JPH05117319A - Production of stereoregular polyolefin - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject polymer having a good particle shape and a controlled mol.wt. distribution by polymerizing an olefin in the presence of a specific catalyst. CONSTITUTION:An olefin is polymerized in the presence of a catalyst comprising (A) a catalyst component, (B) one kind or more of organic metal compounds of the IA, IIA, IIB, IIIB and IVB group metals of the periodic table, and (C) an oxygen-containing organosilicon compound to obtain the objective polymer. The catalyst component A is produced as follows: reacting one kind or more of halogenated Al compounds with a homogeneous solution containing one or more of Mg metal, a hydroxylated organic Mg compound and an oxygen- containing organic Mg compound, an oxygen-containing organic Al compound and an oxygen-containing organic Ti compound, reacting the produced solid product with an electron-donating compound and a halogenated Ti compound, and subsequently contact-reacting the produced solid catalyst component with one or more of an organic Al compound, an organic zinc compound and an organic Mg compound and an oxygen-containing organosilicon compound of the formula.

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, in the (co) polymerization of an α-olefin having 3 or more carbon atoms, a high stereoregular polymer having a good particle shape and a controlled molecular weight distribution can be obtained in a high yield by using a specific catalyst. The present invention relates to a manufacturing method that can be obtained.

[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.

In recent years, magnesium, titanium,
Many proposals have been made for producing a solid catalyst component containing halogen as a main component. However, this magnesium halide-supported catalyst is
Although it is characterized by high activity and high stereoregularity of the polymer, the molecular weight distribution of the obtained polymer is narrow and the formation of high molecular weight polymer is not sufficient, so further improvement is desired. It is rare.

Further, in the vapor phase α-olefin polymerization,
Many proposals have been made to use a magnesium halide-supported catalyst containing a carboxylic acid ester, an organic aluminum compound, and an oxygen-containing organic compound of silicon. In JP-A-58-83006, JP-A-62-11706, JP-A-63-92615, JP-A-2-283703, etc., an oxygen-containing organic compound of silicon having a specific molecular structure is used and A polymer having high stereoregularity is obtained. However, even these catalyst systems are still not sufficient to produce a polymer having a high stereoregularity and a wide molecular weight distribution and a high molecular weight polymer in a high yield, and further improvement is desired.

[0005]

SUMMARY OF THE INVENTION In order to overcome the shortcomings of the prior art, namely to produce a polymer with high rigidity in a non-extraction and deashing process,
Polymer particles with high stereoregularity and wide molecular weight distribution and polymer particles with high molecular weight components that cannot be produced by conventional magnesium halide-supported catalysts have good powder characteristics in a wide particle size control range and high yield. To manufacture at a rate.

[0006]

As a result, a solid catalyst component containing the following specific Mg, Ti, and Cl, an electron-donating compound as an essential component, and an organoaluminum compound, an organozinc compound, and an organomagnesium compound are used. A catalyst component obtained by catalytically reacting at least one member selected from the group with an oxygen-containing organic compound of silicon having a specific molecular structure shown below, an organometallic compound as a co-catalyst, and a specific molecular structure shown below. The inventors have found that the above problems can be solved by using an oxygen-containing organic compound of silicon, and have completed the present invention.

That is, according to the present invention, when a stereoregular polyolefin is produced in the presence of a catalyst composed of a transition metal compound and an organometallic compound, (i) metal magnesium and a hydroxylated organic compound are used as a component (A) of the catalyst. And at least one member selected from the group consisting of oxygen-containing organic compounds of magnesium, (ii) an oxygen-containing organic compound of aluminum and (iii) an oxygen-containing organic compound of titanium, in a uniform solution (iv) at least one halogen A solid product obtained by reacting aluminum halide with (v) an electron-donating compound and (vi) a solid catalyst component obtained by reacting a titanium halide compound with (vii) an organoaluminum compound and organozinc. At least one member selected from the group consisting of compounds and organomagnesium compounds; ii) the general formula ^{t-Bu (R 1) Si} (OR 2)
₂ (t-Bu; tertiary-butyl group, R ¹ ; carbon number 2
20 straight chain hydrocarbon groups,
R ² ; a hydrocarbon component having 1 to 5 carbon atoms), which is a catalyst component obtained by catalytically reacting an oxygen-containing organic compound of silicon, represented by the components (B) of the periodic table, IA, IIA, and IIB,
At least one selected from the group consisting of organometallic compounds of Group IIIB and IVB metals, the general formula t-Bu (R ¹ ) Si (OR ² ) ₂ (t-Bu; tertiary-butyl) as component (C) Group, R ¹ ; straight-chain hydrocarbon group having 2 to 20 carbon atoms, R ² ; hydrocarbon group having 1 to 5 carbon atoms), and a method for producing a stereoregular polyolefin using an oxygen-containing organic compound of silicon It is in.

[0008]

The solid catalyst component used in the present invention is (i) at least one member selected from the group consisting of magnesium metal, a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium, and (ii) an oxygen-containing organic compound of aluminum. (Iii) a solid solution obtained by reacting (iii) a homogeneous solution obtained by reacting an oxygen-containing organic compound of titanium such as an alkoxide of titanium with (iv) an aluminum halide (v) an electron-donating compound , (Vi) can be obtained by reacting a titanium halide compound.

When metal magnesium and an organic hydroxide compound are used in the above (i), various forms of metal magnesium can be used, that is, any shape such as powder, particles, foil or ribbon can be used. Suitable compounds are alcohols and organic silanols.

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

Examples include methanol, ethanol and n.
-Propanol, i-Propanol, n-Butanol,
iso-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n
-Octanol, i-octanol, n-stearyl alcohol, cyclopentanol, cyclohexanol,
Examples thereof include ethylene glycol. Further, benzyl alcohol, phenol, cresol, xylenol,
Hydroquinone etc. can also be illustrated.

