JPH0543617A - Production of stereoregular polyolefin - Google Patents

Abstract

(57) [Summary] [Structure] At least one member selected from metal Mg, a hydroxylated organic compound, and an oxygen-containing organic compound of Mg, and Ti
At least one halogenated Al in a homogeneous solution containing the oxygen-containing organic compound of Si and / or the oxygen-containing organic compound of Si and the oxygen-containing organic compound of Al and / or the B compound.
To obtain a solid product, which is further reacted with at least one Al halide to give an electron-donating compound and a halogenated Ti compound. Catalyst component and I of the periodic table
At least one selected from the group consisting of organometallic compounds of Group A, IIA, IIB, IIIB, and IVB metals;
A method for producing a stereoregular polyolefin using a catalyst system comprising an electron-donating compound. [Effect] A highly stereoregular polymer having a good particle shape can be obtained in high yield.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a stereoregular polyolefin. More specifically, the present invention makes it possible to obtain a highly stereoregular polymer having a good particle shape in a high yield by using a specific catalyst in the (co) polymerization of an α-olefin having 3 or more carbon atoms. The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art Conventionally, as an olefin polymerization catalyst,
Α-type titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, purple γ-type titanium trichloride obtained by reducing titanium tetrachloride with aluminum, or δ obtained by grinding these with a ball mill. Type titanium trichloride and the like are known. Further, as a method for reforming these catalysts, a method of mixing and pulverizing with various modifiers is also known. However, when polymerization is carried out using these catalysts, the polymerization activity is low, and the catalyst residue in the obtained polymer is large, so that the so-called deashing step was essential. Further, in recent years, many proposals have been made regarding the production of solid catalyst components containing magnesium, titanium and halogen as main components. However, many of them are desired to be further improved in activity, polymer stereoregularity, powder characteristics and the like.

The inventors of the present invention have disclosed, as a method for obtaining a stereoregular polyolefin in a high yield, by using a specific solid catalyst component containing Mg, Ti and halogen as the main components.
No. 3-3007, JP-A-63-314210, JP-A-63-317502, JP-A-64-105, and JP-A-1-165608 have been proposed. However, these methods required a large amount of titanium halide compound.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to find a method for overcoming the inadequacies of the prior art, that is, for reducing the amount of titanium halide compound used.

[0005]

As a result, in the method disclosed in the above-mentioned JP-A-64-105, Mg,
A solid product obtained by reacting at least one aluminum halide with a homogeneous solution consisting of Ti or Si is suspended in an organic solvent, and the solid product treated with at least one aluminum halide is further treated with an electron. The present invention has been completed by using a solid catalyst component obtained by reacting a donor compound and a titanium halide compound, an organometallic compound as a co-catalyst, and an electron donor compound.

That is, according to the present invention, in producing a stereoregular polyolefin in the presence of a catalyst composed of a transition metal compound and an organometallic compound, a solid catalyst component (A) is used.
And (i) at least one member selected from the group consisting of (i-1) metallic magnesium and a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium, and (i-2) an oxygen-containing organic compound of titanium and / or (i -3) Isolating a solid product obtained by reacting (ii) at least one aluminum halide with a homogeneous solution containing an oxygen-containing organic compound of silicon and an oxygen-containing organic compound of aluminum / or a boron compound, iii) Further, a solid catalyst component obtained by reacting (iv) an electron-donating compound and (v) a titanium halide compound with a solid product obtained by treating the reaction product with at least one aluminum halide and a component (B). ) As IA, II of the periodic table
At least one selected from the group consisting of organometallic compounds of Group A, IIB, IIIB, and IVB metals and component (C)
Relates to a method for producing a stereoregular polyolefin using a catalyst system composed of an electron donating compound. [Function] Solid catalyst component (A) used in the present invention
Is (i) at least one member selected from the group consisting of (i-1) metallic magnesium, a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium; and (i-2) an oxygen-containing organic compound of titanium and / or (i -3) Isolating a solid product obtained by reacting (ii) at least one aluminum halide with a homogeneous solution containing an oxygen-containing organic compound of silicon and an oxygen-containing organic compound of aluminum / or a boron compound, iii) Furthermore, this reaction product can be obtained by reacting a solid product treated with at least one aluminum halide with (iv) an electron donating compound and (v) a titanium halide compound.

The method (i) for preparing the uniform solution is proposed and described in detail in, for example, JP-A-64-105.

As a method for preparing a homogeneous solution containing magnesium, a hydroxylated organic compound and titanium, for example, metal magnesium is reacted with a hydroxylated organic compound or an oxygen-containing organic compound of titanium such as titanium alkoxide. You can At this time, it is also possible to use a product obtained by previously reacting the metal magnesium, which is the reactant of (i-1), with the hydroxylated organic compound.

Various forms of metallic magnesium, that is, any form such as powder, particles, foil or ribbon can be used.

Suitable hydroxylated organic compounds are alcohols, phenols, and organic silanols.

As alcohols, straight-chain or branched-chain aliphatic alcohols having 1 to 18 carbon atoms, alicyclic alcohols or aromatic alcohols can be used.

As an example, methanol, ethanol, n
-Propanol, i-propanol, n-butanol,
Examples thereof include n-hexanol, 2-ethylhexanol, n-octanol, i-octanol, n-stearyl alcohol, cyclopentanol, cyclohexanol and ethylene glycol.

Further, examples of phenols include phenol, cresol, xylenol and hydroquinone.

The organic silanol has at least one hydroxyl group, and the organic group has an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, a cycloalkyl group, an arylalkyl group. It is selected from compounds having a group, an aryl group, and an alkylaryl group.

Examples thereof include trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol and the like. These hydroxylated organic compounds are used alone or as a mixture of two or more kinds.

