The way to obtain a solid titanium catalyst component, catalyst for polymerization of olefin containing it, and the method of polymerization of olefin

 

(57) Abstract:

The invention includes a solid catalyst component containing magnesium, titanium, halogen and an electron-donating compound, free from the removal of titanium, when washed with hexane at room temperature and has a reduction ratio of the titanium content less than 15% by weight, when washed with o-dichlorobenzene at 90°C. the Catalytic component may be prepared in a way where the solid titanium (i), which is free from the removal of titanium, when washed with hexane at room temperature, in contact with a polar compound having a dipole moment of 0.50 to 4.00 Debye with a decrease in titanium content of at least 25% by weight, whereby get a solid titanium catalyst component having a weight ratio electrondonor connection to the titanium of at least 7. The catalyst for polymerization of olefin containing solid titanium catalyst component, can be used for (co)polymerization of olefins with high activity to obtain polyolefin high stereoregularity with reduced amounts of polyolefin low stereoregularity. 5 S. and 3 C.p. f-crystals, 5 tab., 1 Il.

The present invention Rel is obtain a solid titanium catalyst component, the catalyst for polymerization of olefin containing catalytic component, and to a method of polymerization of olefin using the catalyst.

DESCRIPTION OF THE PRIOR.

The catalysts of the Ziegler-Natta, including titanium catalytic component and alyuminiiorganicheskikh connection, usually widely used as catalysts for polyolefins. The above-mentioned catalysts containing solid titanium catalyst component supported on a carrier, as the titanium catalytic component, as is known, show high activity in the polymerization.

It is also known that catalysts containing catalytic titanium component supported on magnesium chloride, show high activity in the polymerization and get the polyolefins of high stereoregularity when he polymerizable such olefins as propylene and butene.

Also suggested various catalysts capable of obtaining polyolefins higher stereoregularity. For example, it was suggested that the catalyst containing electron-donating compound as the third component together with magnesium chloride as a carrier of solid Titano the use of a catalyst, containing such titanium catalytic component, there is a problem that the polyolefin low stereoregularity is obtained as a byproduct in addition to the polyolefin high stereoregularity. In addition, there are restrictions on the decrease in the amount of polyolefin low stereoregularity, even if it is a catalyst for preparing polyolefin high stereoregularity, which contains electron-donating compound as the third component.

The solid titanium catalyst component obtained by bringing a titanium compound, magnesium compounds, electron-donating compounds, etc., in contact with each other. In the solid titanium catalyst component thus prepared, contained excess titanium compound, which causes polyolefin low stereoregularity. In order to obtain a polyolefin high stereoregularity, it is desirable that the solid titanium catalyst component does not contain an excess of titanium compounds.

It is known that the excess titanium compound may be partially removed when the solid titanium catalyst component is washed with hexane at room temperatureis titanium compound is removed from the solid body, obtained by the reaction of titanium compounds, magnesium compounds, electron-donating compound and so on, when using solvent. For example, published application to Japanese patent N 124909/1984 describes that the excess titanium compound can be effectively washed aromatic hydrocarbon, such as toluene.

However, when the solid titanium catalyst component is washed with an aromatic hydrocarbon, as described above, the electron-donating compound is also removed together with the excess titanium compound, and the resulting solid titanium catalyst component can not make their full impact on reducing the amount of polyolefin low stereoregularity.

Accordingly, there is described an improved solid titanium catalyst component and catalyst containing it, which can produce a polyolefin of high stereoregularity with high activities as well as to reduce the amount of polyolefin low stereoregularity.

THE PURPOSE OF THE INVENTION.

The present invention was created in the circumstances mentioned above, and the aim of the invention is the provision of a solid titanium kataliticheski the ukta, and get the polyolefin high stereoregularity with high activities. Another aim of the invention is a method of obtaining a solid titanium catalyst component. The next objective of the invention is a catalyst for polymerization of olefin containing solid titanium catalyst component, and the method of polymerization of olefin using the catalyst for polymerization of olefin.

SUMMARY OF THE INVENTION.

The solid titanium catalyst component in accordance with the invention contains magnesium, titanium, halogen and an electron-donating compound, and has the following characteristics:

(1) the titanium content shall be not more than 2.5% by weight,

(2) the total content of magnesium and halogen is at least 65% by weight and less than 92% by weight,

(3) the content of the electron-donating compound is in the range from 8 to 30% by weight.

(4) the weight ratio of the electron-donating compound to titanium is in the range from 7 to 40, and

(5) a solid titanium catalyst component is almost free from the removal of titanium, when washed with hexane at room temperature and has a reduction ratio of the titanium content less than 15% of the component in accordance with the invention includes casting

(i) a solid titanium, which includes magnesium, titanium, halogen and an electron-donating compound, and free removal of titanium, when washed with hexane at room temperature, in contact with

(ii) a polar compound having a dipole moment of 0.50 to 4.00 the Debye at a temperature of at least 40oC, to reduce the content of titanium in the solid titanium (i) at least 25% by weight, thereby obtaining a solid titanium catalyst component having a weight ratio of the electron-donating compound to the titanium of at least 7.

The polar compound having a dipole moment of from 0.5 to 4.00 Peter Debye, is the preferred halogen-containing aromatic hydrocarbon.

Preferably, the solid titanium (i), used in contact with a polar compound having a dipole moment of from 0.5 to 4.00 the Debye (ii) had a weight ratio of the electron-donating compound to the titanium of not more than 6.

Solid titanium (i) is preferably solid, obtained by bringing (a) compounds of magnesium in the liquid state, (b) compounds of titanium in the liquid state and (C) electron-donating compound in contact with each other.

This solid titanium (i) can be tnii.

The catalyst for polymerization of olefin in accordance with the invention includes (A) a solid catalytic component (B) ORGANOMETALLIC compound and (C) the organosilicon compound having at least one alkoxy group.

Another catalyst for polymerization of olefin in accordance with the invention is terpolymerization catalyst obtained by terpolymerization or parapolitical of olefin to (A) a solid titanium catalyst component described above, (B) ORGANOMETALLIC compound and, optionally, (C) the organosilicon compound having at least one alkoxy group.

In the present invention a catalyst for polymerization of olefin may be described above terpolymerization catalyst one or, optionally, in combination with (B) ORGANOMETALLIC compound and/or (C) an organosilicon compound having at least one alkoxy group.

The method of polymerization of olefin in accordance with the invention includes a polymerization or copolymerization of olefins in the presence of any one of the above catalysts for polymerization of olefin. In this process, the olefin can be polymerized with high activeliving low stereoregularity.

The drawing shows an example of the stages to obtain a solid titanium catalyst component in accordance with the present invention together with an example of stages to obtain a catalyst of polymerization in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION.

The way to obtain a solid titanium catalyst component, the solid titanium catalyst component, terpolymerization catalyst containing the solid titanium catalyst component, catalyst for polymerization of olefin and method of polymerization of olefin in accordance with the invention will be described in detail later.

The term "polymerization" is used here to denote not only homopolymerization, but also copolymerization, and thus the term "polymer" is used to denote homopolymer and copolymer.

The way to obtain a solid titanium catalyst component (A)

In a method of producing a solid titanium catalyst component in accordance with the invention, the solid titanium (i), which contains magnesium, titanium, halogen and an electron-donating compound and free removal of titanium, when he washed Gecko 4.00 the Debye (ii), at a temperature of at least 40oC, reducing the content of titanium in the solid titanium (i) at least 25% by weight, the resulting solid titanium catalyst component (A) having a weight ratio of the electron-donating compound to the titanium of at least 7 was received.

Solid titanium (i) can be obtained by contacting compounds of magnesium, titanium compounds, electron-donating compounds, etc. in different ways, and there is no specific limitation on the method of its production. In the invention, however, preferably the contacting (a) compounds of magnesium in liquid form, (b) compounds of titanium in liquid form, and (c) electron-donor compound with one another to obtain such a solid as the solid titanium (i).

Each component used for the preparation of the solid titanium (i) and method, following from this, described below in detail.

(a) Compound of magnesium.

For preparing the solid titanium (i) in the invention is preferably used a magnesium compound in the liquid state. The term "magnesium compound in the liquid state" means not only the magnesium compound, which is liquid as such, but also the solid solution compounds of magnesium, lastnosti, and those who do not have the recovery ability.

The magnesium compound having reducing ability, for example, is magyarkanizsa the compound represented by the following formula:

XnMgR2-n,

where n represents the number 0 n < 2; R is hydrogen, alkyl group of 1 to 20 carbon atoms, aryl group of from 6 to 21 carbon atoms or cycloalkyl group from 5 to 20 carbon atoms; when n is 0, two of R may be the same or different; and X represents halogen.

Examples magyarkanizsa compounds having reducing ability include:

dialkylamino compounds such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, directimage, dodecylamine, activprimary and ethylbutylamine;

alkalinity halide, such as etimani chloride, propylene chloride, butylamine chloride, hexylene chloride and nilmini chloride; and

alkalinity alkoxides, such as butylacetamide, ethylbutane and ActiveDocument. Other compounds, such as butylamine hydride, may also be used.

Examples of magnesium compounds having no vosstanovitelem is R>
alkoxysilane halide, such as methoxamine chloride, ethoxyline chloride, isopropoxide chloride, butoxymethyl chloride and octocrylene chloride;

aryloxyalkyl halide, such as enoximone chloride and methyleneimine chloride;

alkoxyimino, such as ethoxyline, isopropoxide, butoxymethyl, n-octoxide and 2-ethylhexylamine; aryloxyalkyl, such as enoximone and dimethylethanolamine; and

the carboxylates of magnesium such as magnesium laurate and magnesium stearate. You can also use magnesium metal and magnesium hydrides.

The magnesium compounds having no resilience, can be obtained from the above-mentioned magnesium compounds having reduction activity, or obtained in situ by obtaining a catalytic component. For example, the magnesium compounds having reducing ability, can be brought into contact with polysiloxane compounds, halogen-containing wilanowie compounds, halogen-containing aluminum compounds, esters, alcohols, halogenated compounds, or compounds having OH group or an active carbon-oxygen bond, to obtain compounds of magnesium, not the TB, or the magnesium compound having no resilience, can form complex compounds or double connection with the previously described ORGANOMETALLIC compounds of other metals, i.e. aluminum, zinc, boron, beryllium, sodium and potassium, or may be a mixture with other metal compounds. Compounds of magnesium, mentioned above, can be used separately or in combination of two or more kinds.