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, It is selected from compounds having an arylalkyl group, an aryl group, and an alkylaryl group.

For example, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol and the like can be mentioned. These hydroxylated organic compounds are used alone or as a mixture of two or more kinds.

In addition, when the solid catalyst component of the component (A) described in the present invention is obtained by using magnesium metal, it reacts with metal magnesium or produces an addition compound for the purpose of promoting the reaction. It is desirable to add such a substance, for example, a polar substance such as iodine, mercuric chloride, an alkyl halide and an organic acid, either alone or in combination of two or more.

Next, as compounds belonging to the oxygen-containing organic compound of magnesium, magnesium alkoxides such as methylate, ethylate and isopropylate.
, Decanolate, methoxyethylate and cyclohexanolate, magnesium alkyl alkoxides such as ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, magnesium phenoxides such as phenate, naphthenate. , Phenanthrene and cresolate, magnesium carboxylates such as acetate, stearate, benzoate, phenylacetate, adipate, sebacate.
, Phthalates, acrylates, and oleates, oxymates such as butyl oxymate, dimethylglyoxymate and cyclohexyl oxymate, hydroxamates, hydroxylamine salts such as N-nitroso-. Examples thereof include N-phenyl-hydroxylamine derivatives, enolates such as acetylacetonate, magnesium silanolates such as triphenylsilanolate. These oxygen-containing organomagnesiums are used alone or as a mixture of two or more kinds.

The oxygen-containing organic compound of aluminum, which is the reaction agent of (ii) above, has the general formula Al (OR ³ ).
An oxygen-containing organic compound represented by _m X _3-m is used. However, in the general formula, R ³ has 1 to 2 carbon atoms.
It represents 0, preferably 1 to 10 hydrocarbon groups. As such a hydrocarbon group, a linear or branched alkyl group,
Examples thereof include a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. m
Represents a number satisfying 0 <m ≦ 3, and X represents a halogen atom.

Specific examples of the oxygen-containing organic compound of aluminum include trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, tri-i-propoxy aluminum, tri-n-butoxy aluminum, and tri-sec-butoxy aluminum. ，
Tri-tert-butoxyaluminum, tri (2-ethylhexoxy) aluminum, triphenoxyaluminum, tribenzyloxyaluminum, dichloromethoxyaluminum, chlorodimethoxyaluminum,
Examples thereof include dichloro (2-ethylhexoxy) aluminum, chlorodi (2-ethylhexoxy) aluminum, dichlorophenoxyaluminum and chlorodiphenoxyaluminum. 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.

The oxygen-containing organic compound of titanium, which is the reactant of (iii) above, may be represented by the general formula [O _p Ti _u (OR
⁴ ) A compound represented by _q ] _n is used. However, in the general formula, R ⁴ has 1 to 20 carbon atoms, preferably 1
The hydrocarbon groups of 10 are shown. As such a hydrocarbon group, a linear or branched alkyl group, a cycloalkyl group,
Examples thereof include an arylalkyl group, an aryl group and an alkylaryl group. p, q and u are p ≧ 0,
represents a number compatible with the valence of Ti when q> 0 and u ≧ 1, and n
Represents an integer. Above all, it is desirable to use an oxygen-containing organic compound of titanium such that 0 ≦ p ≦ 1, 1 ≦ u ≦ 2 and 1 ≦ n ≦ 6.

Specific examples include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-i-propoxide, titanium tetra-n-butoxide, titanium tetra-i-butoxide and tetra ( n-nonyl) titanate, tetra (2-ethylhexyl) titanate, tetracresyl titanate
And hexa-i-propoxydititanate. 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,
It is also possible to use them after mixing or reacting two or more kinds.

As the aluminum halide compound which is the above-mentioned (iv) reactant, the general formula AlR ⁵ _a X _{3-a can be used.}
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 a represents a number 0 <a ≦ 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. The aluminum halide compound is used alone or as a mixture of two or more kinds.

Specific examples of aluminum halides include, for example, ethyl aluminum dichloride, n-propyl aluminum dichloride, 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, diethyl aluminum chloride, di-i-propyl aluminum chloride, di-n-propyl aluminum chloride, di -I-Butyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide and the like can be mentioned.

The electron-donating compound which is the above-mentioned (v) reactant is an ether, an ester, a ketone or a phenol.
, Amine, amide, imine, nitrile, phosphine,
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, malonic acid. Diethyl, diisobutyl malonate, 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, p-ethoxy ethyl benzoate, p- Methyl Ruiru acid, ethyl p- toluic acid, p-tert-butyl benzoate, p-
Ethyl anisate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, Examples thereof include diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate and dibutyl naphthalate. The electron donating compound (v) is used alone or as a mixture of two or more kinds.

As the titanium halide compound which is the above-mentioned (vi), a titanium compound represented by the general formula: Ti (OR ⁶ ) _f X _4-f
A titanium compound represented by In the formula, R ⁶ is 1
Represents a hydrocarbon group having ˜20 carbon atoms, X represents a halogen atom, and f represents a number 0 ≦ f <4. R ⁶
Is preferably selected from linear or branched alkyl groups, alkoxy groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups. The titanium halide compound may be used alone or as a mixture of two or more kinds.

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, and triethoxy titanium chloride. Examples thereof include titanium tetrabromide, titanium tetraiodide, and dichlorodibromotitanium.

Examples of the organoaluminum compound, organozinc compound and organomagnesium compound of the component (vii) include organoaluminum compounds represented by the general formula AlR ⁷ _b X _3-b and general formula R ⁸ _c ZnX _2-c. An organozinc compound and an organomagnesium compound represented by the general formula R ⁹ _d MgX _2-d are used. In the formula, R ⁷ , R ⁸ and R
⁹ represents a hydrocarbon group having 1 to 20 carbon atoms,
X represents a halogen atom, b represents a number 0 <b ≦ 3, c represents a number 0 <c ≦ 2, and d represents a number 0 <d ≦ 2.
R ⁷ , R ⁸ and R ⁹ are preferably selected from linear or branched alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups. The above organoaluminum compound, organozinc compound and organomagnesium compound can be used alone or as a mixture of two or more thereof.

