The method of obtaining the (co)polymers of alpha-olefins

 

(57) Abstract:

Usage: obtain Homo - and copolymers of alpha-olefins. Essence: //polymerization of alpha-olefins is carried out in the presence of a catalyst consisting of alyuminiiorganicheskikh connection, the solid component and an additional component of C4-C18-derived alkoxysilane (0,35-3.00 mol per 1 mol alyuminiiorganicheskikh connection). A solid component of catalyst is obtained by interaction of the hydrocarbon solution of the magnesium compounds selected from the group comprising magnesium chloride, C2-C16-dialkoxybenzene and C1-C10-alkoxysilane, liquid titanium compounds of the General formula Ti(OR)qCl4-qwhere R = C1-C10-alkyl, q = 0,1, or 4, at least one of electrondonor, and during or after the formation of the solid product is injected ester C8-C30-dicarboxylic acid at a molar ratio of the compound of magnesium from 0.05 : 1.00 to 0.50 to : 1,00. As the regulator of MM may be used hydrogen. 1 C.p. f-crystals, 1 Il., 36 table.

The invention relates to a method for producing olefinic polymers (this is the name used to refer to both homopolymers and copolymers of olefin is) olefins.

The invention relates in particular to a method for producing olefin polymers of high order spatial patterns in large quantities by the polymerization of alpha-olefins, the molecules of which contain at least 3 carbon atoms.

In the polymerization of alpha-olefins, the molecules of which contain at least 3 carbon atoms, in accordance with the method of the present invention obtain a polymer exhibiting little or not shown at all the lower order spatial structure even in the case when the melt index of the polymer change from agent to control molecular weight, in particular hydrogen. Moreover, when implementing the method of the present invention by the method of suspension polymerization or by the method of vapor-phase polymerization can be obtained in granular or spherical polymer which has good flowability, high bulk density and a narrow interval of the distribution of particles according to their size, with the majority of the particles is characterized by a moderate amount. The advantage of the method of the present invention also lies in the fact that over time the process of polymerizati tositsa to a method for producing olefin polymers or copolymers, in the exercise of which provides for the polymerization or copolymerization of olefins with denami in the presence of a catalytic system, which includes the following components /A/, /B/ and /C/:

A solid titanium catalyst component containing magnesium, titanium, halogen and an ester selected from the class which includes esters of polycarboxylic acids and esters polyoxicompounds, and the specified catalytic component obtained by introduction of a liquid hydrocarbon solution /I/ magnesium compound (II) into contact with a titanium compound in the liquid state, resulting in a solid product, or at the beginning of the cooking liquid hydrocarbon solution of the magnesium compound (I) and titanium compound (II) with the subsequent reception of the solid product, moreover, the specified reaction obtain the solid product is carried out in the presence of the /D/ at least one electron donor selected from a class which includes the esters of monobasic carboxylic acids, anhydrides of carboxylic acids, ketones, aliphatic ethers, aliphatic carbonates, alcohols containing alkoxygroup, alcohols containing alloctype, the molecules of which contain links P-O-C, and during or after completion of the process of formation of solid product provides for the introduction of this solid product in contact with /E/ complex ether selected from the class of esters of polycarboxylic acids and esters polyoxicompounds;

/B/ ORGANOMETALLIC compound of a metal selected from a class which includes the metals of groups I to III of the periodic table of elements, and

/C/ silicon compound whose molecules contain links Si-O-C and Si-N-C

The present invention relates also to the above-mentioned solid titanium catalyst component.

Up to now, there have been proposed various technologies for solid catalytic component comprising mainly magnesium, titanium, halogen and electrondonor. It is also known that the use of such solid catalyst component in the polymerization of alpha-olefins, the molecules of which contain at least 3 carbon atoms, allows to obtain high spatial regular polymers with high catalytic activity. However, many of these technologies are still desirable to improve in relation to activity katalitichyeskogo polymer of high quality without the need of processing after polymerization, the resultant polymer with a regular spatial structure should be very large and high enough should be the output of polymer product per unit quantity of the transition metal. From this point of view, previously known technology can be quite high for certain types of polymers, but few of them are completely satisfactory in respect of residual halogen in the polymer, causing korrodirovaniju moulding machines.

In addition, many of the catalytic components obtained according to previously known technology, have the disadvantage, which is quite noticeable decrease in the degree of product yield and spatial regularity.

In the description of Japanese patent publication laid N 94580/1979 (Japanese laid out an application dated July 26, 1979) proposed a method for the polymerization of olefins using a catalyst system comprising a compound, which may overlap with the component /C/ catalytic system used in accordance with the present invention. However, this patent document does not describe a component /A/, which is specifically defined in the description of this patent application. In Japanese laid out publication N 36203/1980 (tiled application dated March 13, 1980) also described a method of polymerization of olefin using the catalyst system, is obreteniyu, but nothing is said about the catalytic component of /A/.

In the description of Japanese patent publication laid N 811/1981, laid out for everyone to looking at January 7, 1981 (corresponding to U.S. patent N 4330649), the list of authors, which includes the authors of the present invention, illustrated by way of obtaining olefin polymers or copolymers having a high flowability, the uniformity of particle size and uniformity of distribution of particle sizes, especially acceptable for the polymerization of alpha-olefins containing at least 3 carbon atoms. In the description of this patent is silent about the use of ether polycarboxylic acid and/or ester polioksidony as electrondonor in the process of receiving the above-mentioned solid titanium catalyst component. In addition, in this description says nothing about sharing such a complex ester and the above electrondonor /D/, and also about sharing with the organic compound of silicon /C/.

The authors of the present invention conducted extensive research to develop a more improved method for the polymerization of the, includes titanium catalytic component to /A/, obtained using both electrondonor /D/, and complex ester /E/, selected from esters of polycarboxylic acids and esters polyoxicompounds, as well as the aforementioned components of /B/ and /C/ allows to obtain polymers with exceptionally high qualities in relation to the particle size, distribution of particle size, particle shape and bulk weight with high catalytic efficiency and a very small decrease in activity as the process of polymerization. It was found also that the implementation of the method of the present invention eliminates the disadvantage of the previously known methods, which is that when you try to obtain a polymer with a high melt index by carrying out the polymerization process in the presence of the agent regulating the molecular weight, in particular hydrogen, achieved a significant decrease in the ordering of spatial patterns. In addition, it was found that the use of small amounts of hydrogen allows you to adjust the melt index of the polymer. An unexpected advantage of the present invention also lies in the fact that ispolzovat activity of the catalyst.

The aim of the invention is to develop an improved method for the polymerization of olefins.

The preferred option as magnesium compounds /I/, which is necessary to obtain a solid titanium catalyst component (A) in the implementation of the present invention, it is necessary to use compounds of magnesium, not having no reducing ability, that is, the magnesium compound, free from miniplates link or a magnesium-hydrogen bond. This magnesium compound can be obtained from the magnesium compounds having reducing ability.

Illustrating examples of the magnesium compounds not having no reducing ability include magnesium halides, in particular magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxysilylated, in particular alkoxy, C1-C10manygaloherez, for example, methoxymandelic, amoxiline-chloride, isopropoxyaniline, butoxyaniline and Aktobemunaigaz; aryloxypropanolamine, for example, proximinality, which may be substituted by lower alkyl groups, in particular, proximinality, isopropoxide, butoxymethyl, n-octoxide and 2-ethylhexylamine; aryloxyalkyl, for example, proximally, which may be substituted by lower alkyl groups, and magnesium salts of carboxylic acids, in particular magnesium salts of aliphatic carboxylic acids, the molecules of which contain from 1 to 20 carbon atoms, in particular, magnesium laurate and magnesium stearate. The magnesium compounds may be in the form of complexes or mixtures with other metals. Haloesters magnesium compounds, all of the above magnesium chloride, alkoxysilane and aryloxyalkanoic are preferred among magnesium compounds.

In the preparation of liquid hydrocarbon solution of the magnesium compounds /I/ can be used in various hydrocarbon solvents. Examples of such solvents include aliphatic hydrocarbons, in particular, pentane, hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; aliphatic hydrocarbons, in particular, cyclopentane, Methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclohexene; aromatic hydrocarbons, in particular benzene, toluene, xylene, ethylbenzene, cumene and zymol, and halogenated hydrocarbons, in castor can be prepared by various methods, selected depending on types of the magnesium compound and the solvent, for example, by simple mixing of these two materials, by mixing and heating the mixture or by mixing the magnesium compound with a hydrocarbon solvent in the presence of or followed by treatment with electrondonor able to translate in a dissolved state of the magnesium compound, in particular, alcohol, aldehyde, carboxylic acid, a simple ether or mixtures thereof with each other or their mixtures with other electrondonor simultaneously, if required, heating the mixture.

For example, in the case of dissolution haloesters magnesium compounds /I/ in a hydrocarbon solvent with alcohol this last can be used in amounts of at least about 1 mol. it is preferable in the amount of at least about 1.5 mol. particularly preferably, more than 2 mol. for each mol haloesters magnesium compounds, although the molar ratio between these components can be changed appropriately depending on the type and quantity of the hydrocarbon solvent and the type of magnesium compound. No con is not too large quantities. For example, the alcohol content can reach about 40 mol. preferably up to 20 mol. especially preferably up to about 10 mol. for each mol of the magnesium compound /I/. In that case, when a hydrocarbon solvent using an aliphatic or alicyclic hydrocarbons, alcohols used in the above amount, and alcohol, the molecules of which contain at least 6 carbon atoms, are used in amounts of at least about 1 mol. preferably at least about 1.5 mol. for each mol haloesters magnesium compounds. This is preferred because haloesters magnesium compound can be translated in a dissolved state with the use of alcohols in a small total, and can, thus, to obtain a catalytic component having high activity. In that case, if you only use the alcohol molecules which contain not more than 5 carbon atoms, their number should be at least about 15 mol. for each mol haloesters magnesium compound, and the resulting catalytic component has a low s, in that case, when a hydrocarbon solvent using an aromatic hydrocarbon, haloesters magnesium compound can be translated in a dissolved state with alcohols in the above quantities regardless of the types of these alcohols. Moreover, in the case when, for example, as the titanium compound (II) must be present tetraalkoxysilane when translating in a dissolved state haloesters compounds of magnesium, the use of small amounts of alcohols allows you to put in a dissolved state haloesters magnesium connection.

The preferred option haloesters connection of magnesium should be entered in contact with alcohols in the hydrocarbon environment, usually at room temperature or elevated temperatures, depending on the types of materials used, that is, at temperatures above approximately 65oC, preferably at a temperature of from about 80 to 300oC, more preferably at a temperature of from about 100 to 200oC. Accordingly you can choose the duration of contact. For example, it is in the range from about 15 min to 5 h, predpochtitelnei least 6 carbon atoms, in particular, aliphatic alcohols C6-C20for example, 2-methylpentanol, 2-ethylbutanol, p-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecanoyl alcohol, undecanol, alerby alcohol and stearyl alcohol; alicyclic alcohols C6-C20for example, cyclohexanol and methylcyclohexanol; aromatic alcohols with 7-20 carbon atoms, for example, benzyl alcohol, methylbenzylamine alcohol, isopropylbenzyl alcohol, alpha-methylbenzylamine alcohol and an alpha, alpha-dimethylbenzylamine alcohol, and aliphatic alcohols with 6 to 20 carbon atoms, molecules which include alkoxygroup, in particular n-butylsilane (etilenglikolevye-n-butyl ether and 1-butoxy-2-propanol. Examples of other alcohols are alcohols, the molecules of which contain not more than 5 carbon atoms, in particular methanol, ethanol, propanol, butanol, ethylene glycol and onomatology ether of diethylene glycol.

In the case when the electron donor is used carboxylic acid are acceptable organic carboxylic acid molecules contain at least 7 carbon atoms. Examples of such compounds include acid molecules which contain 7-20 carbon atoms, in castrato and octanoic acid.

Acceptable aldehydes for use as electron donors are those aldehydes, the molecules of which contain at least 7 carbon atoms. Examples of these compounds are those compounds whose molecules contain from 7 to 18 carbon atoms, in particular, Caprylic aldehyde, 2-ethylhexyloxy aldehyde, Caprylic aldehyde and undecylenic aldehyde.

Acceptable amines are amines, the molecules of which contain at least 6 carbon atoms. These examples include amines containing from 6 to 18 carbon atoms, in particular heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecillion and 2-ethylhexylamine.

An example of a simple ester as electron donor is tetrahydrofuran.

The preferred amount of these carboxylic acids, aldehydes, amines and ethers, as well as the preferred temperatures at which they are used largely in line with the above.

