The catalyst or catalyst component for the polymerization or copolymerization of propylene

 

(57) Abstract:

The method of obtaining such and garnisongasse and/or zirconium bearing catalyst component or catalyst on a magnesium-containing media for polymerization or copolymerization of alphaolefins. 19 C.p. f-crystals, 2 tab.

The invention relates to a component of the catalyst or catalyst, which is suitable for use in the reaction stereoregular polymerization or copolymerization of alpha-olefins and particularly relates to a magnesium-containing, titanium containing catalyst component on the substrate or catalyst suitable for receiving homopolymer or copolymer of alpha-olefin.

Although the literature describes many methods of polymerization and copolymerization and the catalytic system used for the polymerization or copolymerization of alpha-olefins, it is desirable to create the components of the catalyst or the catalyst having high catalytic activity in such reactions. It is preferable to develop a method and a catalytic system, which allow to obtain a polymer or copolymer with a specific set of properties. For example, for some applications the desired product with boleh shear rates, than a product with a narrower molecular weight distribution. Many methods of processing of polymers and copolymers, operating high shear rates, for example, injection molding, production oriented fibers, will benefit from using a product with lower viscosity by increasing the speed of processing and reduce power consumption. Thus, it is desirable to develop a catalyst or catalyst component suitable for receiving homopolymer or copolymer of alpha-olefin with a broader molecular weight distribution. It is also important to ensure high activity and a low content of atactic product, measured in soluble in hexane and extracted with hexane fractions formed during the polymerization or copolymerization.

Magnesium-containing components of the catalyst on the substrate on the basis of a halide of titanium or catalytic systems containing these components is well known in the prior art. Typically, these components of the catalyst and catalyst system are evaluated for their activity and stereospecificity. Described numerous ways or stages of processes, aimed at establishing improved Ministers is Efimov. In particular, in U.S. patents NN 4866022, 4988656 and 5013702 disclosed a method of obtaining a particularly preferred catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins, which includes a specific sequence of specific stages of the process leading to the catalyst or catalyst component with exceptionally high activity and stereospecificity in combination with a very good morphology. Described solid insoluble in hydrocarbons, the catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins with excellent activity, stereospecificity and morphological characteristics, which is a product obtained by: 1) obtaining a solution of a magnesium-containing product from hydrocarbonate magnesium or magnesium carboxylate; 2) deposition of solid particles from such magnesium-containing solution by treatment with a halide of the transition metal and organosilicones as agent for regulating morphology; 3) re-deposition of solid particles from a mixture containing cyclic simple ester; and 4) processing of the precipitated particles with a transition metal compound and an electron donor.

In pagnia with carbon dioxide in the environment of alcohol and the reaction hydrocarbonate magnesium transition metal. In U.S. patent 4612299 disclosed a method of producing magnesium carboxylate by reaction of a solution hydrocarbide magnesium with carbon dioxide by precipitation of magnesium carboxylate and its interaction with the transition metal.

While each of the methods described in the aforementioned patents NN 4540679, 4612299, 4866022, 4988656 and 5013702, allows to obtain catalysts or components of catalysts for the polymerization or copolymerization of alpha-olefins having a high activity in the polymerization and copolymerization of alpha-olefins to obtain Homo - and copolymers with desired properties, there is still a need for new catalysts or components of catalysts for the polymerization or copolymerization of olefins and methods for their production, moreover, these catalysts or components of catalysts should possess higher catalytic activity and lead to the production of polymers or copolymers with a broader molecular weight distribution.

For example, in U.S. patent 5227354 described solid insoluble in hydrocarbons, the catalyst or catalyst component and the retrieval method, based on the catalyst or the catalyst components and methods of obtaining them, sauveli component of the catalyst is the product, obtained by:

A) a solution of the magnesium-containing product in a liquid, and magnesium-containing product formed by the reaction of magnesium-containing compound with carbon dioxide or sulfur dioxide;

B) deposition of solid particles from a solution of the magnesium-containing product by treatment with a halide of titanium;

D) processing the precipitated particles with a compound of titanium and an electron donor; and treated precipitated particles with stage D contain magnesium and vanadium and the vanadium is introduced at least (i) one of the above magnesium-containing products on A stage by the interaction of the magnesium-containing compound or product with a vanadium-containing compound or complex; or (ii) above solid particles precipitated on stage B processing of magnesium-containing product of a titanium halide and a vanadium-containing compound or complex; or (iii) the precipitated particles processed at stage B by the connection of titanium, electron donor and vanadium-containing compound or complex, does not contain halide. The catalyst or catalyst component described in the above U.S. patent N 5227354 for polymerization and copolymerization of alpha-olefin lets get the tent is not mentioned on the significant increase in catalytic activity when carrying out polymerization or copolymerization.

In the same U.S. patent N 5084429 described a catalyst for polymerization of olefins containing media, mainly consisting of compounds of magnesium precipitated from the solution, and a catalytic component supported on a carrier selected from the halides of titanium, vanadium halides and vandergalien. The catalyst was prepared by the method comprising: (A) mixing (a) at least one compound of magnesium with (c) saturated or unsaturated monohydroxy or polyhydric alcohol to the reaction dissolved in the presence of (b) carbon dioxide in an inert hydrocarbon solvent to obtain a component (A); (B) mixing the component (A) with (d) a titanium halide and/or vandergalien, and/or a vanadium halide of the General formula VXn(OR8)4-nand (e) at least one boron compound, a silicon compound and/or siloxane with obtaining solid product (I); the interaction of the solid product (I) with (f) a cyclic ether or R12OH, accompanied by dissolution and re-precipitation of the resulting solid product (II), and (D) subsequent interaction of the solid product (II) (g) component (B) consisting of a titanium halide and/or vandergalien, and/or a vanadium halide, eomponents (B) and (h) an electron donor, or is subjected to the reaction (g) with the solid product (III) obtained by the interaction of the solid product (II) b (h) or (h) to (j) an electron donor, thereby forming a solid product (IV), used as a component of the catalyst.

Catalysts for the polymerization of olefins containing other relevant combination of metals, are also described. For example, in U.S. patent N 5082817 disclosed a catalyst for polymerization of olefins, obtained by reaction of the compound of the transition metal, usually titanium, containing at least one bonding metal-halide deposited on a magnesium halide in active form, with a compound of titanium, zirconium, or hafnium containing at least one bonding metal-carbon.

In U.S. patent N 4228263 described a catalyst for polymerization of propylene, which represents the reaction product of metal oxide such as aluminum oxide, titanium oxide, silicon dioxide and magnesium oxide, or their physical mixtures and ORGANOMETALLIC compounds of zirconium, titanium or hafnium.

In addition, the morphology of the polymer or copolymer is often critical and depends on the morphology of the catalyst. Good morphology of the polymer is usually characterized by a homogeneous size and particle shape, narrow distribution of the Ni fine particles usually is of great importance to avoid driving transmission lines components, or return to the cycle. Therefore, it is desirable creation of catalysts and catalyst components for the polymerization and copolymerization of alpha-olefins having a good morphology and, particularly, a narrow distribution of particle size.

Another important property is the relatively high bulk density.

The purpose of the invention to provide an improved catalyst or catalyst component for the polymerization or copolymerization of alpha-olefin, leading to the polymer or copolymer with improved properties, as well as creating a method of producing such a catalyst or catalyst component.

In particular, the purpose of this invention is to provide such a catalyst or catalyst component for the polymerization or copolymerization of alpha-olefin, which ensures the formation of a polymer or copolymer of alpha-olefin with a wide molecular weight distribution.

Another purpose of this invention is to provide a catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins with high activity in the reaction of polymers or copolymers of alpha-olefins.