The oxygen-containing organic compound of titanium, which is the reactant of (i-2), is represented by the general formula [O _a Ti (O
The compound represented by R ¹ ) _b ] _c is used. However,
In the general formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of such a hydrocarbon group include a linear or branched alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. a and b are a ≧ 0,
When b> 0, it represents a number compatible with the valence of Ti, and c represents an integer. Above all, it is desirable to use an oxygen-containing organic compound of titanium such that 0 ≦ a ≦ 1 and 1 ≦ b ≦ 6.

Specific examples include titanium tetraethoxide, titanium tetra-n-propoxide and titanium tetra-
Examples thereof include i-propoxoxide, titanium tetra-n-butoxide, hexa-i-propoxydititanate and the like.
The use of oxygen-containing organic compounds of titanium having several different hydrocarbon groups is also within the scope of the invention. These oxygen-containing organic compounds of titanium may be used alone, or 2
It is also possible to use it after mixing or reacting two or more kinds.

In addition, during the reaction, a substance which reacts with metallic magnesium or produces an addition compound,
For example, it is desirable to add a polar substance such as iodine, mercuric chloride, an alkyl halide and an organic acid, either alone or in combination of two or more.

Further, magnesium, a hydroxylated organic compound,
As a method for preparing a uniform solution containing an oxygen-containing organic compound of silicon and aluminum and / or a boron compound,
For example, it is adjusted by reacting an oxygen-containing organic compound of silicon such as metallic magnesium, a hydroxylated organic compound and a silicon alkoxide with an oxygen-containing organic compound of aluminum such as an aluminum alkoxide and / or a boron compound such as a boron alkoxide and an alkylboron. be able to. In addition, if it is necessary to control the catalyst particle size, the oxygen-containing organic compound of titanium can be added.

As the oxygen-containing organic compound of silicon, those similar to the oxygen-containing organic compound of silicon of the component (C) described later can be used.

As the oxygen-containing organic compound of aluminum, an oxygen-containing organic compound represented by the general formula Al (OR ² ) _d X _3-d is used. However, in the general formula, R ² represents a hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of such a hydrocarbon group include a linear or branched alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. d represents a number satisfying 0 <d ≦ 3, and X
Represents a halogen atom.

Specific examples of the oxygen-containing organic compound of aluminum include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum and tri-sec-butoxyaluminum. ,
Tri-tert-butoxyaluminum, tri (2-ethylhexoxy) aluminum, triphenoxyaluminum, tribenzyloxyaluminum, dichloromethoxyaluminum, chlorodimethoxyaluminum,
Dichloro (2-ethylhexoxy) aluminum, chlorodi (2-ethylhexoxy) aluminum, dichlorophenoxyaluminum, chlorodiphenoxyaluminum and the like can be mentioned. The use of oxygen-containing organic compounds of aluminum having several different hydrocarbon groups is also within the scope of the invention. These oxygen-containing organic compounds of aluminum are used alone or as a mixture of two or more kinds.

As the boron compound, a compound represented by the general formula R ³ _e B
A boron compound represented by (OR ⁴ ) _f X _{3- (e + f)} is used. However, in the general formula, R ³ , R
⁴ is a hydrocarbon group such as a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group, a halogenated hydrocarbon group, and an amino group. Represents a substituted hydrocarbon group or a hydrogen atom, and e and f are 0 ≦ e ≦
3, 0 ≦ e + f ≦ 3, and X represents a halogen atom.

Specific examples of the boron compound include trimethoxyborane, triethoxyborane, tri-n-propoxyborane, tri-i-propoxyborane, tri-n-butoxyborane, tri-i-butoxyborane and tri-se.
c-butoxyborane, tri-tert-butoxyborane, tri (2-ethylhexoxy) borane, triphenoxyborane, tribenzyloxyborane, di-i-propoxymethylborane, di-i-propoxyphenylborane, 2-aminoethyldiphenyl Borane, trimethylene borate (ester of boric acid with 1,3-propanediol), butyl boric acid, triethyl borane, tri-n-butyl borane, tri-i-butyl borane, tri-sec-
Butylborane, tri-sec-isoamylborane, triphenylborane, trimesitylborane, tris (4-fluorophenylborane), B-isopinocanphenyl-
9-borabicyclo (3,3,1) nonane, 9-borabicyclo (3,3,1) nonane, chlorodiethoxyborane,
Dichloroethoxyborane, bromodiethylborane, trichloroborane, tribromoborane and the like can be mentioned. The use of boron compounds with several different substituents is also within the scope of this invention. These boron compounds may be used alone or in 2
Used as a mixture of more than one species.

As the aluminum halide compound which is the reactant of (ii), AlR ⁵ _g X _3-g
The one shown in is used. In the formula, R ⁵ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and g represents a number 0 <g ≦ 2. R ⁵ is preferably selected from a linear or branched alkyl group, an alkoxy group, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. Specific examples of aluminum halides include, for example, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride, i-butyl aluminum dichloride, sesquiethyl aluminum chloride, sesqui-i-butyl aluminum chloride, sesqui-i-. Propyl aluminum chloride, sesqui-n-propyl aluminum chloride, dimethyl aluminum chloride, diethyl aluminum chloride, di-i-propyl aluminum chloride, di-
Examples thereof include n-propyl aluminum chloride, di-i-butyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide and the like. The aluminum halide compound is used alone or as a mixture of two or more kinds.

As the aluminum halide compound which is the above-mentioned (iii) reactant, (i) of the above-mentioned component (A) is used.
The same thing as the aluminum halide compound of i) can be used.

Examples of the electron donating compound which is the above-mentioned (iv) reactant include ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines,
Mention may be made of phosphites, stibines, arsines, phosphorylamides and alcoholates. Of these, esters are preferred, and organic acid esters are most preferred.