The solution in the hydrocarbon solvent compounds of magnesium /I/ can also be prepared using magnesium metal or other compounds of magnesium, which can turn into a connection magnini /I/. For example, this can be achieved by the dissolution and suspendirovanie compounds of magnesium, the molecule of which contains alkyl, CNS, alloctype, acyl, amino group or hydroxyl group, magnesium oxide or magnesium metal in a hydrocarbon solvent comprising an alcohol, amine, aldehyde, carboxylic acid, a simple ether and the like, dissolved in it, and getting haloesters compounds of magnesium /I/, not having no reducing ability with simultaneous gorodilova palodiruyut agent, in particular hydrogen halide, haloesters compound of silicon, halogen, haloesters compound of aluminum, haloesters compound of lithium or haloesters a sulfur compound. Alternatively it is possible to conduct processing of the Grignard reagent, dialkylamino, hydrate of magnesium or of such complex compounds of magnesium with other ORGANOMETALLIC compound, for example, magnesium compounds having reducing ability, which corresponds to the formula MMgR1pR2qXgYswhere the symbol M is denoted by atom of aluminum, zinc, boron or as beryllium, each of the symbols R1UP>4R5R6, NR7R8or SR9each of the symbols R3-R8indicated hydrogen atom or a hydrocarbon group, and the symbol R9marked hydrocarbon group, each of the symbol and indicated by a number that is greater than 0, each of the symbols p, q, r and s are denoted by a number equal to at least 0, the symbol denoted by the atomic valence of the metal M, and b/ is not less than 0.5, p + q + r + s m + 2 and 0 /g + s/ / + / < 1.0, the connection is able to cancel resilience, in particular alcohol, ketone, ether complex, a simple ether, halogenerator acid, silane, siloxane, oxygen, water, acetal or alkoxy-or aryloxyazinyl silicon or aluminum, and dissolved the compound obtained magnesium /I/, not having no reducing ability in a hydrocarbon solvent. In the above formula, examples of the hydrocarbon groups are alkyl groups with 1-20 carbon atoms, in particular ethyl group, through the group, bucilina group, amyl group, exilda group, anjilina group and dodalalala group, and aryl group with 6-20 carbon atoms, in particular phenyl group and Tomilina group.

In Kacha/ you can use titanium compound (II). The preferred compounds are titanium compounds of formula Ti/OR/gX4-gwhere the symbol R is indicated hydrocarbon group; X is marked halogen atom, and g is a number satisfying the inequality 0 g 4. In the above formula, examples of the hydrocarbon groups are alkyl groups of C1-C10and phenyl group which may have a Deputy, as the lower alkyl group, for example, an alkyl group with 1-4 carbon atoms, and a halogen atom.

Specific examples of the titanium compound (II) include tetrachloride titanium, in particular titanium tetrachloride, chetyrehhloristy titanium and chetyrehhloristy titanium: alkoxylated trihalogen, in particular Ti(OCH3Cl3, Ti(OC2H5)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3and Ti(O-ISO-C4H9)Br3alkoxysilylated, in particular Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-C4H9)Cl2and Ti(OC2H5)2Br2; trialgenericviagraho, in particular Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9)Cl and Ti(OC2H5)Br; tetraalkoxysilane,

in particular, the deposits with the halides of hydrogen, halogen-free, other metal compounds, in particular, aluminum compounds and silicon compounds or sulfur compounds. Of them galoidovodorodami compounds of titanium are preferred. Especially preferred are tetrachloride titanium, and from them all especially preferred is tetravalent titanium.

As the titanium compound (II) in the liquid state can be used as an individual compound or a mixture of titanium compounds, which are themselves liquid or may be a solution of the titanium compound in a solvent, in particular, hydrocarbons.

In accordance with the present invention, the solid titanium catalyst component (A) containing magnesium, titanium, halogen and a compound selected from the class comprising esters of polycarboxylic acids and esters polyoxicompounds, can be prepared as follows.

Liquid hydrocarbon solution of the magnesium compound (I) enter into contact with the titanium compound (II) in the liquid state, resulting in a solid product. Another option in the beginning a magnesium compound /I/ titanium soedineniyami at least one electron donor, defined above, and the product is introduced into contact with a complex ester /E/, selected from a class which includes the esters of polycarboxylic acids and esters polyoxicompounds, in the process of obtaining the solid product (option a) or after obtaining the solid product (option /b/).

E-donor /D/ are selected from a class which includes the esters of monocarboxylic acids, aliphatic carboxylic acids, anhydrides of carboxylic acids, ketones, aliphatic ethers, aliphatic carbonates, alcohols containing alkoxygroup, alcohols containing alloctype, organosilicon compounds containing a bond of Si-O-C, and organophosphorus compounds containing a bond P-O-C. preferred Examples of the electron donors include the esters of monocarboxylic acids with 1 to 20 carbon atoms, aliphatic carboxylic acids with 1 to 20, preferably from 1 to 6, carbon atoms, the anhydrides of carboxylic acids of 3-20 carbon atoms, ketones C3-C20, aliphatic esters of C2-C16, aliphatic carbonates C2-C16, alcohols containing alkoxygroup, C3-C20, alcohols containing alloctype, C3-C20, organosilicon compounds containing means, contains the link P-O-C, whose molecules of the organic groups contain 1-10 carbon atoms.

Specific examples of esters of monocarboxylic acids include methylformate, mutifaceted, ethyl acetate, vinyl acetate, propyl, isobutyl acetate, tert. butyl acetate, octylated, etherpiraat, atypical, methylchloride, ethyldichlorosilane, methyl methacrylate, etildronat, methylcyclohexanecarboxylic, methylbenzoate, ethylbenzoic, propylbenzoate, butylbenzoate, octylbenzoic, cyclohexylbenzene, phenylbenzyl, benzyl benzoate, methylfolate, atilola, amitola, ethylbenzoic, methylenethf, ationist and utilitarians.

Specific examples of aliphatic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid and valeric acid.

Specific examples of anhydrides of carboxylic acids are acetic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, trimellitic anhydride and tetrahydrophthalic anhydride.

Specific examples of ketones are acetone, methyl ethyl ketone, ethyl-n-butylketone, acetophenone, benzophenone, cyclohexanone and benzoquinone.

Specific examples alloy ether, ethylbenzylamine ether, etilenglikolevye ether and anisole.

Specific examples of alcohols containing alkoxygroup are butylcellosolve (etilenglikolevye ether).

Specific examples of aliphatic carbonates are dimethylcarbonate, diethylcarbamyl and ethylcarbonate.

Specific examples of organosilicon compounds containing a bond of Si-O-C are methylsilicon, ethyl silicate and diphenyl-dimethoxysilane.

Specific examples of the organophosphorus compounds containing a bond P-O-C are trimethylphosphate and triethylphosphite.

If desired, these electron-donating compounds may be obtained at the place of use in the process of obtaining a catalytic component to /A/.

Examples of preferred esters of polycarboxylic acids or esters polyoxicompounds used in the preparation of the catalytic component to /A/, are such compounds, the main molecular chain which corresponds to the formula:

< / BR>
where R1denotes a substituted or unsubstituted hydrocarbon group, each of R2, R5and R6denotes a hydrogen atom or a substituted or unsubstituted carbohydrate is a hydrogen group, and according to a preferred variant, at least one of R3and R4denotes a substituted or unsubstituted hydrocarbon group or a radical R3and R4can be interconnected and replaced by a hydrogen group, mentioned above, represents a substituted hydrocarbon group containing a heteroatom, in particular, nitrogen atom, oxygen, or sulfur, for example, such a group as C-O-C, COOR, COOH, OH, SO3H-C-N-C - or-NH2.

Examples of the hydrocarbon group in the above formula include alkyl groups of C1-C10in particular methyl, ethyl, propyl, butyl, amyl, hexyl or octyl, aryl group with 6 to 16 carbon atoms, in particular phenyl, TRIALOG, kalilou, benzyl and naftalina group, alkylidene group C1-C10in particular, methylidene, ethylidene or propylidene group, and alkeneamine group with 1-10 carbon atoms, in particular vinyl, allyl, and propenyloxy group. Examples of the ring formed by the connection of R3and R4are cyclohexane, benzene, naphthalene, norbornane and cyclopentane ring.

These hydrocarbon groups can contain such substituents, examples of which are shown voty, the anhydrides of carboxylic acids, ketones, alcohols, containing alkoxygroup, and organosilicon compounds containing the link-O-C, are preferred. Particularly preferred esters of monocarboxylic acids and anhydrides of carboxylic acids.

Specific examples of preferred esters of polycarboxylic acids /E/ include esters of aliphatic polycarboxylic acids C5-C30in particular diethylpyrazine, Diisobutyl-alpha methylglutaric, diethylmalonate, diethylethylene, diethylethanolamine, diethylmalonate, diethylformamide, diethylmalonate, diatribution, monoisostearate, diisooctylphthalate, Diisobutylene, diisobutylphthalate, aminobutiramida-butylmethylether, diallylmethylamine, di-2-ethylhexylphthalate, diisooctylphthalate and esters of dicarboxylic acids with long molecular chains (for example, diethylacetal, diisobutylamine, Diisopropylamine, di-n-butylsilane, di-n-octylsilane and di-2-ethylhexylcarbonate); esters of alicyclic polycarboxylic acids C10-C30in particular diethyl-1,2-cyclohexanecarboxylate and Diisobutyl-1,2-cyclohexanecarboxylate; esters of aromatic polycarboxylic acids C10-C30is leftalt, di-n-butylphthalate, Diisopropylamine, di-n-heptylphenol, di-2-ethylhexylphthalate, di-n-octylphthalate, dineopentyl, dodecylphenol, benzylbutylphthalate, definiltely, diethyldithiocarbamic and dibutyldithiocarbamate and heterocyclic esters of polycarboxylic acids, in particular esters of 3,4-furandicarboxylic acid.

Examples of preferred esters polyoxicompounds /E/ are the esters obtained from aromatic polyoxicompounds with 6-16 carbon atoms and aliphatic carboxylic acids with 1 to 12, preferably from 1 to 7 carbon atoms, in particular 1,2-diacetoxybenzoic, 1-methyl-2,3-diacetoxybenzoic and 2,3-diacetoxynaphthalene.

With the introduction of substances derived from the complex ester selected from the class which includes the esters of polycarboxylic acids and esters polyoxicompounds, the catalytic component of /A/ is not always necessary to use such a compound as a source material. Optionally, you can use the connection, which can be subjected to conversion in this connection in the process of obtaining titanium catalytic component to /A/, and in the process of obtaining a catalytic component to /A/ to turn it into an ester.

is /b/, is, for example, in the range from about 0.01 to 1 mol. preferably from about 0.05 to 0.5 mol. for each mol of compound magnesium /I/. The choice of this number allows you to adjust the particle size of the solid product.

In that case, if the number of electron donor /D/ is too large, if there are too many may be deposited on a solid product that can have the opposite effect, although the degree reverse effect varies according to the type of electron donor /D/. Thus, in a preferred variant, the appropriate amount must be within the above interval.

When a solid product is obtained in the presence of ether polycarboxylic acids and/or polyoximino connection /E/ in accordance with option /and/ on preferred option ester /E/ should be used in an amount of approximately from 0.01 to 1 mol. preferably approximately from 0.1 to 0.5 mol. for each mol of the magnesium compound /I/. Preferably the molar ratio of ester /E/, the precipitated solid product, and electron donor /D/ adjust in the range of about 1:about 0.1-to 2.0, preferably about 1:0.1 to 1.

In a preferred variant it should be at least 1 mol. usually from about 2 to 200 mol. in particular from about 3 to 100 mol. for each mol of compound magnesium /I/.

If a solid product is difficult to obtain by simply introducing a liquid hydrocarbon solution of the magnesium compound (I) into contact with a titanium compound (II) in the liquid state, or if a solid product is difficult to obtain, just leaving a hydrocarbon solution of compounds /I/ and /II/ stand, you can add an additional amount of the titanium compound (II), preferable haloesters titanium compound (II), or you can add another precipitating agent, which allows to obtain a solid product. Examples of such precipitating agent are agents haloiding, in particular halogen, halodurans is their compounds of lithium, haloesters sulfur compounds and haloesters compounds of antimony. Specific examples are chromium, bromine, hydrogen chloride, hydrochloric acid, pentachloride phosphorus, thionyl chloride, thienylboronic, chloride Sulfuryl, phosgene and nitrosylchloride.

Solid products differ according to the formula and the size of the particles depending on the conditions of their acquisition. To obtain a solid product, which is characterized by a uniform shape and uniform particle sizes, the preferred option should be avoided him a quick education. For example, in the case when such a solid product, you must obtain a mixture of compounds /I/ and /II/ in the liquid state with the subsequent reaction between them, it is recommended to mix them at a sufficiently low temperature, which eliminates the possibility of rapid formation of a solid product, and then gradually increase the temperature. In accordance with this method, you can easily get granular or spherical particles of a solid product with a relatively large particle diameter and a narrow interval of the distribution of particles by size.

