a compound of silicon, a compound of aluminum or polyolefin. In some cases, when the use of such a diluent, catalyst component (A) can detect high catalytic activity even when its specific surface area is less than described above.

Ways to get active what about the component of the catalyst, which can be used in the present invention are described in U.S. patents 4771023; 4784983; 4829038; 4861847; 4990479; 5177043; 5194531; 5244989; 5438110; 5489634; 5576259; and 5773537; which in this respect are included in this document for reference.

Compounds having in the molecule at least one bond aluminum-carbon, can be used as alyuminiiorganicheskikh compound as catalyst component (B). Examples alyuminiiorganicheskikh compounds include compounds described by the following formulas (III) and (IV):

Rm11Al(OR12)nHpXq1(III)

In the formula (III), R11and R12may be identical or different, and each represents a hydrocarbon group usually having from 1 to about 15 carbon atoms, preferably from 1 to about 4 carbon atoms; X1represents a halogen atom, and 0<3, 0≤p<3, 0≤n<3 and m+n+p+q=3.

Alyuminiiorganicheskikh compounds include complex alkylated compounds containing aluminum and a metal of group I, described by formula (IV)

M1AlR411(IV)

where M1represents Li, Na or K, and R11represents the same as above.

Examples alyuminiiorganicheskikh compounds described by formula (III)are as follows:

connect the Oia, the described General formula Rm11Al(OR12)3-mwhere R11and R12represent the same as above, and m preferably represents a number, where a 1.5≤m≤3;

compounds described by the General formula Rm11AlX3-m1where R11represents the same as above, X1is a halogen, and m preferably represents a number, where 0<m<3;

compounds described by the General formula Rm11AlH3-mwhere R11represents the same as above, and m preferably represents a number, where 2≤m<3; and

compounds described by the General formula Rm11Al(OR12)nXq1where R11and R12represent the same as above, X1represents a halogen, 0<3, 0≤n<3, m+n+q=3.

Specific examples alyuminiiorganicheskikh compounds described by formula (III)include trialkylaluminium, such as triethylaluminium and tributylamine; trialkylaluminium, such as triisobutylaluminum; dialkylaminoalkyl, such as diethylaminoethoxy and dibutylaminoethanol; alkylaminomethylated, such as atelecommunications and butylaminoethyl; partially alkoxysilane alkylamine, the average composition of anywayse as R the 2.511Al(OR12)0,5; dialkylaminoalkyl, such as diethylaluminium, dibutylaniline and diethylaluminium; alkylaminomethylated, such as ethylaminoethanol, butylaminoethyl and ethylaluminum; partially halogenated alkylamine, such as alkylhalogenide, such as ethylaminoethanol, properlyinstalled and butylimidazole; dialkylaminoalkyl, such as diethylaluminium and dibutylaniline; other partially hydrogenated alkylamine, such as alkylhalogenide, such as arylaliphatic and propylaminoethyl; and partly alkoxysilane and halogenated alkylamine, such as ethylaminoethanol, butylaminoethyl and ethylaminoethanol.

Alyuminiiorganicheskikh compounds further include compounds similar to the compounds described by formula (III), such as those in which two or more aluminum atoms are linked via an oxygen atom or nitrogen. Examples are (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2,

(C2H5)2AlNAl(C2H5)2

C2H5

and methylalumoxane.

Examples alyuminiiorganicheskikh connected to the th, described by formula (IV)include LiAl(C2H5)4and LiAl(C7H15)4.

Component of the catalyst (C) on the basis of alyuminiiorganicheskikh compounds are used in the catalytic system of the present invention in an amount such that the molar ratio of aluminum to titanium (from catalyst component (A)) would be in the range from about 5 to about 1000. In another embodiment, the implementation of the molar ratio of aluminum to titanium in the catalyst system is in the range from approximately 10 to approximately 700. In yet another variant implementation of the molar ratio of aluminum to titanium in the catalyst system is in the range of from about 25 to about 400.

Component of the catalyst (C) is an organosilicon compound containing in its structure (cycloalkyl)methyl group, or you can use the derivative of any one of these groups, such as in the case of machinenow and pinnow. In one embodiment, the implementation of the organosilicon compound contains one (cycloalkyl)methyl link. In another embodiment, the implementation of the organosilicon compound contains two (cycloalkyl)-methyl-level, which are the same or different.

Organosilicon compounds containing at least one (cycloalkyl)methyl link can be described by the formula (V):

where the circle represents one or more cycloalkyl links, each G independently represents alkoxygroup, including methoxy and ethoxypropan, or a hydrocarbon group including alkyl groups such as methyl, ethyl, through bucilina, cyclopropyl, cyclopentamine, tsiklogeksilnogo and 2-ethylhexyl group; h is in the range from 1 to 4 or 1 to 2; each Y independently represents a hydrocarbon group, including those that were mentioned above, hydroxy or halogen; and n is the range from 0 to 3, from 0 to 2 or from 1 to 2. Alkoxy, and alkyl hydrocarbon groups typically contain from 1 to about 8 carbon atoms.

Organosilicon compounds containing at least one (cycloalkyl)methyl link, can also be described by one or more formulas (VI), (VII), (VIII), (IX) and (X):

where each G independently represents alkoxygroup, including methoxy and ethoxypropan, or a hydrocarbon group including alkyl groups such as methyl, ethyl, through bucilina, cyclo is roelina, cyclopentamine, tsiklogeksilnogo and 2-ethylhexyl group; h is in the range from 1 to 4 or 1 to 2; each Y independently represents a hydrocarbon group, including those that were mentioned above, hydroxy or halogen; and n is in the range from 0 to 3, from 0 to 2 or from 1 to 2.

Additional examples of organosilicon compounds are compounds described by the following formulas (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI) and (XXII):

where each R independently represents a hydrocarbon group including alkyl groups such as methyl, ethyl, through bucilina, cyclopropyl, cyclopentamine, tsiklogeksilnogo and 2-ethylhexyl group; each Y independently represents a hydrocarbon group, including those that were mentioned above, hydroxy or halogen; and n is in the range from 0 to 3, from 0 to 2 or from 1 to 2.

Despite the fact that the formulas from (XI) to (XVII) it is not shown on any of the (cycloalkyl)methyl groups in these formulas may not necessarily be the Deputy Y. for Example, one or more of the group can be on (cyclopropyl)methyl group of the formula (XVI).

Examples of organosilicon compounds containing in their structure (cycloalkyl)methyl group or a derivative of any one of the data groups include

bis{(cyclobutyl)methyl}dimethoxysilane,

bis{(cyclopropyl)methyl}dimethoxysilane,

bis{(cyclopentyl)methyl}dimethoxysilane,

bis{(cyclohexyl)methyl}dimethoxysilane,

bis{(cycloheptyl)methyl}dimethoxysilane,

(cyclobutyl)methyl(cyclopropyl)metaldimension,

(cyclopentyl)methyl(cyclopropyl)metaldimension,

(cyclohexyl)methyl(cyclopropyl)metaldimension,

(cycloheptyl)methyl(cyclopropyl)metaldimension,

(cyclobutyl)methyl(cyclopentyl)metaldimension,

(cyclobutyl)methyl(cyclohexyl)metaldimension,

(cyclobutyl)methyl(cycloheptyl)metaldimension,

(cyclopentyl)methyl(cyclohexyl)metaldimension,

(cyclopentyl)methyl(cycloheptyl)metaldimension,

(cyclohexyl)methyl(cycloheptyl)metaldimension,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexanecarboxylic,

(cyclopropyl)methyl-2-celexadepression,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexanecarboxylic,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexanecarboxylic,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexanecarboxylic,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexanecarboxylic,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltrimethoxysilane,

(cyclobutyl)methyltrimethoxysilane,

(cyclopentyl)methyltrimethoxysilane,

(cyclohexyl)methyltrimethoxysilane,

(cycloheptyl)methyltrimethoxysilane,

bis{(cyclobutyl)methyl}detoxifier,

bis{(cyclopropyl)methyl}detoxifier,

bis{(cyclopentyl)methyl}detoxifier,

bis{(cyclohexyl)methyl}detoxifier,

bis{(cycloheptyl)methyl}detoxifier,

(cyclobutyl)methyl(cyclopropyl)metildigoxin,

(cyclopentyl)methyl(cyclopropyl)metildigoxin,

(cyclohexyl)methyl(cyclopropyl)metildigoxin,

(cycloheptyl)methyl(cyclopropyl)metildigoxin,

(cyclobutyl)methyl(cyclopentyl)metildigoxin,

(cyclobutyl)methyl(cyclohexyl)metildigoxin,

(cyclobutyl)methyl(cycloheptyl)metildigoxin,

(cyclopentyl)methyl(cyclohexyl)metildigoxin,

(cyclopentyl)methyl(cycloheptyl)metildigoxin,

(cyclohexyl)methyl(cycloheptyl)metildigoxin,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexanecarboxylic,

(the cycle is propyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexanecarboxylic,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexanecarboxylic,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexanecarboxylic,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexanecarboxylic,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methylthieno sicilan,

(cyclobutyl)methyltriethoxysilane,

(cyclopentyl)methyltriethoxysilane,

(cyclohexyl)methyltriethoxysilane and

(cycloheptyl)methyltriethoxysilane.