Examples of the organic acid esters include aromatic carvone mono- or diesters and aliphatic carboxylic acid mono- or diesters. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, and malon. Acid diisobutyl, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate , Diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, methyl benzoate, ethyl benzoate,
Methyl p-toluate, ethyl p-toluate, p-t
ert-butyl ethyl benzoate, ethyl p-anisate,
α-isobutyl naphthoate, ethyl cinnamate, monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, Examples thereof include diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate and dibutyl naphthalate. The electron donating compound (iv) is used alone or as a mixture of two or more kinds.

The titanium compound represented by the general formula Ti (OR ⁶ ) _h X _4-h is used as the titanium halide compound which is the reactant of the above (v). In the formula, R ⁶ is 1 to
Represents a hydrocarbon group having 20 carbon atoms, h is 0 ≦
It represents a number h <4, and X is the same as above. R ⁶ is preferably selected from linear or branched alkyl groups, alkoxy groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups.

Specific examples of the titanium halide compound include titanium tetrachloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, diethoxy titanium dichloride, triethoxy titanium chloride and the like. Is mentioned. The titanium halide compound may be used alone or as a mixture of two or more kinds.

These reactions are preferably carried out in a liquid medium. Therefore, it should be carried out in the presence of an inert organic solvent, especially if these reactants themselves are not liquid at the operating conditions, or if the amount of liquid reactant is insufficient.

As the inert organic solvent, any of those commonly used in the art can be used, and examples thereof include aliphatic, alicyclic or aromatic hydrocarbons, halogen derivatives thereof, or a mixture thereof. .. For example, isobutane, pentane, isopentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, 1,
3-dichlorobenzene, benzyl chloride, methylene dichloride, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,1,1, -trichloroethane, 1,1,2-trichloroethane, 1 , 1,
1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, carbon tetrachloride, chloroform and the like can be mentioned. These organic solvents may be used alone or as a mixture. By the way, when a halogen derivative or a mixture thereof is used, good results may be obtained in the polymerization activity and the stereoregularity of the polymer.

The homogeneous solutions (i), (i) used in the present invention
The amounts of i), (iii), (iv) and (v) used are not particularly limited, but the molar ratio of the magnesium atom in (i) to the aluminum atom in aluminum halide (ii) is 1: 0. .1-1: 100, preferably 1: 0.1
It is preferable to select the amount of the reactant used so as to be in the range of 1:20. If the ratio of aluminum atoms is out of this range and is too large, the catalytic activity may be low, or good powder properties may not be expected, and if it is too small, good powder properties may not be expected. The molar ratio of the magnesium atom in (i) to the aluminum atom in aluminum halide (iii) is 1: 0.001 to 1: 4.0, preferably 1: 0.
It is preferable to select the amount of the reactant used so as to be in the range of 005 to 1: 1.0.

The molar ratio of the magnesium atom in (i) to the electron donating compound (iv) is 1: 0.05 to 1: 5.0,
It is preferable to select the amount used so that it is preferably 1: 0.1 to 1: 2.0. If you go outside these ranges,
Problems such as low polymerization activity and low stereoregularity of the polymer may occur.

Further, the molar ratio of the magnesium atom in (i) to the titanium halide compound (v) is 1: 1 to 1:10.
It is preferable to select the amount of (v) used so that it falls within the range of 0, preferably 1: 3 to 1:50. If the content is out of this range, problems such as low polymerization activity and coloring of the product may occur.

The reaction condition for obtaining the homogeneous solution (i) is -5.
It is carried out at a temperature of 0 to 300 ° C., preferably 0 to 200 ° C. for 0.5 to 50 hours, preferably 1 to 6 hours in an inert gas atmosphere at atmospheric pressure or under pressure. At this time, a substance that reacts with the same electron-donating compound and / or magnesium metal as the compound (iv) or produces an addition compound, such as iodine, mercuric chloride, an alkyl halide and Uniformity can be achieved in a short time by adding a polar substance such as an organic acid alone or in combination of two or more kinds.

Further, in the reaction of the reaction agent (ii), -5
It is carried out at a temperature in the range of 0 to 200 ° C., preferably −30 to 150 ° C. for 0.2 to 50 hours, preferably 0.5 to 10 hours in an inert gas atmosphere at atmospheric pressure or under pressure. The reaction conditions of the reactant (ii) are extremely important because they play a decisive role in controlling the particle shape and particle size of the solid product particles produced, the solid catalyst component particles, and the polymer particles obtained by using them. is there. Thus, the resulting solid product particles are filtered or decanted to remove residual unreacted products and by-products, and then treated with an inert organic solvent.
It is preferable to perform sufficient washing and use until aluminum is no longer detected.

The reaction of the reactant (iii) is carried out after the reaction of (ii) by -50 to 200 ° C, preferably -30 to 150.
0.2 to 50 hours at a temperature in the range of 0 ° C, preferably 0.
It is carried out at normal pressure or under pressure in an inert gas atmosphere for 5 to 5 hours. The reaction of the reactant (iii) is important for reducing the amount of the subsequent reactant (v) used.

The solid product particles thus obtained may be used as they are, but generally, the remaining unreacted products and by-products are removed by filtration or decantation, and then an inert organic solvent is sufficient. It is preferable to use after extensive washing.

The reaction of the reactant (iv) may be carried out directly with the solid product or in the presence of the reactant (v).
Alternatively, the process may be divided into multiple stages.

The reaction of the reactant (v) may be carried out by dividing it in multiple stages. In this reaction, the general formula R-CH = CH
₂ (wherein R represents a linear or branched substituted / unsubstituted alkyl group having 1 to 10, especially 1 to 8 carbon atoms) and / or ethylene is allowed to coexist. That is also within the scope of the present invention. In these cases,
As a result, there are cases where effects such as an improvement in polymerization activity and stereoregularity of the polymer are observed.