Specific examples of the organic aluminum compound include ethyl aluminum dichloride, n-propyl aluminum dichloride, 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, diethyl aluminum chloride, di-i-propyl aluminum chloride, di-n-propyl aluminum chloride, di -I-Butyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, triisoprenyl aluminum, tri n-hexyl aluminum, tri Examples include n-octyl aluminum and tri (2-methylpentyl) aluminum.

Specific examples of the organozinc compound include, for example, methylchlorozinc, methylbromozinc and methyliodine.
Dezinc, dimethylzinc, ethylchlorozinc, ethylbromozinc, ethyliodozinc, diethylzinc, di-n-propylzinc, n-butylchlorozinc, n-butylbromozinc, n-butyliodozinc, di-n-butylzinc, i -Butylchlorozinc, i-butylbromozinc, i-butyliodozinc, di-butylzinc, sec-butylchlorozinc, sec-butylbromozinc, sec-butyliodozinc, disec-butylzinc, t-butylchlorozinc,
t-butyl bromozinc, t-butyl iodozinc, di-t-
Butylzinc, di-n-hexylzinc, di-n-octylzinc, methylethylzinc, methylbutylzinc, ethylbutylzinc, phenylchlorozinc, phenylbromozinc, phenyliodozinc, diphenylzinc, methylphenylzinc, ethylphenylzinc, n -Butylphenyl zinc, dibenzyl zinc and the like can be mentioned.

Specific examples of the organomagnesium compound include, for example, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, n-propylmagnesium bromide, i-propylmagnesium chloride, i- Propyl magnesium bromide, n-butyl magnesium bromide, n-butyl magnesium iodide, i-butyl magnesium chloride, i-butyl magnesium bromide, i-butyl magnesium iodide, sec-butyl magnesium chloride, sec-butyl magnesium bromide,
sec-Butylmagnesium iodide, t-butylmagnesium chloride, t-butylmagnesium bromide, t-butylmagnesium iodide, n-hexylmagnesium chloride, n-octylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium iodide , Benzyl magnesium chloride, benzyl magnesium bromide, dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, n-butyl n-
Propyl magnesium, n-butyl methyl magnesium, n-butyl ethyl magnesium, n-butyl n-propyl magnesium, di-n-butyl magnesium, di-n
-Hexyl magnesium, i-butyl ethyl magnesium, sec-butyl ethyl magnesium, t-butyl ethyl magnesium, di i-butyl magnesium, di t-
Butyl magnesium and the like can be mentioned.

Further, 7.5 di-n-butylmagnesium.
Triethylaluminum, di-n-butylmagnesium
Complex compounds between organoaluminum compounds such as 2.0 triethylaluminum, organozinc compounds and organomagnesium compounds can also be used.

Component (viii) General formula t-Bu
_{^{(R 1) Si (OR 2}} ) 2 (t-Bu; data - Chari - butyl group, ^{R 1;} linear hydrocarbon group having 2 to 20 carbon atoms, R
² ; an oxygen-containing organic compound of silicon represented by a hydrocarbon group having 1 to 5 carbon atoms), t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butyl-n-butyldimethoxy Silane, t-butyl-n-pentyldimethoxysilane, t-butyl-n
-Hexyldimethoxysilane, t-butyl-n-heptyldimethoxysilane, t-butyl-n-octyldimethoxysilane, t-butyl-n-nonyldimethoxysilane, t-butyl-n-decyldimethoxysilane, t-butyl-n -Undecyldimethoxysilane, t-butyl-
n-dodecyldimethoxysilane, t-butyl-n-tridecyldimethoxysilane, t-butyl-n-tetradecyldimethoxysilane, t-butyl-n-pentadecyldimethoxysilane, t-butyl-n-hexadecyldimethoxysilane, t-butyl-n-heptadecyldimethoxysilane, t-butyl-n-octadecyldimethoxysilane, t-butyl-n-nonadecyldimethoxysilane, t
-Butyl-n-eicosyldimethoxysilane, t-butylethyldiethoxysilane, t-butyl-n-propyldiethoxysilane, t-butyl-n-butyldiethoxysilane, t-butyl-n-pentyldiethoxysilane ,
t-butyl-n-hexyldiethoxysilane, t-butyl-n-heptyldiethoxysilane, t-butyl-n-
Octyldiethoxysilane, t-butyl-n-nonyldiethoxysilane, t-butyl-n-decyldiethoxysilane, t-butyl-n-undecyldiethoxysilane,
t-butyl-n-dodecyldiethoxysilane, t-butyl-n-tridecyldiethoxysilane, t-butyl-n
-Tetradecyldiethoxysilane, t-butyl-n-pentadecyldiethoxysilane, t-butyl-n-hexadecyldiethoxysilane, t-butyl-n-heptadecyldiethoxysilane, t-butyl-n-octadecyl Diethoxysilane, t-butyl-n-nonadecyldiethoxysilane, t-butyl-n-eicosyldiethoxysilane, t-butylethylmethoxyethoxysilane, t-butyl-n-propylmethoxyethoxylane, t-butyl -N-butylmethoxyethoxysilane, t-butyl-n
-Pentylmethoxyethoxysilane, t-butyl-n-hexylmethoxyethoxysilane, t-butyl-n-heptylmethoxyethoxysilane, t-butyl-n-octylmethoxyethoxysilane, t-butyl-n-nonylmethoxyethoxysilane, t-butyl-n-decylmethoxyethoxysilane, t-butyl-n-undecylmethoxyethoxysilane, t-butyl-n-dodecylmethoxyethoxysilane, t-butyl-n-tridecylmethoxyethoxysilane, t-butyl- n-tetradecylmethoxyethoxysilane, t-butyl-n-pentadecylmethoxyethoxysilane, t-butyl-n-hexadecylmethoxyethoxysilane, t-butyl-n-heptadecylmethoxyethoxysilane, t-butyl-n- Octadecyl methoxyethoxy Orchid, t-butyl-n-nonadecylmethoxyethoxysilane, t-butyl-n-eicosylmethoxyethoxysilane, t-butylethyldipropoxysilane, t-butyl-n-propyldipropoxysilane, t-butyl-n -Butyldipropoxysilane, t-
Butylethyldi-i-propoxysilane, t-butyl-
n-propyldi-i-propoxysilane, t-butyl-
n-butyldi-i-propoxysilane, t-butylethylmethoxypropoxysilane, t-butyl-n-propylmethoxypropoxysilane, t-butyl-n-butylmethoxypropoxysilane, t-butylethylethoxypropoxysilane, t-butyl -N-propylethoxypropoxysilane, t-butyl-n-butylethoxypropoxysilane, t-butylethyldibutoxysilane,
t-butylethylbutoxymethoxysilane, t-butylethylbutoxyethoxysilane, t-butylethyldipentoxysilane, t-butylethylpentoxymethoxysilane, t-butyl-n-butyldi-t-butoxysilane, t-butyl Examples thereof include -n-butyldi-sec-butoxysilane and t-butyl-n-butyl-i-pentoxymethoxysilane. The oxygen-containing organic compound of the present silicon may be used alone or as a mixture of two or more kinds.