Organosilicon compounds of the present invention can be obtained in various ways. In the same way one or two equivalent cyclopropyl/cyclobutene Grignard reagent (Grignard reagent with (cyclopropyl)methyl or (cyclobutyl)methyl group, respectively) is injected into the reaction orthosilicates, such as tetraethylorthosilicate or tetraethylorthosilicate. The reagent is then cleaned, using, if necessary, by vacuum distillation. Tetraethylorthosilicate and tetraethylorthosilicate receive as a result of the reaction of silicon tetrachloride with four equivalents of either methanol or ethanol.

Examples of Grignard reagents with (cycloalkyl)methyl group, include compounds described by formula (XXIII)

MgXR13(XXIII)

where X represents a halogen atom such as chlorine or bromine, and R13represents an organic group containing (cycloalkyl)methyl group. Examples of organic groups include substituted or unsubstituted (cyclopropyl)methyl group, a substituted or unsubstituted (cyclobutyl)methyl group, a substituted or unsubstituted (cyclopentyl)methyl group, W is displaced or unsubstituted (cyclohexyl)methyl group and a substituted or unsubstituted (cycloheptyl)methyl group.

In another way component catalytic system (S) based on organosilicon compounds produced by the reaction between monocyclohexyl (i.e. mono(cyclopropyl)methyl-, mono(cyclobutyl)methyl-, mono(cyclopentyl)methyl-, mono(cyclohexyl)methyl-, mono(cycloheptyl)methyltriethoxysilane) and (cycloalkyl)methyl Grignard reagent. For example, (cyclopropyl)harmatan first introduced into reaction with magnesium in the presence of a solvent, for example a simple ether, such as tetrahydrofuran, diethyl ether or di-n-butyl ether, obtaining (cyclopropyl)methyl Grignard reagent (cyclopropyl)methylacrylamide). This reaction can be conducted at a temperature in the range from approximately room temperature to approximately 60aboutC. (Cyclopropyl)methyl Grignard reagent after that enter into the reaction with (cyclopropyl)methyltrimethoxysilane to obtain bis{(cyclopropyl)methyl}of dimethoxysilane; this reaction can be carried out in the presence of simple ether, such as tetrahydrofuran, diethyl ether or di-n-butyl ether, or in the presence of an aliphatic hydrocarbon solvent such as hexane or heptane, or an aromatic hydrocarbon solvent such as toluene, benzene or xylene. This reaction can be performed at the tempo is the atur in the range from about 50 aboutWith up to approximately 200aboutC, preferably at a temperature in the range from about 100aboutWith up to approximately 200aboutC or at a temperature in the range from about 100aboutWith up to approximately 200aboutWith at boiling solvent or distillation under reflux.

Although mono(cycloalkyl)methyltriethoxysilane designed for use in the above reaction, may be a commercial product, it is possible to obtain various known ways. In one method, the desired compound produced by the reaction between (cycloalkyl)methyltrichlorosilane and methanol to alkoxysilane derived silane with the release of hydrogen chloride. Despite the fact that (cycloalkyl)methyltrichlorosilane designed for use in this reaction may be a commercial product, it can be obtained by the reaction of hydrosilation between (cycloalkyl)methane and trichlorosilane (HSiCl3).

(Cycloalkyl)methyl organosilicon compounds, thus obtained, can be identified using one or more methods, such as spectroscopy nuclear magnetic resonance (1H-NMR,13C-NMR), absorption spectrometry in the infrared region, the gas chromatog afia-mass spectrometry and the like.

The organosilicon compound of the present invention when it is used as an electron donor used as one component of a catalytic system of the Ziegler-Natta for polymerization of olefins, makes it possible to obtain polymer (at least part of which is a polyolefin), featuring a wide molecular weight distribution and adjustable degree of crystallinity, while maintaining a high technological characteristics in relation to catalytic activity and output vysokotemperaturnogo polymer.

The organosilicon compound (C) used in the catalytic system of the present invention in an amount such that the molar ratio alyuminiiorganicheskikh connection (In) to (cycloalkyl)methyl organosilicon compound would be in the range from approximately 2 to approximately 90. In another embodiment, the implementation of the molar ratio alyuminiiorganicheskikh connection (cycloalkyl)methyl organosilicon compound is in the range from about 5 to about 70. In yet another variant implementation of the molar ratio alyuminiiorganicheskikh connection (cycloalkyl)methyl organosilicon compound is in the range from about 7 to about 35.

In addition to the organosilicon is soedinenijam, described above, the catalyst system or catalyst component (C) optionally may additionally include one or more organosilicon compounds. For example, in one aspect of the present invention additional organosilicon compound described by formula (XXIV):

R14nSi(OCR15)4-n(XXIV)

where R14and R15represent a hydrocarbon group, and n is in the range of 0≤n<4.

Specific examples of additional organosilicon compounds described by formula (XXIV)include trimethyloxonium, trimethylaluminium, dimethyldiethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, tert-butylmethylether, tert-butylmethylether, tert-amiloridesensitive, diphenylmethylsilane, FemaleCircumcision, diphenyldichlorosilane, bis-o-tridimensional, bis-m-tridimensional, bis-p-tridimensional, bis-p-cardiotoxicity, pisatelbnicaostaetsya, dicyclohexylammonium, cyclohexanedimethanol, cyclohexyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, VINYLTRIMETHOXYSILANE, gamma chloropropionitrile of methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tert-butyltrichlorosilane, n-butyltrichlorosilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, gamma aminopropyltriethoxysilane, chlorotriethylsilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, cyclohexyltrichlorosilane, cyclohexyltrichlorosilane, 2-norbornenedicarboxylic, 2-norbornadiene, 2-norbornenedicarboxylic, ethyl silicate, butylsilane, tributyltinoxide, methyltriethoxysilane, vinyltris-(beta-methoxyethoxy), vinyltriethoxysilane and dimethylhydrogensiloxane.

In another aspect of the present invention additional organosilicon compound described by formula (XXV)

SiR21Rm22(OR23)3-m(XXV)

In the above formula (XXV) 0≤m<3, preferably 0≤m≤2; and R21represents cyclopentyloxy group, cyclopentenyl group, cyclopentadienyls group or a derivative of any of them. A derivative may preferably be, for example, cyclopentyloxy group, substituted alkyl groups of from 1 to about 4, having from 1 to about 4 carbon atoms, alkyl group having from 2 to about 4 carbon atoms, substituted cyclopentyloxy group which may be substituted by alkyl groups in the number is the number from 1 to about 4, having from 1 to about 4 carbon atoms, cyclopentenyl group, substituted alkyl groups of from 1 to about 4, having from 1 to about 4 carbon atoms, cyclopentadienyls group, substituted alkyl groups of from 1 to about 4, having from 1 to about 4 carbon atoms, or indenolol, indanernas, tetrahydroindole or fluorenyl group which may be substituted by alkyl groups of from 1 to about 4, having from 1 to about 4 carbon atoms.