Other objectives and advantages anannya goals are achieved by creating a solid insoluble in the hydrocarbon catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins, which is a product obtained by:

A) preparation of a solution of magnesium-containing product in a liquid, and magnesium-containing product obtained by the interaction of the magnesium-containing compound with carbon dioxide or sulfur dioxide;

B) deposition of solid particles from a solution of the magnesium-containing product by treatment with a compound or complex of titanium; and

D) processing the precipitated particles with a compound of titanium and an electron donor; and treated precipitated particles from step (D) include magnesium-containing component, at least one hafnium - or zirconium bearing component and at least one of the elements: hafnium or zirconium is introduced into at least one product chosen from (i) the said magnesium-containing product of stage A by the reaction of magnesium-containing compound or product with carbon dioxide or sulfur and at least one component from the group comprising hafnium - or zirconium bearing compound or complex, or (ii) of the said solids, besieged at stage B by treating the magnesium-containing product compound or complex of titanium and at least one hafnium - or zirconium bearing compound or complex; or (iii) ukazom compound or complex of hafnium or zirconium.

These objectives of the invention are also achieved by the method according to this invention, including the above stage (A), (B) and (D), to obtain the above-mentioned catalyst or catalyst component.

A detailed description of the preferred variants of the invention.

Solid insoluble in hydrocarbons, the catalyst or catalyst component stereoregular polymerization or copolymerization of alpha - olefins according to the invention is a product obtained by the method according to this invention, which includes a step (A) preparation of a solution of magnesium-containing product in a liquid, and magnesium-containing product is formed by the interaction of magnesium-containing compound with carbon dioxide or sulfur dioxide. Magnesium-containing compound, which is formed of magnesium-containing product is a magnesium alcoholate, hydrocarbonaceous magnesium or hydrocarbon magnesium. When using carbon dioxide, magnesium-containing product is hydrocarbonbased or magnesium carboxylate. When using sulfur dioxide, the resulting magnesium-containing product is hydrocarbonsthat(ROSO2- or hydrocarboncontaining (RSO2-). Pisi carbon.

In the case of the use of magnesium alcoholate formed of magnesium-containing product is hidrocarbonetos magnesium. Usually hydrocarbonbased magnesium can be obtained by the reaction of carbon dioxide with magnesium alcoholate. For example, hydrocarbonbased magnesium can be obtained by suspendirovanie ethoxide magnesium in ethanol, adding carbon dioxide to until atoxic magnesium dissolves with the formation of ethylcarbonate magnesium. If, however, atoxic magnesium suspended in 2-ethyl-hexanol, is formed at least one of the compounds selected from the group comprising 2-ethylhexylcarbonate magnesium, ethylcarbonate magnesium and ethyl/2-ethylhexylcarbonate magnesium. If atoxic magnesium suspended in a liquid hydrocarbon or helodermatidae that does not contain alcohol, the addition of carbon dioxide leads to the destruction of particles ethoxide magnesium, and the reaction product is hydrocarbonbased magnesium is not soluble. The reaction of the magnesium alcoholate with CO2can be represented as follows:

Mg(OR)2+ nCO2_ Mg(OR)2-n(-OC-OR)n,

where n is an integer or fractional to 2 and R - hydrocarbon C1-C20. In addition, you can use the magnesium alcoholate containing two different hydroalcoholic magnesium formula Mg(OR')2where R' has the values listed above. From the viewpoint of catalytic activity and stereospecificity the best results are achieved when using magnesium alcoholate of the formula Mg(OR')2where R' is alkyl-C1- C8, aryl-C6-C12or alkaryl or aralkyl-C7-C12. The best results are obtained when using ethoxide magnesium.

Specific examples of the magnesium alcoholate used according to the invention include: Mg(OCH3)2, Mg(OC2H5)2, Mg(OC4H9)2, Mg(OC6H5)2, Mg(OC6H13)2, Mg(OC9H19)2, Mg(OC10H7)2, Mg(OC12H9)2, Mg(OC12H25)2, Mg(OC16H33)2,

Mg(OC18H37)2, Mg(OC20H41)2, Mg(OCH3)(OC2H5), Mg(OCH3)(OC6H13), Mg(OC2H5)(OC8H17), Mg(OC6H13)(OC20H41), Mg(OC3H7)(OC10H7), Mg(OC2H4Cl)2and Mg(OC16H33)(OC18H37). You can also apply a mixture of magnesium alcoholate, if this is desirable.

Suitable hydrocarbonaceous magnesium has the formula MgR(OR') where R and R' ookii between hydrocellulose magnesium and carbon dioxide used alcohol, hydrocarbonaceous magnesium is the functional equivalent of a magnesium alcoholate, because hydrocarbonaceous magnesium is converted into magnesium alcoholate in alcohol. On the other hand, when the suspension medium contains no alcohol, hydrocarbonaceous magnesium reacts with carbon dioxide as follows:

R-Mg-(OR)+2CO2_ R-C-O-Mg-O-C-OR.

In this case, RC-O-Mg-O-C-OR' is formed of magnesium-containing product.

When the connection of the magnesium forms a magnesium-containing product is hydrocarbon magnesium formula XMgR, where X is halogen and R - hydrocarbon-C1-C20the reaction hydrocarbide magnesium with carbon dioxide leads to the formation of the magnesium carboxylate and may be represented as follows:

X-MgR+CO2_ X-MgOC-R.

If hydrocarbon magnesium contains two gidrolabilna group, the reaction can be represented as follows:

MgR2+2CO2_ Mg(OC-R)2where R is specified for the X-MgR.

Gidrolabilna the magnesium compounds used according to this invention have the structure R-Mg-Q, where Q is hydrogen, halogen or R' (each R' is independently represents hydrocarbon-C1-C20). Specific examples hydrocarbon magnesium, prigoda)2, Mg(C6H5)2, Mg(C6H13)2, Mg(C9H19)2,

Mg(C10H7)2, Mg(C12H9)2, Mg(C12H25)2, Mg(C16H33)2, Mg(C20H41)2, Mg(CH3)(C2H5), Mg(CH3)(C6H13), Mg(C2H5)(C8H17), Mg(C6H13)(C20H41)

Mg(C3H7)(C10H7), Mg(C2H4Cl)2and Mg(C16H33)(C18H37), Mg(C2H5)(H),

Mg(C2H5)(Cl), Mg(C2H5)(Br), and so on, If this is desirable, it is also possible to use mixtures hydrocarbonrich of magnesium compounds. From the point of view of cost and availability dihydrocarvone compounds of magnesium, preferred for use according to this invention, are compounds of the formula MgR2where R is listed above. From the viewpoint of catalytic activity and stereospecificity, the best results are achieved when using halides hydrocarbide magnesium formula MgR'Q', where R' is alkyl-C1-C18, aryl-C6- C12or alkaryl or aralkyl-C7-C12and Q' is chloride or bromide.

Preferably as magnesium-containing compound is arbonet magnesium. For example, you can use the magnesium alcoholate, which is obtained by reaction shavings of magnesium metal with a low molecular weight alcohol, such as methanol, ethanol or 1-propanol, without a catalyst or in the presence of a catalyst, such as iodine or carbon tetrachloride, with the formation of solid magnesium alcoholate. The excess alcohol is removed by filtration, evaporation or decantation.

As diluents or solvents suitable for carbonation of magnesium compounds with the formation of the magnesium-containing product, use alcohols of C1-C12, non-polar hydrocarbons and their galoidoproizvodnykh, ethers, or their mixtures, which are virtually inert to the reactants and preferably are liquid at the temperature at which they are used. The reaction is carried out at an elevated pressure so that even at higher temperatures it was possible to use low-boiling solvents and thinners. Examples of suitable solvents and diluents include alcohols, such as methanol, ethanol, 1 - or 2-propanol, tributyl alcohol, benzyl alcohol, amyl alcohol, 2-ethylhexanol and branched alcohols containing 9 or 10 carbon atoms; alkanes, measures, 1,1,2-trichloroethane, carbon tetrachloride, etc. W aromatic hydrocarbons, such as xylenes and ethylbenzene; and halogenated and hydrogenated aromatics, such as chlorobenzene, o-dichlorobenzene, tetrahydronaphthalene and decahydronaphthalene.

In more detail the process of obtaining magnesium-containing product is dissolved or suspendirovanie magnesium-containing compound in the liquid. Use 10-80 wt. including magnesium-containing compound per 100 wt. including liquid. A sufficient amount of carbon dioxide is passed into the liquid suspension at a rate of 0.1-4 M of carbon dioxide per 1 M magnesium compounds with moderate stirring. To the solution or suspension of magnesium-containing compound under stirring at 0-100oC for 10 min - 24 h add 0.3 to 4 M CO2.