To obtain a solid titanium (i) may also be used other compounds of magnesium than those mentioned above, but most preferably, when the magnesium compound is present in the form of a halogen-containing compounds of magnesium in the end-obtained solid titanium (i). In addition, when using a magnesium compound not containing halogen, the compound of magnesium is preferably in contact with the halogenated compound in the process of obtaining the solid titanium (i).

Of the above compounds, compounds of magnesium, not having resilience, especially halogen-containing compounds of magnesium, particularly magnesium chloride, chloride alkoxyamine and chloride arylacetamide preferred.

When solid sedimentation connection (c-i).

Examples of electron-donor compounds (c-i) include alcohols, phenols, ketones, aldehydes, ethers, amines and pyridine, which will be described below as examples of the electron-donating compound (C).

You can also use metal acid esters, such as tetraethoxysilane, Tetra-n-proposition, Tetra-isopropoxide, tetrabutoxide, tetrahexahedron, tetramethoxysilane and tetraethoxysilane.

Of these the most preferred alcohols and metallic acid esters.

The reaction solubilize the solid compound of magnesium electron-donating compound (c-i) is usually carried out by bringing the solid compound of magnesium in contact with the electron-donating compound (c-i), followed by heating, if necessary. This interaction can be carried out at a temperature of usually from 0 to 200oC, preferably from 20 to 180oC, most preferably from 50 to 150oC.

The solubilization reaction can also be carried out in the presence of a hydrocarbon solvent (d). Examples of hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; alicyclic orexin; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene and chlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene.

(b) a Titanium compound.

In the present invention, preferably used is tetravalent compound of titanium, as a combination of titanium (b) in the liquid state. Tetravalent compound of titanium, for example, is a compound represented by the following formula:

Ti(OR)gX4-g,

where R is a hydrocarbon group with 1-15 carbon atoms, X represents a halogen atom, 0g4.

Examples of such compounds include:

tetrahalide titanium, such as TiCl4, TiBr4and TiI4;

trihalide of alkoxysilane, such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3and Ti(O-i-C4H9)Br3,

dihalide of dialaction, such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-C4H9)2Cl2and Ti(OC2H5)2Br2;

monoglide of tralkoxydim, such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9)3Cl, Ti(OC2HH9)4, Ti(O-i-C4H9)4and Ti(O-2-ethylhexyl)4.

Of these the most preferred tetrahalide titanium, and particularly preferred titanium tetrachloride. These titanium compounds may be used singularly or in combination. Then these compounds can be diluted with hydrocarbons, halogenated hydrocarbons or aromatic hydrocarbons prior to use.

(C) Electron-donating compound.

Examples of electron-donor compounds (C) used to produce the solid titanium (i) include alcohols, phenols, ketones, aldehydes, carboxylic acids, halide organic acids, organic or inorganic esters of acids, ethers, acid amides, acid anhydrides, ammonia, amines, NITRILES, isocyanates, nitrogen-containing cyclic compounds. More specifically there may be mentioned:

alcohols having from 1 to 18 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecylamine alcohol, alerby alcohol, benzyl alcohol, phenethyl alcohol, tomilovy alcohol, isopropyl alcohol and isopropylbenzyl alcohol;

halogenated alcohols, having from 6 to 20 carbon atoms, which may have lower alkyl groups, such as phenol, cresol, Xylenol, ethylphenol, propylene, Nonylphenol, cumylphenol and naphthol;

ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone;

aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, Propionaldehyde, octillery, benzaldehyde, Truelove aldehyde and naphthoic aldehyde;

esters of organic acids having from 2 to 30 carbon atoms, such as methylformate, methyl acetate, ethyl acetate, vinyl acetate, propyl, octylated, cyclohexylacetate, ethylpropane, methylbutyrate, Etisalat, methylchloroform, ethyldichloroarsine, methyl methacrylate, etildronat, ethylcyclohexylamine, methylbenzoate, ethylbenzoic, propylbenzoate, butylbenzoate, octylbenzoic, cyclohexylbenzene, phenylbenzoate, benzyl benzoate, methylfolate, atilola, amitola, ethyl ethylbenzoic, methylenethf, ationist, utilitariansim, -butyrolactone, -valerolactone, coumarin, phtalic, dimethylcarbonate and ethylcarbonate;

halide acids having from 2 to 15 carbon atoms, such as acetylchloride, benzoyl chloride, colwill refer, butylether, Unilever, tetrahydrofuran, anisole and diphenyl ether;

amides of acids, such as N,N-dimethylacetamide, N,N-diethylbenzamide and N,N-diethyltoluamide;

amines, such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylaniline and hexamethylenediamine were,

NITRILES, such as acetonitrile, benzonitrile and tolunitrile;

anhydrides of acids, such as acetanhydride, phthalic anhydride and benzoic anhydride;

the pyrrole, such as pyrrole, methylpyrrole and dimethylpyrrole;

pyrroline;

pyrrolidine;

indoles;

pyridine, such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridin, arylmethylidene, trimethylpyridine, phenylpyridine, benzylpyridine and chloropyridin;

nitrogen-containing cyclic compounds such as piperidine, quinoline and isoquinolines; and

oxygen-containing cyclic compounds such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinafore, methylfuran, dimethylfuran, diphenylfuran, benzofuran, kumaran, phthalan, tetrahydrofuran, Piran and dihydropyran.

Next, ethers of polyhydroxybenzenes, such as 1-methoxyethanol, 2-methoxyethanol, 4-methoxybutanol and 2-butoxyethanol examples of esters of organic acids include polycarboxylate esters, having a structure represented by the following formula:

< / BR>
< / BR>
< / BR>
In the above formulas, R2means substituted or unsubstituted hydrocarbon group, R2, R5and R6denote each hydrogen or a substituted or unsubstituted hydrocarbon group, R3and R4denote each hydrogen or a substituted or unsubstituted hydrocarbon group, and at least one of R3and R4means substituted or unsubstituted hydrocarbon group. R3and R4can be connected to each other to form a cyclic structure. When the hydrocarbon group of R1to R6which may have from 1 to 15 carbon atoms, substituted, the substituents contain heteroatoms such as N, O and S, and have groups such as C-O-C, COOR, COOH, HE, SO3H-C-N-C - NH2.

In particular, examples polycarboxylic esters include:

aliphatic polycarboxylate esters, such as diethylamine, dibutylamine, diethyl-methylsuccinate, Diisobutyl-methylglutaric, diethyl-methylmalonate, diethyl-ethylmalonate, diethyl-isopropylmalonic, diethyl-butylmalonate, diethylformamide, diethyl-diethylmalonate, diethyl-dibutylamine, monoacrylate, Dokukina, di-2-ethylhexylphthalate, dietitican and dioctylsebacate;

alicyclic polycarboxylic esters, such as diethyl-1,2-cyclohexanecarboxylate, Diisobutyl 1,2-cyclohexanecarboxylate, diethylacrylamide and the diethyl Nadiad;

aromatic polycarboxylate esters, such as monoethylfumarate, dimethylphthalate, mutilateral, monoisobutyrate, diethylphthalate, utilizability, di-n-propietat, Diisopropylamine, di-n-butylphthalate, diisobutylphthalate, di-n-heptylphenol, di-2-ethylhexylphthalate, di-n-octylphthalate, dineopentyl, dodecylphenol benzylbutylphthalate, definiltely, diethyldithiocarbamate, dibutyldithiocarbamate, retitrement and dibutylthiourea; and

heterocyclic polycarboxylic esters, such as ethanol, n-butanol, ISO-butanol and 2-ethylhexanol ester of 3,4-furandicarboxylic acid.

Other examples polycarboxylic esters are esters of long-chain dicarboxylic acids, such as diethylacetal, diisobutylamine, diisopropyl ether sabatinovka acid, di-n-butyl ether sabatinovka acid and di-n-ethylhexyloxy ether sabatinovka acid.

In the present invented is also to be used as the electron-donating compound (C).

Polyester compound, for example, means a compound that has two or more atoms selected from carbon, silicon, oxygen, nitrogen, phosphorus, boron and sulfur as the atoms present between the bonds ethers. Of these compounds the most preferred are those in which the atoms are present between two or more ether bonds, are relatively bulky substituents and include many carbon atoms.

Examples of such polyether compounds include represented by the following formula:

< / BR>
< / BR>
where n denotes an integer of 2 n 10, R1to R26mean each Deputy having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, any combination of R1to R26preferably R1to R2nmay form together a ring other than benzene ring and the main chain may contain an atom other than carbon.

Of these compounds it is preferable to use 1,3-diesters and particularly preferably used:

2.2-Diisobutyl-1,3-dimethoxypropane,

2-isopropyl-2-isobutyl-1,3-dimethoxypropane,

2-isopropyl-2-isopentyl-1,3-demeton the cyclohexyl-2-isopropyl-1,3-dimethoxypropane,

2-isopropyl-2-s-butyl-1,3-dimethoxypropane,

2,2-diphenyl-1,3-dimethoxypropane, and

2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane.

The previously described organosilicon compound (C) having at least one CNS group, water, and anionic, cationic or non-ionic surface-active agents can also be used as electrothermo connection (s).

Of the above compounds, esters of carboxylic acids are most preferably used as the electron-donating compound (C). Among them, preferred esters of polycarboxylic acids and esters of aliphatic polyhydroxylated compounds and acid anhydrides.

These electron-donating compounds (C) can be used individually or in combination.

The preparation of the solid titanium (i).

In the present invention, the solid titanium (i) can be obtained from (a) compounds of magnesium in the liquid state, (b) compounds of titanium in the liquid state and (C) electron-donating compound, as described above. Upon contact with these components, the connection of titanium (b) in the liquid state can be used once to obtain a solid body (1), or the resulting solid (1) may be on the Sabbath. When contacting components (a) to (C) to obtain a solid body, such a hydrocarbon solvent (d) as used for the preparation of compounds of magnesium (a) in the liquid state may be used, if necessary.

In the present invention, a solid body (1) or (2) received during the contacting of the components (a) to (C) can be directly used as the solid titanium (i), which will be in contact with a polar compound having a dipole moment of 0.50 to 4.00 the Debye (ii), but preferably, a solid body (1) or (2) was washed with a hydrocarbon solvent prior to use.

In the preparation of the solid titanium (i), organic or inorganic compounds containing silicon, phosphorus, aluminum, etc. can be used as carriers or tools in addition to the above compounds (a) to (C).