Specific examples of the group R21include cyclopentyloxy, 2-methylcyclopentanol, 3-methylcyclopentanol, 2-ethylcyclopentadienyl, 3-propylcyclohexyl, 3-isopropylcyclopentadienyl, 3-butylcyclopentadienyl, 3-(tertiary butyl)cyclopentyl, 2,2-dimethylcyclopentane, 2,3-dimethylcyclopentene, 2,5-dimethylcyclopentene, 2,2,5-trimethylcyclopentanone, 2,3,4,5-tetramethylcyclopentadienyl, of 2.2.5.5-tetramethylcyclopentadiene, 1-cyclopentylpropionyl, 1-methyl-1-cyclopentylamine, cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-3-cyclopentenyl, 3-methyl-3-cyclopentenyl, 2-ethyl-3-cyclopentenyl, 2,2-dimethyl-3-cyclopentenyl, 2,5-dimethyl-3-cyclopentenyl, 2,3,4,5-tetramethyl-3-clopotelul, of 2.2.5.5-tetramethyl-3-cyclopentanediol, 1,3-cyclopentadienyls, 2,4-cyclopentadienyls, 1,4-cyclopentadienyls, 2-methyl-1,3-cyclopentadienyls, 2-methyl-2,4-cyclopentadienyls, 3-methyl-2,4-cyclopentadienyls, 2-ethyl-2,4-cyclopentadienyls, 2-dimethyl-2,4-cyclopentadienyls, 2,3-dimethyl-2,4-cyclopentadienyls, 2,5-dimethyl-2,4-cyclopentadienyls, 2,3,4,5-tetramethyl-2,4-cyclopentadienyls, indenolol, 2-methylindenyl, 2-ethylindole, 2-indenolol, 1-methyl-2-indenolol, 1,3-dimethyl-2-indenolol, indenolol, 2-methylindenyl, 2-indenolol, 1,3-dimethyl-2-indenolol, 4,5,6,7-tetrahydroindole, 4,5,6,7-tetrahydro-2-indenolol, 4,5,6,7-tetrahydro-1-methyl-2-indenolol, 4,5,6,7-tetrahydro-1,3-dimethyl-2-indenolol and fluorenyl group.

In the formula (XXV) R22and R23are the same or different, and each represents a hydrocarbon. Examples R22and R23are alkyl, cycloalkyl, aryl and kalkilya group having 5 or more carbon atoms. In addition, R21and R22can be linked by a bridge across the alkyl group and the like. Preferred additional organic silicon compounds are those compounds described by formula (XXV)in which R21represents cyclopentyloxy group, R22represents Ala the function group or cyclopentyl group, and R23represents an alkyl group, particularly a methyl or ethyl group.

Specific examples of additional organosilicon compounds described by formula (XXV)include tralkoxydim, such as Cyclopentasiloxane, 2-methylcyclopentadienyl, 2,3-dimethylcyclopropanecarboxylate, 2.5-dimethylcyclopropanecarboxylate, Cyclopentasiloxane, cyclopentadienylmagnesium, 3-cyclopentanecarboxylate, 2,4-cyclopentadienylmagnesium, intertrinitarian and fluorenylmethoxycarbonyl; dialkoxybenzene, such as dicyclopentadienyliron, bis(2-methylcyclopentene)dimethoxysilane, bis(3-(tertiary butyl)cyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclobutyl)dimethoxysilane, bis(2,5-dimethylcyclobutyl)dimethoxysilane, dicyclopentadienyliron, dicyclopentadienyltitanium, di(3-cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane, di-2,4-cyclopentadienylmagnesium, bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane, bis(1-methyl-1-cyclopentylmethyl)dimethoxysilane, cyclopentadienylmagnesium, cyclopentadienylmagnesium, diindolymethane, bis(1,3-dimethyl-2-indenyl)dimethoxysilane, cyclopentadienylmagnesium, difluorobenzamidoxime, cyclopentyl unidimensional and interfragmentary; monoatomically, such as tricyclopentadiene, tricyclopentadiene, tricyclopentadiene, tricyclopentadiene, dicyclopentadienyltitanium, dicyclopentadienyliron, dicyclopentadienyltitanium, cyclopentadienylmagnesium, cyclopentadienylmagnesium, cyclopentadienylmagnesium, bis(2,5-dimethylcyclobutyl)cyclopentylmethyl, dicyclopentadienyltitanium, dicyclopentadienyltitanium and deindizierter; and ethylenechlorotrifluoroethylene.

Polymerization of olefins in accordance with this invention is carried out in the presence of the above catalyst system. In one implementation before the main polymerization carried out as described below pre-polymerization. In another embodiment, the implementation of the polymerization carried out without preliminary polymerization.

In the preliminary polymerization, the solid titanium catalyst component (A) is usually used in combination, at least a part alyuminiiorganicheskikh connections (In). The reaction can be carried out in the presence of partial or total amount of organosilicon compound (C) (and optionally additional organosilicon). The concentration of the catalytic system, use the Noi for the preliminary polymerization, can be much higher than the corresponding concentration in the reaction system, the main polymerization.

In the case of the preliminary polymerization, the concentration of the solid titanium catalyst component (a) in the preliminary polymerization is usually in the range from approximately 0.01 to approximately 200 mmol, preferably from about 0.05 to about 100 mmol, when calculating the number of titanium atoms to one liter of an inert hydrocarbon medium, described below. The preliminary polymerization is preferably carried out by adding an olefin and ingredients described above catalytic system to inert hydrocarbon medium and the reaction to olefins under mild conditions.

Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and Methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons, such as telengard and chlorobenzene; and mixtures thereof. In the present invention the liquid olefin can be used instead of part or the full amount of the inert hydrocarbon medium.

The olefin used will precede the school polymerization, may be the same as the olefin used in the main polymerization, or may be different.

The reaction temperature in the preliminary polymerization is sufficient for the resulting pre-polymer, essentially no dissolved least in an inert hydrocarbon medium. In one implementation, the temperature is in the range from about -20aboutC to about 100aboutC. In another implementation, the temperature is in the range from about -10aboutWith up to approximately 80aboutC. In yet another implementation, the temperature is in the range from approximately 0aboutWith up to approximately 40aboutC.

When the preliminary polymerization is optional, you can use the control degree of polymerization, such as hydrogen. Control degree of polymerization is used in an amount such that the polymer resulting from the preliminary polymerization, would be a characteristic viscosity, measured in decaline at 135aboutWith, at least, equal to about 0.2 DL/g and preferably in the range from about 0.5 to 10 DL/g

In one embodiment, the implementation of the preliminary polymerization is desirable to carry out so per gram of the titanium catalyst component (A catalytic system of the polymer would be from approximately 0.1 g to approximately 1000 In another embodiment, the implementation of the preliminary polymerization is desirable to carry out so per gram of the titanium catalyst component (A) polymer would be from about 0.3 g to about 500, If the amount of the polymer resulting from the preliminary polymerization is too high, it can sometimes decrease the efficiency of obtaining the olefin polymer in the core polymerization, and if the resulting olefin polymer will be formed with getting film or other products, that would tend to occur in the molded product fisheye. The preliminary polymerization can be conducted in batch or continuous versions.

After in accordance with what has been described above, will be conducted preliminary polymerization, or by omitting the stage of preliminary polymerization is conducted the main polymerization of an olefin in the presence of the above catalyst system for polymerization of olefins formed from the solid titanium catalyst component (A), alyuminiiorganicheskikh compounds (b) and organosilicon compound (C).

Examples of olefins that can be used in the main polymerization, are alpha-olefins having from 2 to 20 carbon atoms, the e as ethylene, propylene, 1-butene, 4-methyl-1-penten, 1-penten, 1-octene, 1-hexene, 3-methyl-1-penten, 3-methyl-1-butene, 1-mission 1-tetradecene, 1 akoten and vinylcyclohexane. In the method of the present invention, the data of alpha-olefins can be used individually or in any combination.

In one embodiment, the implementations are homopolymerization propylene or 1-butene or conduct the copolymerization of a mixture of olefins containing propylene or 1-butene as a main component. If you will use a mixture of olefins, the proportion of propylene or 1-butene as a main component is usually at least be equal to approximately 50% (mol.), preferably, at least, will be equal to approximately 70% (mol.).

In the preliminary polymerization is possible to adjust the degree of activity for the catalytic system in the main polymerization. In the case of such adjustment, there is a tendency to the formation of a powdery polymer with high bulk density. In addition, if the pre-polymerization, the shape of the particles in the resulting polymer will be spherical, as in the case of suspension polymerization, the suspension will get excellent performance. In addition, in this variant implementation in the polymerization of alpha-olefin having at least PR is about 3 carbon atoms, at high catalyst efficiency can be obtained a polymer with a high rate of stereoregularity.