During the process of suspension polymerization or gas-phase polymerization with ispolzovaniem particle size, which can be obtained according to the above obtained polymer is granulated, with spherical particles, and these particles are distributed in a narrow range, have a high bulk density and good flowability. Used in this description, the term "granular" is used to denote particles, which when viewed on pictures with high magnification look like a mass of fine powder. Depending on the method of preparation of the solid catalytic component in the form of a granulated product can be obtained particles, the shape of which is in the range from particles with a large number of heterogeneous sites to those particles that are almost very close to the ideal areas.

The operation of introducing a liquid hydrocarbon solution of the magnesium compound (I) into contact with a titanium compound (II) in the liquid state can be performed, for example, at a temperature of from about -70 to +200oC. the Temperature of the two input contact of the fluid may vary between them. Usually often preferable to carry out the method of introducing into contact, whereby not provided the temperature is too high, allowing you to get tverdookisnym characteristics. For example, the preferred temperature is from about -70 to +50oC. if the temperature probe is too low, sometimes you can not observe the precipitation of the solid product. In this case, it is desirable to raise the temperature of, for example, to the range from about 50 to 150oC, or continue the operation of contact for an extended period of time to precipitate a solid product.

In a preferred variant, the solid product was washed with excess liquid titanium compound or a liquid halogenated hydrocarbon, preferably titanium tetrachloride, 1,2-dichloroethane, chlorobenzene, methyl chloride and hexachlorethane at least once at a temperature of, component of, for example, from about 20 to 150oC. the product is Then typically washed with a hydrocarbon, then it can be used in the polymerization process. Examples of the hydrocarbon can be the same as described above with reference to the process of making a liquid hydrocarbon solution of the magnesium compound /I/.

The method in accordance with a variant of /a/ is extremely valuable, because it's simple and pozoriste /b/, you can perform the following procedure.

After preparation of the hydrocarbon solution of the magnesium compound (I) and titanium compound (II) or resulting from the introduction of the magnetic connection /I/ into contact in the liquid state with a titanium compound (II) in the liquid state similar to the above option /a/ receive a suspension of the solid product. It is usually possible to implement the method, according to which the suspension is provided by the addition of ether polycarboxylic acid and/or a complex ester of polioksidony connection with the subsequent reaction at the temperature of from about 0 to 150oC. the Number of used electronic donor is the same as in the variant of /a/. The obtained solid product may be washed at least once a liquid titanium compound, preferably in excess of titanium tetrachloride, at a temperature of from about 20 to 150oC.

If desired, in accordance with the present invention can be implemented versions /a/ and /b/ in combination with each other.

In the process of obtaining the solid product of the present invention in accordance with the foregoing may be porous inorganic and/or organic solid connection, due to CEG the Oia. In this case, it is possible to pre-operation introduction porous solid product in contact with the magnesium compound (I) in the liquid state, followed by the introduction of this porous solid product containing liquid magnesium compound into contact with the liquid titanium compound (II).

Examples of such porous solid compounds can serve as silicon dioxide, aluminum oxide, polyolefins and the products obtained by the processing of these compounds galoidsodyerzhascikh compounds, in particular chlorine, bromine, hydrogen chloride, 1,2-dichloroethane and chlorobenzene.

The solid titanium catalyst component /A/ used in accordance with the present invention may be a material obtained in accordance with the above versions /a/ and /b/ with the subsequent washing or without washing the titanium compound, a hydrocarbon and the like.

In a preferred variant of the solid titanium catalyst component to /A/, which can be obtained according to any one of the above options is used for polymerization after thorough washing with a hydrocarbon. In a preferred variant of the obtained solid titanium catalyti the leaves, for example, from about 2 to 100, preferably from about 4 to 50, more preferably from about 5 to 30, and the value of the atomic ratio of halogen and titanium are equal, for example, from about 4 to 100, preferably from about 5 to 90, and more preferably from about 8 to 50, while the molar ratio between the electron donor and the titanium is, for example, from about 0.01 to 100, preferably from about 0.2 to 10, and more preferably from about 0.4 to 6. As indicated above, in many cases, the catalytic component of /A/ is granular or consists of particles are almost spherical shape. Typically, the specific surface area of such material is, for example, at least about 10 m2/g, preferably from about 100 to 1000 m2/,

As the halogen in the solid titanium catalyst component /A/ is chlorine, bromine, iodine, fluorine, two or more of these agents, preferably chlorine. Electron donor, which is part of the catalytic component to /A/, at least contains ester /E/, selected from esters of polycarboxylic acids or esters polyoxicompounds and rum /E/ and other electronic donor /D/ varies depending on the type of electron donor /D/. The catalytic component (A) exhibits good performance even if it contains not more than about 2 mol. preferably not more than about 1 mol. especially preferably not more than 0.5 mol. other electron donor /D/ for each mole of ester /E/.

In accordance with the present invention, the olefins will polimerizuet using a catalytic system comprising a solid titanium catalyst component to /A/.

In accordance with the present invention, the olefins will polimerizuet using a catalytic system consisting of a solid titanium catalyst component A prepared according to the above, the ORGANOMETALLIC compounds /B/ metal of groups I to III of the periodic table of elements and organosilicon /C/.

As examples of the ORGANOMETALLIC compound /B/ can be mentioned the following compounds:

/ 1/ Alyuminiiorganicheskikh compounds whose molecules contain at least one regard, Al-C, for example, alyuminiiorganicheskikh compounds of General formula: R1mAl(OR2)nHpXqwhere each of the symbols R1and R2that may be RIADA from 1 to 15 carbon atoms, preferably from 1 to 4 carbon atoms, X represents an atom of halogena, m is a number defined by the inequality 0m3, n the number defined by the inequality 0n3, p is a number defined by the inequality 0p3, and q the number defined by the inequality 0q3, and m+n+p+q=3.

/ 2/ Complex alkylated products of aluminum and a metal of group I, meets the General formula: M1AlR14where M1represents a lithium atom, sodium or potassium, and the symbol R1defined above.

/ 3/ Valkirye compound of metal of group III, meet the General formula, R1R2M2where the values of the symbols R1and R2defined above, and M2atom of magnesium, zinc or cadmium.

In the above formulas, examples of the hydrocarbon groups for R1and R2are alkyl groups and aryl groups.

Examples alyuminiiorganicheskikh compounds /I/ is shown below.

Compounds of General formula R1mAl(OR2)3-m(where the symbols R1and R2defined above, and the preferred value defined by inequality 1,5m3;

compounds of General formula R1mAlX3-mvalues of R1defined above, X atom galegeae General formula R1mAlH3-mwhere the symbol R1defined above, and the preferred option m is the number defined by the inequality 2m3;

and

compounds corresponding to General formula, R1mAl(OR2)nXqwhere the values of the symbols R1and R2defined above, X denotes a halogen atom, 0m3, 0n3, 0q<3 and m+n+q 3.

Specific examples of ORGANOMETALLIC compounds of the formula I are trialkylaluminium connection, in particular triethylaluminium and tributylamine; trialkylaluminium compounds, in particular triisobutylaluminum; especially alkoxysilane alkylamines connection, for example, dialkylaminoalkyl, in particular diethylaminoethoxy and dibutylaminoethanol; alkylaminocarbonyl, in particular, ethylaminomethyl and butylaminoethyl; connection, the average composition of which corresponds to the formula R1the 2.5Al(OR2)0,5; partially halogenated alkylamine compounds, such as dialkylaminoalkyl, in particular, diethylaluminium, dibutylaniline and diethylaluminium; alkylhalogenide, in particular ethylaminoethanol, butylaminoethyl, in particular ethylaminoethanol, properlyinstalled and butylimidazole; especially hydrogensource alkylamines connection, for example, dialkylaminoalkyl, in particular diethylaluminium and dibutylaniline, alkylhalogenide, in particular arylaliphatic and propylaminoethyl; especially alcoholharmony and halogenated alkylamine connection, for example, alkylalkoxysilane, in particular, ethylaminoethanol, butylaminoethyl and ethylaminoethanol.

Examples of the compounds mentioned in the above paragraph. /2/ are LiAl(C2H5)4and LiAl(C7H15)4.

Examples of the compounds referred to in paragraph (/3/, shown above are diethylzinc and determine. You can also use alkylpolyglucoside, in particular ethylaniline.

In addition, you can apply alyuminiiorganicheskikh compounds, molecules in which two or more aluminum atoms are linked via oxygen atom or nitrogen, similar to joins /I/. Examples of such aluminum compounds are (C2H5)2AlOAl(C2H5)2, (C4H92">

Among the above alyuminiiorganicheskikh compounds trialkylaluminium connection and alkylamine compounds whose molecules are connected by two or more aluminum atoms are preferred.

Examples of organosilicon compounds /molecules containing the bond Si-O-C or Si-N-C, are alkoxysilane and arelatively. Thus, in particular, can be mentioned organosilicon compounds corresponding to General formula RnSi(OR14-nwhere R is a hydrocarbon group, in particular alkyl, cycloalkyl, aryl, alkenylphenol haloalkyl or aminoalkyl group or halogen atom, R1is a hydrocarbon group, in particular alkyl, cycloalkyl, aryl, alkenylphenol or alkoxyalkyl group, and n is the number defined by the inequality 0n 3, it is preferable 0n2, and n groups R or (4 n) groups OR1may be identical or different. In the formula above, the preferred value of the symbol R is a hydrocarbon group, particularly an alkyl group of C1-C10, cycloalkyl group C5-C12, aryl group, C6-C20, Alchemilla group C1-C10, haloalkyl, and the preferred value of R1is a hydrocarbon group C1-C20in particular an alkyl group of C1-C10, cycloalkyl group C5-C12, aryl group C6-C20, Alchemilla group C2-C10or alkoxyalkyl group C2-C10.

Other examples of catalytic component /C/ include siloxanes, the molecules of which contain a group OR1and Silovye esters of carboxylic acids. Examples R1identical to the above. You can also use the reaction product of compounds whose molecules contain a bond of Si-O-C compound whose molecules contain a link O-C obtained in advance or on site. For example, we can mention sharing haloesters silane compounds whose molecules contain no connection Si-O-C, or hydride of silicon with aluminum compound containing alkoxygroup, a compound of magnesium containing alkoxygroup, other metal alcoholate, alcohol, ether formic acid, ethylene oxide, and the like. The organosilicon compound may contain other metal, in particular aluminum and tin.

Examples of preference is methylacetylene, dimethyldiethoxysilane, dimethyldiethoxysilane, diphenylmethylsilane, methylphenyldichlorosilane, diphenyldichlorosilane, ethyltrimethoxysilane, methyltriethoxysilane, VINYLTRIMETHOXYSILANE, phenyltrimethoxysilane, gamma coproparasitological, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltrichlorosilane, venlafaxine, gram-aminopropyltriethoxysilane, harricharan, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, ethyl silicate, butylsilane, tributyltinoxide, methyltriacetoxysilane, vinyl-Tris/beta-methoxyethoxy/-silane, vinyltriethoxysilane, dimethyldiethoxysilane and phenyldimethylchlorosilane. Of them methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, VINYLTRIMETHOXYSILANE, ethyl silicate, diphenylmethylsilane, diphenyldichlorosilane and methyltrimethoxysilane (compounds of formula RnSi(OR1)4-nabove) are particularly preferred.

Component /C/ can be used in the form of an adduct with other compounds.

In accordance with this invention proposes a method of obtaining olefin polymers or copolymerization of at least one olefin with a small amount for example, up to 10 mol. diene in the presence of a catalytic system comprising a solid titanium catalyst component /A/ ORGANOMETALLIC compound /B/ and organosilicon /C/.

Examples of olefins which can be used include olefins, the molecules of which contain from 2 to 10 carbon atoms, in particular ethylene, propylene, 1-butene, 4-methyl-1-penten and 1-octene. They can be homopolymerization, disordered to copolymerizate or be subjected to block copolymerization. As the diene can be used polyunsaturated compound, in particular conjugated diene or non-conjugate diene. Specific examples include butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, ethylidenenorbornene, vinylnorbornene and 1.7-octadiene.

In the polymerization or copolymerization of alpha-olefins, the molecules of which contain at least 3 carbon atoms, can be used catalytic system of the present invention, particularly when the polymerization or copolymerization of alpha-olefins, the molecules of which contain from 3 to 10 carbon atoms, or copolymerization of at least one alpha-olefin with CSOs invention shows extremely valuable characteristics, consisting in the fact that in the polymerization of ethylene using it allows to achieve a high yield of polymer having a narrow interval of the distribution of particle sizes, high bulk density and narrow range of molecular weight distribution.

The polymerization process can be carried out either in the liquid or in the gas phase. During the liquid-phase polymerization process as the reaction medium can be used inert solvents, in particular hexane, hapten and kerosene. If desired, as the reaction medium can be used in the olefin. Accordingly you can find a number of catalyst. For example, in the preferred embodiment, for each liter of the reaction solvent in the case of liquid-phase reactions or per liter of the volume of the reaction zone in the case of the gas-phase reaction component of /A/ is used in amounts of from 0.0001 to 1 mmol. in terms of titanium atom; component /B/ is used in such amount that the number of metal atoms in the component (B) is from 1 to 2000 mol. preferably from 5 to 500 mol. for each mole of titanium atoms in the component /A/, and the /C/ is used in such quantities that kolichestvenno from 0.05 to 1 mol. for each mol of the metal atoms in the component /B/.