Regardless of the above magnesium-containing compounds used to obtain a magnesium-containing product at the stage B of the solid particles precipitated from the solution above magnesium-containing product by treating a solution of compound or complex of titanium and, preferably, in a mixture with an agent that regulates the morphology. As a compound or complex of titanium preferably icolorfolder, particularly suitable for this purpose are organosilane formula where n = 0-4 and R is hydrogen, alkyl, alkoxy, haloalkyl or aryl containing 1-10 C atoms, or halodrol or haloalkylthio containing 1 to 8 C atoms and R'- or, or halogen. Usually R is alkyl or chloroalkyl containing 1 to 8 C atoms and 1 to 4 chlorine atom and R' is chlorine or or containing 1-4 atoms C. Suitable organosilane may contain different R'. You can use a mixture of organosilanes. Preferred organosilane include trimethylchlorosilane, trimethylaluminium, clear, tetraethoxysilane or hexamethyldisiloxane.

The agent controlling the morphology can also be o-, m - or p - diallylphthalate or o-, m - or p-alkylarylsulfonates. Alkali in diallylphthalate may be the same or different and each contains from 1-10, preferably up to 4, carbon atoms.

It is preferable to use o-diallylphthalate, especially o - dibutyl, most preferably o-di-n-butylphthalate or di isobutylphthalate. Other suitable diallylphthalate include DirectInput and dioctylphthalate. In a suitable alkylarylsulfonate alkali contain 1-10, preferably up to 6, C atoms and aralkyl contain 7-10, preferably up to 8 atoms C. Suitably The N 4946816 describe the use of aromatic compounds with 8-10 C atoms in the solvent at any stage NN 1)-3) in the aforementioned U.S. patents NN 4866022, 4540679 and 4612299, at any time before adding a simple ether in stage 3) to control the morphology of the obtained particles of the final product - catalyst or catalyst component.

Specific aromatic compounds with 8-10 C atoms, are suitable as agents regulating the morphology include o-xylene, m-xylene, p-xylene, a mixture of xylenes, ethylbenzene, naphthalene, cumene, pseudocolor, methylethylbenzene, tetrahydronaphthalen and diethylbenzene. Preferred are ethyl benzene, ortho-xylene, meta-xylene, paraxylene and naphthalene. The most preferred is naphthalene. Preferably C8-C10-aromatic compounds in stage B of their invention, although such aromatic compounds can also enter on the stage of A method according to this invention or stage C, discussed below, before adding the cyclic simple ether. Usually with a solvent for the regulation of desirable changes in the morphology of the injected 1000-20000 wt.h. or 0.1-2 wt.% such C8-C10-aromatic compounds per million parts of the total quantity present materials. It is preferable to use 2000-10000 hours per million of such C8-C10-aromatic compounds. If watchescase connection.

Particles deposited on the stage In process stage D compound of titanium and an electron donor. Compounds of titanium (IV) used in stage D, are the halides of titanium and haloalcohols containing 1-20 C atoms on alcoholate group, for example, methoxy, ethoxy, butoxy, hexose, phenoxy, decoke, naphthoxy, dodecane, acetoxy. You can use, if so desired, mixtures of titanium compounds. The preferred titanium compounds are the halides and haloalcohols containing 1-8 C atoms in alcoholate group. Examples of such compounds are: TiCl4, TiBr4, Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OC4H9)Cl3, Ti(OC6H5)Cl3, Ti(OC6H13)Br3, Ti(OC8H17)Cl3, Ti(OCH3)2Br2, Ti(OC2H5)2Cl2, Ti(OC6H13)2Cl2,

Ti(OC8H17)Br2, Ti(OCH3)3Br, Ti(OC2H5)3Cl, Ti(OC4H9)3Cl, Ti(OC6H13)3Br and Ti(OC8H17)3Cl. From the point of view of maximum activity and stereospecificity preferred tetrachloride titanium, especially TiCl4.

Organic donors to elizabethany, are organic acids, anhydrides of organic acids, esters of organic acids, alcohols, ethers, aldehydes, ketones, amines, oxides, amines, amides, thiols, various esters and amides of phosphoric acid, etc. If desired, you can apply a mixture of organic electron donor.

Specific examples of suitable oxygen-containing electron donor include organic acids and esters used as modifiers, aliphatic alcohols, e.g. methanol, ethanol, propanol, bugenyi, pentanol, hexanol and so on, aliphatic diols and triodes, for example, ethylene glycol, PROPANEDIOL, glycerin, butanediol, butanetriol, pentandiol, potentialy, hexandiol, hexanetriol etc., aromatic alcohols, for example, phenol, di-, tri - and tetrahydrobenzene, Naftali and dihydroxynaphthalene, Arakelova alcohols, for example, benzyl, phenylethanol, phenylpropanol, phenylbutazone, phenylpentane, phenylhexanoic and so on; algarroba alcohols, for example, Cresols, xileno, ethylphenol, propilenru, butylphenol, pentylphenol, sexyfemale and so on; dialkyl ethers, e.g. dimethyl, diethyl, metaliteracy, dipropylamine, dibutylamine, daintily, dihexyl injuly esters and lexically ether; algarroba ethers, such as anisole, phenetol, propylpiperonyl ether, BUTYLPEROXY ether, interfamily ether, hexylphenyl ether and so on; kelvinjay and arielly esters, for example, phenyleneoxy and finallllly esters; dearlove esters, for example, diphenyl and cyclic ethers, such as dioxane, trioxane.

Specific examples of other suitable oxygen-containing organic electron donors include aldehydes, such as formaldehyde, acetaldehyde, Propionaldehyde, Butyraldehyde, valeraldehyde, capronaldehyde and so on, Benzylalcohol, tolualdehyde and alpha tolualdehyde; and ketones, such as acetone, diethylketone, methyl ethyl ketone, DIPROPYLENE, dibutyltin, dipentylester, digoxigenin and so on, cyclobutanone, Cyclopentanone and cyclohexanone, acetophenone, propiophenone, butyrophenone, valerophenone, capriano, etc., and benzophenone.

Specific examples of suitable nitrogen-containing organic electron donors include triticeae amines in which at least one of the groups linked to the nitrogen atom contains at least two carbon atoms, for example, dimethylethylamine, methyldiethylamine, N,N'-tetramethyl-Ethylenediamine, triethylamine, tri-n-butylamine, dimethyl-n-hexylene is arylamino)benzenes, etc.,; saturated heterocyclic amines and their derivatives, for example, pyrrolidine, piperidine, 2-methylpyrrolidine, 2 - methylpiperidin, 2,5-dimethylpyrrole, 2,6-dimethylpiperidin, 2,4,6-trimethylpyridine, 2,2,6,6-tetramethylpiperidine and etc.; unsaturated heterocyclic amines and their derivatives, for example, pyridine, pyrimidine, pikolines, lutidine, collidine, ethylpyridine, diethylpyrazine, triethyleneamine, benzylpyridine, methylpyrimidine, ethylpyrimidine, benzylpyrimidines etc.

Examples of serosoderjaschei organic electron donors include thiols such as methanethiol, ethanthiol, acondition, propandiol, potentially, butandiol, hexandiol etc., thioethers, for example, ethylthioethyl, ethylthio-n-butane, etc.; and other toanalog the above-described oxygen-containing organic electron donor.

Specific examples of suitable phosphorus-containing organic electron donors include phosphorus-containing analogues of the above-described nitrogen-containing organic electron donors, for example, triethylphosphine, ethyldimethylamine, triphenylphosphine, etc.,

Examples of suitable organic electron donor containing two or more atoms selected from the group comprising oxygen, and the measures ethanolamine, hydroxyanisole, aminotriazole etc.; aminoacid, for example, lutidine-N-oxide and kallidin-N-oxide; amino esters, for example, bis-(2-ethoxyethyl)amine; timeslot, for example, teoksessa acid, Tomislava acid, towleroad acid, diamentina acid, etc.; organosulfate, for example, methanesulfonate, econsultation, phenylsulfonyl and so on; various derivatives of phosphoric acid, for example, trimethylphosphite, tri-n-propylphosphine, triphenylphosphite, three(ethylthio)FOSFA, triamide HEXAMETHYL-phosphoric acid and so on; and phosphine oxide, for example, oxide trimethylphosphine, triphenylphosphine oxide, etc.