Examples of carriers include Al2O3, SiO2B2O3, MgO, CaO, TiO2, ZnO, SnO2, BaO, ThO and resins, such as stradivariuses copolymer. Of them TiO2, Al2O3, SiO2and stradivariuses copolymer is preferably used.

For example, solid (1) or (2) (or the solid titanium (i)) can be obtained from the above components in slidermania connection such as those mentioned previously in the description of the ORGANOMETALLIC compound (B) may be used.

(1) a magnesium Compound in the liquid state, which includes the magnesium compound, the electron-donating compound (c-i) and a hydrocarbon solvent, in contact with the connection of titanium (b) in the liquid state during or after contact with alyuminiiorganicheskikh compound to precipitate a solid.

In this process, the electron-donating compound (C) is in contact with the contact product of at least one time.

(2) a Contact product of an inorganic carrier and the organosilicon compound (a) in the liquid state are brought into contact with the titanium compound (b) in the liquid state and electron-donor compound (C).

In this process the contact product of an inorganic carrier and magyarkanizsa connection (a) in the liquid state can be pre-reduced in the interaction with the halogen-containing compound and/or alyuminiiorganicheskikh connection.

(3) Inorganic or organic carrier and a compound of magnesium (a) in the liquid state, which includes the magnesium compound, the electron-donating compounds is followed by contacting with a compound of titanium (b) in the liquid state.

In this way the electron-donating compound (C) is in contact with the contact product of at least one time.

(4) a Solution containing a magnesium compound, a compound of titanium (b) in the liquid state and optional electron-donating compound (c-i) and/or a hydrocarbon solvent, in contact with inorganic or organic carrier and electron-donor compound (C).

Magyarkanizsa connection (a) in the liquid state in contact with a titanium compound (b) in the liquid state and then with electron-donor compound (C).

(6) Magyarkanizsa connection (a) in the liquid state in contact with a halogen-containing compound and then with a titanium compound (b) in the liquid state.

In this process, the electron-donating compound (C) used at least once.

(7) Alkoxysilane the magnesium compound (a) is in contact with the connection of titanium (b) in the liquid state and electron-donor compound (C).

(8) the Solution of complex compounds of magnesium and electron-donor compounds (c-i) in a hydrocarbon solvent, i.e., the magnesium compound in the liquid state, is in contact with the connection of titanium (b) in the liquid state and the electron is), i.e., the magnesium compound (a) in the liquid state, is in contact with alyuminiiorganicheskikh connection and then is in contact with the connection of titanium (b) in the liquid state.

In this way the electron-donating compound (C) is in contact with the contact product of at least one time.

(10) the magnesium Compound (a) having no resilience in the liquid state, is in contact with the titanium compound (b) in the liquid state in the presence or absence of electron-donor compounds (C).

In this way electron-donating compound is in contact with the contact product of at least one time.

(11) the reaction Product (solid (1)) obtained by any of methods (1) through (10) comes into contact with the connection of titanium (b) in the liquid state.

(12) the reaction Product (solid (1)) obtained by any of methods (1) through (10), is in contact with the electron-donating compound (C) and a compound of titanium (b) in the liquid state.

The contact components can be carried out at a temperature of usually from -70 to +200oC, preferably from -50 to +150oC, most preferably from -30 to +130oC.

The number of components used to produce the solid is about, for example, electron-donating compound (C) may be used in amounts of from 0.01 to 10 mol, preferably from 0.1 to 5 mol and a compound of titanium (b) may be used in amounts of from 0.01 to 1,000 mol, preferably from 0.1 to 200 mol, both based on 1 mol of compound magnesium.

In the present invention, it is preferable to obtain a solid body (1) of the above (8) or to get a hard body (2) of the above (11) or (12), which includes the method (8). In particular, it is preferable to obtain a solid body (1) fashion (8).

As the catalyst for polymerization of olefin containing a solid body (1) may exhibit a high activity in homopolymerization propylene and can provide a propylene random copolymers having a reduced content of soluble in decane components, solid body (1) is preferred.

In these ways, when the magnesium compound (a) in the liquid state obtained from a compound of magnesium and electron-donor compounds (c-i), in contact with the connection of titanium (b) in the liquid state and then with electron-donor compound (C), esters of polycarboxylic acids and/or ethers of polyhydroxyalkane and preferably the scientists as stated above, can be used directly as the solid titanium (i), but it is preferable to wash their hydrocarbon solvent at a temperature from 0 to 150oC.

Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as hexane, heptane, octane, Noonan, Dean and Zetan; halogenate aromatic hydrocarbon solvents such as toluene, xylene and benzene; and halogenated aromatic hydrocarbon solvents, which will be described later. From them it is most preferable to use aliphatic hydrocarbon solvents and halogenate hydrocarbon solvents.

For washing solid hydrocarbon solvent can be used in an amount of usually from 10 to 500 ml, preferably from 20 to 100 ml, per 1 g of the solid.

Solid titanium (i), obtained as described above, includes magnesium, titanium, halogen and an electron-donating compound, and preferably has a weight ratio of the electron-donating compound to the titanium of not more than 6.

Solid titanium (i) free from removal of titanium, when washed with hexane at room temperature.

Contact processing polarities (ii), having a dipole moment of 0.50 to 4.00 the Debye to obtain a solid titanium catalyst component (A).

Examples of polar compounds (ii) having a dipole moment of 0.50 to 4.00 the Debye (referenced simply as polar compounds), used for contact with solid titanium (i) include halogenated aromatic hydrocarbons, such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, trichlorobenzene, ,,- trichlorotoluene, o-chlorotoluene, benzylchloride and 2-chlorobenzylchloride; halogenated aliphatic hydrocarbons, such as 1,2-dichloroethane, 1,1,2,2-tetrachlorethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane and 1-chloropentane; and halogenated silicon compounds such as diphenyldichlorosilane and methylprednisolon. Of them preferred halogenated aliphatic hydrocarbons.

The contact between the solid titanium (i) with the polar compound (ii) can be carried out at a temperature of usually 40 to 200oC, preferably from 50 to 180oC, most preferably from 60 to 160oC for from 1 minute to 10 hours, preferably from 10 minutes to 5 hours.

This interaction of the polar setpattern from 10 to 1000 ml, on 1 g of the solid titanium (i).

The contact between the solid titanium (i) with the polar compound (ii) preferably takes place in an atmosphere of inert gas under stirring. For example, in a glass flask equipped with a stirrer and thoroughly purged with nitrogen, a suspension of solid titanium (i) and polar compounds (ii) is stirred at the above temperature within the aforementioned period of time when from 100 to 1000 rpm, preferably from 200 to 800 rpm, for the interaction between the solid titanium (i) with the polar compound (ii).

Solid titanium (i) and the polar compound (ii) after contact can be separated from each other by filtering.

Due to the contact between the solid titanium (i) with the polar compound (ii), the solid titanium catalyst component having a titanium content lower than that of the solid titanium (i) can be obtained. More specific here can be obtained solid titanium catalyst component (A), in which the content of titanium in the solid titanium (i) reduced by at least 25% by weight, preferably from 30 to 95% by weight, most preferably from 40 to 90% by weight.

The solid titanium catalyst component (A) of the invention obtained as described above, includes magnesium, tigania titanium solid titanium catalyst component (A) not more than 2.5% by weight, preferably from 2.2 to 0.1% by weight, most preferably from 2.0 to 0.2% by weight, particularly preferably from 1.8 to 0.3% by weight, wonderful from 1.4% to 0.4% by weight.

(2) the Total content of magnesium and halogen, at least 65% by weight and less than 92% by weight.

(3) the content of the electron-donating compound in the range from 8 to 30% by weight.

(4) the Weight ratio of the electron-donating compound to the titanium of at least 7, preferably from 7.5 to 35, more preferably from 8 to 30, particularly preferably from 8.5 to 25.

(5) a Solid titanium catalyst component (A) is free from the removal of titanium, when washed with hexane at room temperature. Washing the solid titanium catalyst component hexane means that the solid titanium catalyst component is washed with hexane usually from 10 to 500 ml, preferably from 20 to 100 ml, per 1 g of the solid titanium catalyst component for 5 minutes. Room temperature between 15 and 25oC.

The amount of magnesium, halogen, titanium and electron-donating compounds here are each in percent by weight based on the unit weight of the solid titanium catalyst component (A), and magnesium, halogen and titanium on the elk by gas chromatography.

Then the solid titanium catalyst component (A) has a reduced titanium content less than 15% by weight, preferably less than 10% by weight, when the component (A) washed o-dichlorobenzene at 90oC. Washing the solid titanium catalyst component (A) o-dichlorobenzene means that 0.5 g of the solid titanium catalyst component (A) are in contact with 100 ml of o-dichlorobenzene at 90oC for 1 hour.

When using the solid titanium catalyst component (A) of the invention such as a catalytic component for the polymerization of olefin, the olefin can be polymerized with high activity. Moreover, the amount of polyolefin low stereoregularity obtained as a by-product, can be reduced, and the polyolefin high stereoregularity can be obtained.

(B) ORGANOMETALLIC compound.

Upon receipt of the catalyst for polymerization of olefin of the invention, the ORGANOMETALLIC compound is used together with the solid titanium catalyst component (A). ORGANOMETALLIC coupling means preferably ORGANOMETALLIC compound containing a metal selected from I-III group of the Periodic TA is s, and ORGANOMETALLIC compound of a metal of Group II.

Alyuminiiorganicheskikh the connection represented, for example, by the following formula:

RanAlX3-n,

where Randmeans hydrocarbon group of 1 to 12 carbon atoms, X is halogen or hydrogen, and n means 1 to 3.

In the above formula, Rameans hydrocarbon group of 1 to 12 carbon atoms, i.e., alkyl group, cycloalkyl group or aryl group.

Some examples of this include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl. Examples of such alyuminiiorganicheskikh compounds include:

trialkylaluminium, such as trimethylaluminum, triethylaluminum, triisopropanolamine, triisobutylaluminum, trioctylamine and three 2-ethylhexylamine;

alkenylamine, such as isoprenaline;

halide dialkylamide, such as dimethylaluminum chloride, diethylaluminum chloride, Diisopropylamine chloride, diisobutylaluminum chloride and dimethylaluminum bromide;

alkylamines polytonality, such as methylamine polutoraglazy, ethylaluminum polutoraglazy, Isopropylamine on the such as methylamine dichloride, ethylaluminum dichloride, Isopropylamine dichloride and ethylaluminum dibromide; and

alkylamines hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride.