Before or during polymerization catalyst components /A/, /B/, /C/, you can enter into contact with each other. If it is put into contact with one another, before polymerization, only two of them can be chosen freely and then enter into mutual contact. Either two or three components can be partially taken and put into contact with each other. The introduction of these components into contact with each other can be carried out in an atmosphere of inert gas or in the atmosphere of the olefin.

The preferred process temperature of polymerization is in the range from about 20 to 200oC, more preferably from about 50 to 180oC. the Pressure ranges from atmospheric to about 100 kg/cm2preferably from about 2 to 50 kg/cm2. The polymerization process can be conducted periodically, semi-continuous or continuous. Such a polymerization can also be carried out in two or more stages, in which support different reaction conditions.

In the case when the proposed method is carried out in the process stereospecific polymerization of alpha-olefins, mo is decennale spatial patterns, can be obtained with high catalytic efficiency. Despite attempts to obtain a polymer having a high melt index, using hydrogen in the polymerization of olefin using known up to the present time such catalytic components, resulting in the tendency has been to a considerable decrease in the ordering of the spatial patterns, the use of the catalytic system in accordance with the present invention minimizes this tendency.

As for the high activity of the catalyst, the yield of polymer per unit amount of the solid titanium catalyst component (A) exceeds the output produced by previously known techniques for obtaining polymers with the same degree of ordering of the spatial structure. Thus can be reduced in the resulting polymer catalytic residue, in particular halogen. This allows you to not only eliminate the need for removal of catalyst, but also significantly reduce the tendency to korrodirovaniju molding equipment in the process of formation.

In the case when the method of the present invention Et for granulated polymer or polymer with almost spherical particles, that looks like the product of aggregation of fine-grained powders. This granular polymer or polymer spherical particles has good flowability, and in some cases can be used directly, without pre-tabletting. Another advantage is that the melt index of the polymer can be changed by using a reduced amount of agent to control molecular weight, in particular hydrogen than in conventional catalytic systems, and surprisingly, the increase in the number of agent to control molecular weight makes it possible to increase the catalytic activity of the catalyst is that it is distinguished from the previously known catalysts. In conventional catalytic systems increase the number of agent regulation of the molecular weight when attempting to obtain a polymer having a high melt index, leads to a decrease in the partial pressure of olefin monomer and, consequently, to reduced activity of the catalytic system. The catalytic system of the present invention allows us to be freed from the need to resolve such problems, because its activity to a certain extent Though the activity of known catalytic systems over time in the process of polymerization decreases, this phenomenon can hardly be observed in relation to the catalytic system of the present invention. The advantages of the present invention are manifested even in the case when the catalytic system is used in conditions of multi-stage polymerization process, as it allows significantly increase the amount of polymer product.

As the catalytic system of the present invention very hour at high temperatures, the reduction in the degree of ordering of the spatial structure can hardly be seen even in the polymerization of propylene at a temperature of, component of, for example, approximately 90oC.

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

At a temperature of 130oC for 2 h held a reaction between 4,76 (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 (150 mmol) of 2-ethylhexanol alcohol, resulting in the prepared homogeneous solution. To this solution was added to 1.11 g (7.5 mmol) of phthalic anhydride and the mixture is further stirred at a temperature of 130oC for 1 h, which allow the solution was cooled to room temperature and fully added dropwise within 1 h in 200 ml (1.8 mol) of titanium tetrachloride, the temperature of which was maintained at a level of -20oC. After the append operation has completed within 4 h the temperature of the mixture was raised to 110oC, when the temperature reached 110oC it added of 2.68 ml (12.5 mmol) of diisobutylphthalate. The mixture is then passed at this temperature for 2 h with stirring. After completion of the reaction, the reaction mixture was subjected to hot filtration, the collected solid fraction. This solid fraction is again suspended in 200 ml of titanium tetrachloride and at a temperature of 110oC for 2 h held a reaction. After completion of the reaction, the solid portion was collected by hot filtration and washed by the Dean, the temperature of which was maintained at a level of 110oC, and hexane until, while in the wash liquids has not ceased to find no free titanium compound.

The solid titanium catalyst component (A) synthesized by the above method, kept in suspension in hexane. Part of this suspension is dried in order to check the composition of the catalyst. In the result, it was found that the obtained solid titanium catalyst component (A) consisted of 3.1 wt. titanium, 56,0 wt. chlorine, of 17.0 wt. magnesium and 20.9 wt. diisobutylphthalate.

oC and propylene was polymerizable within 2 hours during polymerization the pressure was maintained at 7 kg/cm2(excessive pressure).

After completion of the polymerization, the slurry containing the resulting polymer was filtered, resulting in a white powdered polymer and liquid layer. After drying, the amount of white powdery polymer amounted to 379.2, After extraction with boiling n-heptane the remainder of this polymer was 98.9%, the melt index (YR/MI) of the polymer was equal to 7.5, and its apparent density of 0.44 g/ml, the Distribution of particle sizes such white powdery polymer shown in the table.1. In the concentration of liquid layer received 1.9 grams soluble in the solvent of the polymer. Thus, the activity was 25400 g of polypropylene/mmol. titanium, while the rate for stereoregularity /PS/ (I. I) polymer was generally equal to 98.4%

Examples 2 to 6. The experiment of example 1 was repeated, except that in this case the number of odor ltati summarized in table.2.

Examples 7 and 8. The experiment of example 1 was repeated except that the polymerization was carried out at a temperature of respectively 80 and 90oC. the results Obtained are given in table.3.

Example 9. A 2-liter autoclave was loaded with 500 g of propylene, and at room temperature in the autoclave was introduced 0.25 mmol of triethylaluminum, of 0.025 mmol of diphenyldichlorosilane and 0.005 mmol in terms of the atomic number of titanium catalytic component (A) described in example 1. Later in the autoclave was introduced 750 ml of hydrogen. The temperature is raised to 80oC for 1 h was carried out the polymerization of propylene. After drying, the amount of the obtained polymer was in General 192,3, After extraction of the polymer with boiling n-heptane, the residue was 98.6% of its IL was equal to 3.2, and apparent density -0,48 g/ml Thus, the activity for this period of time was 38500 g of polypropylene/mmol of titanium.

Examples 10 to 14. The process of example 9 was repeated except that in the polymerization used the 0.375 mmol of triethylaluminum, 0,0188 mmol of phenyltriethoxysilane and 0.0025 mmol in terms of the atomic number of titanium catalytic component (A) described in example 1, and prinnie the results are given in table.4.

Example 15. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature in the autoclave was introduced 2.51 mmol of triethylaluminum, 0.125 mmol of diphenyldichlorosilane and 0.015 mmol in terms of the atomic number of titanium catalytic component (A) described in example 1. After administration of 200 ml of hydrogen, the temperature was raised to 70oC and propylene was polymerizable within 2 hours during polymerization, the excess pressure was maintained at 7 kg/cm2. The reaction mixture was subjected to the treatment according to the same procedure as described in example 1. The results obtained are given in table.5.

Example 16. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature, the autoclave was added 2.51 mmol of triethylaluminum, 0,225 mmol of phenyltriethoxysilane and 0.015 mmol (in terms of automarine the amount of the titanium catalyst component (A) described in example 1. After administration of 200 ml of hydrogen, the temperature was raised to 70oC for 2 h spent the polymerization of propylene. During this process the excess pressure was maintained at 7 kg/cm2. The reaction mixture is further subjected to processing the first autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature, the autoclave was added 2.51 mmol of triethylaluminum, 0.30 mmol of VINYLTRIMETHOXYSILANE and 0.015 mmol (in terms of atomic number of titanium catalytic component (A) described in example 1. After administration of 200 ml of hydrogen, the temperature was raised to 70oC for 4 h had surgery polymerization of propylene. During polymerization, the excess pressure was maintained at 7 kg/cm2. Next, the reaction mixture was treated similarly to the foregoing example 1. The results obtained are given in table.5.

Example 18. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature in the autoclave was added 2.51 mmol of triethylaluminum, 0.45 mmol of methyltrimethoxysilane and 0.015 mmol (in terms of atomic number of titanium catalytic component (A) described in example 1. After adding 200 ml of hydrogen, the temperature was raised to 70oC for 2 h had surgery polymerization of propylene. During this operation the polymerization of the excess pressure was maintained at 7 kg/cm2. Next, the reaction mixture was subjected to processing similar to the above example 1. The results obtained are given in table.5.

Example 19. A 2-liter autoclave was loaded with 750 ml of cleaned up the Oia, 0.30 mmol of tetraethoxysilane and 0.015 mmol (in terms of atomic number of titanium catalytic component (A) described in example 1. After introduction into the autoclave of 200 ml of hydrogen, the temperature was raised to 70oC for 4 h had surgery polymerization of propylene. During polymerization, the excess pressure was maintained at 7 kg/cm2. This reaction mixture was subjected to processing similar to the above example 1. The results obtained are given in table.5.

Example 20. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature, the autoclave was added 2.51 mmol of triethylaluminum, 0,225 mmol of ethyltriethoxysilane and 0.015 mmol (in terms of atomic number of titanium catalytic component to /A/, described in example 1. After introduction into the autoclave of 200 ml of hydrogen, the temperature was raised to 70oC for 4 h had surgery polymerization of propylene. During this polymerization, the excess pressure was maintained at 7 kg/cm2. Next, the reaction mixture was subjected to processing similar to the above example 1. The results obtained are given in table.5.

Example 21. A 2-liter autoclave was loaded with 750 ml of illumine, 0,225 mmol of vinyltriethoxysilane and 0.015 mmol (in terms of atomic number of titanium catalytic component to /A/, described in example 1. After administration of 200 ml of hydrogen, the temperature was raised to 70oC for 4 h had surgery polymerization of propylene. Next, the reaction mixture was subjected to processing similar to the above example 1. The results obtained are given in table.5.

Example 22. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature in the autoclave was added 2.51 mmol of triethylaluminum, 0,225 mmol of methylphenyldichlorosilane and 0.015 mmol in terms of the atomic number of titanium catalytic component to /A/, described in example 1. After introduction into the autoclave 220 ml of hydrogen, the temperature was raised to 70oC for 2 h had surgery polymerization of propylene. During this polymerization, the excess pressure was maintained at 7 kg/cm2. Next, the reaction mixture was subjected to processing similar to the above example 1. The results obtained are given in table.5.

Example 23. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature in this car mmol (in terms of atomic number of titanium catalytic component to /A/, described in example 1. After introduction into the autoclave of 200 ml of hydrogen, the temperature was raised to 70oC for 2 h had surgery polymerization of propylene. During this polymerization, the excess pressure was maintained at 7 kg/cm2. Next, the reaction mixture was subjected to processing similar to the above example 1. The results obtained are given in table.5.

Example 24. Preparation of the titanium catalyst component /A/:

Spent the reaction was 4.76 g (50 mmol) of anhydrous magnesium chloride with 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexanol alcohol at a temperature of 130oC for 2 h to obtain a homogeneous solution. Then to this solution was added to 1.11 g (8.5 mmol) of phthalic anhydride. To dissolve the phthalic anhydride and the mixture was stirred at a temperature of 130oC for 1 h Prepared homogeneous solution was cooled to room temperature and completely within 1 h was added to 200 ml (1.8 mmol) of titanium tetrachloride, the temperature of which was maintained at a level of -20oC. After completion of this addition the temperature of the mixed solution for 4 h increased to 110oC. When the temperature reached 110oC, the mixture was added 3.5 g (12.5 mmol) of di-n-butil solid fraction, which was collected by hot filtration of the reaction mixture. Solid fraction then again suspended in 200 ml of titanium tetrachloride and again stood at the temperature of 120oC within 2 hours After completion of the reaction the solid fraction was collected by hot filtration, and fully washed by the Dean, the temperature of which was maintained at a level of 120oC, and hexane until, while in the wash liquid has not ceased to find any free titanium compound.

The obtained catalytic component /A/ kept in hexane in the form of sludge. Part of this sludge is dried in order to check the composition of the catalyst. The obtained catalytic component /A/ contained, as it was installed, 2.1 wt. titanium.

Using the obtained solid titanium catalyst component similar to the above example 1 had surgery polymerization of propylene. The results obtained are given in table.6.