The solid catalyst component obtained in the present invention is obtained by reacting the component (iv) with a homogeneous solution obtained by reacting the components (i), (ii) and (iii) above. It can be prepared by reacting the solid product with the above-mentioned components (v) and (vi). 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, and mixtures thereof. It 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 above components (i), (ii), (iii), (iv), which are used to obtain the solid catalyst component.
The amounts of (v) and (vi) used are not particularly limited, but the molar ratio of the magnesium atom (i) to the oxygen-containing organic compound (ii) of aluminum is 1: 0.01 to 1:20, and in particular 3000 μm or more. If it is intended to obtain pellet-sized polymer particles of, it is desirable to select the range of 1: 0.05 to 10. Also, magnesium atom (i)
The molar ratio of the oxygen-containing organic compound (iii) of titanium and titanium is 1: 0.01 to 1:20, preferably 1: 0.0.1 to obtain pellet-sized polymer particles with very good powder characteristics.
It is preferable to select the amount to be used so as to be 1 to 1: 5.
Further, magnesium atom and aluminum halide (i
The ratio of aluminum atoms in v) is 1: 0.1 to 1: 1.
It is preferable to select the amount of the reaction agent used so that it is in the range of 00, preferably 1: 0.1 to 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 obtained, or if it is too small, good powder properties may not be obtained.

The magnesium atom (i) and the electron donating compound (v) are used in a molar ratio of 1: 0.05 to 1: 5.0, preferably 1: 0.1 to 1: 2.0. It is preferable to choose the amount. Outside of these ranges, problems such as low polymerization activity and low stereoregularity of the polymer may occur. Further, the molar ratio of magnesium atom (i) to titanium halide compound (vi) is from 1: 1 to
It is preferable to select the amount used so as to be in the range of 1: 100, 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 conditions for obtaining a homogeneous solution from the reactants (i), (ii) and (iii) are -50 to 300 ° C.
Preferably, at a temperature of 0 to 200 ° C., 0.5 to
It is carried out at normal pressure or under pressure in an inert gas atmosphere for 50 hours, preferably 1 to 6 hours. Further, at this time, by adding an electron donating compound similar to the compound (v), homogenization can be performed in a shorter time. Further, in the reaction of the reactants (iv), (v) and (vi), it is -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 10 hours.

The reaction conditions of the reactant (iv) are important,
It is extremely important because it plays 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 using them.

Further, the reaction of the reactant (vi) may be carried out by dividing it in multiple stages. When addition of the reaction of the reaction agent (vi), in the general formula R-CH = CH ₂ (wherein, R 1 to 10
In the presence of ethylene and / or α-olefin represented by a straight chain or branched chain substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a hydrogen atom). In these cases, an effect such as resulting in improvement of polymerization activity and stereoregularity of the polymer may be recognized.

The solid catalyst component thus obtained is filtered or decanted to remove residual unreacted substances and by-products, and then thoroughly washed with an inert organic solvent or isolated after washing. The component (vii) and the component (v) obtained by heating under normal pressure or reduced pressure to remove the inert organic solvent are used.
Used for catalytic reaction with iii).

Further, prior to the main polymerization, a small amount of an organometallic compound component is added to give a compound of the general formula: R-CH = CH ₂ (wherein
R represents a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and particularly 1 to 8 carbon atoms), and a prepolymer obtained by polymerizing a small amount of an α-olefin and / or ethylene. After that, it can be used. The obtained solid catalyst component is at least -member selected from the group consisting of the organoaluminum compound, organozinc compound and organomagnesium compound of the above component (vii) and the above component (v).
iii) catalytic reaction with the oxygen-containing organic compound of silicon represented by the general formula ^t Bu (R ¹ ) Si (OR ² ) ₂ to obtain the catalyst component (A).

The amounts of the above-mentioned components (vii) and (viii) used for obtaining the catalyst component (A) are not particularly limited, but Ti in the solid catalyst component (or its prepolymer) and the above-mentioned components are used. (Vii) metal atoms (Al, Zn,
The amount used is preferably selected such that the atomic ratio of Mg) is 1: 0.01 to 1: 200, preferably 1: 0.1 to 1:50. The metal atom (Al,
The atomic ratio of (Zn, Mg) to Si in the component (viii) is 1: 0.01 to 1: 100, preferably 1: 0.
It is preferable to select the amount to be used so as to be 01 to 1:20.