You can also use as alyuminiiorganicheskikh connection, the connection represented by the formula:

RanAlY3-n,

where Rameans the same as above; Y represents-ORbgroup, - OSiRc3group-OAlRd2group, -NRe2group-SiRf3group or-N(Rg)AlRh2group; n indicates 1 or 2; Rb, Rc, Rdand Rhmean each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl or the like; Remeans hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl or the like; and Rfand Rgmean each methyl, ethyl or the like.

Examples of such alyuminiiorganicheskikh compounds include:

(i) compounds of the formula RanAl(ORb)3-ni.e. dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;

(ii) the compounds of formula RanAl(OSiRc)3-n, i.e. Et2Al(OSiMe3), (iso-Bu)2Al(OSiMe3and (iso-Bu)2Al(OSiEt3);

(iii) UB>;

(iv) compounds of the formula RanAl(NRe2)3-n, i.e., Me2AlNEt2Et2AlNHMe, Me2AlNHEt, Et2AlN(Me3Si)2and (iso-Bu)2AlN(Me3Si)2;

(v) the compounds of formula RanAl(SiRf2)n, i.e., (iso-Bu)2AlSiMe3;

(vi) the compounds of formula RanAl[N(Rg)AlRh2]3-n, i.e. Et2AlN(Me)-AlEt2and (iso-Bu)2AlN(Et)Al(iso-Bu)2.

Further, compounds similar to the above compounds, for example alyuminiiorganicheskikh connection, where two or more atoms of aluminum are linked via an oxygen atom or a nitrogen atom, can also be used. Examples of such compounds include (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2and (C2H5)2AlN(C2H5)Al (C2H5)2.

Moreover, iluminacin, such as methylaluminoxane, can also be used.

From alyuminiiorganicheskikh compounds mentioned above, preferred are those represented by the formulas Ra3Al, RanAl(ORb)3-nand RanAl(OAlRd2)3-n. Alkyl complex with the de M1means Li, Na or K, and Rjmeans hydrocarbon group of 1 to 15 carbon atoms. Examples of such compounds include LiAl(C2H5)4and LiAl(C7H15)4.

ORGANOMETALLIC compound of a metal of Group II represented by the following formula:

RkR1M2,

where Rkand R1indicate each a hydrocarbon group of 1 to 15 carbon atoms or halogen, Rkand R1may be the same or different except that both of them are halogen, and M2means Mg, Zn or Cd.

Examples of such compounds include diethylzinc, determine, butylethylamine, chloride of ateline and chloride butylamine.

The compounds mentioned above may be used alone or in combination.

(C) the Organosilicon compound.

To obtain catalyst for polymerization of olefin in the invention the organosilicon compound having at least one alkoxy group is used together with the solid titanium catalyst component (a) and the ORGANOMETALLIC compound (B). The organosilicon compound can be represented by formula (c):

RnSi(OR')4-n(C)

Ethyl silicate and butylsilane can also be used.

In the present invention the organosilicon compound of the formula (C) is preferred, if represented by the following formula (c-i):

RanSi(ORb)ameans secondary or tertiary hydrocarbon group, Ramay be the same or different; Rbmeans hydrocarbon group of 1 to 4 carbon atoms; when 4-n is 2 or 3, ORbmay be the same or different.

In the silicone compound of formula (c-i) - dimensional group, secondary, or tertiary hydrocarbon group includes cyclopentyl, cyclopentenyl and cyclopentadienyl, which may be substituted, a hydrocarbon group, where the carbon adjacent to Si is secondary or tertiary.

Examples of substituted cyclopentyl groups include cyclopentyloxy group having alkyl groups such as 2-methylcyclopentene, 3-methylcyclopentanol, 2-ethylcyclopentane, 2-n-butylcyclopentadienyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,3-diethyltoluene, 2,3,4-trimethylcyclohexanol, 2,3,5-trimethylcyclohexanol, 2,3,4-triethylsilanol, tetramethylcyclobutane and tetraethylsilane.

Examples of substituted cyclopentyl groups include cyclopentadienyl group having alkyl groups such as 2-methylcyclopentene, 3-methylcyclopentanol, 2-ateltico the 4-trimethylcyclopentanone, 2,3,5-trimethylcyclopentanone, 2,3,4-triethylsilanol, tetramethylcyclopentadienyl and tetramethylcyclopentadienyl.

Examples of the substituted cyclopentadienyls groups include cyclopentadienyls group having alkyl groups such as 2-methylcyclopentadienyl, 3-methylcyclopentadienyl, 2-ethylcyclopentadienyl, 2-n-butylcyclopentadienyl, 2,3-dimethylcyclopentane, 2,4-dimethylcyclopentane, 2,5-dimethylcyclopentane, 2,3-diethyltoluenediamine, 2,3,4-trimethylcyclopentanone, 2,3,5-trimethylcyclopentanone, 2,3,4-triethylchlorosilane, 2,3,4,5-tetramethylcyclopentadienyl, 2,3,4,5-tetramethylcyclopentadienyl, 1,2,3,3,5-pentamethylcyclopentadienyl and 1,2,3,4,5-pentamethylcyclopentadienyl.

Examples of the hydrocarbon group, where the carbon adjacent to Si is a secondary carbon, include isopropyl, verbatim, veramil and - methylbenzyl. Examples of the hydrocarbon group, where the carbon adjacent to Si means tertiary carbon include tertbutyl, treamill, ,- dimethylbenzyl and substituted.

When n is 1, examples of the organosilicon compounds represented by formula (c-i), include tralkoxydim, such as cyclopentylmethyl, 2-methylcyclopentadienyl, 2,3-dimethylcyclopropanecarboxylate, cyclohexyltrichlorosilane, 2-norbornenedicarboxylic and 2-norbornenedicarboxylic.

When n is 2, examples of the organosilicon compounds represented by formula (c-i) include dialkoxybenzene, such as dicyclopentadienyliron, tributyltinoxide, tributyltinoxide, treatmentmedicationsother, dicyclohexylammonium, cyclohexanedimethanol, cyclohexyltrichlorosilane and 2-norbornenedicarboxylic.

When n represents 2, the organosilicon compound of the formula (c-i) means preferably dimethoxysilane the compound represented by the following formula (c-ii):

< / BR>
where Raand Rcindicate each independently cyclopentyl, substituted cyclopentyl, cyclopentenyl, substituted cyclopentenyl, cyclopentadienyl, substituted cyclopentadienyl or hydrocarbon group, where the carbon adjacent to Si, means a secondary or tertiary carbon.

Examples of organosilicon compounds represented by formula (c-ii) include:

dicyclopentadienyliron,

dicyclopentadienyliron,

dicyclopentadienyltitanium,

di-t-butyldimethylsilyl,

di(2-methylcyclopentene the>di(2,3-dimethylcyclobutyl)dimethoxysilane,

di(2,4-dimethylcyclobutyl)dimethoxysilane,

di(2,5-dimethylcyclobutyl) dimethoxysilane,

di(2,3-diacetylenes) dimethoxysilane,

di(2,3,4-trimethylcyclohexyl)dimethoxysilane,

di(2,3,5-trimethylcyclohexyl)dimethoxysilane,

di(2,3,4-triethylsilanol)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(2-methylcyclopentanol)dimethoxysilane,

di(3-methylcyclopentanol)dimethoxysilane,

di(2-ethylcyclopentane)dimethoxysilane,

di(2-n-butylcyclopentadienyl)dimethoxysilane,

di(2,3-dimethylcyclopentene)dimethoxysilane,

di(2,4-dimethylcyclopentene)dimethoxysilane,

di(2,5-dimethylcyclopentene)dimethoxysilane,

di(2,3,4-trimethylcyclopentanone)dimethoxysilane,

di(2,3,5-trimethylcyclopentanone)dimethoxysilane,

di(2,3,4-triethylsilanol)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(2-methylcyclopentadienyl)dimethoxysilane,

di(3-methylcyclopentadienyl)dimethoxysilane,

di(2-ethylcyclopentadienyl)dimethoxysilane,

di(2-n-butylcyclopentadienyl)ethoxysilane,

di(2,5-dimethylcyclopentane)dimethoxysilane,

di(2,3-diethyltoluenediamine)dimethoxysilane,

di(2,3,4-trimethylcyclopentanone)dimethoxysilane,

di(2,3,5-trimethylcyclopentanone)dimethoxysilane,

di(2,3,4-triethylchlorosilane)dimethoxysilane,

di(2,3,4,5-tetramethylcyclopentadienyl)dimethoxysilane,

di(2,3,4,5-tetramethylcyclopentadienyl)dimethoxysilane,

di(1,2,3,4,5-pentamethylcyclopentadienyl)dimethoxysilane,

di(1,2,3,4,5-pentamethylcyclopentadienyl)dimethoxysilane,

di-treemiddleposition,

di - dimethylbenzyl) dimethoxysilane,

di(substituted)dimethoxysilane,

the substituted-tributyltinoxide,

cyclopentyl-tributyltinoxide,

diisobutyldimethoxysilane,

diversitycomposition,

deploymentdirectory, and

isopropyl-verbalargumentative.

When n means 3, examples of the organosilicon compounds represented by formula (c-i), include monoatomically, such as tricyclopentadiene,

tricyclopentadiene,

dicyclopentadienyltitanium,

dicyclopentadienyliron,

dicyclopentadienyltitanium,

cyclopentadienylmanganese the compounds are preferred ethyltriethoxysilane, n-propyltriethoxysilane, tributyltinoxide, vinyltriethoxysilane, phenyltriethoxysilane, VINYLTRIMETHOXYSILANE, diphenylmethylsilane, FemaleCircumcision, bis-n-tridimensional, n-trimethylammonium, dicyclohexylammonium, cyclohexanedimethanol, 2-norbornenedicarboxylic, 2-norbornenedicarboxylic, phenyltriethoxysilane, hexanitroethane, Cyclopentasiloxane, tricyclopentadiene, cyclopentadienylmagnesium and dimethoxysilane represented by formula (c-ii). Particularly preferred dimethoxysilane represented by formula (c-ii), especially dicyclopentadienyliron, di-tributyltinoxide, di(2-methylcyclopentene)dimethoxysilane, di(3-methylcyclopentene)dimethoxysilane and di-treemiddleposition.