From the point of view of the behavior of the catalyst and technological characteristics of the electron donors which are preferred according to this invention include C1-C6-alkalemia esters of aromatic carboxylic acids and halogen-, hydroxyl-, oxoalkyl, alkoxy - and/or arylacetamides aromatic monocarboxylic acids. Among them, particularly preferred alkalemia esters of benzoic, halogenating, phthalic, terephthalic and isophthalic acids, where alkyl contains 1 to 6 carbon atoms, for example, methylbenzoate, methylpropanoate, ethylbenzoic, achillobator, ethylbromoacetate when using diesters.

The electron donor, preferably is o-, m - or p-diallylphthalate or o-, m - or p-alkylarylsulfonate. Alkali in diallylphthalate may be the same or different and each contains from 1 to 10, preferably up to 4, atoms C. it is Preferable to use about di alkylphenate, especially di-n-butylphthalate or di isobutylphthalate. Other suitable diallylphthalate are DirectInput and dioctylphthalate. In a suitable alkylarylsulfonate alkali contain 1-10, preferably up to 6, C atoms and aralkyl contain from 7 to 10, preferably up to 8, atoms C. Preferably use o-alkylarylsulfonate. Suitable alkylarylsulfonate include benzyl-n-butylphthalate and benzenesulfonate.

At stage D (stage activation) particles formed at the stage B, the titanium halide and the organic electron donor react at temperatures of from -10oC to 170oC, usually during the period of time from several minutes to several hours and contact in quantities which provide an atomic ratio of titanium to magnesium in the particles (calculated for magnesium in the magnesium compound, which is formed of magnesium-containing product), equal at least to 0.5:1. Preferably, this ratio stipulated in the catalyst component, but it is usually not necessary to exceed the ratio of titanium to magnesium equal to 20:1, because only a part of titanium attached to the product pre-treatment at the time of its receipt. It is more preferable to set the ratio of titanium to magnesium in the range of from 2: 1 to 15:1 to ensure a sufficient amount of titanium in the catalyst that leads to a good activity for economical usage of titanium in the process of preparation of the catalyst. The electron donor is used in an amount of from 1.0 mol to g-a titanium compound titanium, preferably, from 0.001 to 0.6 mol/g-titanium compound titanium. The best results are achieved when this ratio is 0.01 to 0.3 mol/g-titanium.

Preferably, the electron donor and a compound of titanium in contact with the deposited solid particles in the presence of an inert hydrocarbon or haloesters compounds as the diluent, although you can use other methods. Suitable diluents are those compounds indicated above as diluents for stages A, B, or C (described below) and which are virtually inert to the components used and are liquid at temperatures used or which can be maintained in W is of podstawy, where to podstawy D-1 particles from step B is treated with titanium tetrachloride and then on podstawy D-2 - titanium tetrachloride in the presence of a mixture of the above first and second electron donor.

More preferably, the additional processing includes a substage, MIS D-3 with application of liquid aromatic hydrocarbon, e.g. toluene, and subsequent substage, MIS-D-4 - treatment with titanium tetrachloride. In some cases, to obtain a solid component of catalyst with the highest activity when carrying out polymerization or copolymerization of alpha-olefins, especially propylene, substage, MIS D-3 is repeated as substage, MIS D-3 before podstawy D-4.

According to a preferred variant of the present invention prior to stage D of the particles deposited at the stage B, presidida additional stage C from a solution containing a cyclic simple ether, and then pereosazhdeniya particles are processed at stage D, the compound of the transition metal and the electron donor. According to the usual procedure resultant deposition rates (stage C) particles precipitated at the stage B, fully solubilized in solvent - cyclic simple ether and then the particles give periostitis with particle formation Odinak the walking cyclic ethers, for example, tetrahydropyran and 2-methyltetrahydrofuran to solubilize the particles at the stage of B. you Can also use the thioethers, for example, tetrahydrothiophene. In some cases, for example, using of 2.2.5.5-tetramethyl-tetrahydrofuran and tetrahydropyran-2-methanol, when heated to 130-185oF (54,4 - 85oC) occurs pereosazhdeniya. Can also be used other compounds acting in the same way, i.e., those that can solubilisate particles generated at the stage B, and from which they can parasagitta solid homogeneous particles, for example, oxide, cyclohexane, cyclohexanone, ethyl acetate and phenyl acetate. You can use a mixture of these compounds.

The diluent, which can be used at any of these stages A, B or D or at the stage C of the resultant deposition rates should be substantially inert to the reactants and preferably be liquid at process temperatures. It is preferable to carry out a specific phase at elevated pressure, to apply the solvent with low boiling points even at higher temperatures. Suitable diluents are aromatic liquid connection, although you can use other liquid coal and substituted aromatic compounds. A particularly suitable solvent is a halogenated aromatic compound, for example, chlorobenzene, or a mixture of halogenated aromatic hydrocarbons, such as chlorobenzene, halogenated aliphatic compounds, such as dichloroethane. Suitable are also high-boiling aliphatic liquids, such as kerosene. You can apply a mixture of diluents. One of the suitable components of the solvent is Isopar Gwhich isoparaffin C10(average)-hydrocarbon, boiling at 156-176oC.

Other examples include alkanes, e.g. hexane, cyclohexane, methylcyclohexane, heptane, octane, Nanan, decane, undecane, etc., haloalkane, for example, 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride, etc., aromatic hydrocarbons such as benzene, toluene, xylenes and ethylbenzene, and halogenated and hydrogenated aromatics, such as chlorobenzene and o - dichlorobenzene.

Each of these stages A, B and D, and phase C of the resultant deposition rates spend almost in the absence of water, oxygen, carbon monoxide and other impurities that can adversely affect the behavior of the catalyst or catalyst component is under inert gas, for example, nitrogen or argon, or other suitable means. In addition, the entire process or part of it can be done in the presence of one or more alpha-olefins, which, when entered in the source system in gaseous form, can serve to eliminate poisons for the catalyst. The presence of one or more alpha-olefins may also lead to improved stereospecificity. Suitable alpha-olefins include ethylene, propylene, butene-1, penten-1, 4-methylpentene-1, hexene-1, and mixtures thereof. Of course, any applicable alpha-olefin must be relatively high purity, for example, the brand going for polymerization, or even cleaner. Other techniques that help to exclude the presence of other poisons include cleaning of any solvent to be used, for example, the percolation through molecular sieves and/or silica gel, to its use and drying and/or cleaning of other reagents.

In the result of the above process stage D get a solid reaction product suitable for use as catalyst or catalyst component. To such use it is desirable to remove incompletely reacted starting materials of the solid product Rea is zbawiciela, suitable solvent, such as a liquid hydrocarbon or chloropetalum, preferably within a short period of time after the completion of the process of obtaining, as prolonged contact between a component of the catalyst and unreacted source substances may adversely affect the characteristics of the catalyst.

In the solid component of catalyst according to this invention obtained by the method of the present invention, the atomic ratio of magnesium to titanium is at least 0,3: 1 and preferably from 0.4:1 to 20:1 and, more preferably, from 0.5:1 to 3:1. The atomic ratio of silicon to titanium can typically vary from 0.1:1 to 2, 0:1, preferably is 0.3:1-1:1.

The catalyst or catalyst component in this invention contains at least one carriageway component or zirconium bearing component. In the method according to this invention the treated precipitated particles with stage D contain at least one hafnium - or zirconium bearing component, as well as magnesium and titanium containing components.

At least one of the components of: hafnium or zirconium is introduced into at least one product selected from: (i) a magnesium-containing is it hafnium - or zirconium bearing compound or complex, or (ii) above solid particles deposited at the stage B, by treating the magnesium-containing product compound or complex of titanium and at least one hafnium - or zirconium bearing compound or complex, or (iii) above precipitated particles treated at a stage D by treatment of a compound of titanium, an electron donor and at least one hafnium - or zirconium bearing compound or complex.