Example 25. Preparation of solid titanium catalyst component /A/:

Spent the reaction was 4.76 g (50 mmol) of anhydrous magnesium chloride with 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexanol alcohol for 2 hours at a temperature of 130oC, resulting in an od is the song data anhydride. The resulting homogeneous solution was cooled to room temperature and for 1 h fully dropwise added to 200 ml (1.8 mol) of titanium tetrachloride, the temperature of which was maintained at a level of -20oC. After complete addition the mixture was heated to a temperature of 100oC for 4 h When the temperature reached 110oC, was added to 2.6 ml (18.0 mmol) of diethylphthalate. At this temperature the mixture stand for 2 hours After 2-hour reaction, the solid fraction was isolated from the reaction mixture by hot filtration. The solid fraction is again suspended in 200 ml of titanium tetrachloride and again carried out the reaction at a temperature of 120oC within 2 hours After completion of the reaction the solid fraction was again collected by hot filtration and washing with Dean, the temperature of which was maintained at a level of 120oC, and hexane until complete disappearance in the washing liquid of any free of detectable titanium compounds.

Prepared solid titanium catalyst component to /A/, described above, was stored in the form of slurry in hexane. Part of this sludge is dried in order to check the composition of the catalyst. The obtained solid titanium catalyst component /A/ materialteknologi component /A/ similar to the above example 1 had surgery polymerization of propylene. The results obtained are given in table.6.

Example 26. Preparation of solid titanium catalyst component /A/:

Spent the reaction between the value of 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexanol alcohol at a temperature of 130oC for 2 h, resulting in a homogenous solution. Next to this solution was added to 1.11 g (7.5 mmol) of phthalic anhydride and the mixture was stirred at a temperature of 130oC for 1 h to dissolve the phthalic anhydride. The resulting homogeneous solution was cooled to room temperature and for 1 h completely was added dropwise to 200 ml (1.8 mmol) of titanium tetrachloride, the temperature of which was maintained at a level of -20oC. After completion of this operation was added to the mixture for 4 h was heated to a temperature of 110oC. When the temperature of the mixture reached 110oC, it was added to 2.9 ml (12.5 mmol) of Diisopropylamine and the mixture is then passed at this temperature for 2 hours After 2-hour reaction, the solid fraction was isolated from the reaction mixture by hot filtration. This solid fraction is again suspended in 200 ml of titanium tetrachloride and again carried out the reaction at a temperature of 120decanol, the temperature of which was maintained at a level of 120oC, and hexane until then, until no longer be detected in the wash liquid any available titanium compounds.

The solid titanium catalyst component to /A/, prepared according to the above, stored in the form of a slurry in hexane. Part of this sludge is dried in order to check the composition of the catalyst. Finish solid titanium catalyst component /A/ contained, as it was found, 2.9 wt. titanium.

Using this finish solid titanium catalyst component /A/ had surgery propylene polymerization similarly to the foregoing example 1. The results obtained are given in table.6.

Example 27. The preparation of the catalytic component to /A/:

the 5.25 g C2H5OMoCl, 23,2 ml of 2-ethylhexanol alcohol and 50 l Dean was stirred at room temperature for about 1 hour In ready homogeneous solution was added to 1.11 g of phthalic anhydride and the reaction was carried out at a temperature of 130oC for 1 h, resulting phthalic anhydride dissolved in a homogeneous solution. Then the solution was cooled to room temperature. Thus prepared homogeneous solution is supported at the level -20oC. the mixture is subjected to processing similar to the above example 1, which has prepared a catalytic component to /A/.

Polymerization:

Propylene was polymerizable similarly described above in example 15, except that in this case used catalytic component to /A/, prepared according to the above. The polymerization activity was 23700 g of polypropylene/mmol of titanium and PS polymer, in General, were 96,0% Apparent density of the polymer was equal 0,42 g/ml.

Example 28. The preparation of the catalytic component to /A/:

Spent the reaction between 150 ml technologo solution containing 50 mmol ethylbutylamine and 17.0 ml of 2-ethylhexanol at a temperature of 80oC for 2 h, resulting in a homogeneous solution. This solution was then added to 1.11 g (7.5 mmol) of phthalic anhydride, resulting in a completely homogeneous solution. This homogeneous solution was added dropwise with stirring introduced for 1 h in 200 ml of titanium tetrachloride, the temperature of which was maintained at a level of 20oC. and Then held the same process described in example 1, resulting in a catalytic component to /A/.

Example 29. The preparation of the catalytic component to /A/:

Spent the reaction between the value of 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane, 3.4 ml (10 mmol) of tetraethoxysilane and 17.9 ml (115 mmol) of 2-ethylhexanol alcohol at a temperature of 130oC for 2 h, resulting in a homogenous solution. To this solution was added to 1.11 g (7.5 mmol) of phthalic anhydride and the mixture was stirred at a temperature of 130oC for 1 h to dissolve the phthalic anhydride. Prepared homogeneous solution was cooled to room temperature and for 1 h dropwise entirely introduced into 200 ml (1.8 mmol) of titanium tetrachloride, the temperature of which was maintained at a level of -20oC. and Then held the same operation as that described in example 1, resulting in a solid titanium catalyst component to /A/.

Polymerization:

Propylene polymerization similarly to the described above in example 15 using the obtained solid titanium catalyst component to /A/. The results obtained are given in table.7.

Example 30. Preparation of solid titanium catalyst component /A/:

The solid catalytic component /A/ brightledge anhydride used 1,43 (10 mmol) of ethylbenzoic. Such catalytic component /A/ contained 2.4 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 1 using a solid catalytic component to /A/. The results obtained are given in table.8.

Example 31. Preparation of solid titanium catalyst component /A/:

The solid catalytic component Are synthesized analogously to the above example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride used of 1.80 ml (15.6 mmol) of benzoyl chloride, resulting in the process of preparation of the catalyst obtained 2-ethylhexanoate. The finished solid catalyst component /A/ contained 3.1 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 1 using a solid catalytic component to /A/. The results obtained are given in table.8.

Example 32. Preparation of solid titanium catalyst component /A/:

The solid catalytic component of /A/ was prepared similarly to the foregoing example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic ANS. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 15 using a solid titanium catalyst component to /A/. The results obtained are given in table.8.

Example 33. Preparation of solid titanium catalyst component /A/:

The solid catalytic component of /A/ was prepared similarly to the foregoing example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride used 1,12 ml (15 mmol) of propionic acid. The finished solid catalyst component /A/ contained 3.1 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 15 using the solid catalytic component to /A/. The results obtained are given in table.8.

Example 34. Preparation of solid titanium catalyst component /A/:

The solid catalytic component of /A/ was prepared similarly to the foregoing example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride used 7.5 mmol of diphenylmethane. The obtained solid catalyst component /A/ contained 2.5 wt. titanium.

Polym Agogo titanium catalytic component to /A/. The results obtained are given in table.8.

Example 35. Preparation of solid titanium catalyst component /A/:

The solid catalytic component Are synthesized analogously to the above example 1, except that instead of 1.11 g (7.5 mmol) of phthalic anhydride used is 1.82 ml (15 mmol) of diethylmalonate. The obtained solid catalyst component /A/ contained 4.3 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 15 using a solid catalytic component to /A/. The results obtained are given in table.8.

Example 36. Preparation of solid titanium catalyst component /A/:

The solid catalytic component of /A/ was prepared similarly to the foregoing example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride was used to 0.88 ml (7.5 mmol) of tetramethylsilane. The finished solid catalyst component /A/ contain a 5.1 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 15 using a solid titanium catalyst component to /A/. The results obtained St the solid catalytic component of /A/ was prepared similarly to the foregoing example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride used 0,99 ml (7.5 mmol) of n-butylcellosolve. The finished solid catalyst component /A/ contained 5.5 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 15 using a solid catalytic component to /A/. The results obtained are given in table.8.

Example 38. Preparation of solid titanium catalyst component /A/:

The solid catalytic component of /A/ was prepared similarly to the foregoing example 1, except that in this case instead of 1.1 g (7.5 mmol) of phthalic anhydride used a 4.86 ml (20 mmol) 2-ethylhexanoate. The finished catalytic component /A/ contained 3.1 wt. titanium.

Polymerization:

Propylene was polymerizable similarly described above in example 15 using prefabricated titanium catalytic component to /A/. The results obtained are given in table.8.

Example 39. A 2-liter autoclave was loaded with 750 ml of purified hexane, and in an atmosphere of propylene at room temperature in the autoclave was introduced 2.51 mmol of triethylaluminum, 0.15 mmol of phenyltriethoxysilane and 0.015 m the introduction into the autoclave 100 ml of hydrogen, the temperature was raised to 60oC. When the temperature of the polymerization system reached 60oC, the autoclave was introduced a gas mixture of propylene and ethylene containing 8,2 mol. ethylene, and within 2 h in an autoclave maintained excessive polymerization pressure of 2 kg/cm2. After the polymerization was filtered, slamm, which contained the polymer, the resulting reaction mixture was divided into white powder and a liquid layer. After drying, it was found that the number of the obtained white powdery polymer was 273,2, IL this polymer was 6.9, and its apparent density was equal to 0.37 g/ml By measuring the IR spectrum of this white powdery polymer was found that it contained a 5.0 mol. the isolated ethylene. By the method of differential scanning calorimetry found that the melting temperature (TWthis polymer was 135oC. the concentration of liquid layer received 14.8 g soluble in the solvent of the polymer. Thus, the catalytic activity was 19200 g of polypropylene/mmol of titanium, and the polymer yield was equal 94,9%

Examples 40 to 47. The preparation of the catalytic component to /A/:

Catalytic component /A/ butylphthalate used 12.5 mmol of each of the compounds, listed in table.9.

Polymerization:

Propylene was polymerizable similarly described above in example 15, except that in this case used a catalytic component to /A/, prepared according to the above. The results obtained are given in table.9.

Example 48. The preparation of the catalytic component to /A/:

50 mmol of the solid substance obtained by the reaction butylamine chloride with silicon tetrachloride, 25 ml of decane and 23.4 ml of 2-ethyl-hexyl alcohol, held at a temperature of 130oC for 2 h, resulting in a homogeneous solution. Then added to 1.11 g of phthalic anhydride and at the same temperature for 1 h spent the reaction, resulting in the newly formed a homogenous solution. Then the solution was subjected to processing similar to the above example 1, resolute which received the catalytic component to /A/.

Polymerization:

Propylene was polymerizable similarly described above in example 15, except that in this case used a catalytic component to /A/, prepared according to the above. The results obtained are given in table.10.

Example 49. Preparation of catalytic components which do 5.73 g dioxirane, and 23.4 ml of 2-ethylhexanol alcohol and 50 ml of decane. Ready homogeneous solution was added to 1.11 g of phthalic anhydride and at the same temperature for 1 h was carried out a reaction. A freshly prepared homogeneous solution was subjected to processing similar to the above example 1, the resulting catalytic component to /A/.

Polymerization:

Propylene was polymerizable similarly described above in example 15, except that in this case used a catalytic component to /A/, prepared according to the above. The results obtained are given in table.10.

Examples 50 and 51. The preparation of the catalytic component to /A/:

Catalytic component of /A/ was prepared similarly to the foregoing example 1, except that instead of 2-ethylhexanol alcohol used each of the compounds listed in table.11.

Polymerization:

Propylene was polymerizable similarly described above in example 15, except that in this case used a catalytic component to /A/, prepared according to the above. The results obtained are given in table.11.

Example 52. A 2-liter autoclave was loaded 1000 ml of purified hexane and EA atomic number of titanium catalytic component to /A/, prepared in example 1. The autoclave was hermetically closed, after which the temperature was increased to 80oC. At a temperature of 80oC excessive pressure increased to 3 kg/cm2the introduction of the hydrogen, after which the autoclave was introduced ethylene to a total gauge pressure of 8 kg/cm2. The temperature was maintained at 90oC for 2 h after 2 h after injection of the ethylene feed to the autoclave this last stopped and the contents of the autoclave was quickly cooled.

After the polymerization was filtered slurry containing the resulting polymer, in the collected white powdery polymer. The amount of white powdery polymer after drying was $ 316, the Apparent density of this polymer was 0.39 g/ml, and IL was equal to 5.1. The obtained polymer was characterized by a very good distribution of particle sizes, as shown in the table.12. The distribution of the molecular weights of the white powdery polymer was measured by gel permeation chromatographic analysis, the result, it was found that the magnitude of the ratio of Molecular weight /MP 3.9.

The results are presented in table.12.

Example 53. A 2-liter autoclave plan and 0.02 mmol (in terms of atomic number of titanium catalytic component to /A/, obtained in the foregoing example 1, after which the inlet of the catalyst in the autoclave was blocked. Later in the autoclave was introduced 50 ml of hydrogen. The contents of the autoclave were heated to a temperature of 60oC, and then stood at the same temperature for 2 hours after 2 hours the contents of the autoclave was quickly cooled.

After polymerization, the slurry, which included the resulting polymer was filtered, resulting in its divided into a white powdery polymer and a liquid phase. The number of the obtained white powdery polymer after drying was 213,2, the Apparent density of this polymer was equal to 0.31 g/ml, and its characteristic viscosity amounted to () of 5.5. By concentrating the liquid phase obtained 3.1 g soluble in the solvent of the polymer. Thus, the catalyst activity was 10800 g polymer/mmol of titanium, and the polymer yield to 98.6 wt.