If homopolymerization or copolymerization of these olefins as co monomer can be used polyunsaturated compound such as a conjugated diene or non-conjugate diene. Examples of comonomers include styrene, butadiene, Acrylonitrile, acrylamide, alpha-methylsterol, chloresterol, vinyltoluene, divinylbenzene, diallylphthalate, alkyl methacrylates and alkylacrylate. In one embodiment, the implementation of the comonomers include thermoplastic and elastomeric monomers.

In the method of the present invention the main polymerization of an olefin is usually carried out in the gas or liquid phase. In one implementation, if the main polymerization is carried out in the mode of reaction occurring in the suspension, the solvent in the reaction can be used the above-mentioned inert hydrocarbon. Alternatively, in another embodiment, the implementation of the solvent in the reaction can be used olefin which is liquid at the reaction temperature. In yet another variant implementation as a solvent in the reaction it is possible to use an inert hydrocarbon and the olefin which is liquid at the reaction temperature.

In one embodiment, the implementation of polymerization (main polymerization) of this breath is retene uses catalytic system, containing titanium catalyst component (A) in an amount of from about 0.001 to about 0.75 millimole calculated as the number of Ti atoms per one liter of the volume of the polymerization zone, alyuminiiorganicheskikh connection (In) in an amount of from about 1 to about 2,000 moles per one mole of titanium atoms in the titanium catalyst component (a) and the organosilicon compound (C) in an amount of from about 0.001 to about 10 moles, calculated as the number of Si atoms in the organosilicon compound (C)per mol of the metal atoms in alyuminiiorganicheskikh connection (In). In another embodiment, the implementation of polymerization uses a catalyst system containing the titanium catalyst component (A) in an amount of from approximately 0.005 to approximately 0.5 mmol, calculated as the number of Ti atoms per one liter of the volume of the polymerization zone, alyuminiiorganicheskikh connection (In) in an amount of from about 5 to about 500 moles per one mole of titanium atoms in the titanium catalyst component (a) and the organosilicon compound (C) in an amount of from about 0.01 to about 2 moles, calculated as the number of Si atoms in the organosilicon compound (C)per mol the metal atoms in the Alu is anyorganization connection (In). In yet another variant implementation of polymerization uses a catalytic system containing organosilicon compound (C) in an amount of from about 0.05 to about 1 mole, calculated as the number of Si atoms in the organosilicon compound (C)per mol of the metal atoms in alyuminiiorganicheskikh connection (In).

The components of the catalyst (A), (b) and (C) you can enter into contact with each other at the time of the main polymerization or during the preliminary polymerization to the main polymerization. With this introduction to the contact prior to the main polymerization can be selected and put in contact with each other, any desired two components with the subsequent addition of the third component. Alternatively, in contact with each other, you can enter only part of two or three components. Before polymerization ingredients catalytic system can be put in contact with each other in an atmosphere of inert gas or in the atmosphere of the olefin.

If alyuminiiorganicheskikh connection (In) and the organosilicon compound (C) partially used in the preliminary polymerization, the catalytic system, subjected to preliminary polymerization is used in conjunction with other components of the catalytic system. The catalytic system is subjected stage PR is dwarfelles polymerization, may contain product prior to polymerization.

The use of hydrogen during the polymerization facilitates the adjustment of the molecular weight of the resulting polymer and makes the adjustment of the contribution, and the resulting polymer can be characterized by a high rate of flow of the melt. In this case, in accordance with the methods of the present invention the rate of stereoregularity in the resulting polymer and the catalytic activity of the system is not reduced.

In one implementation, the temperature of polymerization in the present invention is in the range from about 20aboutWith up to approximately 200aboutC. In another implementation, the temperature of polymerization in the present invention is in the range from about 50aboutWith up to approximately 180aboutC. In one embodiment, the implementation of the pressure during polymerization is usually in the range from about atmospheric pressure to about 100 kg/cm2. In another embodiment, the pressure during polymerization is usually in the range from about 2 kg/cm2to about 50 kg/cm2. The main polymerization can be performed at periodic, semi-continuous or continuous variants. The polymerization can also be carried out in two or more stages at different is cnyh the reaction conditions. Thus obtained olefin polymer can be homopolymers, statistical copolymer or a block copolymer.

Since the yield of stereoregular polymer obtained per unit amount of the solid titanium catalyst component in the present invention is high, the amount of catalyst residues in the polymer, in particular a halogen content in it, can be relatively reduced. Accordingly, it is possible to omit the operation to remove the catalyst from the resulting polymer, and forming olefin polymer product can be effectively prevented the occurrence of corrosion of the mold.

In addition, the olefin polymer obtained by using a catalytic system of the present invention, has a very small content of the amorphous component of the polymer and therefore a small content of the component soluble in the hydrocarbon. As a result, the film formed from the obtained as a result of this polymer has a low tack surface.

The polyolefin obtained by the method of the present invention, is excellent in regard to the distribution of particle size, particle diameter and bulk density, and the resulting cooliolevi different narrow distribution of composition.

In another preferred in which the version of the implementation of the present invention in the presence of the above-described catalytic system will copolymerize propylene and alpha-olefin, having 2 or from about 4 to about 20 carbon atoms. The catalytic system may be a system subjected to the above preliminary polymerization.

In the preliminary polymerization is possible to adjust the degree of activity for the catalytic system in the main polymerization. In the case of such adjustment, there is a tendency to the formation of a powdery polymer with high bulk density. In addition, if the pre-polymerization, the shape of the particles in the resulting polymer will be spherical, as in the case of suspension polymerization, the suspension will get excellent performance. Accordingly, in this implementation variant of the method of obtaining a propylene copolymer, the resulting copolymer powder or slurry of the copolymer become easy to handle.

Alpha-olefin having 2 carbon atoms, a is ethylene, and examples of alpha-olefins having from about 4 to about 20 carbon atoms are 1-butene, 1-penten, 4-methyl-1-penten, 1-octene, 1-hexene, 3-methyl-1-penten, 3-methyl-1-butene, 1-mission vinylcyclohexane, 1-tetradecene and the like.

In the main polymerization of propylene can be copolymerisate with two or more of such alpha on arinami. For example, you can copolymerizate propylene with ethylene and 1-butene. In one embodiment, the implementation of propylene will copolymerized with ethylene, 1-butene or ethylene and 1-butene.

The block copolymerization of propylene and another alpha-olefin can be carried out in two stages. The polymerization in the first stage can be homopolymerization of propylene or copolymerization of propylene with another alpha-olefin. It is preferable that the copolymerization of propylene and ethylene or propylene, ethylene and 1-butene. In one implementation, the number of monomers polymerized in the first stage, is in the range from about 50 to about 95% (wt.). In another embodiment, the implementation of a number of monomers, depolimerization in the first stage, is in the range from about 60 to about 90% (wt.). In the present invention the polymerization at the first stage, you at least need to spend in two or more stages with the same or different polymerization conditions.

In one embodiment, the implementation of the polymerization at the second stage is preferably carried out so that the molar ratio of propylene to the other alpha-olefins (alpha-olefins) would be in the range from about 10/90 to about 90/10. In another embodiment, the implementation of the polymerization at the second stage it is advisable to conduct is so so that the molar ratio of propylene to the other alpha-olefins (alpha-olefins) would be in the range of from about 20/80 to about 80/20. In yet another variant implementation of the polymerization at the second stage is preferably carried out so that the molar ratio of propylene to the other alpha-olefins (alpha-olefins) would be in the range of from about 30/70 to about 70/30. In the second stage polymerization, it is possible to provide a step for a crystalline polymer or copolymer with another alpha-olefin.

Thus obtained propylene copolymer may be a statistical copolymer or the above-described block copolymer. This propylene copolymer generally contains from about 7 to about 50% (mol.) links formed from alpha-olefin having 2 or from about 4 to about 20 carbon atoms. In one embodiment, the implementation of propylene statistical copolymer contains from about 7 to about 20% (mol.) links formed from alpha-olefin having 2 or from about 4 to about 20 carbon atoms. In another embodiment, the implementation of propylene statistical copolymer contains from about 8 to about 18% (mol.) links formed from alpha-olefin having 2 or from about 4 to when listello 20 carbon atoms. In one embodiment, the implementation of the propylene block copolymer contains from about 10 to about 50% (mol.) links formed from alpha-olefins having 2 or 4 to 20 carbon atoms. In another embodiment, the implementation of the propylene block copolymer contains from about 20 to about 40% (mol.) links formed from alpha-olefins having 2 or 4 to 20 carbon atoms.