The catalytic reaction conditions for obtaining the catalyst component (A) are −50 to 150 ° C., preferably 0 to 100 ° C., for 0.5 to 20 hours, preferably 1 to 5
It is carried out at normal pressure or under pressure in an inert gas atmosphere for a time. At this time, the solid catalyst component is crushed, or in order that the contact reaction does not become nonuniform, the above-mentioned inert solvent is allowed to coexist,
It is preferable to cause a catalytic reaction by stirring.

The catalyst component (A) thus obtained may be used as it is, after removing unreacted substances and by-products which remain by filtration or decantation, and after sufficient washing with an inert organic solvent. It is also possible to use those which have been isolated after washing and which have been heated under normal pressure or reduced pressure to remove the inert organic solvent.

Catalyst component (A) obtained as described above
Is used for olefin polymerization by combining with the organometallic compound of component (B) and the electron-donating compound of component (C).

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,
Examples thereof include triethylaluminum, tri-i-butylaluminum, tri-n-butylaluminum, tri-n-decylaluminum, tetraethyltin and tetrabutyltin.

Above all, a trialkylaluminum represented by the general formula AlR ¹⁰ ₃ is preferable. However, in the general formula, R ¹⁰ represents a linear or branched alkyl group having 1 to ¹⁰ carbon atoms.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, triisoprenylaluminum, tri-n.
-Hexylaluminum, tri-n-octylaluminum, tri (2-methylpentyl) aluminum.

Alkyl aluminum halides, alkyl aluminum hydrides and alkyl aluminum alkoxides represented by the general formula R ¹¹ _e AlY _3-e can also be used. However, in the general formula, R ¹¹ represents a linear or branched alkyl group having 1 to 10 carbon atoms.
Y represents halogen, hydrogen or an alkoxy group.

Specific examples include dimethyl aluminum chloride, methyl aluminum sesquichloride, methyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum. Chloride, isobutyl aluminum dichloride, diethyl aluminum iodide, diethyl aluminum fluoride, diethyl aluminum bromide, diisobutyl aluminum hydride, diethyl aluminum hydride, diethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, diisobutyl aluminum ethoxide, diiso It includes chill aluminum isopropoxide. These organometallic compounds are used alone or as a mixture of two or more kinds.

As the component (C), the above-mentioned component (vii
The same thing as the oxygen-containing organic compound of silicon represented by the general formula ^t Bu (R ¹ ) Si (OR ² ) ₂ of i) can be used. The oxygen-containing organic compound of the present silicon may be used alone or in combination of two or more kinds. Further, it may be the same as or different from the one used in the above component (viii).

The catalyst component (A) is used in an amount of 0.001 titanium atom in the catalyst component (A) per liter of the reactor.
It is preferred to use in an amount corresponding to ~ 2.5 milligram atoms.

The organometallic compound of the component (B) is 1 to 2000 mol per 1 gram atom of titanium in the catalyst component (A).
(mol), preferably used in an amount corresponding to 2-500 mol.

The general formula t-Bu (R ¹ ) Si of the component (C)
The oxygen-containing organic compound of silicon represented by (OR ² ) ₂ is 0.0 per mol of the organometallic compound of the component (B).
It is used in an amount corresponding to 01 to 20 mol, preferably 0.01 to 5 mol.

The feeding mode of the three components in the present invention is not particularly limited, and for example, a method of feeding the component (A), the component (B) and the component (C) separately into the polymerization vessel, or A method in which the component (A) and the component (B) are brought into contact with each other and then the component (C) is brought into contact therewith, and the component (B) and the component (C) are brought into contact with each other and then the component (A) is brought into contact therewith to carry out the polymerization. It is possible to employ a method such as a method in which the component (A), the component (B) and the component (C) are brought into contact with each other in advance for polymerization.

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.

As the olefin to be polymerized in the method for producing a stereoregular polyolefin of the present invention, ethylene and / or an α-olefin of the general formula R-CH = CH ₂ (wherein R is 1-10, especially 1 A straight-chain or branched-chain substituted / unsubstituted alkyl group having 8 carbon atoms).

Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 1-octene.

These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. In copolymerization, two or more kinds of the above α-olefins, or
Polymerization is carried out using α-olefins and dienes such as butadiene and isoprene. Of these, it is particularly preferable to carry out the polymerization using propylene, 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.

The reactor used in the polymerization step can be appropriately used if it is one usually used in the art. 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.

[0062]

The first effect is that the molecular weight and molecular weight distribution of the polymer can be easily controlled. In particular, it is possible to produce a polymer having a wide molecular weight distribution and a high molecular weight polymer in a high yield as compared with a conventional magnesium halide-supported catalyst, and the stereoregularity of the produced polymer is extremely high. Therefore, a highly rigid polymer can be produced.

The second effect is to obtain polymer particles having a small number of fine particles and a high bulk density having an average particle diameter of an intended size, particularly to obtain pellet-sized polymer particles having a particle diameter of several mm. It is effective in powder properties, such as when it is applied, and is particularly effective when applied to gas phase polymerization. It is also possible to obtain polymer particles having a very narrow particle size distribution. Therefore, in the polymerization step, the formation of deposits in the polymerization apparatus is prevented, and particularly in the slurry polymerization method, the separation and filtration of the polymer slurry in the polymer separation and drying steps become easy, The fine particles of the above are prevented from scattering outside the system, and in addition, the improvement of the fluidity improves the drying efficiency. Further, in the transfer process, there is no occurrence of a bridge or the like in the silo, and a trouble in transfer is solved.

The third 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 need to worry about coloring of the product, and no purification of the polymer is required, which is extremely economical.

The fourth effect is that the stereoregularity of the polymer is extremely good. Therefore, it is extremely advantageous for polymer production by a gas phase polymerization method without using a reaction medium.

[0066]

EXAMPLES The present invention will be shown below with reference to 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) is JISK 72.
It was measured under 10 conditions and 14 conditions.