The solid catalyst component (A) thus obtained
May be used as it is, but generally, unreacted materials and by-products that remain are removed by filtration or a decantation method, followed by thorough washing with an inert organic solvent, and then suspended in the inert organic solvent. To use. It is also possible to use a product which is isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent. Further, prior to the main polymerization, by adding a small amount of an organometallic compound component of the general formula R-CH = CH ₂ (wherein, R 1 to 1
A linear or branched substituted or unsubstituted alkyl group having 0, especially 1 to 8 carbon atoms) and a small amount of α-olefin and / or ethylene to prepare a prepolymer, which is then used. You can also do it.

The solid catalyst component of the component (A) obtained as described above is combined with the organometallic compound of the component (B) and the electron-donating compound of the component (C),
Used for olefin polymerization.

Examples of the organometallic compound as the component (B) include organometallic compounds composed of a metal such as lithium, magnesium, zinc, tin or aluminum and an organic group. As the above organic group, an alkyl group can be mentioned as a representative. As this alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is used.
Specifically, for example, n-butyl lithium, diethyl magnesium, diethyl zinc, trimethyl aluminum, triethyl aluminum, tri-i-butyl aluminum, tri-n-butyl aluminum, tri-n-decyl aluminum, tetraethyl tin or tetra. Butyl tin and the like can be mentioned. Above all, it is preferable to use a trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms. Also, the carbon number is 1 to
Alkyl metal halides having 20 alkyl groups such as ethyl aluminum sesquichloride, diethyl aluminum chloride, diisobutyl aluminum chloride, or alkyl metal alkoxides such as diethyl aluminum ethoxide can also be used. These organometallic compounds are used alone or as a mixture of two or more kinds.

As the electron donating compound of the component (C),
Organic acid esters, silicon-containing oxygen-containing organic compounds, nitrogen-containing organic compounds and the like are preferable.

Examples of the organic acid ester include the same compounds as the reaction agent (iv) used in the preparation of the solid catalyst component of the component (A). Of these, preferred are aliphatic carboxylic acid esters and aromatic carboxylic acid esters. Specific examples of the aliphatic carboxylic acid ester include ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate and ethyl butyrate having 2 to 18 carbon atoms. As the aromatic carboxylic acid ester, methyl benzoate, ethyl benzoate, methyl p-toluate, having 8 to 24 carbon atoms,
Examples thereof include ethyl p-toluate, methyl anisate, and ethyl anisate. The above organic acid esters may be used alone, or may be used by mixing or reacting two or more kinds.

As the oxygen-containing organic compound of silicon, the oxygen-containing organic compound of silicon represented by the general formula R ⁷ _s Si (OR ⁸ ) _t X _{4- (s + t)} is used. However,
In the general formula, R ⁷ and R ⁸ represent a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms or a hydrogen atom. Examples of such a hydrocarbon group include a straight chain or branched chain alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. s and t are 0 ≦ s ≦ 3, 1 ≦ t ≦ 4, 1 ≦ s + t
Represents a number of ≦ 4, and X is the same as above.

As a specific example, tetramethoxysilane,
Tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-pentoxysilane, tetra-
n-hexoxysilane, tetraphenoxysilane, tetrakis (2-ethylhexoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-methoxyethoxy) silane, methyltrimethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane , Phenyltrimethoxysilane, vinyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane. Ethoxysilane, n-butyltriethoxysilane,
Phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, triethoxysilane, ethyltri-i-propoxysilane, vinyltri-i-propoxysilane, i-pentyltri-n
-Butoxysilane, methyltri-i-pentoxysilane, ethyltri-i-pentoxysilane, methyltri-
n-hexoxysilane, phenyltri-i-pentoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, i-butyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyldimethoxysilane , Dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, methyldodecyldiethoxysilane, methyloctadecyldiethoxysilane, methylphenyldiethoxysilane, methyldiethoxysilane, dibenzyldiethoxysilane, diethoxysilane, Dimethyldi-n-butoxysilane, dimethyldi-i-pentoxysilane, diethyldi-i-pentoxysilane, di-i-butyldi-i-pentoxysilane, diphenyldi i- pentoxy silane, diphenyl di -n- oct silane, diisobutyl dimethoxy silane, trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl silane, trimethyl -i-
Propoxysilane, trimethyl-n-propoxysilane, trimethyl-t-butoxysilane, trimethyl-i
-Butoxysilane, trimethyl-n-butoxysilane,
Alkoxysilanes or aryloxysilanes such as trimethyl-n-pentoxysilane and trimethylphenoxysilane, and haloalkoxysilanes or haloaryloxysilanes such as dichlorodiethoxysilane, dichlorodiphenoxysilane and tribromoethoxysilane. .. The oxygen-containing organic compound of silicon may be used alone, or two or more kinds may be mixed or reacted and used.

Examples of the nitrogen-containing organic compound include compounds having a nitrogen atom in the molecule and having a function as a Lewis base.

Specifically, acetic acid N, N-dimethylamide, benzoic acid N, N-dimethylamide, toluic acid N,
Amide compounds such as N-dimethylamide, 2,2
6,6-tetramethylpiperidine, 2,6-diisopropylpiperidine, 2,6-diisobutylpiperidine,
2,6-diisobutyl-4-methylpiperidine, 2,
2,6-trimethylpiperidine, 2,2,6,6-tetraethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis ( 2,2,6,6-Tetramethyl-4-piperidyl) sebacate and other piperidine compounds, 2,6-diisopropylpyridine, 2,6-
Pyridine compounds such as diisobutylpyridine and 2-isopropyl-6-methylpyridine, 2,2,5,5-tetramethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2,2,5-trimethylpyrrolidine, 1,2,
Pyrrolidine compounds such as 2,5,5-pentamethylpyrrolidine and 2,5-diisobutylpyrrolidine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine, tert-butyldimethylamine, diphenylamine, di- Examples thereof include amine compounds such as o-tolylamine and aniline compounds such as N, N-diethylaniline and N, N-diisopropylaniline. The above nitrogen-containing organic compounds may be used alone, or may be used by mixing or reacting two or more kinds. These electron donating compounds may be used in combination.