Organosilicon compounds mentioned above may be used in combination of two or more kinds.

The catalyst for polymerization of olefin.

The catalyst for polymerization of olefin according to the invention is formed from:

(A) a solid titanium catalyst component

(B) alyuminiiorganicheskikh connection and

(C) the organosilicon compound having at least one al Astelin to be used in addition to the above components (A), (B) and (C).

For example, there may be used:

the above-mentioned polyethers;

2,6-substituted piperidine; 2,5-substituted piperidine;

substituted methylenediamine, such as N,N,N',N'-tetramethylmethylenediamine and N,N,N',N'-tetramethylenebis;

nitrogen-containing electron-donating compounds such as 1,3-bibenzimidazole and 1,3-dibenzyl-2-phenylimidazole;

phosphorus-containing electron-donating compounds, such as phosphites, i.e., triethylphosphite, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphate, triisobutylene, diethyl-n-butylphosphate and diethylphenylphosphine; and

oxygen-containing electron-donating compounds such as 2,6-substituted tetrahydropyran and 2,5-substituted tetrahydropyranyl.

These components can be used independently or in combination.

In the present invention terpolymerization the catalyst may be formed from the above components.

Terpolymerization the catalyst may be formed Faure(FR)polimerizuet the olefins or the like in the presence of the solid titanium catalyst component (A) ORGANOMETALLIC compound (B), and optionally, silicone joint is odnymi atoms, such as ethylene, propylene, 1-butene, 1-penten, 1-hexene, 3-methyl-1-butene, 3-methyl-1-penten, 3-ethyl-1-penten, 4-methyl-1-penten, 4,4-dimethyl-1-penten, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene and 1 achozen. You can also use other vinyl compounds and unsaturated compounds, as described above. These monomers can be used alone or in combination.

the olefin used in terpolymerization may be the same or different from the above-olefin used in the polymerization.

There are no specific restrictions on the way of achieving terpolymerization. For example, terpolymerization can be carried out under conditions where the olefins or polyene compounds are liquid or in the presence of an inert solvent, or in gas phase. Preferably, the polymerization was carried out in the presence of an inert solvent in such a way that the monomers are added in an inert solvent and terpolymerization was achieved under relatively mild conditions. In this case, terpolymerization can be carried out under such conditions that the resulting prepolymer was dissolved or not restorefolder did not dissolve.

Terpolymerization preferably achieved at a temperature of usually about -20 to +100oC, preferably from -20 to 80oC, more preferably from about -10 to +40oC.

Terpolymerization may be performed periodically, semi-continuous or continuous manner.

The concentration of catalyst in the system terpolymerization may be higher than in the system main polymerization.

In terpolymerization concentration of catalytic components vary depending on the types of used catalytic components, but it is desirable that the concentration of the solid titanium catalyst component (A) was in the range of usually from 0.001 to 5,000 mol, preferably about 0.01 to 1,000 mmol, particularly preferably from 0.1 to 500 mmol in terms of titanium atom, counting on 1 l of the volume of the polymerization.

ORGANOMETALLIC compound (B) is used in an amount such that the Faure(co)polymer was obtained in an amount of from 0.01 to 2000 g, preferably from 0.03 to 1000 g, more preferably from 0.05 to 200 g, counting on 1 g of the solid titanium catalyst component (A), and is used in amount of usually about from 0.1 to 1000 mol, preferably about 0.5 to 500 Eskom component (A).

In terpolymerization organosilicon compound (C) may not be used in an amount of usually from 0.01 to 50 mol, preferably from 0.05 to 30 mol, more preferably from 0.1 to 10 mol, counting on 1 mol of titanium atom in the solid titanium catalyst component (A).

The molecular weight modifier such as hydrogen may be used in terpolymerization.

When terpolymerization catalyst was obtained in the form of a suspension, as described above, it can be used in this form in the subsequent polymerization, but it can also be used after separation from the suspension.

Terpolymerization catalyst mainly forms the catalyst for olefin together with the ORGANOMETALLIC compound (B) and organosilicon compound (C), but in some cases only terpolymerization the catalyst may be used as a catalyst for polymerization of olefin. When the organosilicon compound (C) is not used in the process of terpolymerization, it can be added to terpolymerization the catalyst in the polymerization process for the formation of a catalyst for polymerization of olefin.

The catalyst for polymerization of olefin image>/P>The method of polymerization of olefin.

In the method of polymerization of olefin according to the invention, the olefin is polymerized or lightly copolymerized in the presence of a catalyst for polymerization of olefins comprising a solid titanium catalyst component (A), the ORGANOMETALLIC compound (B) and the organosilicon compound (C) or including terpolymerization catalyst.

Any of a-olefins with 2 or more carbon atoms, as described above, can be used in terpolymerization.

Can also be used:

cycloolefin, such as cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclinea and 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4 a,5,8,8A-octahydronaphthalene; and

vinyl compounds such as styrene, dimethylstyrene, Allington, allylnormorphine, vinylnaphthalene, allitalia, Olivenza, vinylcyclopentane, vinylcyclohexane, vinylcyclopentane and allyltrimethylsilane.

Of them, preferred are ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-penten, 4-methyl-1-penten, vinylcyclohexane, dimethylstyrene, alliteratively and alienation.

Next, small amounts of diene compounds can be copolymerizable with olepi the-hexadien, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadien, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidenenorbornene, vinylnorbornene and Dicyclopentadiene.

These compounds can be used individually or in combination.

In the present invention, the polymerization can be carried out in the liquid phase, including the solution and the suspension or in the gas phase. When the polymerization is carried out in suspension, the above-mentioned inert organic solvent or an olefin which is liquid at the reaction temperature, can be used.

In the polymerization of the solid titanium catalyst component (A) or terpolymerization the catalyst is used in amount of usually about 0.001 to 100 mmol, preferably about 0.005 to 20 mmol in terms of titanium atom, per 1 l of the volume of the polymerization.

ORGANOMETALLIC compound (B) is used in an amount of usually about 1 to 2,000 mol, preferably from 2 to 500 mol, perennialism compound (C) is used in an amount of usually about 0.001 to 10 mol, mainly from 0.01 to 5 mol, per 1 mol of the metal atom in the ORGANOMETALLIC compound (B).

If terpolymerization the catalyst used in the method of polymerization, the addition of the ORGANOMETALLIC compound (B) and organosilicon compound (C) may be omitted according to circumstances. When the catalyst for polymerization of olefin is formed from terpolymerization catalyst component and (B) and/or component (C), components (B) and (C) can be used in the above-mentioned quantities.

If the hydrogen used in the polymerization, the molecular weight of the obtained polymer can be modified, and, in addition, a polymer having a high speed melt fluidity can be obtained.

In the method of polymerization of olefin according to the invention, the polymerization temperature is in the range typically from 20 to 300oC, preferably about 50 to 150oC, and pressure of the polymerization is in the range from atmospheric pressure to 100 kg/cm2preferably from about 2 to 50 kg/cm2although they vary depending on the type of olefin, polymerization method, etc.

According to the method of the invention, the polymerization moennig conditions. According to the present invention, not only the homopolymer of the olefin, but also a statistical copolymer or block copolymer of two or more types of olefin can be obtained. The polymerization method of the invention is particularly suitable for the preparation of highly stereoregular of homopolymer propylene and statistical copolymer of propylene and ethylene and/or olefin of 4 to 20 carbon atoms in which the content is soluble in decane components is reduced.

The number of comonomers, reacting with propylene ranges from 0 to 500 g, preferably from 0.5 to 100 g, more preferably from 5 to 10, and from 0 to 2000 g, preferably from 10 to 1000 g, more preferably from 50 to 500 g for olefin with at least 4 carbon atoms. The resulting copolymer contains propylene units in an amount of at least 58 mol.%, preferably at least 90 mol.%, more preferably at least 93 mol.%, both calculated per 1 kg of propylene.

The ethylene content and the content of C4-C20-olefin in the copolymer of propylene and ethylene and/or C4-C20the olefin can be measured by the method described below.

The term "ethylene" ethylene content means an isolated ethylene. The term "epreryvno polymerized. The content of the isolated ethylene can be measured as follows. In hydroforming machine (produced by Toho Press Seisakusho) 0.5 g of the sample was heated for 2 minutes and was partially degirolami at 20 ATM and then clutched 10 seconds at 80 ATM. Then the obtained product was pressed at 100 MPa for 1 min through hydroforming machine, which circulates cooling water, to obtain a film. In this operation iron lining was used to establish the thickness of the obtained film about 0.3 mm absorption Spectrum of the infrared rays in the region from 800 to 650 cm-1was measured for the films obtained by the diffraction grating IR spectrophotometer (DS-701 G, produced by Nippon Bunko K. K.) to obtain a transmission coefficient. In the resulting graph the tangent common to the point of maximum in the region of 760 cm-1and the point of maximum in the region of 700 cm-1was held, and this tangent is taken as the base line. The transmittance (T%) min absorption at 733 cm-1and the transmittance (T0%) the point of intersection of the base line and the perpendicular from point min absorption at 733 cm-1to the line of the wave numbers were calculated. Using the results, it was calculated the absorption at 733 cm-1(DOia:

The content of the isolated ethylene (%)=6.17 (D733/L),

where D733means the absorption at 733 cm-1and L (mm) denotes a thickness of the film used for the measurement.

The content of 1-butene (C4representing the contents of C4-C20-olefin, can be measured as follows. The film was obtained from 0.5 g of the sample in the same way as described above. In this operation iron lining is used to make the thickness of the obtained film about 0.3 mm absorption Spectrum of the infrared rays in the region from 800 to 700 cm-1was measured for the films obtained by the diffraction grating IR spectrophotometer (DS-701G type, manufactured by Nippon Bunko K. K. ) to obtain a transmission coefficient. In the resulting graph the tangent common to the point of maximum in the area of 775 cm-1and the point of maximum in the region of 750 cm-1was held, and this tangent is taken as the base line. The transmittance (T%) min absorption at 765 cm-1and the transmittance (T0%) the point of intersection of the base line and the perpendicular from point min absorption at 765 cm-1to the line of the wave numbers were calculated. Using the results, it was calculated the absorption at 765 cm-1(D765= log(T765/L),

where D765means the absorbance at 765 cm-1and L (mm) denotes a thickness of the film used for the measurement.

The result of the invention.

When using the catalyst for polymerization of olefin containing solid catalytic component of the invention, the amount of polyolefin low stereoregularity produced as a by-product, can be reduced, and the polyolefin high stereoregularity can be obtained with a surprisingly high activity in the polymerization.