The xylene-soluble component (hereinafter abbreviated as _XY ), which is an index of stereoregularity, is measured as follows. After dissolving 4 g of the polymer in 200 ml of xylene, the polymer was allowed to stand in a constant temperature bath at 25 ° C. for 1 hour, the deposited portion was filtered off, and the filtrate was recovered.
After the xylene was evaporated, it was further vacuum dried to obtain a xylene-soluble portion. _XY represents the weight of the xylene-soluble part as a percentage with respect to the weight of 4 g of the original polymer. Also, II is
The ratio of the insoluble polymer after Soxhlet extraction with boiling n-heptane to the total amount of the produced polymer is shown by weight percentage.

The activity represents a polymer production amount (g) per 1 g of a solid catalyst component containing no prepolymerized component.

Molecular weight distribution of polymer (Qw = Mw / Mn)
Was measured at 140 ° C. by GPC (150C manufactured by Waters, column: Toso-GMH6-HT) using orthodichlorobenzene as a solvent. Note that polystyrene (maximum Mw = 8420000) was used as a standard substance, and other polyethylene and C ₃₂ H ₆₆ were used to create a calibration curve.

The intrinsic viscosity [η] of the polymer was measured with an orthodichlorobenzene solution at 140 ° C. Incidentally, there is a relationship of [η] = 1.88 × 10 ⁻⁴ × Mv ^0.725 between the intrinsic viscosity [η] and the viscosity average molecular weight Mv.

The broadness and narrowness of the particle size distribution of the polymer particles can be determined by plotting the results of classification of the polymer particles with a sieve on established logarithmic paper, obtaining the geometric standard deviation from the approximated straight line by a known method, and calculating the common logarithm (hereinafter σ). Further, the average particle diameter is a value obtained by reading the particle diameter corresponding to the weight integrated value of 50% on the approximate straight line. Fine particle content is 1 particle size
The ratio of fine particles having a particle size of 05 μ or less is shown as a weight percentage.

Example 1 (a) Preparation of 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. 401.7g
(3.1 mol), titanium tetra-n-butoxide 21
0 g (0.62 mol) and tri-i-propoxyaluminum 252 g (1.23 mol) were added, the temperature was raised to 90 ° C., and the mixture was stirred under a nitrogen seal for 1 hour. Continue to 14
The temperature is raised to 0 ° C. and the reaction is performed for 2 hours to obtain a homogeneous solution containing magnesium, titanium and aluminum (Mg-Ti-Al
Solution) was obtained.

A Mg-Ti-Al solution was added to a baffled flask having an internal volume of 500 ml in an amount of 0.066 mol in terms of Mg.
After charging and cooling to 0 ° C., 20.5 g (0.13 mol) of isobutylaluminum dichloride was added to 12 parts of hexane.
A solution diluted with a mixed solvent of 0 ml and 50 ml of 1,2-dichloroethane 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 washed with hexane.

The slurry containing the white solid product thus obtained was charged into 1 l of a glass magnetic stirring type autoclave, and then 125 g of titanium tetrachloride (0.66 mo).
l) was diluted with 125 g of chlorobenzene, and the whole solution was added. Then, 7.3 g of diisobutyl phthalate (0.026 m
ol) was added and reacted at 100 ° C. for 3 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 stirred at 100 ° C. for 2 hours. Hexane was added to the product, and the washing operation was sufficiently performed until no liberated titanium compound was detected. Thus, a slurry of the solid catalyst component suspended in hexane was obtained. When the supernatant was removed and the product was dried under a nitrogen atmosphere and subjected to elemental analysis, Ti was 2.8% by weight.

The interior of the stainless steel electromagnetic stirring type autoclave having an internal volume of 1 l was sufficiently replaced with nitrogen, and 5.0 g of the obtained solid catalyst component, 300 ml of hexane, and 12.5 mmol of triethylaluminum were sequentially added, After adjusting the autoclave internal pressure to 0.1 kg / cm ² G and adjusting the internal temperature to 20 ° C., stirring was started, and 15 g of propylene was fed for 20 minutes while maintaining the internal temperature at 20 ° C., and thereafter. Stir for 30 minutes. The propylene prepolymer of the solid catalyst component thus obtained was separated by filtration and thoroughly washed with hexane. The yield after removing the supernatant liquid and drying in a nitrogen atmosphere is 1
It was 8.5 g.

The total amount of the propylene prepolymer of the above solid catalyst component was placed in a flask having an internal volume of 500 ml, and 300 ml of hexane and 11.7 m of triethylaluminum were added thereto.
mol, t-butyl-n-propyldimethoxysilane 1
1.7 mmol was added, and the mixture was stirred at room temperature for 30 minutes. Then, the catalyst component (A) was obtained by washing with n-pentane by a gradient method and drying under a nitrogen stream.

(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 1.2 mmol of triethylaluminum as a catalyst component (B) and a catalyst component (C )
As an additive, 0.29 mmol of t-butyl-n-propyldimethoxysilane and 37 mg of the catalyst component (A) (corresponding to 10 mg of the solid catalyst component) were sequentially added, and the internal pressure of the autoclave was 0.1 kg / cm ² G. To 0.2 kg / cm ² G of hydrogen, liquid propylene 2000 m
After adding 1 liter and starting stirring, the temperature was raised to 70 ° C. and polymerization was performed for 90 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 produced polymer was 441 g, and the activity was 44100 g per 1 g of the solid catalyst component containing no prepolymerized component.
/ G. When various characteristics of the polymer particles were examined,
MFR 1.6g / 10min. , _XY 1.0%, Qw
6.0, bulk density 0.49 g / cm ³ , average particle size 1660
The results obtained were μ, σ 0.11, and fine particle content 0% by weight.
The produced polymer particles were spherical.

Example 2 (a) Preparation of catalyst component (A) The same preparation as in (a) of Example 1 was carried out.