The solid catalyst component (A) is used in the reactor 1
It is preferable to use an amount corresponding to 0.001 to 2.5 mmol (mmol) of titanium atom per liter.
The organometallic compound of the component (B) is 0.02 to 50 mmol, preferably 0.2 to 5 m, per 1 liter of the reactor.
Used at a concentration of mol. The electron donating compound of the component (C) is 0.001 to 50 mm per 1 liter of the reactor.
ol, preferably used at a concentration of 0.01-5 mmol.

The manner of feeding the three components in the present invention is not particularly limited, and for example, the solid catalyst component (A),
A method of separately feeding the component (B) and the component (C) to the polymerization vessel, or a method of contacting the solid catalyst component (A) with the component (B) and then contacting with the component (C) for polymerization. A method in which the component (B) and the component (C) are brought into contact with each other, and then the solid catalyst component (A) is brought into contact therewith to perform polymerization. A method of polymerizing can be adopted.

The olefin polymerization is carried out in the gas phase or the liquid phase at a reaction temperature below the melting point of the polymer. When the polymerization is carried out in the liquid phase, the olefin itself may be used as the reaction medium, but an inert solvent may be used as the reaction medium. The inert solvent may be any of those commonly used in the art, in particular 4
Suitable are alkanes, cycloalkanes having up to 20 carbon atoms, such as isobutane, pentane, hexane, cyclohexane and the like.

The olefin to be polymerized in the method for producing a stereoregular polyolefin of the present invention is represented by the general formula R
-CH = CH ₂ α-olefin (wherein R is 1 to 10)
, Especially linear or branched, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms). Specific examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-octene and the like. These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. In the copolymerization, two or more kinds of ethylene and / or α-olefin, or α-olefin and a diene such as butadiene or isoprene can be used for the polymerization. Particularly, it is preferable to carry out the polymerization using propylene alone, propylene and ethylene, propylene and the above-mentioned α-olefin other than propylene, and propylene and dienes.

The polymerization reaction conditions are not particularly limited as long as the reaction temperature is lower than the melting point of the polymer, but the reaction temperature is usually 20 to 100 ° C. and the pressure is ^{2 to} 50 kg / cm ² G.

As the reactor used in the polymerization step, any reactor usually used in the art can be appropriately used. The polymerization operation can be carried out in any of a continuous system, a semi-batch system and a batch system using a stirred tank reactor, a fluidized bed reactor or a circulation reactor. It is also possible to carry out the reaction in two or more steps under different polymerization reaction conditions.

[0057]

The first effect is that the amount of titanium halide compound used can be reduced. Therefore, the catalyst cost can be reduced, and the amount of waste liquid generated can be reduced, which is economical. Moreover, since the amount of the used catalyst raw material per unit reactor volume is reduced, the productivity of the catalyst can be improved.

The second effect is that extremely high stereoregular polymer particles can be obtained. In particular, since it is not necessary to remove the atactic polypropylene component, it is effective when applied to gas phase polymerization without using a reaction medium.

The third effect is that polymer particles having few fine particles and an extremely narrow particle size distribution and excellent powder characteristics can be obtained. Therefore, in the gas phase polymerization method, the formation of deposits in the polymerization apparatus is prevented, and in the slurry polymerization method, the separation and filtration of the polymer slurry are facilitated in the polymer separation and drying steps. The fine particles of coalescence are prevented from scattering outside the system, and in addition, the fluidity is improved and the drying efficiency is improved. Further, in the transfer process, there is no occurrence of a bridge or the like in the silo, and the transfer trouble is eliminated.

The fourth effect is that a polymer having an extremely high polymerization activity and not requiring a deashing step for the purpose of removing catalyst residues can be obtained. Since it is highly active, there is no concern about coloring or odor of the product, and no purification of the polymer is required, which is extremely economical.

[0061]

EXAMPLES The present invention is shown below by examples, but the present invention is not limited to these examples. In the examples and comparative examples, the melt flow rate (hereinafter abbreviated as MFR) was measured according to JIS K7210 condition 14. The xylene-soluble component (hereinafter abbreviated as Xy), which is an index of stereoregularity, was measured as follows.
That is, after dissolving 4 g of the polymer in 200 ml of xylene, the polymer was allowed to stand in a thermostat at 25 ° C. for 1 hour, and the deposited portion was filtered,
After the filtrate is collected and most of the xylene is evaporated, it is further vacuum dried to collect the xylene-soluble portion, which is calculated as a percentage of the original sample. The activity represents a polymer production amount (g) per 1 g of the solid catalyst component (A).

Example 1 (a) Preparation of solid catalyst component (A) A 3 l flask equipped with a stirrer was charged with 15 g (0.62 mol) of magnesium metal powder, and 0.75 g of iodine and 2-ethylhexanol were added thereto. 402 g (3.1
mol), 211 g of titanium tetra-n-butoxide
(0.62 mol), diisobutyl phthalate 61.2 g
(0.22 mol) was added, the temperature was raised to 90 ° C., and the mixture was stirred under a nitrogen blanket for 1 hour. Subsequently, the temperature was raised to 140 ° C. and the reaction was carried out for 2 hours to obtain a uniform solution containing magnesium and titanium (Mg—Ti solution).

Mg-Ti was added to a flask having an internal volume of 500 ml.
The solution was charged with 0.066 mol in terms of Mg, cooled to 0 ° C., and then isobutylaluminum dichloride 20.5
A solution prepared by diluting g (0.13 mol) in 157 ml of hexane was added over 2 hours. After the total amount was added, the temperature was raised to 70 ° C. over 2 hours to obtain a slurry containing a white solid product. The solid product was separated by filtration and then thoroughly washed with hexane.