EXAMPLES.

The present invention will be further described, referring to the following examples, but it should be construed that the invention is not limited to these examples.

Example 1.

Preparation of solid titanium catalyst component (a-1). Preparation of solid titanium (i).

7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexanol alcohol were mixed, and the mixture was heated at 130oC for 2 hours to obtain a homogeneous solution. To the solution was added 1.67 g (11.5 mmol) of phthalic anhydride, and the mixture was stirred at 130oC for another 1 hour to dissolve the phthalic anhydride in rettore dropwise added to 200 ml (1.8 mol) of titanium tetrachloride (TiCl4supported at -20oC for 1 hour. After drip adding the temperature of the resulting solution was raised to 110oC for a period of 4 hours. When the temperature reached 110oC, 5.03 ml (18.8 mmol) of diisobutylphthalate added to the solution, followed by stirring at the same temperature for 2 hours.

After 2-hour reaction, the obtained solid (1) was recovered by hot filtration, resuspending in 275 ml of TiCl4and then heated again at 110oC within 2 hours.

After the reaction the obtained solid (2) was recovered by hot filtration, and then washed with toluene at 100oC and then with hexane. Suspension of a rigid body (2) in 100 ml of hexane was stirred with a spatula for about 30 seconds and filtered. This stage is repeated until such time as the titanium compound was no longer detected in the filtrate.

Thus the solid titanium (i) was obtained as a hexane slurry. Part of the solid titanium (i) was selected and dried for analysis of its composition.

In the solid titanium (i) contained 2.4% by weight titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13% by weight of diisobutylphthalate.

Interaction with on-dal and then 1.0 mmol (in relation to the titanium atom) of the solid titanium (i).

The internal temperature of the reactor was maintained at 70oC, and the mixture was stirred at 400 rpm for 1 hour using interfering blades.

After heating and stirring, the obtained solid was recovered by filtration, and washed three times with hexane to obtain a solid titanium catalyst component (a-1).

Part of the solid titanium catalyst component (a-1) was separated and dried for analysis of its composition.

In the solid catalytic titanium component (a-1) contained 1.3% by weight titanium, 60.0% by weight of chlorine, 20.0% by weight of magnesium and 11.3% by weight of diisobutylphthalate. Consequently, the weight ratio of the electron-donating compound to the titanium was 8.69, and the titanium content decreased by 45.8% by weight compared to solid titanium (i) before contact with o-dichlorobenzene.

Washing the solid titanium catalyst component (a-1) o-dichlorobenzene at 90oC.

0.5 g of the titanium catalyst component (a-1) were placed in a 200 ml glass reactor thoroughly purged with nitrogen. To the reactor was added 100 ml of o-dichlorobenzene. The internal temperature in the reactor was maintained at 90oC, and the mixture was stirred at 400 rpm for 1 hour,romily twice with hexane and dried in vacuum.

The content of titanium in the solid titanium catalyst component (a-1) after washing was 1.2% by weight. Therefore, the decrease of the ratio of the titanium content lavage o-dichlorobenzene at 90oC was 7.7% by weight.

Getting terpolymerization catalyst (I-1).

In a 200 ml glass reactor thoroughly purged with nitrogen, was placed 100 ml of purified hexane, and then put 2 mmol of triethylaluminum, 0.4 mmol of dicyclopentadienyliron and 0.2 mmole (with respect to the titanium atom) of the solid titanium catalyst component (a-1). Then propylene was served with a speed of 1.0 l/h for 1 hour.

After the filing of propylene obtained solid was removed by filtration, washed twice with water and resuspendable the Dean. The entire quantity of the suspension was placed in a catalytic vessel for receiving terpolymerization catalyst (I-1).

The polymerization.

In a 1 l autoclave were placed 400 ml of purified heptane and then made 0.4 mmol of triethylaluminum, 0.4 mmol of dicyclopentadienyliron and 0.008 mmol (with respect to the titanium atom) terpolymerization catalyst (I-1) in an atmosphere of propylene at 60oC. Then added 100 ml of hydrogen, and the system was heated to increase the polymerization the pressure was maintained at 5 kg/m2-G. After the polymerization, the slurry containing the resulting polymer was filtered to separate a white granular polymer from the liquid phase. The results are presented next in Table 1.

Example 2.

Preparation of solid titanium catalyst component (a-1). Contact with o-dichlorobenzene.

In a 200 ml glass reactor thoroughly purged with nitrogen were introduced 100 ml of o-dichlorobenzene and then 1.0 mmol (in relation to the titanium atom) of the solid titanium (i) obtained in Example 1.

The internal temperature of the reactor was maintained at 100oC, and the mixture was stirred at 400 rpm for 1 hour using interfering blades.

After heating and stirring the obtained solid was removed by filtration and washed three times with hexane to obtain a solid titanium catalyst component (a-2).

Part of the solid titanium catalyst component (a-2) was separated and dried for analysis of its composition.

In the solid titanium catalyst component (a-2) contained 1.1% by weight titanium, 60.0% by weight of chlorine, 20.5% by weight of magnesium and 11.4% by weight of diisobutylphthalate. Consequently, the weight ratio of the electron-donating compound to the titanium botttom with o-dichlorobenzene.

Washing the solid titanium catalyst component (a-2) o-dichlorobenzene at 90oC.

Washing o-dichlorobenzene at 90oC was performed in the same manner as in Example 1, except that the solid titanium catalyst component (a-2) was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium catalyst component (a-2) after washing was 1.1% by weight. Therefore, the decrease in titanium content lavage o-dichlorobenzene at 90oC was 0% by weight.

Getting terpolymerization catalyst (I-2).

Terpolymerization catalyst (I-2) was obtained in the same manner as in Example 1, except that 0.2 mmol (calculated as titanium atom) of the solid titanium catalyst component (a-2) were used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (based on titanium atom) terpolymerization catalyst (I-2) was used instead terpolymerization catalyst (I-1). The results given the same (a-3). Contact with trichlorotoluene.

The solid titanium catalyst component (a-3) was obtained in the same manner as in Example 2, except that 100 ml ,,- trichlorotoluene were used instead of o-dichlorobenzene.

In the solid titanium catalyst titanium component (a-3) contained 1.0% by weight titanium, 60.0% by weight of chlorine, 20.0% by weight of magnesium and 11.3% by weight of diisobutylphthalate. Therefore, the weight ratio of the electron-donating compound to the titanium was 11.3, and the titanium content was decreased by 58.3% by weight compared to the titanium containing solid (i) before interaction with trichlorotoluene.

Washing the solid titanium catalyst component (a-3) o-dichlorobenzene at 90oC.

Washing o-dichlorobenzene at 90oC was performed in the same manner as in Example 1, except that the solid titanium catalyst component (a-3) was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium catalyst component (a-3) after washing was 1.0% by weight. Therefore, the reduced ratio of the titanium content in the washing o-dichlorobenzene was 0% by weight.

Comparative Example 1.

Preparation of solid titanium catalyst component (a-4).

The solid titanium catalyst component was obtained in the same manner as in Example 1, except that the solid titanium (i) was brought into contact with 100 ml of toluene instead of o-dichlorobenzene.

In the solid titanium catalyst component (a-4) contained 1.5% by weight titanium, 60.5% by weight of chlorine, 20.0% by weight of magnesium and 8.7% by weight of diisobutylphthalate. Therefore, the weight ratio of the electron-donating compound to the titanium was 5.8, and the titanium content decreased by 37.5% by weight compared to the titanium containing solid (i) before contact with toluene.

Washing the solid titanium catalyst component (a-4) o-dichlorobenzene CIP 90oC.

Washing o-dichlorobenzene at 90oC was performed in the same manner as in Example 1, except that the solid titanium catalyst component (a-4) was used instead of the solid titanium catalyst cation was 1.2% by weight. Therefore, the reduction ratio of the titanium content in the washing o-dichlorobenzene was 20% by weight.

Getting terpolymerization catalyst (I-4).

Terpolymerization catalyst (I-4) was obtained in the same manner as in Example 1, except that 0.2 mmole (with respect to the titanium atom) of the solid titanium catalyst component (a-4) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (with respect to the titanium atom) terpolymerization catalyst (I-4) was used instead terpolymerization of catalysate (I). The results are presented in Table 1.

Comparative example 2.

Preparation of solid titanium catalyst component (A-5).

The solid titanium catalyst component (A-5) was obtained in the same manner as in Example 1, except that the solid titanium (i) was brought into contact with the 40oC with 100 ml of tributylamine instead of o-dichlorobenzene.

In the solid titanium catalyst component (A-5) contained 1.6% by weight titanium, 60.0% by weight of chlorine, 20.0% by weight of magnesium and 9.5% .93, and the titanium content was reduced to 33.3% by weight compared to the titanium containing solid (i) before contact with tertbutylamine.

Washing the solid titanium catalyst component (A-5) o-dichlorobenzene at 90oC.

Washing o-dichlorobenzene at 90oC conducted in such manner as in Example 1 except that the solid titanium catalyst component (A-5) was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium catalyst component (A-5) after washing was 1.2% by weight. Therefore, the decrease in titanium content lavage o-dichlorobenzene at 90oC was 25% by weight.

Getting terpolymerization catalyst (I-5).

Terpolymerization catalyst (I-5) was obtained in the same manner as in Example 1, except that 0.2 mmol (based on titanium atom) of the solid titanium catalyst component (A-5) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (with respect to the titanium atom) foreigntable forth in Table 1.

Comparative Example 3.

Washing the solid titanium (i) o-dichlorobenzene at 90oC.

Washing o-dichlorobenzene at 90oC was performed in the same manner as in Example 1, except that the solid titanium (i) obtained in Example 1 was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium (i) after washing was 1.2% by weight. Therefore, the decrease of the ratio of the titanium content lavage o-dichlorobenzene at 90oC was 50% by weight. In the solid titanium (i) the weight ratio of the electron-donating compound to the titanium was 5.42.

Getting terpolymerization catalyst (I-6).