(B) Polymerization of propylene The inside of a stainless steel electromagnetic stirring type autoclave having an internal volume of 3 l was sufficiently replaced with argon, and 2.6 mmol of triethylaluminum as a catalyst component (B) and a catalyst component (C ), T-butyl-n-propyldimethoxysilane 0.39 mmol, and catalyst component (A) 35 mg
(Corresponding to 9.5 mg of solid catalyst component) in sequence,
0.33 kg / cm ² G of hydrogen was added. After adding 780 g of liquid propylene and starting stirring, the temperature was raised to 80 ° C., and 1
Polymerized for 20 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 polymer produced was 538 g, which corresponds to an activity of 56600 g / g. When various properties of the polymer particles were examined, MFR 1.2 g / 10 min. , X _Y 0.
The results were 5%, Qw 6.2, bulk density 0.49 g / cm ³ , average particle size 2120μ, σ 0.11, and fine particle content 0% by weight. The produced polymer particles were spherical.

Example 3 (a) Preparation of catalyst component (A) The catalyst component (A) was prepared in the same manner as in (a) of Example 1.

(B) Polymerization of propylene A magnetic stirrer of stainless steel with an internal volume of 1.5 l was used.
The inside of the toclave was sufficiently replaced with nitrogen, and 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 1.09 mmol (125 mg) of triethylaluminum as a catalyst component (B)
As catalyst component (C), 0.21 mmol (52 mg) of t-butyl-n-propyldimethoxysilane and 56 mg of catalyst component (A) (corresponding to 15 mg of solid catalyst component) were sequentially added, and 60 ml of hydrogen was added. The temperature was raised to 75 ° C., propylene was supplied so that the polymerization pressure became 5 kg / cm ² G, and the polymerization was performed for 120 minutes. After completion of the polymerization reaction,
At the same time as stirring was stopped, unreacted propylene in the system was discharged, the polymer was separated by filtration from the polymer slurry, and the polymer was dried. As a result, the amount of the filtered polymer was 123 g.
The activity corresponded to 8200 g / g. When various characteristics of the polymer particles were examined, MFR 1.1 g / 10 min. , II9
9.5%, Qw 6.0, bulk density 0.45 g / cm ³ , average particle size 1140 μ, σ 0.12, fine particle content 0% by weight
Got the result. The produced polymer particles were spherical.

Example 4 Using the catalyst component (A) prepared in Example 1, Example 1
(B) of Example 1 except that 0.29 mmol of t-butyl-n-hexyldimethoxysilane was used instead of t-butyl-n-propyldimethoxysilane used as the catalyst component (C) in (b) of Polymerization of propylene was carried out under the same conditions as.

The result was an activity of 48500 g / g.
When various properties of the polymer particles were measured, MFR 1.3 g
/ 10 min. , X _Y 0.8%, Qw 6.0, bulk density 0.49 g / cm ³ , average particle size 1700 μ, σ 0.1
1, the result of fine particle content 0% by weight was obtained. The produced polymer particles were spherical.

Example 5 When preparing the catalyst component (A), t-butyl-n- which was used as the component (viii) in (i) of Example 1 was used.
A catalyst component (A) was obtained in the same manner as in (i) of Example 1, except that 11.7 mmol of t-butyl-n-butyldimethoxysilane was used instead of propyldimethoxysilane. The resulting catalyst component (A) was used in place of t-butyl-n-propyldimethoxysilane used as the catalyst component (C) in (b) of Example 1 to obtain t-butyl-n-butyldimethoxysilane. Polymerization of propylene was carried out under the same conditions as in (B) of Example 1 except that 29 mmol was used. As a result, the activity was 42800 g / g. When various characteristics of the polymer particles were measured, MFR
1.7 g / 10 min. , _XY 0.6%, Qw6.3,
Bulk density 0.49 g / cm ³ , average particle size 1630 μ, σ
A result of 0.11 and a fine particle content of 0% by weight was obtained. Also,
The polymer particles produced were spherical.

Example 6 When preparing the catalyst component (A), t-butyl-n- which was used as the component (viii) in (a) of Example 1 was used.
A catalyst component (A) was obtained in the same manner as in (i) of Example 1, except that 11.7 mmol of t-butyl-n-hexyldimethoxysilane was used instead of propyldimethoxysilane. Using the resulting catalyst component (A), t-butyl-n-hexyldimethoxysilane 0.10 was used instead of t-butyl-n-propyldimethoxysilane used as the catalyst component (C) in Example 1 (b). Polymerization of propylene was carried out under the same conditions as in (B) of Example 1 except that 29 mmol was used.

As a result, the activity was 45,000 g / g.
When the properties of the polymer particles were measured, the MFR was 1.6 g.
/ 10 min. , _XY 0.7%, Qw 6.5, bulk density 0.49 g / cm ³ , average particle size 1660μ, σ 0.1.
1, the result of fine particle content 0% by weight was obtained. The produced polymer particles were spherical.

Example 7 In the preparation of the catalyst component (A), 13.7 mmol of diethylzinc was used in place of the triethylaluminum used as the component (vii) in (a) of Example 1 except that 11.7 mmol of diethylzinc was used. A catalyst component (A) was obtained in the same manner as in (A) of 1. Polymerization of propylene was carried out using the obtained catalyst component (A) under the same conditions as in (1) of Example 1.
The result was an activity of 47100 g / g. Various properties of the polymer particles were measured and found to be MFR 1.4 g / 10 mi
n. , X _Y 1.1%, Qw 6.5, bulk density 0.49 g /
The results were as follows: cm ³ , average particle size 1700μ, σ 0.11, fine particle content 0% by weight. The produced polymer particles were spherical.