In the solid component of catalyst obtained by the method according to this invention, the atomic ratio of magnesium to hafnium, in the calculation of basic metals is in the range from 2, 5:1, preferably from 15:1 to 1000:1, preferably up to 35:1 and the atomic ratio of titanium to hafnium, in the calculation of basic metals is in the range from 0.05:1, preferably from 1: 1 to 100:1, preferably 10:1. The atomic ratio of magnesium to zirconium, based on the elemental metal, is in the range from 20:1, preferably from 64:1 to 925:1, preferably up to 563:1 and the atomic ratio of titanium to zirconium in the calculation of the elemental metal, is from 2:1, preferably from 8:1 to 130:1, preferably up to 70:1.

Carriageways compound or complex that is used on stageat tetrachloride or hafnium dichloride garretsen. Usually suitable carriageway compounds and complexes include complexes of hafnium (IV), in which the hafnium is attached to the carbon atom or the oxygen atom of the ligand, for example, a complex of hafnium tetrachloride with a simple ester or ether complex-ligand, or not containing halogen complexes of hafnium with alcoholate, -diketonates, oxalates, acetates, benzoate, phthalates and hafnium complexes with ligands derived from cyclopentadienyl, for example, indenolol, fluorenyl etc.

As zirconium bearing compound or complex used in stages A, B and D, it is preferable to use zirconium halide, especially tetravalent zirconium or dihalogenide of zirconocene. Usually can be used tetrachloride zirconium dichloride zirconocene or zirconium acetylacetonate. Usually, the appropriate circumistances compounds and complexes include complexes of zirconium, in which the zirconium is attached to the carbon atom or the oxygen ligand, for example, not containing halogen complexes of zirconium alcoholate with-diketonates, oxalates, acetates, benzoate, phthalates, and complexes of zirconium with ligands derived from cyclopentadienyl, for example, indenolol, fluorenyl, etc. According to the nature of the stages A, B and D, is introduced into the above-mentioned magnesium-containing product at the stage by reacting A magnesium-containing compound or product with carriageways compound or complex and carbon dioxide. Alternatively, at least a portion of the total quantity of hafnium entered on at least one of the stages A, B and D, is introduced into the above-mentioned solid particles deposited at the stage B, by treating the magnesium-containing product compound of hafnium or hafnium complex. According to the most preferred version of this invention the solid particles deposited at the stage B, are processed at stage D carriageways compound or complex. Most preferably, the entire quantity of hafnium injected at stage D.

According to a preferred variant, at least a portion (preferably, the entire quantity) quantity of zirconium entered on at least one of the stages A, B and D, is introduced or at stage B by treating the magnesium-containing product compound of titanium or zirconium bearing compound or complex, most preferably, dihalogenide zirconocenes, or at the stage D by treating the precipitated particles with a compound of titanium, an electron donor and tetragonites additionally contained vanadium-containing component. Vanadium is introduced into at least one of the following products: (i) the above magnesium-containing product at the stage by reacting A magnesium-containing compound or product with a vanadium-containing compound or complex, or (ii) the above-mentioned solid particles deposited at the stage B, by treating the magnesium-containing product compound or complex of titanium and vanadium-containing compound or complex, or (iii) above precipitated particles treated at a stage D compound of titanium, electron donor and vanadium-containing compound or complex that does not contain halogen.

Despite the addition of vanadium described in this paragraph, hafnium and/or zirconium is injected as described above.

In the preferred solid component of catalyst obtained by the method according to this invention, the atomic ratio of magnesium to vanadium in the calculation of basic metals is in the range from 2.5:1, preferably from 11:1 to 75: 1, preferably up to 65:1 and the atomic ratio of titanium to vanadium in the calculation of basic metals is in the range from 0.05:1, preferably from 1:1 to 10:1, preferably up to 8:1.

Vanadium-containing compound or complex which is at the stage B, preferably, the halide is vanadium (III) or (IV), especially trichloride or vanadium tetrachloride. You can usually use the vanadium tetrachloride, trichloride vanadium solutions trichloride vanadium in tetrahydrofuran or dichloromethane, vanadium acetylacetonate and dicyclopentadienyl vanadium. In General, suitable vanadium compounds and complexes include complexes of vanadium (III) or (IV), in which the vanadium is attached to the carbon atom or oxygen ligand, for example, a complex of trichloride or vanadium tetrachloride with ester ligand or ligand on the basis of simple ester not containing halogen complexes of vanadium, which is used solely as a means for the introduction of vanadium component at the stage D with, for example, alcoholate, -diketonates, oxalates, acetates, benzoate, phthalates, and complexes of vanadium with ligands based on derivatives of cyclopentadienyl, for example, indenyl, fluorenyl etc.

Carriageway, circumistances components, and, optionally, the vanadium component can be entered on the same stages A, B, or D, or each of the above-mentioned metals may be introduced at various stages. Preferably, the hafnium is introduced at stage D, Tsaritsa at stage D, the target application of the catalyst or catalyst component for the polymerization or copolymerization of alpha-olefin allows to obtain a polymer or copolymer with a broader molecular weight distribution.

When metal is introduced only hafnium and its introduction is carried out in stage A or B or stage A or B, and at stage D, the resulting catalyst or catalyst component has a high activity in the polymerization or copolymerization of alpha-olefins, but the resulting polymer or copolymer is not characterized by a broader molecular weight distribution. If hafnium is introduced only at the stage D, and vanadium or zirconium - stage A or B, using the resulting catalyst or catalyst component in the polymerization or copolymerization of alpha-olefin leads to the formation of the polymer or copolymer with a broader molecular weight distribution, and only when the vanadium and/or zirconium is introduced in the form of inorganic compounds or complex, the resulting catalyst or catalyst component has a high activity in the polymerization or copolymerization of alpha-olefin.

Before use of the catalyst and is merisalu and encapsulation of the catalyst or catalyst component. In General, it is very preferable to terpolymerization before applying the catalyst or catalyst component for the polymerization and copolymerization. When the polymerization catalyst or catalyst component according to the invention is preferably involved in terpolymerization alpha-olefin to use them as a catalyst or catalyst component for the polymerization or copolymerization of alpha-olefin. If terpolymerization the catalyst or catalyst component and socialization-alyuminiiorganicheskikh connection, for example, triethylamine, in contact with an alpha olefin, such as propylene, the polymerization conditions, preferably in the presence of a modifier, for example, silane and an inert hydrocarbon, such as hexane. Usually the weight ratio of polymer/catalyst or catalyst component in the formed prepolymer is from 0.1:1 to 20:1. If terpolymerization around the catalyst particles or catalyst component is formed shell of the polymer, which in many cases improves the morphology of the particles, activity, stereospecificity and abrasion resistance. A particularly suitable method of terpolymerization described in U.S. patent N 4579836, which is listed as references in the report on posttotalitarian, includes metal alkyl II or group III and, usually, one or more modifiers. Suitable alkilani metals II and IIIA groups are compounds of the formula MRmwhere M is the metal II or IIIA group, each R, independently, is an alkyl containing 1-20 carbon atoms and m corresponds to the valence of M. Examples of the metal M is magnesium, calcium, zinc, cadmium, aluminum, and gallium. Examples of suitable Akilov R are methyl, ethyl, butyl, Ixil, decyl, tetradecyl and eicosyl. From the point of view of the characteristics of a component of the catalyst is preferred as Akilov metals II and IIIA group alkali magnesium, zinc and aluminum, in which the alkyl radicals contain from 1 to 12 carbon atoms. Specific examples of such compounds include Mg(CH3)2, Mg(C2H5)2, Mg(C2H5)(C4H9), Mg(C4H9)2, Mg(C6H13)2, Mg(C12H25)2, Zn(CH3)2,

Zn(C2H5)2, Zn(C4H9)2, Zn(C4H9)(C8H17), Zn(C6H13)2, Zn(C6H13)3and Al(C12H25)3. It is more preferable to apply alkali magnesium, zinc or aluminum containing 1-6 carbon atoms in the strong radical, and especially triethylaluminum and triisobutylaluminum or mixtures thereof. If you prefer, you can use alkali metals containing one or more atoms of halogen or hydride groups, for example, ethylaminoethanol, diethylaluminium, diethylaluminium, diisobutylaluminium etc.