Example 54. A 2-liter autoclave after purging with nitrogen uploaded 1 l (580 mmol) of the pure butene-1 and at a temperature of 0oC in the autoclave was introduced 1.0 mmol of triethylaluminum, 0.7 mmol of diphenyldichlorosilane and 0.02 mmol (in terms of atomic number of titanium catalytic component to /A/, prepared according to the ate 300 ml of hydrogen. The contents of the autoclave is then heated to 35oC and kept at this temperature for 2 hours after a 2-hour time period for terminating the polymerization was added 10 ml of methanol. Unreacted butene-1 was removed from the autoclave by blowing. The obtained white powdery polymer was dried and determined its amount. It amounted to 263, the Residue after extraction of the polymer with boiling n-heptane was 96,5%

Additional working examples X/1-X/61 + X/62 X/73 and comparative examples C-X 1 C-X/53 and comparative examples C-R/1 C-R/10 + C-R/11 C-R/12

Example X/1. Preparation of solid titanium-containing catalytic component to /A/.

The reaction mixture containing the value of 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexanol alcohol were heated at 130oC for 2 h until a homogeneous solution. To this solution was added 7 mmol normal octane acid, and the resulting solution was stirred at 130oC for another 1 h thus Obtained homogeneous solution was cooled to room temperature and dropwise whole amount of the obtained solution was added to 200 ml (1.8 mmol) of titanium tetrachloride at -20oC for one hour. After terature water mixture reached 110oC, was added 12.5 mmol of diisobutylphthalate. The mixture is then passed at this temperature with stirring for two hours. After these two hours solid (fraction) was collected by hot filtration. This solid fraction is then re-suspended in 200 ml of titanium tetrachloride and left at 110oC again for two hours. After completion of the reaction was collected by hot filtration of the solid fraction and carefully washed her in hexane and decane at 110oC to total absence in the wash fluid traces of free compounds of titanium. The result was a solid titanium-containing catalytic component to /A/.

Polymerization:

In an autoclave with an internal capacity of 2 l was loaded with 750 ml of purified hexane. Then there was added 2.51 mmol of triethylaluminum, 0.125 mmol of diphenyldichlorosilane and 0.015 mmol (based on titanium) obtained above catalytic component to /A/ at room temperature in an atmosphere of propylene. After introduction into the autoclave of 200 ml of hydrogen, the temperature was raised to 70oC and held the polymerization of propylene. The pressure during the polymerization was maintained equal to 7 kg/cm2(excessive pressure i.e. gauge).

After Zavorotny the polymer and the liquid phase. The white powdery polymer after drying was 308,8, the Degree of extraction residue with boiling n-heptane equal to 98.5% of Its apparent density equal 0,41 g/ml there was obtained 6.4 g soluble in the solvent of the polymer after condensation of the liquid phase. Accordingly, the activity of the catalyst amounted to 21,000 g-polymer/mmol-Ti, and 1.1 pure polymer 96.5% of the results are shown in table.1.

Examples X/2-X/10, X/13 X/15 and X/28-X/30.

Solid titanium-containing catalytic component /A/ obtained in accordance with the procedure of example X/1, except for one thing - instead of n-octane acid of example X/1 used an electron-donating compound /D/, is provided in each of the tables C/1/ C/2/. Polymerization of propylene was conducted then using this catalytic component to /A/. The results are shown in table. C/1/ C/2/.

Examples X/16, X/19.

Solid titanium-containing catalytic component of /A/ was obtained in accordance with the procedure of example X/1, except for one thing - instead of n-octane acid of example X/1 used phthalic anhydride, and instead of diisobutylphthalate used essential connection /E/, are given in table. the tats are given in table.2.

Examples X/18 X/24 X/27. Solid titanium-containing catalytic component of /A/ was obtained in accordance with the procedure of example 29 of the present description, except for one point instead of tetraethoxysilane of example 29 was used connection of alkoxysilane table. C/2/. Polymerization of propylene was carried out using this catalytic component to /A/. The results are shown in table. C/2/.

Examples X/20 X/23. Solid titanium-containing catalytic component of /A/ was obtained in accordance with the procedure of example 28 of the present description, except for one point instead of ethylbutylamine of example 28 was used connection alkoxyamine table. C/2/. Polymerization of propylene was carried out using this catalytic component. The results are shown in table. C/2/.

Examples X/31 X/34. The experiment was carried out in accordance with example 2 of the present description, except for one point instead of 0.125 mmol of phenyltriethoxysilane of example 1 was used 0,225 mmol silane compounds shown in the table. C/3/. The results are shown in table. C/2/.

Examples X/35-X/50 X/52. The experiment was conducted according to example 1, the crust is ethylaluminum and instead 0.125 mmol of triethoxysilane of example 1 was used of 0.075 mmol of silane compounds, are given in table. C/3/ C/4/. The results are shown in table. C/2/ C/3/.

Example X/51. The experiment was conducted in accordance with example 1 of the present description, except that instead of 2.51 mmol of triethylaluminum used 0.75 mmol of triethylaluminum and 0.75 mmol of n-decyltriethoxysilane of example 1. The results are shown in table. C/3/.

Example X/53. In an autoclave with an internal capacity of 2 l was loaded with 750 ml of purified hexane. After filling the internal volume of the polymerization sisami propylene by purging at room temperature was added 20 ml of 1,9-decadiene. After administration of 200 ml of hydrogen in the polymerization system, the temperature was raised to 60oC. In accordance with the procedure of example 1 of the present description using the supply system of the catalyst was loaded into the autoclave, 1.5 mmol of triethylaluminum, 0.15 mmol of cyclohexyldimethylamine and 0.03 mmol in terms of titanium catalytic component to /A/, obtained in example 1 of the present description. The temperature was increased to 70oC and within two hours he spent the copolymerization of propylene-1,9-octadien. The pressure during the polymerization was maintained equal to 7 kg/cm2(excessive pressure, i.e. manageritalia of transactions received 422,2 g of a white powdery polymer. The degree of extraction with boiling n-heptane equal to 98.8% of the Apparent density of the polymer 0.40 g/ml, the melt Index of the specified white powdery polymer was equal to 0.7 g/10 min, and melting point, determined by the method of differential calorimetry equal 155,5oC. there was obtained 1.1 g of the polymer soluble in the solvent by condensation of the liquid phase. The activity of the catalytic system is equal 14,100 g/polymer/mmol of titanium and 1,1 pure polymer equal to 98.5% of the results are presented in table. C/3/.

Example X/54. The experiment was carried out in accordance with the procedure of example 33 of the present description, except that instead of 15 mmol propionic acid used 3 mmol propionic acid instead of 12.5 mmol of diisobutylphthalate in example 33 was used 5.5 mmol of diisobutylphthalate. The results obtained are presented in table. C/3/.

Example X/55. Was repeated procedure of example 33 of the present description, except for one moment 2.25 mmol propionic acid was used instead of 15 mmol and instead of 12.5 mmol of diisobutylphthalate used to 22.5 mmol of diisobutylphthalate. The results are shown in table. C/3/.

Example X/56. Was repeated PR is the iMER X/54, used to 22.5 mmol of diisobutylphthalate. The results are shown in table. C/3/.

Example X/57. Was repeated procedure of example X/54, except for one point instead of 3 mmol propionic acid used in example X/54, took to 22.5 mmol propionic acid. The results are shown in table. C/3/.

Example X/58. Preparation of solid titanium-containing catalytic component to /A/.

23,8 g (250 mmol) of anhydrous magnesium chloride, 125 ml of the Dean and 117 ml (750 mmol) of 2-ethylhexanol alcohol was heated for 2 h until a homogeneous solution at 130oC. To this solution was added 75 mmol of ethylbenzoic, and the solution was stirred at 130oC another hour. Thus obtained homogeneous solution was cooled at room temperature, and the entire amount dropwise added to 100 ml (0.9 mmol) of titanium tetrachloride, maintained at -15oC for one hour. After completion of the addition the temperature of the water mixture increased within 4 h to 120oC. the mixture is Then passed at this room temperature under stirring for another two hours. After the reaction for two hours solid fraction was collected by hot filtration. This solid fraco temperature reached 120oC, the system has added 35 mmol of diisobutylphthalate. The temperature of the system was maintained at the same level with stirring for two hours. After these two hours of solid fraction was collected by hot filtration. This solid material suspended again in 300 ml of titanium tetrachloride, and the suspension was heated again for two hours at 120oC. After completion of the reaction the solid fraction was collected by hot filtration and thoroughly washed in hexane and decane at 110oC until complete disappearance of traces of free compounds of titanium in the wash liquid. Got a solid titanium-containing catalytic component to /A/.

Polymerization

In an autoclave with an internal capacity of two liters downloaded 750 ml of purified hexane. Then, the autoclave was loaded with 0.75 mmol of triethylaluminum, of 0.075 mmol of diphenyldichlorosilane and 0.015 mmol (based on titanium) obtained above catalytic component to /A/ at room temperature in an atmosphere of propylene. After administration of 200 ml of hydrogen, the temperature was raised to 70oC and held for two hours the polymerization of propylene. Subsequent processing of the polymer was carried out according to the procedure outlined in the CSO titanium-containing catalytic component to /A/.

0,952 g (10 mmol) of anhydrous magnesium chloride, 5 ml of the Dean and 4.7 ml (30 mmol) 2-ethylhexanol alcohol was heated for two hours at 130oC until a homogeneous solution. To this solution was added 1.5 mmol of phthalic anhydride, and the solution was stirred under heating at 130oC another hour. Thus obtained homogeneous solution was cooled at room temperature, and its number dropwise added to 200 ml (1.8 mmol) of titanium tetrachloride, maintained at -20oC for one hour. After completion of the addition the temperature of this aqueous mixture was raised to 110oC for four hours. As soon as the temperature reached 110oC, to the water mixture was added 2.5 mmol of diisobutylphthalate. The mixture is then passed at the same temperature under stirring for two hours. After the reaction for two hours solid material was filtered on a funnel for hot filtration. The obtained solid fraction suspended again in 200 ml of titanium tetrachloride, and the suspension was again heated at 110oC for two hours. After completion of the reaction, the solid material was again filtered over for hot filtration and thoroughly washed in hexane and Dec the way, received the catalytic component to /A/.

Polymerization

The polymerization was carried out according to the procedure described in example X/58. The results are shown in table. C/3/.

Example X/60. Was repeated procedure of example 15 of the present description, except for one point instead of 0.125 mmol of diphenyldichlorosilane of example 15 was used 1.25 mmol of diphenyldichlorosilane. The results obtained are presented in table. C/3/.

Example X/61. Was repeated procedure of example 15 of the present description, except for one point instead of 0.125 mmol of diphenyldichlorosilane of example 15 was used in this case 5,02 mmol of diphenyldichlorosilane. The results obtained are presented in table. C/3/.

Comparative examples C/X-1 and C/X-53. Examples of comparison corresponding to the above examples were conducted as follows. Namely, when receiving the solid titanium-containing catalytic component /A/ depending on the above respective experiments (examples), the catalytic component of /D/, used in each experiment, was applied in the same amount instead of the catalytic component, /E/, in order to obtain a solid titanium-containing rolled, Poslednyaya was conducted in accordance with the terms and conditions of each example And, specifically, in s-1, for example, phthalic anhydride was used instead of diisobutylphthalate used in the preparation of the solid titanium-containing catalytic component to /A/ in the example 1 of the present description, to obtain a solid titanium-containing catalytic component to/A/. Then, polymerization of propylene was carried out analogously to the procedure described in example 1 of the present description. The following procedures were used in comparative examples C-R/1 C-R/7.

Comparative examples C-R/1 and C-R/2. Was repeated procedure of example 15 of the present description, except for one point instead of 12.5 mmol, used in the example 15, was used in the C R/1/ 0.5 mmol of diisobutylphthalate, while the C-R/2 65 mmol of diisobutylphthalate. The results obtained are presented in table. D/4/.

Comparative examples C-R/3 and C-R/4. Was repeated procedure of example 15 of the present description with the exception of one time instead of 7.5 mmol of phthalic anhydride used in example 15, in the example of R/3 was using 1.0 mmol of phthalic anhydride as in example C-R/4, respectively, 65 mmol. The results obtained are presented in table. D/4/.