Isobutylaluminum dichloride 0.4 was added to the slurry containing the white solid product thus obtained.
After adding g (2.6 mmol), the mixture was reacted at 30 ° C. for 30 minutes. The solid product was separated by filtration and washed thoroughly with hexane.

The internal volume of the slurry containing this solid product was 1
1 g of a glass magnetic stirring type autoclave was charged, and 56 g (0.29 mol) of titanium tetrachloride was added to chlorobenzene.
After the total amount of the solution diluted with 6 g was added, 3.9 g (0.014 mol) of diisobutyl phthalate was added and reacted at 100 ° C. for 4 hours. The solid part was collected by filtering the product, suspended again in a solution prepared by diluting 56 g of titanium tetrachloride with 56 g of chlorobenzene, and reacted at 100 ° C. for 2 hours to obtain a solid catalyst component (A). The solid catalyst component (A) was filtered off, hexane was added, and the washing operation was sufficiently performed until no liberated titanium compound was detected.

Thus, a slurry of the solid catalyst component (A) suspended in hexane was obtained. The supernatant liquid was removed, the product was dried under a nitrogen atmosphere, and elemental analysis revealed that Ti was 2.4 wt.
%Met.

(B) Polymerization of propylene The inside of a stainless steel electromagnetic stirring type autoclave having an internal volume of 5 l was sufficiently replaced with nitrogen, and 1.0 mmol of triethylaluminum as a catalyst component (B) and a catalyst component (C).
As diphenyldimethoxysilane 0.25mmo
l, and the solid catalyst component (A) were added successively 10 mg, to adjust the internal pressure of the autoclave to 0.1 kg / cm ² G, hydrogen 0.2 kg / cm ² G was added, liquid propylene 200
After adding 0 ml and starting stirring, the temperature was raised to 70 ° C. and 90
Polymerized for minutes. After the completion of the polymerization reaction, stirring was stopped and unreacted propylene in the system was released to collect the produced polymer. As a result, the amount of the polymer produced was 332 g, and the activity 33
Corresponding to 200 g / g. When various properties of the polymer particles were examined, MFR 2.9 g / 10 min. , Xy1.0
%, And the bulk density was 0.45 g / cm ³ . The produced polymer particles were spherical.

Example 2 The procedure of Example 1 (a) was repeated except that 0.5 g (3.9 mmol) of diethylaluminum chloride was used instead of the isobutylaluminum dichloride used as the component (iii) in Example 1. A solid catalyst component was obtained by the same method. Using the obtained solid catalyst component, propylene was polymerized under the same conditions as in Example 1 (b). The result was an activity of 28600 g / g. When the various properties of the polymer particles were measured, the MFR was 3.0 g / 10 m.
in. , Xy 1.8%, and bulk density 0.46 g / cm ³ .

Example 3 (a) of Example 1 except that 0.4 g (3.5 mmol) of ethyl aluminum dichloride was used in place of the isobutyl aluminum dichloride used as the component (iii) in Example 1. A solid catalyst component (A) was obtained by the same method. Obtained solid catalyst component (A)
Was used to polymerize propylene under the same conditions as in (1) of Example 1. The result was an activity of 24100 g / g. When various properties of the polymer particles were measured, MFR2.
8 g / min. , Xy 1.0%, bulk density 0.45 g / c
A result of m ³ was obtained.

Example 4 In place of the isobutylaluminum dichloride used as the component (iii) in Example 1, 0.4 g (1.6 mmol) of sesquiethylaluminum chloride was used.
A solid catalyst component (A) was obtained by the same method as in (1) of Example 1 except that was used. Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 31500 g / g. When various characteristics of the polymer particles were measured, MFR
7.1 g / 10 min. , Xy 1.7%, bulk density 0.4
A result of 6 g / cm ³ was obtained.

Example 5 (a) of Example 1 except that 0.6 g (2.7 mmol) of diethyl aluminum iodide was used in place of the isobutylaluminum dichloride used as the component (iii) in Example 1. A solid catalyst component (A) was obtained by the same method as described in (1). Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. As a result, the activity was 23200 g / g. When various characteristics of the polymer particles were measured, MFR
3.6 g / 10 min. , Xy 1.7%, bulk density 0.4
A result of 7 g / cm ³ was obtained.

Example 6 The procedure of Example 1 (a) was repeated except that 0.3 g (3.4 mmol) of dimethylaluminum chloride was used instead of the isobutylaluminum dichloride used as the component (iii) in Example 1. A solid catalyst component (A) was obtained by the same method. Obtained solid catalyst component (A)
Was used to polymerize propylene under the same conditions as in (1) of Example 1. As a result, the activity was 26600 g / g. When various properties of the polymer particles were measured, MFR3.
6 g / 10 min. , Xy1.6%, bulk density 0.45g
A result of / cm ³ was obtained.

Example 7 Example 1 (a) was repeated except that 16.5 g (0.13 mol) of ethyl aluminum dichloride was used in place of the isobutyl aluminum dichloride used as the component (ii) in Example 1. A solid catalyst component (A) was obtained by the same method. Obtained solid catalyst component (A)
Was used to polymerize propylene under the same conditions as in (1) of Example 1. The result was an activity of 31300 g / g. When various properties of the polymer particles were measured, MFR2.
5 g / 10 min. , Xy1.1%, bulk density 0.45g
A result of / cm ³ was obtained.

Example 8 Instead of the isobutylaluminum dichloride used as the component (ii) in Example 1, 22.3 g (0.09 mol) of sesquiethylaluminum chloride was used.
A solid catalyst component (A) was obtained by the same method as in (1) of Example 1 except that was used. Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 28500 g / g. When various characteristics of the polymer particles were measured, MFR
2.7 g / 10 min. , Xy1.5%, bulk density 0.4
A result of 6 g / cm ³ was obtained.