In yet another variant implementation of the copolymers obtained by using a catalytic system of the present invention contain from about 50% to about 99% (wt.) poly-alpha-olefins and from about 1% to about 50% (wt.) the comonomers (such as thermoplastic or elastomeric monomers). In another embodiment, the implementation of the copolymers obtained by using a catalytic system of the present invention contain from about 75% to about 98% (wt.) poly-alpha-olefins and from about 2% to about 25% (wt.) the comonomers.

You must understand that where there is no reference to polyunsaturated compound which can be used, the method of polymerization, the amount of the catalytic system and the conditions of the polymerization, it is possible to use the same description as that for the above variants of the implementation.

The catalysts/methods of the present invention results in the Yat to obtain poly-alpha-olefins, the contents of fractions, soluble in xylene, (XS) which is in the range from about 2% to about 10% depending on the specific used (cycloalkyl)methyl organosilicon. In another embodiment implemented in accordance with the present invention receive poly-alpha-olefins, the content of the fractions, soluble in xylene, (XS) which is in the range from about 3% to about 6%, depending on the particular used (cycloalkyl)methyl organosilicon. XS denotes the percentage of the solid polymer, which is soluble in xylene. Low value XS% in the General case corresponds to vysokoenergeticheskom the polymer (i.e. a higher degree of crystallinity), while a high value XS% in the General case corresponds to a polymer with a low isotacticity.

For example, in one implementation, when used in the catalytic system as (cycloalkyl)methyl organosilicon bis{(cyclobutyl)methyl}-dimethoxysilane polypropylene polymer made with it was characterized by a size XS in the range from approximately 2% to approximately 4%. In another implementation, when used in the catalytic system as (cycloalkyl)methyl crimnial the organic compounds bis{(cyclopropyl)methyl}of dimethoxysilane propylene polymer, obtained with its help, characterized by the value of XS in the range from approximately 4% to approximately 6%.

In one embodiment, the implementation catalyst efficiency (measured in kilograms of the obtained polymer per gram of catalyst) in the catalytic system of the present invention, at least equal to approximately 25. In another embodiment, the implementation efficiency of the catalyst in the catalytic system of the present invention, at least equal to approximately 30. In yet another variant implementation, the effectiveness of the catalyst in the catalytic system of the present invention, at least equal to approximately 32.

The catalysts/methods of the present invention result in a poly-alpha-olefins, indexes melt flow (MFI) which are in the range of from about 5 to about 9, depending on the particular used (cycloalkyl)methyl organosilicon. For example, in one implementation, when used in the catalytic system as (cycloalkyl)methyl organosilicon bis{(cyclobutyl)methyl}-dimethoxysilane polypropylene polymer made with it, was characterized by the largest MFI in the range from about 7 to about 8. In another variant of realization when using the catalyst as (cycloalkyl)methyl organosilicon bis{(cyclopropyl)methyl}of dimethoxysilane polypropylene polymer, obtained with its help, was characterized by the largest MFI in the range from about 6 to about 7. In some cases, the relatively large size of the MFI shows what can be achieved relatively high catalyst efficiency. MFI (velocity) was measured in accordance with ASTM D 1238.

The catalysts/methods of the present invention result in a poly-alpha-olefins, characterized by a relatively narrow molecular weight distribution. In one embodiment, the implementation of Mw/Mn of the polypropylene polymer obtained using a catalyst system containing (cycloalkyl)methyl organosilicon compound is in the range from approximately 3 to approximately 5.5. In another embodiment, the implementation of Mw/Mn of the polypropylene polymer obtained using a catalyst system containing (cycloalkyl)methyl organosilicon compound is in the range from about 3.5 to about 5.

In accordance with this invention a polypropylene copolymer, such as polypropylene statistical copolymer with a high melting point can be obtained in large quantities and with great output. In addition, you can reduce the amount of by-product in the form of a copolymer, soluble the hydrocarbon. Polymerization without any problems can be performed even in suspension. Since the amount of the copolymer produced per unit quantity of titanium, large, surgery to remove the catalyst after polymerization can be deleted.

Propylene statistical copolymer obtained in accordance with the present invention, has an excellent weldability, property to make the property weldability other materials, transparency and property, caking, and it contains a small amount of material soluble in the hydrocarbon.

The present invention can produce a propylene block copolymer, which is inherent in one or more properties, such as excellent flowability in the melt formability, rigidity, impact strength and impact strength, at high catalyst efficiency and good processability of the process of obtaining. Moreover, as a result of selecting one of (cycloalkyl)methyl organosilicon compounds can be installed on a desirable level indicator isotacticity for the resulting poly-alpha-olefin. Using (cycloalkyl)methyl organosilicon compounds of the present invention leads to the production of catalysts, at the same time high efficiency of katal the congestion and allowing to achieve one or more properties, such as excellent flowability in the melt formability, rigidity, impact strength and impact strength.

Another advantage inherent in the present invention, is that valid are relatively large error bounds on the number to be added (in the catalytic system) organosilicon compounds with minimal changes in terms of isotacticity and catalytic activity in this regard. In many cases, the use of organosilicon compounds that do not contain (cycloalkyl)methyl-level changes in the amount of organosilicon compound added to the catalyst to obtain a polyolefin, lead to significant changes in respect of either catalytic activity or isotacticity the resulting polymer, or both.

The following examples illustrate the present invention. If only in the following examples and elsewhere in the description and the claims do not specify the other, all parts and percentages will be massive, all temperatures are expressed in degrees Celsius, and pressure is equal to atmospheric pressure or close to it.

EXAMPLE 1

1. Preparation of solid titanium catalyst component (A):

The reactor was thoroughly purged azo who ohms with a high degree of purity, introduced anhydrous magnesium chloride (0.05 mol), toluene (75 ml), epoxypropan (0.1 mol) and tributyl phosphate (0.03 mol). The temperature was increased to 50aboutWith under stirring and the mixture is then kept at this temperature for 2 hours before until the solids did not dissolve completely. To the solution was added phthalic anhydride (0,008 mol) and the solution kept at 50aboutEven within 1 hour. The solution was cooled to -25aboutC. for 1 hour was added dropwise a titanium tetrachloride (55 ml). The solution was heated to 80aboutC for 3 hours while it was the precipitation of the solid product. Added diisobutylphthalate (of 0.0125 mol) and kept the mixture at a temperature of 80aboutC for 1 hour.

The solid fraction was collected through filtration, and washed with toluene (2x100 ml). Received a brown-yellow solid residue. The solid phase is then for 2 hours at 90aboutC was treated with a mixture of toluene (60 ml) and titanium tetrachloride (40 ml). After the filtrate was removed, the stage of processing is repeated. The solid phase was washed with dichloroethane (100 ml) and then hexane (4x100 ml).

The solid catalyst component (A)obtained in accordance with the above method, contained 1,92% (wt.) titanium, 17,5% (wt.) magnesium, 56,5% (wt.) chlorine, 13,2% (wt.) diisobutylphthalate, 0,32% (wt.) tributyl phosphate. It is useful surface area was equal to approximately 290 m 2/year

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as a component (C), bis{(cyclobutyl)methyl}dimethoxysilane (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 70aboutC. In the autoclave, propylene was introduced and kept the pressure 7 kg/cm2. The temperature was kept equal to 70aboutC. Propylene was polymerizable within 2 hours. The amount of polymer obtained was equal to 435,

EXAMPLE 2

1. Preparation of solid titanium catalyst component (A):

The reactor was thoroughly purged with nitrogen with high purity, was administered anhydrous magnesium chloride (0.05 mol), toluene (75 ml), epoxypropan (0.1 mol) and tributyl phosphate (0.03 mol). The temperature was increased to 50aboutWith under stirring and the mixture is then kept at this temperature for 2 hours before until the solids did not dissolve completely. To the solution was added phthalic anhydride (0,008 mol) and the solution kept at 50aboutEven for 1 the Asa. The solution was cooled to -25aboutC. for 1 hour was added dropwise a titanium tetrachloride (55 ml). The solution was heated to 80aboutC for 3 hours while it was the precipitation of the solid product. Added diisobutylphthalate (of 0.0125 mol) and kept the mixture at a temperature of 80aboutC for 1 hour.