Example 8 When preparing the catalyst component (A), ethyl tributylaluminum was used in place of the triethylaluminum used as the component (vii) in (a) of Example 1 and ethylbutylmagnesium was 11.7 mmo.
A catalyst component (A) was obtained in the same manner as in (i) of Example 1 except that 1 was used. Polymerization of propylene was carried out using the obtained catalyst component (A) under the same conditions as in (1) of Example 1. The result was an activity of 43000 g / g.
When the properties of the polymer particles were measured, the MFR was 1.6 g.
/ 10 min. , X _Y 1.0%, Qw 6.2, bulk density 0.49 g / cm ³ , average particle size 1650 μ, σ 0.1
1, the result of fine particle content 0% by weight was obtained. The produced polymer particles were spherical.

Example 9 (B) of Example 1 except that the catalyst component (A) prepared in (A) of Example 1 was used and no hydrogen was added in (B) of Example 1. Polymerization of propylene was carried out under the same conditions as. The result was an activity of 27200 g / g.
When the various properties of the polymer particles were measured, [η] 5.5d
1 / g, _XY 1.1%, bulk density 0.48 g / cm ³ , average particle size 1420μ, σ 0.11, fine particle content 0% by weight
Got the result.

Example 10 Using the catalyst component (A) prepared in Example 6, propylene was polymerized under the same conditions as in Example 6 except that hydrogen was not added. The result was an activity of 22800 g / g. When various properties of the polymer particles were measured, [η]
5.1 dl / g, _XY 1.1%, bulk density 0.48 g / c
The results were m ³ , mean particle size 1330μ, σ 0.11, and fine particle content 0% by weight.

Comparative Example 1 Using 37 mg of the propylene prepolymer as the solid catalyst component prepared in (a) of Example 1, propylene was polymerized in the same manner as in (b) of Example 1.

As a result, the activity was 36000 g / g.
Various properties of the polymer particles were measured and found to be MFR 5.0 g.
/ 10 min. , X _Y 1.0%, Qw = 4.9, bulk density 0.48 g / cm ³ , average particle size 1550 μ, σ 0.1
A result of 0 and a fine particle content of 0% by weight was obtained. The produced polymer particles were spherical.

Comparative Example 2 When preparing the catalyst component (A), t-butyl-n- which was used as the component (viii) in (i) of Example 1 was used.
Example 1 except that 11.7 mmol of diphenyldimethoxysilane was used instead of propyldimethoxysilane.
A catalyst component (A) was obtained by the same method as in (A). Using the obtained catalyst component (A), except that 0.29 mmol of diphenyldimethoxysilane was used instead of t-butyl-n-propyldimethoxysilane used as the catalyst component (C) in (b) of Example 1. (B) of Example 1
Polymerization of propylene was carried out under the same conditions as.

The result was an activity of 35,200 g / g.
Various properties of the polymer particles were measured and found to be MFR 4.5 g
/ 10 min. , _XY 1.1%, Qw4.5, bulk density 0.48 g / cm ³ , average particle size 1520 μ, σ 0.1
A result of 0 and a fine particle content of 0% by weight was obtained. The produced polymer particles were spherical.

Comparative Example 3 When preparing the catalyst component (A), t-butyl-n- which was used as the component (viii) in (i) of Example 1 was used.
Other than using 11.7 mmol of t-butyl-methyldimethoxysilane instead of propyldimethoxysilane,
A catalyst component (A) was obtained in the same manner as in Example 1, (a). Using the obtained catalyst component (A), (B) of Example 1
T-butyl-n- used as catalyst component (C) in
Other than using 0.29 mmol of t-butyl-methyldimethoxysilane instead of propyldimethoxysilane,
Polymerization of propylene was carried out under the same conditions as in Example 1, (b). The result was 22700 g / g of activity. Various properties of the polymer particles were measured and found to be MFR 2.3 g / 1
0 min. , _XY 1.0%, Qw 4.8, bulk density 0.4
The results were 8 g / cm ³ , average particle size 1330 μ, σ 0.11, and fine particle content 0% by weight. The produced polymer particles were spherical.

Comparative Example 4 Using the catalyst component (A) prepared in Comparative Example 2, propylene was polymerized under the same conditions as in Comparative Example 2 except that hydrogen was not added. The result was 23700 g / g of activity. When various properties of the polymer particles were measured, [η] 3.7 dl / g, _XY 1.2%, bulk density 0.48 g / cm ³ , average particle size 1350 μ, σ0.
11, the result of fine particle content 0% by weight was obtained.

The polymerization results of Examples 1 to 8 are shown in Table 1, the polymerization results of Examples 9 to 10 and Comparative Example 4 are shown in Table 2, and the polymerization results of Comparative Examples 1 to 3 are shown. The results are summarized in Table 3.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[Brief description of drawings]

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

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) metal magnesium and a hydroxylated organic compound, and magnesium as a component (A) of the catalyst. (Iv) at least one aluminum halide in a homogeneous solution containing at least one member selected from the group consisting of oxygen-containing organic compounds, (ii) an oxygen-containing organic compound of aluminum and (iii) an oxygen-containing organic compound of titanium The solid product obtained by the reaction is reacted with (v) an electron-donating compound and (vi) a titanium halide compound to form a solid catalyst component, and (vii) an organoaluminum compound, an organozinc compound and an organic compound. At least one member selected from the group consisting of magnesium compounds, and (viii) the general formula t- ^{u (R 1) Si (OR} 2)
₂ (t-Bu; tertiary-butyl group, R ¹ ; carbon number 2
20 linear hydrocarbon group, R ² ; hydrocarbon group having 1 to 5 carbon atoms), which is a catalyst component obtained by catalytic reaction of an oxygen-containing organic compound of silicon; IA, IIA, IIB,
At least one selected from the group consisting of organometallic compounds of Group IIIB and IVB metals, the general formula t-Bu (R ¹ ) Si (OR ² ) ₂ (t-Bu; tertiary-butyl) as component (C) Group, R ¹ ; linear hydrocarbon group having 2 to 20 carbon atoms, R ² ; hydrocarbon group having 1 to 5 carbon atoms) and stereoregularity using a catalyst system composed of an oxygen-containing organic compound of silicon Method for producing polyolefin.