Typical catalytic system for the polymerization or copolymerization of alpha-olefins is obtained by combination of titanium containing catalyst or catalyst component on the carrier according to this invention and alkyl aluminum in combination with at least one acetalization or modifier, usually an electron donor, preferably a silane. Typically, in this catalytic system, the atomic ratio of aluminum : titanium equal 10-500, preferably 30-300. The molar ratio of aluminum : electron donor in these catalytic systems is 2:60. A typical molar ratio of aluminum : silane equal 3-50.

To optimize activity and stereospecificity such a system is preferable to use one or more modifiers, usually of electron donors, including silanes, mineral acids, ORGANOMETALLIC chalcogenide derivatives of hydrogen sulfide, organic acids, modifiers said system, are organic compounds containing oxygen, silicon, nitrogen, sulfur and/or phosphorus. Such compounds include organic acids, their anhydrides and esters, alcohols, ethers, aldehydes, ketones, silanes, amines, aminoacid, amides, tealy, various esters and amides of phosphoric acid, etc. Can also use a mixture of organic electron donor.

Specific organic acids and their esters are benzoic acid, haloidbenzenes acid, phthalic acid, isophthalic Piletilevi and their alkalemia esters, where the alkyl contains 1 to 6 C atoms, for example, methylcarbonate, butylbenzoate, isobutylbenzene, methylenethf, ationist, methyl-p-toluate, hexylbenzoate, cyclohexylbenzene and Diisobutyl-phthalate, as they give good results by activity and stereospecificity and convenient to use.

Mentioned catalytic system with socialization preferably contains aliphatic or aromatic silane as a modifier. The preferred silanes are alkyl, aryl and/or alkoxy-substituted silanes containing hydrocarbon fragments from 1-20 atoms C. Particularly preferred silanes of the formula SiY4where all groups Y-tinctorially aliphatic silanes include isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisobutyldimethoxysilane, diphenylmethylsilane, ditretbutilfenol and tributyltinoxide.

The catalyst or catalyst component in this invention is used in the process stereospecific polymerization or copolymerization of alpha-olefins containing 3 or more carbon atoms, for example, propylene, butene-1, pentene-1,4-methylpentene-1 and hexene-1, and mixtures thereof or mixtures thereof with ethylene. The catalyst or catalyst component in this invention is particularly effective in stereospecific polymerization or copolymerization of propylene or mixtures thereof with ethylene or higher alpha-olefin in an amount up to 20 mol.%. According to the invention vysokobaricheskie polyalpha-olefins or copolymers obtained when contacting at least one alpha-olefin with the above-described catalyst or catalyst component in this invention under the conditions of polymerization or copolymerization. These conditions include the temperature and time of polymerization or copolymerization, the pressure of the monomer(s), to avoid contamination of the catalyst, the choice of medium for the polymerization or copolymerization, the use of additives to regulate malevolous methods of polymerization or copolymerization in suspension, in the mass or in the gas phase.

The amount of catalyst or catalyst component in this invention depends on the choice of the method of polymerization or copolymerization, the size of the reactor, the source of the monomer(s) and other factors well known to the specialist, and can be determined on the basis of the following examples. Typically, the catalyst or catalyst component is used in an amount of from 0.2 to 0.02 mg/g of the polymer or copolymer formed during the reaction.

Regardless of the method of polymerization or copolymerization, the polymerization or copolymerization should be carried out at temperatures sufficiently high to ensure an acceptable rate of polymerization or copolymerization and reduce residence time in the reactor, but not so high as to lead to inappropriately high levels stereomotion products due to too high speed of polymerization or copolymerization. Usually temperatures are in the range from 0 to 120oC, preferably from 20 to 95oC, from the viewpoint of obtaining good properties of the catalyst and high outputs. It is more preferable to carry out the polymerization at temperatures of from 50 to 80oC.

x monomer of about atmospheric or above. Typically, the pressure of the monomer ranges from 20 to 600 F./inch2(137,9-4136,8 kPa), although in the gas phase pressure of the monomer should not be lower than the vapour pressure at the temperature of polymerization or copolymerization of alpha-olefin, which need to depolimerizuet.

The polymerization or copolymerization is typically from 30 min to several hours during polymerization in mass at the corresponding average time of stay in the reactor of a continuous action. For reactions in the autoclave, the polymerization or copolymerization is from 1 to 4 h In suspension environments, the polymerization or copolymerization can be adjusted as desired. Usually in continuous suspension process for the polymerization or copolymerization varies from 30 min to several hours.

Diluents suitable for use in the polymerization or copolymerization in suspension include alkanes and cycloalkanes, for example, pentane, hexane, heptane, n-octane, isooctane, cyclohexane and methylcyclohexane; alkylaromatic compounds, for example, toluene, xylene, ethylbenzene, isopropylbenzene, atilola, n-propylbenzoyl, diethylbenzene, and mono - and dialkylated; and halogenated and hydrogenated aromatics with Molekulyarnye liquid paraffin or mixtures of these compounds and other well-known diluents.

It is often desirable to subject the medium for the polymerization or copolymerization cleaning before use, for example, by distillation, percolation through molecular sieves, by contacting with the connection type alkylamine able to remove traces of impurities, or other appropriate methods.

Examples of processes of gas-phase polymerization or copolymerization, for which a suitable catalyst or catalyst component according to the invention include processes carried out in reactors with a mixing layer and a fluidized bed and are described in U.S. patents NN 3957448, 3965083, 3971786, 3970611, 4129701, 4101289, 3652527 and 4003712 included as references.

Typical processes of gas-phase polymerization or copolymerization of olefins is carried out in systems containing at least one reactor where add the olefin and the components of the catalyst, and which contains a mixed layer formed of polymer particles. Usually the components of the catalyst are added together or separately through one or more inlets through adjustable valve only or the first reactor.

Olefinic monomer is usually injected into the reactor through the gas return system in the cycle in which the unreacted morometii a homopolymer, formed from the first monomer in the first reactor, reacts with the second monomer in the second reactor.

In the polymerization or copolymerization of olefin in the environment through the system to return the gas in the loop for temperature control, you can add coolant, which may be a liquid monomer.

Regardless of the method of implementation of a process for the polymerization or copolymerization is carried out in conditions that exclude the presence of oxygen, water and other substances, poisoning the catalyst. In addition, according to the invention, the polymerization or copolymerization can be carried out in the presence of additives regulating the molecular weight of the polymer or copolymer. Usually for this purpose use hydrogen, which is well known to specialists. Although this is usually not required, upon completion of polymerization or copolymerization, or when it is desirable to terminate the polymerization or copolymerization, or at least temporarily deactivate the catalyst or catalyst component, it is possible to carry out the contacting of the catalyst with water, alcohols, acetone, or other suitable decontamination officers of the catalyst according to the methods well-known specialist in this field.

definition polyalpha-olefins. The outputs of homopolymer or copolymer is quite high in comparison with the amount used of the catalyst so that the resulting products can be used without separation of catalyst residues. Further, the number stereotactically by-products is relatively small, i.e., they can also not be separated. The polymers and copolymers obtained in the presence of the inventive catalyst can be processed into articles by extrusion, injection molding and other known methods.

Example 1. Stage A - getting the solution alkalicarbonate magnesium.

In the reactor of 2 l, equipped with a mechanical stirrer and flushed with dry nitrogen, was placed a mixture of 153 g ethoxide magnesium, 276 ml of 2-ethyl-1-hexanol and 1100 ml of toluene. The mixture is stirred with a speed of 450 rpm under a pressure of 30 lb/inch2(206,8 kPa), created by the CO2and heated at 93oC for 3 h the resulting solution was moved into a flask with a volume of 2 L. the Total volume of solution equal to 1530 ml of 1 mol of ethoxide magnesium used 1,320 m 2-ethylhexanol. The solution contains 0.1 g-EQ of ethoxide magnesium per ml of solution.