Example 9 Example 7 (a) was repeated except that 0.3 g (2.4 mol) of ethyl aluminum dichloride was used instead of the isobutyl aluminum dichloride used as the component (iii) in Example 7. A solid catalyst component (A) was obtained by the same method. Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 29400 g / g.
Various properties of the polymer particles were measured and found to be MFR 2.6 g.
/ 10 min. , Xy 1.3%, bulk density 0.46 g / c
A result of m ³ was obtained.

Example 10 (a) of Example 8 except that 0.5 g (2.0 mol) of sesquiethylaluminum chloride was used instead of the isobutylaluminum dichloride used as the component (iii) in Example 8. A solid catalyst component (A) was obtained by the same method as described in (1). Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 29,500 g / g. When various characteristics of the polymer particles were measured, MFR
2.5 g / 10 min. , Xy1.6%, bulk density 0.4
A result of 6 g / cm ³ was obtained.

Example 11 (a) of Example 7 except that 0.4 g (1.6 mol) of sesquiethylaluminum chloride was used in place of the isobutylaluminum dichloride used as the component (iii) in Example 7. A solid catalyst component (A) was obtained by the same method as described in (1). Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 31300 g / g. When various characteristics of the polymer particles were measured, MFR
2.6 g / 10 min. , Xy1.5%, bulk density 0.4
A result of 5 g / cm ³ was obtained.

Example 12 2.2 g of ethyl benzoate was used instead of the diisobutyl phthalate used as the component (iv) in Example 1.
A solid catalyst component (A) was obtained in the same manner as in (i) of Example 1 except that (0.015 mol) was used.

Using the obtained solid catalyst component (A), 0.25 mmol of methyl p-toluate was used in place of the diphenyldimethoxysilane used as the component (C) in (b) of Example 1. Other than that, propylene was polymerized under the same conditions. The result was an activity of 14200 g / g. When various characteristics of the polymer particles were measured, MFR
3.7 g / 10 min. , Xy 3.3%, bulk density 0.4
A result of ³ g / cm ³ was obtained.

Example 13 (a) Preparation of solid catalyst component (A) The same procedure as in (a) of Example 1 was carried out.

(B) Vapor phase polymerization of propylene The inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 1 l was sufficiently replaced with nitrogen, and (a) of the above-mentioned Example 1 was used.
5.0 g of solid catalyst component (A), 300 ml of hexane,
12.5 mmol of triethylaluminum was sequentially added,
After adjusting the internal pressure of the autoclave to 0.1 kg / cm ² G and the internal temperature to 20 ° C., stirring was started, and 10 g of propylene was supplied for 20 minutes while maintaining the internal temperature at 20 ° C.
Stir for minutes. The propylene prepolymer of the solid catalyst component (A) thus obtained was separated by filtration and sufficiently washed with hexane to obtain a hexane slurry of the propylene prepolymer of the solid catalyst component (A). The yield after removing the supernatant liquid and drying under a nitrogen atmosphere was 11.3 g.

The inside of the stainless steel electromagnetic stirring type autoclave having an internal volume of 5 l was sufficiently replaced with nitrogen, and 4.0 mmol of triethylaluminum was used as the catalyst component (B).
As catalyst component (C), 1.0 mmol of diphenyldimethoxysilane and 90 mg of the prepolymer of the above solid catalyst component (A) were sequentially added, and glass beads (φ1.0
mm) was added. Internal pressure of autoclave 0.1k
g / cm ² G, hydrogen was added at 0.2 kg / cm ² G, and after stirring (300 rpm) was started, the temperature was adjusted to 80 ° C.,
Propylene gas was added to adjust the inside of the system to 28 kg / cm ² G. Then, propylene gas was continuously supplied so as to maintain the pressure in the system, and propylene was polymerized at the same temperature for 2 hours. After the completion of the polymerization reaction, stirring was stopped and unreacted propylene in the system was released to collect the produced polymer. As a result, the polymer produced was 492 g, which corresponds to an activity of 12300 g / g in terms of solid catalyst component (A). When various properties of the polymer particles were measured, MFR3.
0 g / 10 min. , Xy 1.0%, bulk density 0.46 g
A result of / cm ³ was obtained.

Example 14 (a) Preparation of solid catalyst component (A) It was prepared under the same conditions as in Example 9 above.

(B) Gas phase polymerization of propylene Under the same conditions as in (b) of Example 13, propylene prepolymerization of the solid catalyst component (A) and propylene polymerization were carried out. The result shows that the activity is 11 in terms of the solid catalyst component (A).
It was 600 g / g. When the various properties of the polymer particles were measured, MFR 2.8 g / 10 min. , Xy1.3
%, And the bulk density was 0.45 g / cm ³ .

Example 15 (a) Preparation of solid catalyst component (A) It was prepared in the same manner as in (a) of Example 1 above.

(B) Gas phase polymerization of propylene In Example 13, (b), 30 g of 4-methyl-1-pentene was used instead of propylene used for the prepolymerization.
Was used to obtain 16.5 g of a 4-methyl-1-pentene prepolymer of the solid catalyst component (A), and propylene was polymerized under the same conditions except that this was used for gas phase polymerization. .. The result shows that the activity is 1030 in terms of the solid catalyst component (A).
It was 0 g / g. When various properties of the polymer particles were measured, MFR 3.1 g / 10 min. , Xy 1.1% and a bulk density of 0.45 g / cm ³ .