The solid fraction was collected through filtration, and washed with toluene (2x100 ml). Received a brown-yellow solid residue. The solid phase is then for 2 hours at 90aboutC was treated with a mixture of toluene (60 ml) and titanium tetrachloride (40 ml). After the filtrate was removed, the stage of processing is repeated. The solid phase was washed with dichloroethane (100 ml)and then hexane (4x100 ml).

The solid catalyst component (A)obtained in accordance with the above method, contained 1,92% (wt.) titanium, 17,5% (wt.) magnesium, 56,5% (wt.) chlorine, 13,2% (wt.) diisobutylphthalate, 0,32% (wt.) tributyl phosphate. Its specific surface area was equal to approximately 290 m2/year

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as a component (C), bis{(cyclopropyl)methyl}dimethoxysilane (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of atoms of Titus is a, the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 70aboutC. In the autoclave, propylene was introduced and kept the pressure 7 kg/cm2. The temperature was kept equal to 70aboutC. Propylene was polymerizable within 2 hours. The amount of polymer obtained was equal to 435,

Although the invention has been described in connection with certain variants of implementation, it is necessary to understand that after reading the description specialists in the relevant field will become apparent various modifications. Therefore, it is necessary to understand that the invention described herein is intended to include such modifications that fall within the scope of the attached claims.

Additional examples

Example 3.

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as a component (C), (cyclobutyl)methyl(cyclopropyl)metaldimension (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid component kata is Isadora (A), received in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 72°C. In the autoclave, propylene was introduced and kept the pressure of 6.7 kg/cm2. The temperature was kept equal to 72°C. Propylene was polymerizable for 2.5 hours.

EXAMPLE 4

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as a component (C), (cyclopropyl)methyl(cyclopentyl)metaldimension (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 68°C. In the autoclave, propylene was introduced and kept the pressure of 7.2 kg/cm2. The temperature was kept equal to 68°C. Propylene was polymerizable within 3 hours.

EXAMPLE 5

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was introduced hexane technical num is the notes (800 ml), triethylaluminium (0,0025 mol) as a component (C), (cyclobutyl)methyl(cyclohexyl)metaldimension (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 71°C. In the autoclave, propylene was introduced and kept the pressure of 7.1 kg/cm2. The temperature was kept equal to 71°C. Propylene was polymerizable for 1.5 hours.

EXAMPLE 6

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as a component (C), (cyclopentyl)methyl(cyclohexyl)metaldimension (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 71°C. In the autoclave, propylene was introduced and kept the pressure of 7.1 kg/cm2. The temperature was kept equal to 71°C. Propylene was polymerizable for 1.5 hours.

EXAMPLE 7

Molchanie solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as component (B), (cyclohexyl)methyltrimethoxysilane (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 70°C. In the autoclave, propylene was introduced and kept the pressure 7 kg/cm2. The temperature was kept equal to 70°C. Propylene was polymerizable for 2.5 hours.

EXAMPLE 8

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as component (B), (cyclopentyl)methyltrimethoxysilane (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 70°C. In the autoclave, propylene was introduced and videris is whether the pressure is 7 kg/cm 2. The temperature was kept equal to 70°C. Propylene was polymerizable for 2.5 hours.

EXAMPLE 9

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as component (B), (cyclobutyl)methyltrimethoxysilane (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A)obtained in accordance with what has been described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 67°C. In the autoclave, propylene was introduced and kept the pressure of 6.6 kg/cm2. The temperature was kept equal to 67°C. Propylene was polymerizable within 3 hours.

EXAMPLE 10

1. Preparation of solid titanium catalyst component (A) of Example 1.

2. Polymerization in solution.

In a stainless steel autoclave with a volume of 2 liters, which was thoroughly purged with propylene, was administered technical grade hexane (800 ml), triethylamine (0,0025 mol) as component (B), (cyclopropyl)methyltrimethoxysilane (0,000125 mol) as a component (C) and 0.5 mg, in terms of the number of titanium atoms, of the solid catalyst component (A), p is obtained in accordance with the what was described above. After the introduction of 0.41 l (standard volume) of hydrogen, the temperature was increased to 67°C. In the autoclave, propylene was introduced and kept the pressure of 6.6 kg/cm2. The temperature was kept equal to 67°C. Propylene was polymerizable within 3 hours.

1. Catalytic system for polymerization of olefins containing solid titanium catalyst component; alyuminiiorganicheskikh connection with at least one link aluminum-carbon; organosilicon compound having at least one (cycloalkyl)methyl group, used as an external electron donor.

2. The catalytic system according to claim 1, where the solid titanium catalyst component obtained by contacting compounds of titanium with the magnesium compound in the presence of at least one compound selected from an internal electron donor, an organic epoxy compounds and organophosphorus compounds.

3. The catalytic system according to claim 1, where alyuminiiorganicheskikh compound contains at least one compound selected from triethylaluminum, tributylamine, triisobutylaluminum, diethylaminoethoxy, dibutylaminoethanol, atelecommunications, butylaminoethyl, diethylaluminium, dibutyltindilaurate, diethylaluminium, e is illuminotecnica, butylaminoethyl, atelecommunications, ethylaminoethanol, properlyinstalled, butylimidazole, diethylaminoacetate, dibutylaniline, etilamingidrokhlorida, propylaminoethyl, ethylaminoethanol, butylaminoethyl, ethylaminoethanol, (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2, methylalumoxane, LiAl(C2H5)4and LiAl(C7H15)4.

4. The catalytic system according to claim 1, where the catalyst system contains from about 0.001 to about 0.75 millimole solid titanium catalyst component, from about 1 to about 2000 moles alyuminiiorganicheskikh connection on one mol of titanium atoms in the solid titanium catalyst component and from about 0.001 to about 10 moles of organosilicon compounds.

5. The catalytic system according to claim 1, where the organosilicon compound contains at least one compound selected from the group consisting of

bis{(cyclobutyl)methyl}of dimethoxysilane,

bis{(cyclopropyl)methyl}of dimethoxysilane,

bis{(cyclopentyl)methyl}of dimethoxysilane,

bis{(cyclohexyl)methyl}of dimethoxysilane,

bis{(cycloheptyl)methyl}dimmock is isiana,

(cyclobutyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclohexyl)methyl(cyclopropyl)methyldiethanolamine,

(cycloheptyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclopentyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclobutyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclopentyl)methyl(eclogitic)methyldiethanolamine,

(cyclohexyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexylamine,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)is ethylcyclohexylamine,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexylamine,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexylamine,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexylamine,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltrimethoxysilane,

(cyclobutyl)methyltrimethoxysilane,/p>

(cyclopentyl)methyltrimethoxysilane,

(cyclohexyl)methyltrimethoxysilane,

(cycloheptyl)methyltrimethoxysilane,

bis{(cyclobutyl)methyl}of diethoxyethane,

bis{(cyclopropyl)methyl}of diethoxyethane,

bis{(cyclopentyl)methyl}of diethoxyethane,

bis{(cyclohexyl)methyl}of diethoxyethane,

bis{(cycloheptyl)methyl}of diethoxyethane,

(cyclobutyl)methyl(cyclopropyl)metildigoxin,

(cyclopentyl)methyl(cyclopropyl)metildigoxin,

(cyclohexyl)methyl(cyclopropyl)metildigoxin,

(cycloheptyl)methyl(cyclopropyl)metildigoxin,

(cyclobutyl)methyl(cyclopentyl)metildigoxin,

(cyclobutyl)methyl(cyclohexyl)metildigoxin,

(cyclobutyl)methyl (cycloheptyl)metildigoxin,

(cyclopentyl)methyl(cyclohexyl)metildigoxin,

(cyclopentyl)methyl(cycloheptyl)metildigoxin,

(cyclohexyl)methyl(cycloheptyl)metildigoxin,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentene is diethoxyethane,

(cyclopropyl)methylcyclohexanecarboxylic,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexanecarboxylic,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexanecarboxylic,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexanecarboxylic,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl) methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(CEC heptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexanecarboxylic,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltriethoxysilane,

(cyclobutyl)methyltriethoxysilane,

(cyclopentyl)methyltriethoxysilane,

(cyclohexyl)methyltriethoxysilane and

(cycloheptyl)methyltriethoxysilane.