Cf (910 mmol ) of anhydrous magnesium chloride, 455 ml of decane and to 426.2 ml (2,730 mmol) 2-ethylhexanol alcohol were heated at 130oC for two hours until a homogeneous solution. To this solution was added to 136.5 mmol phthalic anhydride, and the solution was stirred at 130oC one hour to dissolve the phthalic anhydride in the above homogeneous solution. Thus obtained homogeneous solution was cooled at room temperature and all received a number of homogeneous solution is dropwise added to 100 ml of 0.91 mmol) of titanium tetrachloride, maintained at -20oC for one hour. After completion of the addition the temperature of the water mixture was raised to 110oC for 4 hours as soon As the temperature reached 110oC, added to the system 227,5 mmol of diisobutylphthalate. Then the system has stood at the same temperature under stirring for two hours. After two hours the reaction was filtered solid material. This solid material suspended again in 200 ml of titanium tetrachloride and continued stirring at 110oC for two hours. After completion of the reaction, the solid material was filtered and thoroughly washed in hexane and decane at 110oC to complete absence of traces of free connection LASS="ptx2">

Polymerization

Using the solid titanium-containing catalytic component to /A/, spent the polymerization of propylene according to the procedure of example C-R/4. The results are shown in table. D/4/.

Comparative examples C-R/6 and C-R/7. Was repeated procedure of example 15 of the present description, except for one point instead of 0.125 mmol of diphenyldichlorosilane used in example 15, C-R/6 used 0,00251 mmol, while the C-R/7 used to 25.1 mmol of diphenyldichlorosilane. The results obtained are presented in table. D/5/.

Comparative example C-R/8. Preparation of solid titanium-containing catalytic component to /A/.

47,6 g (50 mmol) of anhydrous magnesium chloride was heated with 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexanol alcohol at 130oC for two hours to obtain a homogeneous solution. To this solution was added to 1.11 g (7.5 mmol) of phthalic anhydride and 1.5 ml (7.5 mmol) of diphenyldichlorosilane, and the solution was heated with stirring at 130oC one hour to dissolve the phthalic anhydride in the above homogeneous solution. Thus obtained homogeneous solution was cooled at room temperature, and its number dropwise added to 200 ml (1.8 to modnay mixture was raised for four hours to 110oC. Then the system was stirred at this temperature for two hours. After a two-hour reaction, the solid material was collected by hot filtration. This solid material suspended in 200 ml of titanium tetrachloride, and the resulting suspension was again heated at 110oC for two hours. After completion of the reaction, the solid material was filtered on a funnel for hot filtration and thoroughly washed in hexane and decane at 110oC to complete absence of traces of free compounds of titanium in the wash liquids. Thus was obtained a solid titanium-containing catalytic component to /A/.

Polymerization

Polymerization of propylene was carried out according to the procedure described in example 15 of the present description, but only in this case, the polymerization process is not used diphenylimidazole. The results obtained are presented in table. D/4/.

Comparative example C-R/9. Preparation of solid titanium-containing catalytic component /A/

value of 4.76 g (50 mmol) of magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexanol alcohol were heated at 130oC for 2 h until a homogeneous solution. To this solution was added to 1.11 g (7.5 mmol what mperature another hour to dissolve the phthalic anhydride in the above homogeneous solution. Thus obtained homogeneous solution was cooled at room temperature and the whole dropwise added to 200 ml (1.8 mmol) of titanium tetrachloride, maintained at -20oC for one hour. After completion of the addition the temperature of the water mixture was raised to 110oC for four hours, then after reaching the temperature of the solution 110oC to this aqueous mixture was added 34 ml (12.5 mmol) of diisobutylphthalate. After that, the system was kept at this temperature and was stirred for two hours. After a two-hour reaction, the solid material was collected by hot filtration and thoroughly washed in hexane and decane at 110oC to complete absence of traces of free compounds of titanium in the wash liquids. Thus obtained solid titanium-containing catalytic component to /A/.

Polymerization

Polymerization of propylene was carried out according to the procedure of example 15 of the present description, but only in the polymerization process is not used in this case diphenylimidazole. The results obtained are presented in table. D/4/.

New additional examples X/62 and X/73 and new additional comparison examples C-R/11 and C-R/12.

Example X/62. Was p is dimethoxysilane, used in example 1, in this case used 7,53 mmol of diphenyldichlorosilane. The results obtained are presented in table.1.

Example X/63. Was repeated procedure of example 15 of the present description, with the following exception instead 0.125 mmol of diphenyldichlorosilane used in example 15, in this case used 0,100 mmol of diphenyldichlorosilane. The results obtained are presented in table.1.

Example X/64. In an autoclave with an internal capacity of two liters downloaded 750 ml of purified hexane. Then there also downloaded 0,705 mmol of triethylaluminum at 40oC atmosphere of propylene. On the other hand has prepared the following mixture of 3.0 mmol of triethylaluminum, 0.5 mmol of di-n-propyltrimethoxysilane and 1 mmol in terms of titanium catalytic component (A) described in example 1, was added to the hexane so that the total volume was 100 ml, and the resulting mixture was stirred at room temperature for one hour, 1.5 ml of this mixture was added to the above autoclave. After administration of 200 ml of hydrogen in the autoclave temperature was raised to 70oC and within two hours were in the polymerization of propylene. The pressure during the polymerization process was equal to 7 kg/cm2. Completed the table.1.

Example X/65. Was repeated procedure of example 15 of the present description, but instead of triethylaluminum used in example 15, in this case was taken triisobutylaluminum. The results obtained were presented in table.2.

Example X/66. Was repeated procedure of example 15 of the present description, only instead of triethylaluminum used in the polymerization of propylene in example 15, in this case, was used tri-n-octyl-aluminum. The results obtained were presented in table.2.

Example X/67. Was repeated procedure of example 15 of the present description, but instead of 2.51 mmol of triethylaluminum used in the polymerization of propylene in example 15, in this case used to 1.67 mmol of triethylaluminum and 0.84 mmol Queen chloride ethylaluminum. The results obtained are presented in table.2.

Example X/68. Was repeated procedure of example 15 of the present description, except for one point instead of triethylaluminum used in the polymerization of propylene in example 15, in this case used tri-n-decyl aluminum. The results are shown in table.2.

Example X/69. Was repeated procedure of example 15 this oesse polymerization of propylene in example 15, in this case, used to 37.5 mmol of triethylaluminum and 1,875 mmol of diphenyldichlorosilane. The results obtained are presented in table.3.

Example X/70. Was repeated procedure of example 15 of the present description, but in this case used 15 mmol of triethylaluminum and 0.75 mmol of diphenyldichlorosilane instead of 2.51 mmol of triethylaluminum and 0.125 mmol of diphenyldichlorosilane used in the polymerization of propylene in example 15. The results are shown in table.3.

Example X/71. Was repeated procedure of example 15 of the present description, but instead of 2.51 mmol of triethylaluminum and 0.125 mmol of diphenyldichlorosilane used in the polymerization of propylene in example 15, in this case used to 0.75 multilateralise and 0,0375 mmol of diphenyldichlorosilane. The results are shown in table.3.

Example X/72. Was repeated procedure of example 15 of the present description, but instead of 2.51 mmol of triethylaluminum and 0.125 mmol of diphenyldichlorosilane used in the polymerization of propylene in example 15, in this case used 0,525 mmol of triethylaluminum and 0,0263 mmol of diphenyldichlorosilane. The results are shown in table.3.

Example X/73. Was to repeat what cicilan instead 0.125 mmol of diphenyldichlorosilane, used in example 15. The results are shown in table.1.

Comparative example C-R/11. Was repeated procedure of example 15 of the present description, but instead 0.125 mmol of diphenyldichlorosilane used in the polymerization of propylene in example 15, in this case used 12,55 mmol of diphenyldichlorosilane. The results obtained are presented in table.1.

Comparative example C-R/12.

Was repeated procedure of example 15 of the present description, with the exception of one time instead of 2.51 mmol of triethylaluminum and 0.125 mmol of diphenyldichlorosilane used in the polymerization of propylene in example 15, in this case used of 0.075 mmol of triethylaluminum and 0,0375 mmol of diphenyldichlorosilane. The results are shown in table.3.

Comparative examples C-16/1 C-16-23. Comparative examples according to the working examples were carried out as follows. And, that, in the preparation of the solid titanium-containing catalytic component /A/ depending on the working examples, the catalytic component of /D/, used in each experiment, were used in the same amount instead of the catalytic component of /E/ to get a solid catalyzing conducted in the same way, as in each example. For example, in C-16/1 phthalic anhydride was used instead of diethyldithiocarbamate used in the preparation of the solid titanium-containing catalytic component A in example 1 of the present description, when receiving the titanium containing solid catalytic component to /A/. Subsequent polymerization of propylene was conducted in the same manner as in example 15 of the present description.

The closest prototype of this proposal is the aforementioned U.S. patent N 4330649 (similar to Japanese application laid N 811/1981), issued in the name of the Applicant. This patent disclosed a similar, excellent catalyst component and A catalyst for similar purposes. In the prototype component A of the catalyst was prepared from the compound of Mg and Ti. Added the compound (I) an electron donor. This component (I) you can choose from many classes of compounds. This explanation in column 7, line 61ffU.S. patent. Among these many classes of compounds mentioned esters of organic acids, anhydrides of organic acids, tertiary amines, esters phosphites, esters of phosphates, carboxylic amides, NITRILES, etc., In the U.S. patent esters of organic acids represent neefirnyh compounds. Very characteristic for all these compounds is that they all relate to monocarboxylic acids, there are provided solely esters of monocarboxylic acids.

Therefore, the component (E) used in the present invention, that is, esters of C8-C30dicarboxylic acids are clearly new, so it is such a component is not used in the above-mentioned prototype.

No matter what mention of the many classes of compounds (D) electron donor and that many of these classes are listed in the opposed patent, that is, refers to esters of carboxylic acids that are clearly and exclusively are monocarboxylic acids. For professionals in this field it says nothing about the use of specific compounds (E) in accordance with the present invention, which are special esters of C8-C30dicarboxylic acids.

This is especially true, even though in column 13, lines 15-35 U.S. patent N 4330649 mentioned that during polymerization can be electron donors. Again stated many classes of compounds for donor Alazani and also esters of aromatic carboxylic acids, including phthalates and dinitrophenolate. However, it is very important that the simultaneous presence took place during the polymerization, and does not shown the presence of these compounds in obtaining the component (A) of the catalyst. In the present invention, the component (A) of the catalyst should contain specific ester of dicarboxylic acid. In the famous prototype of the component (A) of the catalyst does not contain such ester. If to compare the conditions of copolymerization, reveals another significant difference is that the catalyst in accordance with the present invention must contain a specific siloxane compound, which is not the catalyst for the prototype. Consequently, it is impossible to compare the final catalyst and links on the conditions under which polymerization occurs, because the final catalysts differ in their composition. Thus, component (A) of the catalyst in accordance with the present invention is different from component (A) of the prototype, since the latter does not contain a specific complex ester of dicarboxylic acid (reference to ester of dicarboxylic acids contained in a wide variety of classes of chemical compounds, incidentally, refers to the end-ka who have on the one hand, to obtain the component of the catalyst and, on the other hand, all the final catalyst under the conditions of polymerization. Thus, the column 13 is not talking about the structure of the component (A) of the catalyst. Columns 7 and 8 it is also clear the requirement that electrondonor has no active hydrogen, whereas in column (13) reveals electron-donating components that can have active hydrogen atoms to create a catalyst. These components include, for example, acids, amines (without any requirement that they must be tertiary), etc.

Thus, in the prototype there is absolutely nothing that would give an opportunity to the person skilled in the art to use for obtaining the component (A) of the catalyst specific complex ester of dicarboxylic acid (S) in combination with donor component (D), wherein component (A) used to produce the final catalyst by adding a siloxane compound (C).

If the specialist in this field of technology is to solve the problem of the present invention and if he will use the well-known U.S. patent, he would have to do the following:

a) select a specific class electrondonor is within the selected class to make a different and independent second choice, that is, esters of C8-C30dicarboxylic acids and

C) to use this selected narrow band in combination with electrondonor (D)

for final use in combination with siloxane compounds (C) for specific resins. In other words, the object of the present invention is the combination of different elections and for professionals it would be impossible to find a solution that set forth in this formula of the present invention.

The use of the catalyst component (A) in accordance with the present invention leads to the production of the catalyst (by adding a specific siloxane component), which is significantly different from the catalyst of the prototype. As is known, upon receipt of polyolefins, in particular polypropylene (hereafter PP) the use of gaseous hydrogen is appropriate (and often necessary) to act as a tie-breaker circuits. Therefore, in many examples, the polymerization is carried out as in the present invention, and in the opposed patent in the presence of hydrogen. The activity of the catalyst in accordance with the present invention increases with increasing amounts of hydrogen. Catalyst-PRSA, this is illustrated in table.13.

On this basis, it is clear that the use of the catalyst component (a) and the final catalyst using it leads to the production of polyolefin another type, for example, polypropylene, if you apply the same conditions (from the point of view of the number of hydrogen). Thus, the application of the above catalysts under those conditions and the same amount of hydrogen leads to the production of products of different types. This difference is illustrated in column I. and always the catalysts in accordance with the present invention have high values of I. it is obvious that a product with a higher value I. has superiority over those with a lower value I. in the normal situation.

in the Above-mentioned situation, illustrated in PL.13, indicates that under identical conditions of polymerization and, in particular, when applying the same amount of hydrogen the catalyst is in accordance with the present invention is much higher. It should also be emphasized that the activity can be mapped only in the case when the conditions of polymerization are identical (not when similar or identical to the engagement of experts in this field.