Terpolymerization catalyst (I-6) was obtained in the same manner as in Example 1, except that 0.2 mmol (based on titanium atom) of the solid titanium (i) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (with respect to the titanium atom) terpolymerization catalyst (I-6) was used instead terpolymerization catalyst (I-1). The results of t is from Perkin-Elmer Co. in the following way. The sample was heated from room temperature to 200oC with a speed of 320oC/min, maintained at 200oC for 10 min and then cooled to 30oC at a rate of 10oC/min Exothermic curve given by the crystallization of the polymer in the cooling process, received in accordance with the analytical program DSC-7 to determine the temperature at the exothermic peak, which is denoted as "Tc". Then the sample was kept at 30oC for 5 minutes and then was heated to 200oC at a rate of 10oC/min Endothermic curve given by the melting of the polymer in the heating process, was obtained in accordance with the analytical program DSC-7 for determining the temperature of an endothermic peak, which was regarded as the melting point of Tm".

Soluble in n-decane components were measured as follows. In a 1 l flask was placed 3 g of the sample, 20 mg of 2,6-di-tertbutyl-4-METHYLPHENOL and 500 ml of n-decane, and the mixture was heated to 145oC, obtaining a solution which was then cooled to 23oC for a period of 8 hours and maintained at 23oC for 8 hours. Saducees solid was separated from n-technologo solution containing the dissolved polymer, filetype constant weight, and the weight was measured. Soluble in decane component was defined as the percentage ratio of the weight of the dissolved polymer to the weight of the sample.

Molecular mass (Mw) and molecular weight distribution (Mw/Mn) of the polymer was measured by gel permeation chromatography using TSK mixed polystyrene gel column (G3000-G7000), elyuirovaniya o-dichlorobenzene at 140oC.

The specific weight of the polymers was measured in accordance with JIS K-6721.

Example 4.

Preparation of solid titanium catalyst component (A-6).

The solid titanium catalyst component (A-6) was obtained in the same manner as in Example 1, except that the temperature of contacting a solid titanium (i) with o-dichlorobenzene was changed to 130oC 70oC.

In the solid titanium catalyst component (A-6) contained 0.9% by weight titanium, 61% by weight of chlorine, 20.5% by weight of magnesium and 8.7% by weight of diisobutylphthalate. Therefore, the weight ratio of the electron-donating compound to the titanium was 9.67, and the titanium content was reduced to 62.5% by weight compared to the titanium-containing solid (i) before contact with o-dichlorobenzene.

Washing the solid titom 90oC conducted in such manner as in Example 1 except that the solid titanium catalyst component (A-6) was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium catalyst component (A-6) after washing was 0.9% by weight. Therefore, the decrease in titanium content lavage o-dichlorobenzene at 90oC was 0% by weight.

Getting terpolymerization catalyst (I-7).

Terpolymerization catalyst (I-7) was obtained in the same manner as in Example 1, except that 0.2 mmol (based on titanium atom) of the solid titanium catalyst component (A - 6) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (with respect to the titanium atom) terpolymerization catalyst (I-7) was used instead terpolymerization catalyst (I-1). Output (granulated) polymer was 90.0 g and the amount soluble in the solvent component was 0.0, moreover, activity in the polymerization was 2,200 g-PP/g-cat. The amount of soluble d melting point (Tm) 164.5oC, the specific gravity of 0.41 g/ml, Mw438,000 and Mw/Mn3.79.

Example 5.

Preparation of solid titanium catalyst component (a-7) 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexanol alcohol were mixed, and the mixture was heated at 130oC for 2 hours to obtain a homogeneous solution. To the solution was added 1.67 g (11.5 mmol) of phthalic anhydride, and the mixture was stirred at 130oC for another 1 hour to dissolve the phthalic anhydride in the solution.

The obtained homogeneous solution was cooled to room temperature, and then the entire quantity of the solution is dropwise added to 200 ml (1.8 mol) of titanium tetrachloride (TiCl4supported at -20oC for 1 hour. After the addition the temperature of the resulting solution was raised to 110oC for a period of 4 hours. When the temperature reached 110oC, 5.03 ml (18.8 mmol) of diisobutylphthalate added to the solution, followed by stirring at the same temperature for 2 hours.

After 2-hour reaction, the obtained solid (1) (the solid titanium (i)-2) was recovered by hot filtration and then washed with decane of 110oC and then with hexane at room tktable. This stage is repeated until such time as the titanium compound was no longer detected in the filtrate.

In the solid titanium (i)-2 contained 3.9% by weight titanium, 52.0% by weight of chlorine, 17.5% by weight of magnesium and 17.2% by weight of diisobutylphthalate.

Contact 1.2.4-trichlorobenzene. Solid titanium (i)-2, obtained above, resuspendable in 375 ml of 1,2,4-trichlorobenzene and heated at 130oC for 1 hour.

After completion of the reaction the obtained solid was recovered by hot filtration and washed with decane of 110oC and then with hexane. A suspension of the solid in 100 ml of hexane was stirred with a spatula for about 30 seconds and filtered. This stage is repeated until then, until he discovered the absence of the titanium compounds in the filtrate.

Thus, the solid titanium catalyst component (a-7) was obtained in the form of a hexane suspension. Part of the solid titanium catalyst component (a-7) was separated and dried for analysis of its composition.

In the solid titanium catalyst component (a-7) contained 1.4% by weight titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13.6 weight diisobutylphthalate. Therefore, the weight ratio of the electron-donating compound to the titanium was 9.71, and coderresult.

Washing the solid titanium catalyst component (a-7) o-dichlorobenzene at 90oC.

0.5 g of the titanium catalyst component (a-7) were placed in a 200 ml glass reactor thoroughly purged with nitrogen. To the reactor was added 100 ml of o-dichlorobenzene. The internal temperature in the reactor was maintained at 90oC, and the mixture was stirred at 400 rpm for 1 hour using interfering blades. After stirring the obtained solid was removed by filtration, washed twice with hexane and dried in vacuum.

The content of titanium in the solid titanium catalyst component (a-7) after washing was 1.4% by weight. Therefore, the decrease of the ratio of the titanium content lavage o-dichlorobenzene at 90oC was 0% by weight.

Getting terpolymerization catalyst (I-8).

Terpolymerization catalyst (I-8) was obtained in the same manner as in Example 1, except that the solid titanium catalyst component (a-7) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (on etnoistoria (I-1). The results are shown in Table 2.

Example 6.

Preparation of solid titanium catalyst component (a-8).

The solid titanium catalyst component (a-8) was obtained in the same manner as in Example 5, except that 11.5 moles of 2-n-butoxyethanol was used instead 11.5 mmol phthalic anhydride in the preparation of solid titanium (i)-2.

In the solid titanium catalyst component (a-8) obtained by the interaction with 1,2,4-trichlorobenzene, contained 1.0% by weight titanium, 56% by weight of chlorine, 18% by weight of magnesium and 19.5% by weight of diisobutylphthalate. Therefore, the weight ratio of the electron-donating compound to the titanium was 19.5, and the titanium content was reduced by 83.3% by weight compared to what it was before contact with 1,2,4-trichlorobenzene.

Washing the solid titanium catalyst component (a-8) o-dichlorobenzene at 90oC.

Washing o-dichlorobenzene at 90oC conducted in such manner as in Example 1 except that the solid titanium catalyst component (a-8) was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium catalyst component (a-8) after prom is> was 0% by weight.

Getting terpolymerization catalyst (I-9).

Terpolymerization catalyst (I-9) was obtained in the same manner as in Example 1, except that 0.2 mmol (based on titanium atom) of the solid titanium catalyst component (a-8) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (with respect to the titanium atom) terpolymerization catalyst (I-9) was used instead terpolymerization catalyst (I-1). The results are shown in Table 2.

Example 7.

Preparation of solid titanium catalyst component (A-9).

The solid titanium catalyst component (A-9) was obtained in the same manner as in Example 5, except that 0.06 g of TiO2suspended in TiCl4supporting -20oC, for the preparation of the solid titanium (i)-2.

In the solid titanium catalyst component (A-9) obtained by the interaction with 1,2,4-trichlorobenzene, contained 2.1% by weight titanium, 56% by weight of chlorine, 19% by weight of magnesium and 18.0% by weight of diisobutylphthalate. Therefore, WG compared with the that was before contact with 1,2,4-trichobezoar.

Washing the solid titanium catalyst component (A-9) o-dichlorobenzene at 90oC. Washing of o-dichlorobenzene at 90oC conducted in such manner as in Example 1 except that the solid titanium catalyst component (A-9) was used instead of the solid titanium catalyst component (a-1).

The content of titanium in the solid titanium catalyst component (a-8) after washing was 2.1% by weight. Therefore, the decrease in titanium content lavage o-dichlorobenzene at 90oC was 0% by weight.

Getting terpolymerization catalyst (I-10).

Terpolymerization catalyst (I-10) was obtained in the same manner as in Example 1, except that 0.2 mmol (based on titanium atom) of the solid titanium catalyst component (A-9) was used instead of the solid titanium catalyst component (a-1).

The polymerization.

Polymerization of propylene was conducted in the same manner as in Example 1, except that 0.008 mmol (with respect to the titanium atom) terpolymerization catalyst (I-10) was used instead terpolymerization catalyst (I-1). the key was placed 400 g of propylene, 3.0 l of ethylene and 4.5 liters of hydrogen, and the temperature is brought to 60oC. In the autoclave then was placed 0.6 mmole of triethylaluminum, 0.6 mmol of dicyclopentadienyliron and 0.003 mmol (with respect to the titanium atom) terpolymerization catalyst (I-7) obtained in Example 4, and the system was maintained at 70oC for 30 minutes to achieve the copolymerization of propylene and ethylene. The results are shown below in Table 3.

Example 9.

The polymerization. The copolymerization of propylene was conducted in the same manner as in Example 8, except that the amount of ethylene was changed to 4.0 liters. The results are shown below in Table 3.

Example 10.

The polymerization.

The copolymerization of propylene was conducted in the same manner as in Example 8, except that the amount of ethylene, triethylaluminum and dicyclopentadienyliron changed to 2.5 l, 0.8 mmol and 0.8 mmol, respectively, and 0.004 mmol (with respect to the titanium atom) terpolymerization catalyst (I-8) obtained in Example 5 was used instead terpolymerization catalyst (I-7). The results are shown below in Table 3.

Example 11.

The polymerization.

The copolymerization of propylene was conducted the same is e in Table 3.

Example 12.

Preparation of solid titanium catalyst component (A-10). Preparation of solid titanium (i).

7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexanol alcohol were mixed, and the mixture was heated at 130oC for 2 hours to obtain a homogeneous solution. To the solution was added 1.67 g (11.5 mmol) of phthalic anhydride, and the mixture was stirred at 130oC for another 1 hour to dissolve the phthalic anhydride in the solution.