6. The catalytic system used for the polymerization of olefins containing solid titanium catalyst component obtained by contacting compounds of titanium with the magnesium compound, and the solid titanium catalyst component contains from about 0.01 to about 500 moles of a compound of titanium on one mole of the compounds of magnesium; alyuminiiorganicheskikh connection with at least one link aluminum-carbon, where the catalyst system, the molar ratio of aluminum to titanium is in the range from about 5 to about 1000; organosilicon compound having at least one (cycloalkyl)methyl group, are used as external donor electrons, where the catalyst system, the molar ratio alyuminiiorganicheskikh compounds and organosilicon compounds is in the range from approximately 2 to approximately 90.

7. The catalytic system according to claim 6, where the organosilicon compound contains at least one compound selected from the group consisting of

bis{(cyclobutyl)methyl}of dimethoxysilane,

bis{(cyclopropyl)methyl}of dimethoxysilane,

bis{(cyclopentyl)methyl}of dimethoxysilane,

bis{(cyclohexyl)methyl}of dimethoxysilane,

bis{(cycloheptyl)methyl}of dimethoxysilane,

(cyclobutyl)methyl(picoprobe)methyldiethanolamine,

(cyclopentyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclohexyl)methyl(cyclopropyl)methyldiethanolamine,

(cycloheptyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclopentyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclobutyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclopentyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclohexyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexylamine,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexylamine,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexylamine,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexylamine,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutene is isiana,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexylamine,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltrimethoxysilane,

(cyclobutyl)methyltrimethoxysilane,

(cyclopentyl)methyltrimethoxysilane,

(cyclohexyl)methyltrimethoxysilane,

(cycloheptyl)methyltrimethoxysilane,

bis{(cyclobutyl)methyl}of diethoxyethane,

bis{(cyclopropyl)methyl}of diethoxyethane,

bis{(cyclopentyl)methyl}of diethoxyethane,

bis{(cyclohexyl)methyl}of diethoxyethane,

bis{(cycloheptyl)methyl}of diethoxyethane,

(cyclobutyl)methyl(cyclopropyl)metildigoxin,

(cyclopentyl)methyl(cyclopropyl)metildigoxin,

(cyclohexyl)methyl(cyclopropyl)metildigoxin,

(cycloheptyl)methyl(cyclopropyl)metildigoxin,

(cyclobutyl)methyl(cyclopentyl)metildigoxin,

(cyclobutyl)methyl(cyclohexyl)metildigoxin,

(cyclobutyl)methyl(cycloheptyl)metildigoxin,

(cyclopentyl)methyl(cyclohexyl)metildigoxin

(cyclopentyl)methyl(cycloheptyl)metildigoxin,

(cyclohexyl)methyl(cycloheptyl)metildigoxin,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexanecarboxylic,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexanecarboxylic,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexanecarboxylic,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexanecarboxylic,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexanecarboxylic,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltriethoxysilane,

(cyclobutyl)methyltriethoxysilane,

(cyclopentyl)methyltriethoxysilane,

(cyclohexyl)methyltriethoxysilane and

(cycloheptyl)methyltriethoxysilane.

8. A method of producing a catalyst used for the polymerization of olefins, comprising the interaction of the Grignard reagent with (cycloalkyl)methyl group, orthosilicates obtaining organosilicon compounds having (cycloalkyl)methyl link; mixing the organosilicon compounds used as an external electron donor, with aluminiowa the practical connection having at least one link aluminum-carbon, and solid titanium component of the catalyst to obtain a catalyst.

9. The method of claim 8, where the Grignard reagent comprises a compound described by formula (XXIII)

where X represents a halogen atom;

R13represents an organic group containing one or more representatives selected from the group consisting of (cyclopropyl)methyl, (cyclobutyl)methyl group, (cyclopentyl)of methyl (cyclohexyl) methyl group and (cycloheptyl)bromide.

10. The method of claim 8, where the organosilicon compound comprises at least one compound selected from the group consisting of

bis{(cyclobutyl)methyl}of dimethoxysilane,

bis{(cyclopropyl)methyl}of dimethoxysilane,

bis{(cyclopentyl)methyl}of dimethoxysilane,

bis{(cyclohexyl)methyl}of dimethoxysilane,

bis{(eclogitic)methyl}of dimethoxysilane,

(cyclobutyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclohexyl)methyl(cyclopropyl)methyldiethanolamine,

(cycloheptyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclopentyl)methyldiethanolamine,

(cyclobutyl)met the l(cyclohexyl)methyldiethanolamine,

(cyclobutyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclopentyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclohexyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexylamine,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexylamine,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)m is telekomunikatsijni,

(cyclohexyl)methylcyclohexylamine,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexylamine,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexylamine,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltrimethoxysilane,

(cyclobutyl)methyltrimethoxysilane,

(cyclopentyl)methyltrimethoxysilane,

(cyclohexyl)methyltrimethoxysilane,

(cycloheptyl)methyltrimethoxysilane,

bis{(cyclobutyl)methyl}of diethoxyethane,

bis{(cyclopropyl)methyl}of diethoxyethane,

bis{(cyclopentyl)methyl}of diethoxyethane,

bis{(cyclohexyl)methyl}of diethoxyethane,

bis{(cycloheptyl)methyl}detoxify is on,

(cyclobutyl)methyl(cyclopropyl)metildigoxin,

(cyclopentyl)methyl(cyclopropyl)metildigoxin,

(cyclohexyl)methyl(cyclopropyl)metildigoxin,

(cycloheptyl)methyl(cyclopropyl)metildigoxin,

(cyclobutyl)methyl(cyclopentyl)metildigoxin,

(cyclobutyl)methyl(cyclohexyl)metildigoxin,

(cyclobutyl)methyl(cycloheptyl)metildigoxin,

(cyclopentyl)methyl(cyclohexyl)metildigoxin,

(cyclopentyl)methyl(cycloheptyl)metildigoxin,

(cyclohexyl)methyl(cycloheptyl)metildigoxin,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexanecarboxylic,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexylamine is isiana,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexanecarboxylic,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexanecarboxylic,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexanecarboxylic,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltriethoxysilane,

(cyclobutyl)methyltriethoxysilane,

(cyclopentyl)IU is intratonsilar,

(cyclohexyl)methyltriethoxysilane and

(cycloheptyl)methyltriethoxysilane.

11. The method of polymerization comprising the polymerization or copolymerization of alpha-olefin in the presence of a catalytic system containing a solid titanium catalyst component; alyuminiiorganicheskikh connection with at least one link aluminum-carbon; organosilicon compound having at least one (cycloalkyl)methyl group, used as an external electron donor.

12. The method of polymerization according to claim 11, where, during the polymerization to maintain the temperature in the range from about 20°C to about 200°and a pressure in the range from about atmospheric pressure to about 100 kg/cm2.

13. The method of polymerization according to claim 11, where the organosilicon compound contains at least one compound selected from the group consisting of

bis{(cyclobutyl)methyl}of dimethoxysilane,

bis{(cyclopropyl)methyl}of dimethoxysilane,

bis{(cyclopentyl)methyl}of dimethoxysilane,

bis{(cyclohexyl)methyl}of dimethoxysilane,

bis{(cycloheptyl)methyl}of dimethoxysilane,

(cyclobutyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclohexylmethyl(cyclopropyl)methyldiethanolamine,

(cycloheptyl)methyl(cyclopropyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclopentyl)methyldiethanolamine,

(cyclobutyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclobutyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclopentyl)methyl(cyclohexyl)methyldiethanolamine,

(cyclopentyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclohexyl)methyl(cycloheptyl)methyldiethanolamine,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexylamine,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexylamine,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketone the silane,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexylamine,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexylamine,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)methylcyclohexylamine,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltrimethoxysilane,

(cyclobutyl)methyltrimethoxysilane,

(cyclopentyl)methyltrimethoxysilane,

(cyclohexyl)methyltrimethoxysilane,

(cycloheptyl)methyltrimethoxysilane,

bis{(cyclobuta is)methyl}of diethoxyethane,

bis{(cyclopropyl)methyl}of diethoxyethane,

bis{(cyclopentyl)methyl}of diethoxyethane,

bis{(cyclohexyl)methyl}of diethoxyethane,

bis{(cycloheptyl)methyl}of diethoxyethane,

(cyclobutyl)methyl(cyclopropyl)metildigoxin,

(cyclopentyl)methyl(cyclopropyl)metildigoxin,

(cyclohexyl)methyl(cyclopropyl)metildigoxin,

(cycloheptyl)methyl(cyclopropyl)metildigoxin,

(cyclobutyl)methyl(cyclopentyl)metildigoxin,

(cyclobutyl)methyl(cyclohexyl)metildigoxin,

(cyclobutyl)methyl(cycloheptyl)metildigoxin,

(cyclopentyl)methyl(cyclohexyl)metildigoxin,

(cyclopentyl)methyl(cycloheptyl)metildigoxin,

(cyclohexyl)methyl(cycloheptyl)metildigoxin,

(cyclobutyl)methylcyclobutaneethyl,

(cyclobutyl)methylethylketoxime,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylisobutylketone,