(C) From the above it is obvious that the use of the component (A) in the final catalyst leads to the production of olefins having a different melt index (compared with the catalyst of the prototype). It is also clear that there is a need for polyolefins and, in particular, polypropylene, i.e. products with other indexes of the melt. Certain applications require a specific range of melt indexes and, thus, providing products with a higher value I. in combination with other indexes of the melt leads to a new type of polymer. This makes it possible to obtain plastic, to a much greater degree meets the necessary requirements.

Experiments (trials 1 and 2) was carried out, taking the conditions of example 2, prototype, however, using ester /E/ and using the component catalyst /With/ in combination in test No. 1 (the present invention).

From the results of these experiments shows that the test No. 1 (the present invention) shows a much more increased activity (g of polypropylene per mmol of titanium) over time compared with test No. 2 (comparative).

The drawing shows the results VicePresident the spine, negligible over time of polymerization. As a result, the use of the catalyst component (A) of the present invention shows much more increased activity (g of polypropylene per mmol of titanium) compared with the conventional catalyst. It was not known at all that such an effect can be achieved, and the present invention enables to obtain the polymer is very advantageous from the industrial point of view by.

Test No. 1 (the present invention).

The receiving component of the catalyst:

Anhydrous magnesium chloride (4,76 g), 23,2 ml of 2-ethylhexanol alcohol and 25 ml of decane were subjected to interaction at a temperature of 120oC for 2 h until a homogeneous solution, after which the mixture was added to 2.3 ml of ethyl ester of benzoic acid. A homogeneous solution was cooled to a temperature of -20oC and added dropwise to 200 ml of titanium tetrachloride for 1 h with stirring. The mixture was maintained at a temperature of 110oC for 2 h with stirring, after which the solid fraction was collected by filtration. This solid fraction is again suspended in 200 ml of titanium tetrachloride, the temperature of the suspension was raised to 110oC is for 2 h with stirring. After 2-hour reaction, the solid fraction was collected by hot filtration, the solid fraction is again suspended in 200 ml of titanium tetrachloride, and then the suspension is again maintained at a temperature of 110oC for 2 h with stirring. After completion of the reaction the solid fraction was again collected by hot filtration and were washed with decane and hexane at a temperature of 110oC as long, until it was discovered loose coupling of titanium in the drilling fluid. Solid titanium component (a) synthesized by the above method contains 1.9 wt. titanium, 62 wt. chlorine, 20 wt. magnesium, 13.1 wt. diisobutylphthalate and 0.7 wt. ethyl ester of benzoic acid.

Polymerization of propylene:

Polymerization of propylene was carried out under the same polymerization conditions as in example 2 of the patent application of Japan N 811/1981, except that the polymerization time was set at 2 and 3 h, and 0.5 mmol of methyl-p-colorata was replaced by 0.5 mmol of phenyltriethoxysilane. The results are shown in table.14.

Test No. 2 (comparative).

Component of the catalyst obtained in accordance with example 2 of the patent application of Japan N 811/1981 and polymerization of propylene was carried out in which you are given in table.14.

Further, the applicant shall submit a revised formula of the invention, where the electron donor is limited in accordance with the examples of the description.

On the positive effect of this proposal, the following clearly shows that all of the examples of the present invention, in which used identical polymerization conditions, achieved the main predominant technical, it has a positive effect. All the working and comparative examples show that without any exception.

The term "activity" as it is used in the present invention may be understood from the description, for example, S. 37. In Example 1, the polymerization is carried out with the component (A) of the catalyst, which is added aluminum compound and a siloxane compound having the 70oC for two hours with 200 ml of hydrogen. In this Example, 1 is achieved, the activity value equal 25400. Experiments according to Examples 2-6 were carried out in identical conditions, but was changed amount of hydrogen. From table. 2 we can immediately establish that "activity" increases dramatically with the number of hydrogen. In Example 3, the amount of activity already reaches 30800.

Example 2 (column 14, line 65 to column 15, line 40/41) PA is Yes. From this point of view is just an Example 3 of the present invention can be compared with Example 2 of the prototype, because, otherwise, you can install only the difference due to the addition of hydrogen, but no difference in the components of the catalyst or catalysts depending on what is of interest.

Under identical conditions of polymerization catalyst of Example 2 of the invention, which is the same in Examples 1-6, is much better, because values of activity reflects only the influence of the amount of hydrogen, as mentioned above.

Applied by the applicant, the term "activity" should be understood as "General output" in the applicable conditions of polymerization.

From the foregoing it is obvious that a reasonable comparison can only be made under identical conditions of polymerization, which includes:

the same number of H2;

the same polymerization;

the same temperature during polymerization;

the same ratio of component (A) with component (B) to(A1) or (Si).

The applicant spent a lot of such tests, each of which shows the superiority of this system. These tests were conducted in IDing cases shown, what component (A) of the catalyst leads to catalyst gives higher yield and quality of the product, i.e. a product having a higher index I. This product is also different from the point of view of the melt index. As you know, the compounds with defined melt indexes are used in many household appliances. This shows the value of 1.1, which is always higher than in the examples of the present invention.

The applicants have undertaken significant work to ensure that the formula was fully confirmed, working examples and comparative examples, which are presented here in Appendix.

In order to make more evident the fact that the formula is confirmed by the examples, as well as the advantages and superiority of the subject matter of this invention, are presented below table:

Table A(1), A(2), A(3): working examples 1-54 (originally filed in the main application);

Table B(1) working examples 16/1 16/23 (optional submitted);

Table C(1) C(2) C(3): additional working examples X/1 X/61.

Table D(1) comparative examples C-1 C-50 were carried out as in examples 1, 2, 15, 16, 17, 19, 20, 21, 25, 26, 28, 29, 30, 32, 33, 41, 44, 45, 48, 49 and 50 of table A(1) A(3), except that the component (E), ispolzovat in these polymers;

Table E(3) E(4): presents, similar to the one shown in table B(1), a comparison of working examples X/1-X/53 (table C(1) C(3)) and for the corresponding comparative examples C-X(1) C-X(53) (table D(3) D(4)).

Table D(2): comparative examples C-16/1 C-16/23 were carried out as specified in table D(1) for additional working examples 16/1 16/23 (see table B(1));

Table D(3) D(4): comparative examples C-X 1 C-X/53 were conducted (as shown in table D(1) for additional examples X/1 X/53, as well as for additional comparative examples C-R/1 C-R/5);

In tables F(1), F(2) F(3) F(4) presents various compounds (compounds of magnesium, titanium compounds, Elektro component D, essential component E), as shown in all the working examples, and the molar ratio (E)/Xg (D)Mg.Ti/Mg.

Table E(1) E(3) below. In these tables provide a comparison of the activity of the catalyst obtained according to the present invention, and catalyst, is known from U.S. patent N 4330649.

Table E(1): the data presented polymerization obtained in the working examples 1-50 (table A(1) A(3)) in comparison with the data obtained in the respective comparative examples (table D(1)).

Table E(2): PR is niteljnykh examples C-16(1) C-16/23 (table D(2)).

1. The method of obtaining the (co)polymers of alpha-olefins (co)polymerization of alpha-olefins in the presence of a catalyst consisting of alyuminiiorganicheskikh compound and a solid component obtained by the interaction of the hydrocarbon solution of the magnesium compounds selected from the group comprising magnesium chloride, C2C16-dialkoxy and C1- C10-alkoxysilane, liquid titanium compounds of General formula

Ti(OR)qCl4-q,

where R is C1C10-alkyl;

q 0,1, or 4

at least one electron-donating compound selected from the group comprising esters of C2C20-monocarboxylic acids, aliphatic C1C10-carboxylic acids, anhydrides C2C10-carboxylic acids, C3- C15-ketones, aliphatic simple C1- C15-ethers, aliphatic C3- C15-carbonates, simple C3C10-minefire of ethylene glycol and C1C10organic phosphates, before the formation of the solid product, wherein the catalyst used is a catalyst, optionally including C4- C18- C30-dicarboxylic acid at a molar ratio of ester C8C30-dicarboxylic acid compound of magnesium from 0.05 to 1.00 to 0.50 to 1.00, electron-donating compound, the magnesium compound is from 0.05 to 1.00 to 0.50 to 1.00 and the connection of the titanium compound of magnesium from 2 1 to 200 1.

2. The method according to p. 1, wherein the process is carried out in the presence of hydrogen as molecular weight regulator.

 

Same patents:

The invention relates to a pre-polymerized catalyst [I] obtained by preliminary polymerization-olefin and polyene compounds with the use of compounds of the transition metal catalyst component [A] and the ORGANOMETALLIC catalyst component [A] containing a metal selected from the metals of Groups I-III of the periodic system, with a total quantity of-olefin and polyene compounds from 0.01 to 2000 g per 1 g of the compound of the transition metal catalyst component [A]
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The invention relates to the field of polymers and relates to a method of obtaining a solid component of catalyst for the (co)polymerization of ethylene, the solid component of catalyst, catalyst for (co)polymerization of ethylene and method of (co)polymerization of ethylene
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The invention relates to the chemistry of high molecular compounds, and to methods of producing polymers of higher-olefins, effectively reducing hydrodynamic resistance (SDS) of hydrocarbon liquids

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

FIELD: metalloorganic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to class of metallocene compounds of the general formula (I) wherein Y means fragment of the formula (II) wherein A means sulfur or selenium atom; B means carbon atom; D means carbon atom; R1, R2, R3, R4 and R5 mean hydrogen atom or hydrocarbon groups; Z is taken among fragment of the formula (II) and fragment of the formula (III) wherein R6, R7, R8 and R9 mean hydrogen atom or hydrocarbon groups; L means bivalent bridge group; M means zirconium atom; X means halogen atom; p = 2. Above described metallocenes are useful especially for polymerization of propylene.

EFFECT: improved preparing method, valuable properties of metallocenes.

15 cl, 5 tbl, 18 ex

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: vinylcyclohexane-based polymer or copolymer with isotactic structure.

SUBSTANCE: claimed polymer or copolymer may be obtained using comonomers selected from at least one monomer of group including olefine, (meth)acrylic alkyl esters, cyclopentadiene, cyclohexene, cyclohexadiene, optionally substituted norbornene, dicyclopentadiene, optionally substituted tetracyclododecenes, alkylated in nuclear styrene, alpha-methylstyrene, divinylbenzene, vinyl ester, vinyl ether, vinyl acetate, vinyl acid, (meth)acrylonitrile, maleic anhydride. Polymer contains more than 50.1 % and less than 74 % of isotactic diads.

EFFECT: polymer of high transparency useful as material for substrate in optical memory devices.

3 cl, 4 ex, 2 tbl

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR

13
, where Mt represents boron atom and R1, identical or different, are selected from halogen and halogenated C6-C30-aryl groups.

EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.

14 cl, 1 tbl, 32 ex

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

FIELD: polymers, chemical technology, catalysts.

SUBSTANCE: invention relates to the modified chrome oxide catalytic systems on a carrier used for polymerization of olefins and to a method for preparing polymers and ethylene copolymers. Invention describes a method for preparing copolymer of ethylene and 1-hexene wherein indicated copolymer shows swelling value by mass less about 380% and wherein swelling extruded flow is less about 42%, cracking resistance under external stress (ESCR) (condition A) is above about 400 h, onset of destruction of extrusion flow is at least about 2000 c-1 and result in testing for outlet for 1 min is at least about 1200 g/min in the content of xylene-soluble substances is less 0.7% and less 2 wt.-% of substance with molecular mass less 1000 Da. Method involves contact of the following components under condition of suspension polymerization in isobutene as a solvent at temperature from about 93.3°C to 110°C: (a) monomer of ethylene; (b) 1-hexene; (c) catalytic system comprising chrome applied on silicon dioxide-titanium oxide carrier that comprises from about 0.5 to about 3 wt.-% of titanium relatively to carrier mass wherein indicated catalytic system shows the surface square in the range from about 100 m2/g to about 500 m2/g, pore volume in the range from about 0.6 to about 1.4 ml/g and indicated catalytic system is activated at temperature in the range from about 538°C to about 650°C; (d) from about 0.1 to about 2.0 mg/kg relatively to a diluting agent in reactor, trialkylboron; and (e) extraction of copolymer. Also, invention describes copolymer of ethylene and 1-hexene prepared by above described method, catalytic composition and composition comprising copolymer of ethylene and 1-hexene. Invention provides enhanced yield of polymer, preparing copolymer of ethylene of high density with high resistance against cracking under stress, creating a polymer that is processed good in forming by bulge.

EFFECT: improved method for polymerization.

13 cl, 3 tbl, 1 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

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

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