The obtained homogeneous solution was cooled to room temperature, and then the entire quantity of the solution is dropwise added to 200 ml (1.8 mol) of titanium tetrachloride (TiCl4supported at -20oC for 1 hour. After the addition the temperature of the resulting solution was raised to 110oC for a period of 4 hours. When the temperature reached 110oC, 5.03 ml (18.8 mmol) of diisobutylphthalate added to the solution, followed by stirring at the same temperature for 2 hours.

After 2-hour reaction, the obtained solid (1) was removed by hot filtration, resuspendable in 275 ml of TiCl4and then again heated at 110oC within 2 hours.

After completion of the reaction,Uspenskiy rigid body (2) in 100 ml of hexane was stirred with a spatula for about 30 seconds and filtered. This stage is repeated until such time as the titanium compound was no longer detected in the filtrate.

Thus the solid titanium (i) received as a hexane slurry. Part of the solid titanium (i) picked and dried for analysis of its composition.

In the solid titanium (i) contained 2.5% by weight titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13% by weight of diisobutylphthalate.

Contact with a polar compound.

In a 200 ml glass reactor thoroughly purged with nitrogen were introduced 100 ml of o-dichlorobenzene and then 1.0 mmole (with respect to the titanium atom) of the solid titanium (i).

The internal temperature of the reactor was maintained at 100oC, and the mixture was stirred at 400 rpm for 1 hour using a blade stirrer.

After heating and stirring the obtained solid was removed by filtration and washed three times with hexane to obtain a solid titanium catalyst component (A-10).

Part of the solid titanium catalyst component (A-10) was separated and dried for analysis of its composition.

In the solid titanium catalyst component (A-10) contained 0.95% by weight titanium, 60.0% by weight of chlorine, 20.5% by weight of magnesium and 11.4% by weight of diisobutylphthalate.

After the filing of propylene obtained solid was removed by filtration, washed twice with purified hexane and resuspendable the Dean. The entire quantity of the suspension was placed in a catalytic vessel for receiving terpolymerization catalyst (I-11).

The polymerization.

In a 1 l autoclave were placed 400 ml of purified heptane and further contributed 0.4 mmole of triethylaluminum, 0.4 mmole of dicyclopentadienyliron and 0.008 mmole (with respect to the titanium atom) terpolymerization catalyst (I-11) in a propylene atmosphere at 60oC. Then 100 ml of hydrogen was added, and the system was heated to 70oC and kept at this temperature for 1 hour to complete the polymerization of propylene. During the polymerization the pressure was maintained at 5 kg/m2-G. After the polymerization, the slurry containing the resulting polymer was filtered to separate a white granular polymer from the liquid phase. The results below e with polar connection" polar compounds, presented in Table 4 were used instead of o-dichlorobenzene. The results of polymerization are shown in Table 5.

Comparative Example 4.

The procedure of Example 12 was repeated, except that the Contact with the polar compound" was not performed. The results of polymerization are shown in Table 5.

Comparative Example 5.

The procedure of Example 12 was repeated, except that in Contact with the polar connection toluene, given in Table 4 was used instead of o-dichlorobenzene. The results of polymerization are shown in Table 5.

Examples 16 and 17.

The procedure of Example 12 was repeated, except that in Contact with the polar compound" trilobata dissolved in decane at concentrations given in Table 4 was used instead of o-dichlorobenzene. The results of polymerization are shown in Table 5.

Examples 18 and 19.

The procedure of Example 12 was repeated, except that in Contact with the polar compound" solid titanium interacted with dichlorobenzene at temperatures given in Table 5.

Example 20.

The procedure of Example 12 was repeated, except that in Contact with the polar compound" diphenyldichlorosilane given in Table 4, solbriller 6.

The procedure of Example 12 was repeated, omitting the fact that in Contact with the polar compound" solid titanium interacted with phthalic chloride, the data in Table 4, instead of o-dichlorobenzene at 70oC. the Results of polymerization are shown in Table 5.

1. The way to obtain a solid titanium catalyst component for polymerization of olefins, comprising magnesium, titanium, halogen and an electron-donating compound and having the following characteristics: (1) the titanium content shall be not more than 2.5% by weight, (2) the total content of magnesium and halogen is at least 65% by weight and less than 92% by weight, (3) the content of the electron-donating compound is in the range from 8 to 30% by weight, (4) the weight ratio of the electron-donating compound to titanium is in the range from 7 to 40 and (5) the above-mentioned solid titanium catalyst component is almost free from exhaust titanium compounds as a result of washing with hexane at room temperature and has a reduction ratio of the titanium content less than 15% by weight in the washing o-dichlorobenzene at 90oC, comprising contacting a solid titanium component with a polar compound, characterized in that the connection and which is free from exhaust titanium compounds as a result of washing with hexane at room temperature, carried out with a polar compound having a dipole moment of 0.50 to 4.00 Debye at a temperature of at least 40oC to reduce the content of titanium in the solid titanium at least 25 wt.%.

2. The method according to p. 1, characterized in that as polar compounds using halogenated aromatic hydrocarbon.

3. The method according to p. 1 or 2, characterized in that the solid titanium means solid (1) obtained by bringing (a) compounds of magnesium in the liquid state (b) compounds of titanium in the liquid state and (C) electron-donating compound in contact with each other.

4. The method according to p. 1 or 2, characterized in that the solid titanium means a solid substance (2), obtained by a process comprising bringing a compound of magnesium in the liquid state (b) compounds of titanium in the liquid state and (C) electron-donating compound in contact with each other to obtain a solid substance (1) and then bringing solids (1) into contact with (b) a compound of titanium in the liquid state.

5. The catalyst for polymerization of olefins, comprising: (A) a solid titanium catalyst component (C) alyuminiiorganicheskikh connection and (C) the organosilicon compound imets component, obtained by the method according to any of paragraphs.1 to 4.

6. The method of polymerization or copolymerization of olefins in the presence of a polymerization catalyst, wherein the catalyst used catalyst under item 5.

7. Terpolymerization catalyst comprising a prepolymer or propolymer of olefin with (A) a solid titanium catalyst component (C) alyuminiiorganicheskikh compound, and optionally (C) organosilicon compound having at least one alkoxygroup, characterized in that the component (A) is a solid titanium catalyst component obtained by the method according to any of paragraphs.1 to 4.

8. The method of polymerization or copolymerization of olefins in the presence of terpolymerization catalyst, characterized in that as terpolymerization catalyst using the catalyst according to p. 7.

 

Same patents:

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

The invention relates to a solid catalyst component obtained by a process comprising a stage of bringing (a) a liquid magnesium compounds into contact with (b) a liquid compound of titanium in the presence of (C) organosilicon compounds having inactive hydrogen in an amount of from 0.25 to 0.35 mol per 1 mol of compound of magnesium (a) increasing the temperature of the obtained contact product (i) to a temperature of from 105 to 115oWith and holding the contact product at this temperature

The invention relates to a method for producing polyethylene by polymerization of ethylene at elevated temperature and pressure in the presence of a catalyst consisting of zirconocene and socializaton - methylalumoxane, while the polymerization of ethylene is carried out at a temperature of 100-150oC, a pressure of 4-8 bar in the presence of a catalyst containing as zirconocene a compound selected from the group including rat-dimethylsilane - bis-1-(2-methyl-4-phenylindane)zirconiated, rat - dimethylsilane-bis-1-(2-metalcrafter)zirconiated, rat - dimethylsilane-bis-1-(2-methyl-4,5-benzhydryl)zirconiated

The invention relates to metal coordination complexes with hard structure

The invention relates to a solid catalyst component obtained by a process comprising a stage of bringing (a) a liquid magnesium compounds into contact with (b) a liquid compound of titanium in the presence of (C) organosilicon compounds having inactive hydrogen in an amount of from 0.25 to 0.35 mol per 1 mol of compound of magnesium (a) increasing the temperature of the obtained contact product (i) to a temperature of from 105 to 115oWith and holding the contact product at this temperature

The invention relates to the technology of producing homopolymers or copolymers of ethylene with vinyl acetate by the method of high pressure in a tubular reactor and can be used in the chemical and petrochemical industry

The invention relates to a method for producing a catalyst used for the polymerization of olefins, by contacting compounds of magnesium with a halogenated titanium compound

The invention relates to new multi-core metallocene compounds of the formula I, in which M1denotes a metal of group IVб of the Periodic system of the elements; X is a halogen atom; L and L1are the same or different and represent a substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl; denotes a group of formula (a), in which R1denotes a divalent hydrocarbon bridging group, the residues R2are the same and denote WITH1-C4is an alkyl group; M2denotes the silicon, as well as the way they are received, containing the catalytic system, a method for producing a polyolefin and a polymer molded product

The invention relates to a new organoboron compound having catalytic activity, of the formula I

[RjM-Xd-MRj]a-bAc+(I)

in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, C is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3

The invention relates to a new organoboron compound having catalytic activity, of the formula I

[RjM-Xd-MRj]a-bAc+(I)

in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, C is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3

The invention relates to a method for producing polyethylene by polymerization of ethylene at elevated temperature and pressure in the presence of a catalyst consisting of zirconocene and socializaton - methylalumoxane, while the polymerization of ethylene is carried out at a temperature of 100-150oC, a pressure of 4-8 bar in the presence of a catalyst containing as zirconocene a compound selected from the group including rat-dimethylsilane - bis-1-(2-methyl-4-phenylindane)zirconiated, rat - dimethylsilane-bis-1-(2-metalcrafter)zirconiated, rat - dimethylsilane-bis-1-(2-methyl-4,5-benzhydryl)zirconiated

The invention relates to a method of hydroisomerization n-paraffins with a long chain

The invention relates to a method of preparation of highly efficient catalysts based on polyamidine phthalocyanine cobalt for oxidative treatment of hydrocarbon distillates, diesel fuel, waste water and gas emissions from sulfur compounds

The invention relates to chemistry, in particular to a method for photochemical catalyst and its use for hydrogen in the course of photochemical reactions

The invention relates to catalytic chemistry, namely a process for the production of catalytically active layers, and receive carriers of catalysts that can be used for deep oxidation of organic compounds and carbon monoxide in the exhaust gas chemistry, petrochemistry and internal combustion engines

The invention relates to the field of catalysts (co)polymerization of dienes and vinylaromatic connections
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