Comparative Example 1 (a) Preparation of solid catalyst component (A) A 3 l flask equipped with a stirrer was charged with 15 g (0.62 mol) of metallic magnesium powder, and 0.75 g of iodine and 2-ethylhexanol were added thereto. 402 g (3.1
mol), 211 g of titanium tetra-n-butoxide
(0.62 mol), diisobutyl phthalate 61.2 g
(0.22 mol) was added, the temperature was raised to 90 ° C., and the mixture was stirred under a nitrogen seal for 1 hour. Subsequently, the temperature was raised to 140 ° C. and the reaction was carried out for 2 hours to obtain a uniform solution containing magnesium and titanium (Mg—Ti solution).

Mg-Ti was added to a flask having an internal volume of 500 ml.
-The solution was charged with 0.066 mol in terms of Mg, cooled to 0 ° C, and then isobutylaluminum dichloride 20.
A solution prepared by diluting 5 g (0.13 mol) in 157 ml of hexane was added over 2 hours. After the total amount was added, the temperature was raised to 70 ° C. over 2 hours to obtain a slurry containing a white solid product. The solid product was separated by filtration and then thoroughly washed with hexane.

The thus-obtained slurry containing the white solid product was placed in a glass electromagnetic stirring autoclave having an internal volume of 1 l, and 125 g (0.66 mol) of titanium tetrachloride was added.
Was added with 56 g of chlorobenzene, and the whole solution was added. Then, 7.3 g of diisobutyl phthalate (0.026 mo
1) was added, and the mixture was reacted at 100 ° C. for 4 hours. The solid part was collected by filtering the product, suspended again in a solution prepared by diluting 125 g of titanium tetrachloride with 125 g of chlorobenzene, and reacted at 100 ° C. for 2 hours to obtain a solid catalyst component (A). The solid catalyst component (A) was filtered off, hexane was added, and the washing operation was sufficiently performed until no liberated titanium compound was detected.

Thus, a slurry of the solid catalyst component (A) suspended in hexane was obtained. The supernatant liquid was removed, the product was dried under a nitrogen atmosphere, and elemental analysis revealed that Ti was 2.4 wt.
%Met.

Using the solid catalyst component (A) thus obtained, propylene was polymerized under the same conditions as in Example 1 (b). As a result, the activity was 33900 g / g. When the properties of the polymer particles were measured, the MFR was 1.5 g / 10 m.
in. , Xy 1.0%, and bulk density 0.47 g / cm ³ .

The amount of titanium tetrachloride used in the preparation of the solid catalyst component (A) in Comparative Example 1 was more than twice that in the Example.

Comparative Example 2 A solid catalyst component (A) was obtained by the same method as in (i) of Example 1 except that the isobutylaluminum dichloride added as the above-mentioned component (iii) in Example 1 was not allowed to act. It was Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 20700 g / g. When various properties of the polymer particles were measured, MFR 3.3 g /
10 min. , Xy 2.3%, bulk density 0.45 g / cm
³ results were obtained.

Comparative Example 3 The same as (i) of Example 1 except that 125 g (0.66 mol) of titanium tetrachloride was used in place of the isobutylaluminum dichloride used as the component (ii) in Example 1. The solid catalyst component (A) was obtained by the method. Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1. The result was an activity of 1700 g / g. When various characteristics of the polymer particles were measured, MFR 2.7 g / 10 min. , X
The results were y 1.4% and bulk density 0.20 g / cm ³ .

Comparative Example 4 The same as (i) of Example 1 except that 168 g (0.99 mol) of silicon tetrachloride was used instead of the isobutylaluminum dichloride used as the component (ii) in Example 1. The solid catalyst component (A) was obtained by the method. Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (B) of Example 1.

As a result, the activity was 100 g / g and the activity was extremely low. When various characteristics of the polymer particles were measured, MF
R3.1 g / 10 min. , Xy 2.1%, bulk density 0.
The result was 22 g / cm ³ .

Comparative Example 5 2.2 g of ethyl benzoate was used instead of the diisobutyl phthalate used as the component (iv) in Comparative Example 1.
A solid catalyst component (A) was obtained in the same manner as in (A) of Comparative Example 1 except that (0.015 mol) was used.

That is, the amount of titanium tetrachloride used in the preparation of the solid catalyst component (A) in Comparative Example 5 was more than twice that in Example 12.

Using the obtained solid catalyst component (A), 0.25 mmol of methyl p-toluate was used in place of the diphenyldimethoxysilane used as the component (C) in (b) of Example 1. Other than that, propylene was polymerized under the same conditions. The result was an activity of 15400 g / g. When various characteristics of the polymer particles were measured, MFR
3.2 g / 10 min. , Xy 3.0%, bulk density 0.4
A result of 4 g / cm ³ was obtained.

The propylene polymerization results of Examples 1 to 15 and Comparative Examples 1 to 5 are shown in Table 1 and Table 2, respectively.

[0101]

[Table 1]

[0102]

[Table 2]

[Brief description of drawings]

FIG. 1 shows a preparation diagram (flow chart) of a catalyst used in the present invention.

Claims (1)

[Claims] 1. When producing a stereoregular polyolefin in the presence of a catalyst composed of a transition metal compound and an organometallic compound, (i) (i-1) metallic magnesium and an organic hydroxide compound are used as a solid catalyst component (A). At least one member selected from the group consisting of a compound and an oxygen-containing organic compound of magnesium, and (i-2) an oxygen-containing organic compound of titanium and / or (i-3) an oxygen-containing organic compound of silicon and an oxygen-containing organic compound of aluminum. Isolating a solid product obtained by reacting (ii) at least one aluminum halide with a homogeneous solution containing a boron compound, and (iii) further adding the reaction product to at least one aluminum halide. Obtained by reacting the treated solid product with (iv) an electron-donating compound and (v) a titanium halide compound. And a solid catalyst component to be used as the component (B) of the periodic table, IA, IIA, IIB,
A process for producing a stereoregular polyolefin using a catalyst system comprising at least one selected from the group consisting of organometallic compounds of Group IIIB and IVB metals and an electron-donating compound as component (C).