(cyclopropyl)methylethylketoxime,

(cyclopropyl)methylcyclopentadienyl,

(cyclopropyl)methylcyclohexanecarboxylic,

(cyclopropyl)methyl-2-Ethylhexylglycerin,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylisobutylketone,

(cyclobutyl)methylethylketoxime,

(cyclobutyl)methylcyclopentadienyl,

(cyclobutyl)methylcyclohexanecarboxylic,

(cyclobutyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylcyclobutaneethyl,

(cyclopentyl)methylethylketoxime,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylisobutylketone,

(cyclohexyl)methylethylketoxime,

(cyclohexyl)methylcyclopentadienyl,

(cyclohexyl)methylcyclohexanecarboxylic,

(cyclohexyl)methyl-2-Ethylhexylglycerin,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylisobutylketone,

(cyclopentyl)methylethylketoxime,

(cyclopentyl)methylcyclopentadienyl,

(cyclopentyl)methylcyclohexanecarboxylic,

(cyclopentyl)methyl-2-Ethylhexylglycerin,

(cycloheptyl)methylcyclobutaneethyl,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylisobutylketone,

(cycloheptyl)methylethylketoxime,

(cycloheptyl)methylcyclopentadienyl,

(cycloheptyl)m is testiclepainmorecondition,

(cycloheptyl)methyl-2-Ethylhexylglycerin,

(cyclopropyl)methyltriethoxysilane,

(cyclobutyl)methyltriethoxysilane,

(cyclopentyl)methyltriethoxysilane,

(cyclohexyl)methyltriethoxysilane and

(cycloheptyl)methyltriethoxysilane.

14. The method of polymerization according to claim 11, where the effectiveness of the catalyst in the catalytic system, at least, equal to approximately 25 kg of the obtained polymer/g of catalyst.

15. The method of polymerization according to claim 11, where the alpha-olefin contains at least one compound selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-mission 1-tetradecene, 1 eicosene and vinylcyclohexane.

16. The method of polymerization according to claim 11, further comprising removing the polymer containing a polyolefin having a content of fractions soluble in xylene in the range of from about 2% to about 10%.

17. The method of polymerization according to claim 11, further comprising removing the polymer containing a polyolefin having a melt flow index in the range from about 5 to about 9.

Priority items:

22.08.2000 all claims 1 to 17 in respect of a catalyst containing organosilicon compound comprising (cyclobutyl)methyl group and (cyclepro who yl)methyl group;

15.08.2001 all claims 1 to 17 in respect of a catalyst containing organosilicon compound comprising (cycloalkyl)methyl group other than (cyclobutyl)methyl group and (cyclopropyl)methyl group.



 

Same patents:

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

The invention relates to methods for macromolecular higher poly-alpha-olefins and catalysts for carrying out the method

The invention relates to a method for producing a catalyst for polymerization of olefins and method of polymerization of olefin monomers with its use

The invention relates to the manufacture of catalysts, namely the production of catalysts of the Ziegler-Natta, which can be used for the synthesis of high molecular weight Homo - and copolymers-olefins, α-olefins and polar monomers, rubbers, in particular in the production of polypropylene

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to the catalyst component used in polymerization of olefins comprising Mg, Ti, halogen and at least two electron-donor compounds wherein indicated catalyst component and at least one of electron-donor compounds repenting in the amount in the range from 20 to 50 mole% with respect to the complete amount of donors are chosen from succinic acid esters that are not extractable by above 25 mole% and at least one additional electron-donor compound that is extractable by above 35 mole%. Indicated components of catalyst provides preparing polymers possessing good insolubility level in xylene, high content level of stereoblocks and broad MWD value that is suitable for preparing polymers used in the region using bi-oriented polypropylene films. Also, invention relates to catalyst used in polymerization of olefins, methods for preparing propylene polymers and propylene polymer.

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to components of catalyst used in synthesis of ethylene (co)polymers by using methods of (co)polymerization in the gaseous phase, in suspension or in mass. The prepolymerized catalyst for polymerization of ethylene being optionally in mixtures with olefins of the formula: -CH2=CHR wherein R represents (C1-C12)-alkyl group comprises a non-stereospecific solid component of catalyst comprising Ti, Mg and halogen. A solid component of catalyst is prepolymerized with α-olefin of the formula: -CH2=CHR1 wherein R1 represents (C1-C8)-alkyl group in the presence of alkylaluminum compound in the mole ratio Al/Ti from 0.001 to 50 in such degree that the amount of α-olefin prepolymer is up to 100 g/g of solid component of catalyst. Also, invention describes a method for (co)polymerization of ethylene that is carried out in the presence of the prepolymerized catalyst and alkylaluminum compound. Invention provides preparing polymers of high bulk density and high activity, and decreasing formation of small particles also.

EFFECT: improved and valuable properties of catalyst.

18 cl, 8 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely phenyltrichloromethane PhCCl3. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 4 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

The invention relates to methods for macromolecular higher poly-alpha-olefins, in particular polyacene, and catalysts for carrying out the method

The invention relates to the components of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and at least one 1,3-W, which forms complexes with anhydrous magnesium dichloride in an amount of less than 60 mmol per 100 g of MgCl2and without substitution reactions with TiCl4or reacting in the amount less than 50 mol%, and at least one ester of mono - or polycarboxylic acid, and 1,3-diesters selected from compounds of the formula (II)

where the group RIIIidentical or different, represent hydrogen or C1-C18hydrocarbon group; groups of RIVidentical or different, have the same meaning as RIIIexcept that they cannot be hydrogen; each of the groups RIII- RIVmay contain heteroatoms selected from Halogens, N, O, S and Si, and the radicals RVidentical or different, are selected from the group consisting of hydrogen; Halogens, preferably C1 or F; C1-C20alkyl radicals with a straight or branched chain; C3-C20cycloalkyl,6e radicals Rvcan be connected to each other to form a condensed cyclic structures, saturated or unsaturated, optionally substituted, RVIradicals selected from the group consisting of halogen, preferably C1 or F; C1-C20alkyl radicals, linear or branched; C3-C20cycloalkyl, C6-C20aryl, C7-C20alkalinic and C7-C20Uralkalij radicals; the radicals RVand RVIoptionally contain one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both

The invention relates to a component of a solid catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from substituted succinates formula

The invention relates to a method for producing a catalyst for polymerization of olefins and method of polymerization of olefin monomers with its use

FIELD: polymerization processes and catalysts.

SUBSTANCE: inventors claim organometallic catalytic system for production of elastomer stereoblock polypropylene via polymerization of propylene, which system contains octahedral hexafluorine-substituted bis-acetylacetonate complex of formula (CF3COCHCOCF3)2MCl2, where M represents Ti or Zr, and, as organoaluminum compound, AlR3, where R represents ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl, and; additionally, organomagnesium compound MgR2 or MgRX, where R is alkyl radical with 1-4 carbon atoms and X = Cl, Br, or I, M/Mg/Al molar ratio being 1.0:2.0:(100-500). Claimed is also a method for production of elastomer stereoblock polypropylene via polymerization of propylene in presence of homogenous catalyst system at transition metal complex concentration 10-3-10-5 mole/L.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 22 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention provides catalytic composition prepared from polymerization catalytic system and at least one gelation agent, said gelation agent being selected from group including diester phosphates, steroid and anthryl derivatives, amino acid-type gelation agents, and tetraoctadecylammonium bromide and said polymerization catalytic system being selected from common-type catalytic compounds with transition metal and metallocene catalytic compounds. Invention discloses method of preparing indicated catalytic system and a method of continuous polymerization of an olefinic monomer.

EFFECT: expanded in catalytic polymerization processes.

17 cl, 2 tbl

The invention relates to methods for macromolecular higher poly-alpha-olefins, in particular polyacene, and catalysts for carrying out the method
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