Stage B - the formation of solid particles.

In the reactor of 1 l load 150 ml of toluene, 20.5 ml of tetraethoxysilane and 14 ml of t is/min at 22-27oC for 15 min add using Gomby 114 ml hydrocarbon-magnesium carbonate from the stage A. Deposited solids.

Stage - pereosazhdeniya.

After the mixture containing the precipitate, stirred for 5 min, quickly added using a syringe 27 ml of tetrahydrofuran (THF). The temperature in the reactor increased from 26 to 38oC. Then continue stirring speed of 300 rpm and a temperature within 15 min raises to 60oC. the Resulting solid is dissolved in THF. After 5 min after adding THF solids presidida from the solution. Stirring is continued at 60oC for 1 h, after which the stirring is stopped and the resulting solid is precipitated. The supernatant is decanted, the residue is washed with twice 50 ml of toluene.

Stage D - treatment compound of titanium (IV) (stage activation).

To the precipitate from step C in a reactor with a volume of 1 l add 125 ml of toluene and 50 ml of titanium tetrachloride (substage, MIS-D-1). The resulting mixture was heated to 116oC for 30 min and stirred at a speed of 300 rpm for one hour. After stopping stirring the obtained solids are precipitated and nedosa the 1.8 ml di-n-butylphthalate (Ph) to the solid particles, the mixture is stirred at a speed of 300 rpm at 117oC for 90 min, the solid particles are precipitated, the supernatant decanted. After adding 95 ml of toluene in the sub-phases D-3 the mixture is heated to 91oC within 30 minutes After cessation of mixing solid particles are precipitated, the supernatant decanted. Add 95 ml of toluene, the mixture was stirred at 91oC for 30 min, the solid particles are precipitated, and the supernatant decanted. On the sub-phases D-4 add 63 ml of titanium tetrachloride, the mixture is heated at 91oC under stirring for 30 min, after which the stirring is stopped, the supernatant liquid decanted. The precipitate is washed 4 times with 50 ml of hexane and excrete solid (4.9 g).

The distribution of the catalyst particles size measured by laser diffraction analyzer (Shimadzu Model SALD-1100) found that the distribution of particle size (PSD) as follows: d1011.2 in MK, d50- 22,1 MK and d90- 34.1 MC. d10, d50 and d90 means that 10, 50 and 90%, respectively, of the particles have a size less 11,2, 22,1 and 34.1 MK, respectively. d50 is the average particle size.

Trial polymerization of propylene in suspension resulted in the production of polymer with the output of the industry (BD) $ 27.2 f/ft3(435,7 kg/m3).

Periodic suspension polymerization of propylene is carried out in a reactor with a volume of 2 l with 71oC and a pressure of 150 lb/inch2(1135,5 kPa) in the presence of 7 mm of hydrogen with stirring at 500 rpm for 2 hours as socializaton used triethylaluminium (tea), as a modifier - diisobutyldimethoxysilane. Charged to the reactor, tea/modifier, a titanium component, hydrogen and propylene in the specified order. Exit (kg of polymer g of the solid catalyst) is determined by the content of magnesium in the polymer and in some cases based on the weight of the solid catalyst used to obtain the polymer.

"Soluble" is defined by the evaporation of solvent from an aliquot of the filtrate to obtain a number of derived soluble polymer, indicated as wt.% (%Sol) such soluble polymer in the calculation of the sum of the weights of solid polymer in the filtrate and soluble polymer.

"Extractable" is determined by measuring the weight loss of the dry sample of the crushed polymer after extraction with boiling n-hexane for 3-6 h, indicated as wt. % (% Ext) solid polymer is removed by extraction. The viscosity of the solid polymer ismeo example 1 are used in the examples 2-26, except as stated below. Example 2 repeating the process of example 1, but at the stage B instead of 0.5 g of the dichloride of garretsen enter 1,0, example 3 repeating example 1, but instead of 0.5 g of the dichloride of garretsen on stage B enter 2,0, example 4 repeat example 1, but instead of adding a dichloride of garretsen at the stage B is injected 0.5 g of hafnium tetrachloride in 90 ml of toluene, 21 ml of 2-ethyl-1-hexanol and 11.4 g ethoxide magnesium on A stage at a pressure of CO230 f/inch2(206,8 kPa) in an autoclave with a volume of 200 ml.

Example 5 repeating example 1, but in addition to 0.5 g of the dichloride of garretsen at the stage B is injected 2.0 g of hafnium tetrachloride in the sub-phases D-1. Example 6 repeating the procedure of example 5, but at the stage B add 1.0 g, instead of 0.5 g of the dichloride of harricana. In example 7 doing everything as in example 1, but at the stage B is not injected 0.5 g, 3.0 g of dichloride of garretsen and stage D-1 add 2.5 g of hafnium tetrachloride.

In example 8 repeat the procedure of example 1, but instead of 0.5 g of the dichloride of garretsen on stage B add 1.7 ml of 1 M solution of trichloride vanadium in a mixture of dichloromethane and tetrahydrofuran, and at a stage D-1 injected 2.0 g of hafnium tetrachloride.

In each of examples 9 and 10 repeat the procedure of example 8, but instead of 1.7 ml add to stage B of 2.5 and 3.4 ml 7 ml add to 5.1 ml of trichloride vanadium and sub-phases D-1 instead of 2.0 g injected 1.5 g trichloride hafnium.

In each of examples 12 and 13 repeat the procedure of example 1, but at the stage B instead of dichloride of garretsen administered 1.0 g and 1.5 g of dichloride of zirconocene respectively. In example 14 is repeated procedure of example 1, but instead of 0.5 g of the dichloride of garretsen on stage B add 1.0 g of dichloride of zirconocene, and sub-phases D-1 injected 2.0 g of hafnium tetrachloride. Example 15 is a repetition of example 14.

In example 16 is repeated procedure of example 14, but at the stage B does not impose any dichloride zirconocene or dichloride garretsen and stage D-1 instead of 2.0 g add 4.0 g of hafnium tetrachloride.

In example 17 is repeated procedure of example 5, but at the stage B is not injected 0.5 g, a, 1.5 g of dichloride of harricana. In example 18 is repeated procedure of example 1, but at the stage B instead of dichloride of garretsen added 0.52 g of dichloride of vanadocene and sub-phases 0-1 3.0 g of hafnium tetrachloride. In example 19 is repeated procedure of example 18, but at the stage B instead of 0.52 g type of 0.77 g of the dichloride of vanadocene and stage D-1 injected 2.0 g of hafnium tetrachloride instead of 3.0, In example 20 repeat the procedure of example 19, but at the stage B add 0.5 g of dichloride of zirconocene instead of dichloride of vanadocene and stage D-1 instead of 2.0 g of hafnium tetrachloride injected 1.5, example 21 is repeated the procedure p is AI B and phase D-1 is not injected 1.5 g, and 1.0 g of hafnium tetrachloride.

In example 23 is repeated procedure of example 16, but at the stage D-1 instead of hafnium tetrachloride add 2.5 g of zirconium tetrachloride. In example 24 is repeated procedure of example 18, but at the stage B instead of 0.52 g of the dichloride of vanadocene impose 0.4 g and at the stage D-1 instead of hafnium tetrachloride administered 0.5 g of zirconium tetrachloride.

In example 25 is repeated procedure of example 1, but at the stage B do not add dichloride garretsen, and at the stage D-1 injected 0.5 g of dichloride of harricana. In example 26 is repeated example 1, but at the stage B dichloride garretsen not enter, stage D-2 instead of 1.8 ml add 2.4 ml of di-n-butylphthalate, stage D-31exclude and stage D-4 instead of 63 ml injected with 125 ml of titanium tetrachloride. Thus, examples 25 and 26 are comparative, illustrating the catalysts that were obtained or entirely without the use of compounds of hafnium or with the addition of organic compounds of hafnium only at the stage D.

The number of substances used on stages and podstavek method, the metal content in the obtained solid component of catalyst are presented in table.1. Molar ratio of magnesium to the second metal on A stage are presented in table.1 only in case of application of the obtained components of the solid catalyst. The output of the polypropylene described by a periodic method in suspension, % Sol % Ext, BD, MFR, Mn, Mw, Mz, Mz+1and Mw, Mnfor polypropylene obtained at each phase of this method, also shown in table.2.

Examples 25 and 26 illustrate the catalysts, which are similar to the catalysts obtained in examples 1 to 24, except that they do not contain very hafnium, zirconium, or vanadium, or contain hafnium, introduced by the addition of dichloride of garretsen at the stage D-1.

When comparing the results given in table.2, it is seen that a significant increase in catalytic activity is achieved in examples 1-15, the production of polymer with a broader molecular weight distribution according to examples 16 to 19, 23 and 24, and the joint increase of catalytic activity and the production of polymer with a broader molecular weight distribution in examples 20-22, which illustrates the advantages of the catalyst according to this invention.

From the above description it is evident that the objectives of this invention are achieved. Although described only some versions of the invention, the person skilled in the art it is obvious that the possible alternatives and various modifications is congestion or a component of a catalyst for polymerization of propylene or copolymerization of propylene with ethylene or higher alpha-olefins, which are solid not soluble in the hydrocarbon product obtained (a) preparation of a solution of magnesium-containing component obtained by the interaction of the magnesium-containing compound with carbon dioxide or sulfur dioxide in the liquid; b) deposition of solid particles from a solution of magnesium-containing component by processing the compound or complex of titanium, and C) processing the precipitated particles with a compound of titanium and an electron donor, characterized in that it further comprises a hafnium - or zirconium bearing component is introduced either at the stage of (a) in the magnesium-containing component by reacting a magnesium-containing component or magnesium-containing compound with carbon dioxide or sulfur dioxide with carriageways or zirconium bearing compound or complex, or at the stage (b) in the precipitated solids by treating the magnesium-containing component, compound or complex of titanium and hafnium - or zirconium bearing compound or complex, or at the stage (C) in the treated precipitated particles by treating the precipitated particles with a compound of titanium, an electron donor and a compound or complex of hafnium or zirconium.

2. The catalyst or who is eastview with carbon dioxide.

3. The catalyst or catalyst component under item 2, characterized in that the atomic ratio of magnesium and titanium in the calculation of basic metals in the treated precipitated particles formed in stage (C), 0,3 20,0 1,0.

4. The catalyst or catalyst component under item 2, characterized in that the atomic ratio of titanium and hafnium in the calculation of basic metals in the treated precipitated particles formed in stage (b) is 0.05 100,0 1,0.

5. The catalyst or catalyst component under item 2, characterized in that the atomic ratio of magnesium and hafnium in the calculation of basic metals in the treated precipitated particles formed in stage (b) is 2.5 1000,0 1,0.

6. The catalyst or catalyst component under item 2, characterized in that garnisongasse compound or complex that is used in stage (a) or (b) is a hafnium halide.

7. The catalyst or catalyst component under item 6, characterized in that used garnisongasse compound or complex is a tetrachloride or hafnium dichloride garretsen.

8. The catalyst or catalyst component under item 2, characterized in that the total kolichestvo catalyst under item 1, characterized in that the atomic ratio of magnesium and zirconium in the calculation of basic metals in the treated precipitated particles formed in stage (b) is 20 925 1.

10. The catalyst or catalyst component under item 1, characterized in that the atomic ratio of titanium and zirconium in the calculation of basic metals in the treated precipitated particles formed in stage (b), is 2

130 1.

11. The catalyst or catalyst component under item 1, characterized in that the zirconium bearing compound or complex is tetravalent zirconium or dihalogenide of zirconocene.

12. The catalyst or catalyst component under item 1, characterized in that at least a portion of the total quantity of zirconium, enter one of the steps (a), (b) and (C), introduced in the stage (b) by treating the magnesium-containing component, compound or complex of titanium dichloride and zirconocene or at the stage (C) by treating the precipitated particles with a compound of titanium, an electron donor and tetrachloride Zirconia.

13. The catalyst or catalyst component under item 2, characterized in that the treated precipitated particles from step (C) include magni is t, moreover, vanadium enter or magnesium-containing component on the stage (a) by reacting a magnesium-containing compound or component with a vanadium-containing compound or complex, or solid particles deposited on the stage (b), by treating the magnesium-containing component, compound or complex of titanium and vanadium-containing compound or complex, or precipitated particles processed in stage (b), by treating the precipitated particles with a compound of titanium, an electron donor and a compound or complex of vanadium, not containing halogen.

14. The catalyst or catalyst component on p. 13, characterized in that all the amount of vanadium is injected at one stage (b) or (C).

15. The catalyst or catalyst component on p. 13, characterized in that the atomic ratio of titanium and vanadium in the calculation of basic metals in the treated precipitated particles formed in stage (b) is 0.05 to 10.0 and 1.0.

16. The catalyst or catalyst component on p. 13, characterized in that the atomic ratio of magnesium to vanadium in the calculation of basic metals in the treated precipitated particles formed in stage (b) is 2.5 75,0 1,0.

17. the and / or complex represents a halide of vanadium (III) or vanadium (IV).

18. The catalyst or catalyst component under item 13, wherein at least a portion of the total quantity of vanadium introduced at one stage (a), (b) and (C), introducing solid particles deposited on the stage (b), by treating the magnesium-containing component, compound or complex of titanium and vanadium-containing compound or complex.

19. The catalyst or catalyst component under item 13, wherein at least a portion of the total quantity of vanadium introduced at one stage (a), (b) and (C), enter at the stage (C) by treating the precipitated particles with a compound of titanium, an electron donor and vanadium-containing compound or complex that does not contain halogen.

20. The catalyst or catalyst component under item 2, characterized in that the solid particles precipitated at stage (b), then dissolve and periostat of cyclic simple ether and then pereosazhdeniya particles treated in stage (b) a transition metal compound and an electron donor.

 

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The invention relates to the catalytic polymerization and relates to a method of preparation of the catalyst for polymerization of olefins

The invention relates to metal coordination complexes with hard structure
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The invention relates to a continuous method for the polymerization of alpha-olefin having from 2 to 12 carbon atoms, which is held in gas-phase polymerization reactor by contacting the gaseous reaction mixture with a catalyst based on chromium oxide associated with a granular substrate and activated by heat treatment, in which the polymerization reactor is introduced (A) alpha-olefin, and (C) the catalyst at a constant speed

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The invention relates to a titanium containing catalyst component for the polymerization of ethylene, which in large polymerization activity can be obtained a polymer of ethylene with a narrow size distribution of particles, the catalyst for polymerization of ethylene comprising this titanium containing component and the polymerization of ethylene using a specified catalyst for polymerization of ethylene

FIELD: polymerization catalysts.

SUBSTANCE: invention describes metallocene catalytic component of catalytic system for production of polyolefin with isotactic or syndiotactic/isotactic block structure with length of monomer unit up to C10, said component having general formula R"(CpR1R2R3)(Cp'R1R2')MQ2, where Cp represents cyclopentadienyl ring substituted by at least one substituent; Cp' is substituted fluorenyl ring; R" structural bridge imparting steric rigidity; R1 optional substituent in cyclopentadienyl ring located at a distance to bridge and including a bulky group XR*3 wherein X is selected from group IVA elements and R*, the same or different, are hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms; R2 optional substituent in cyclopentadienyl ring, nearest to bridge and not vicinal to remote substituent, which substituent has formula YR# wherein Y is selected from group IVA elements and R#, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R3 optional substituent in cyclopentadienyl ring, nearest to bridge and being hydrogen or having formula ZR$ wherein Z is selected from group IVA elements and Rs, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R1' and R2' are independent substituents in fluorenyl ring, one of them having formula AR3’’’ wherein A is selected from group IVA elements and each of R’’’ represents independently hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms and the other being hydrogen or second group AR3’’’; M is transition metal from group IVB or vanadium and each Q is either hydrocarbon radical with 1-20 carbon atoms or halogen.

EFFECT: enabled preparation isotactic or syndiotactic/isotactic block polymer with length of monomer unit up to C10.

30 cl, 13 dwg, 2 tbl, 10 ex

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