JPH11228616A - Alpha-olefin polymerization catalyst and production of alphaolefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a highly stereoregular α-olefin polymer with slight fine powder and good powder disposition, and to obtain a highly active catalyst without need of removing catalyst residues and amorphous polymers. SOLUTION: This catalyst for α-olefin polymerization is composed of (A) a component which is prepared by the following process: a titanium compound of the formula Ti (OR<1> )a X4-a , (R<1> is a 1-20C hydrocarbon group; X is a halogen atom; (a) satisfies the relationship: 0<(a)<=4) is reduced with an organomagnesium compound in the presence of a Si-O bond-bearing organosilicon compound and/or ester compound to form a solid product <=1.5 wt.% in titanium content, which, in turn, is treated with an ether compound, titanium tetrachloride and an organic acid halide compound followed by a mixture of an ether compound and titanium tetrachloride, (B) an organoaluminum compound, and (C) an electron-donating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer. More specifically, using a novel catalyst having extremely high catalytic activity per solid catalyst and per titanium atom, the catalyst residue and the amorphous polymer are extremely low, and the isotactic high stereoregularity having excellent mechanical properties and processability is provided. The present invention relates to an α-olefin polymerization catalyst for producing a soluble α-olefin polymer and a method for producing an α-olefin polymer.

[0002]

2. Description of the Related Art As a method for producing an isotactic polymer of an α-olefin such as propylene and butene-1, a solid catalyst component obtained by using a transition metal compound belonging to Groups 4 to 6 of the periodic table and a solid catalyst component are prepared. It is well known to use so-called Ziegler-Natta catalysts comprising organometallic compounds of groups 1, 2, and 13.

[0003] In producing an α-olefin polymer,
An amorphous polymer is by-produced in addition to a highly stereoregular α-olefin polymer having high industrial value. This amorphous polymer has little industrial value and greatly affects the mechanical properties when the α-olefin polymer is processed into a molded product, film, fiber, or other processed product. Also, the formation of an amorphous polymer causes loss of raw material monomers,
At the same time, a production facility for removing the amorphous polymer is required, which causes industrial disadvantages. Accordingly, it is preferable that the catalyst for producing the α-olefin polymer has no such an amorphous polymer, or very little if any.

[0004] Further, a catalyst residue comprising a transition metal component and an organic metal component remains in the obtained α-olefin polymer. Since this catalyst residue may cause problems in various points such as the stability and processability of the α-olefin polymer, a deashing facility for removing and stabilizing the catalyst residue is required. This disadvantage can be improved by increasing the catalytic activity expressed in terms of the weight of the formed α-olefin polymer per unit weight of the catalyst, and the equipment for removing the catalyst residue is not required. Can also reduce the manufacturing cost.

A Ti—Mg composite solid catalyst obtained by reducing a tetravalent titanium compound with an organomagnesium compound in the coexistence of an organosilicon compound to form a eutectic of magnesium and titanium is used as an organic cocatalyst. It is known that a certain degree of high stereoregularity and high activity polymerization of α-olefin can be realized by using in combination with an aluminum compound and an organosilicon compound as a third component of polymerization (Japanese Patent Publication No. 3-43283; 1-3950
No. 8).

[0006] The applicant of the present invention has previously proposed that, when the tetravalent titanium compound is reduced with an organomagnesium compound in the presence of an organosilicon compound in the above-mentioned method, an ester compound is further allowed to coexist to achieve higher stereoregularity. It has been proposed that high-activity polymerization can be realized (JP-A-7-216017).

[0007] In each case, although no extraction and no demineralization process is possible, further improvement is desired. Specifically, in order to improve the quality of the α-olefin polymer, it is desired to realize further highly stereoregular polymerization without sacrificing the particle size distribution and the like. In particular, in applications where higher rigidity of the polymer is desired, such as in the field of injection molding, a highly stereoregular polymer directly produces high rigidity quality. The emergence of a catalyst having a catalyst is desired.

[0008]

Under such circumstances,
The problem to be solved by the present invention, that is, an object of the present invention is to provide a method for producing a highly stereoregular α-olefin polymer having less fine powder and good powder properties, and a catalyst capable of producing the α-olefin polymer. An object of the present invention is to provide an α-olefin polymerization catalyst having sufficiently high catalytic activity so that removal of residues and an amorphous polymer is unnecessary.

[0009]

That is, the present invention provides (A) S
In the presence of an organosilicon compound and / or an ester compound having an i-O bond, a compound represented by the general formula Ti (OR ¹ ) _a X
A titanium compound represented by _4-a (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is a number satisfying 0 <a ≦ 4); The titanium content of the solid product obtained by reduction is 1.5% by weight or less, and the solid product is treated with an ether compound, titanium tetrachloride, and an organic acid halide compound. Using a titanium compound-containing solid catalyst component obtained by treating with a mixture of titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound, (B) an organoaluminum compound, and (C) an electron-donating compound Α-olefin polymerization catalyst, and α-olefin homopolymerization or α-olefin and ethylene or other α-olefin copolymerization using the catalyst The present invention relates to a method for producing an olefin polymer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. (A) Titanium compound The titanium compound used in the synthesis of the solid catalyst component (A) of the present invention is a compound represented by the general formula Ti (OR ¹ ) _a X _4-a (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. , X is a halogen atom, a is 0
<A ≦ 4. ) Is a titanium compound. Specific examples of R ¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl,
alkyl group such as tert-amyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, aryl group such as phenyl group, cresyl group, xyler group, naphthyl group, allyl group such as propenyl group, benzyl group, etc. And the like. Among them, those having 2 to 1 carbon atoms
An alkyl group having 8 and an aryl group having 6 to 18 carbon atoms are preferred. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use a titanium compound having two or more different OR ¹ groups.

Examples of the halogen atom represented by X include a chlorine atom, a bromine atom and an iodine atom. In this,
Particularly chlorine atoms give favorable results.

The value of a of the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a is a number satisfying 0 <a ≦ 4, and preferably satisfying 2 ≦ a ≦ 4. The number, particularly preferably a = 4.

As _a method for synthesizing the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a , a known method can be used. For example, a method of reacting Ti (OR ¹ ) ₄ with TiX ₄ at a predetermined ratio, or a method of reacting TiX ₄ with a corresponding alcohol (eg, R ¹ OH) in a predetermined amount can be used. These titanium compounds may be used after being diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Specifically, the general formula Ti (OR ¹ ) _a X _4-a
As titanium compounds represented by, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide such as titanium tetraiodide, methoxy titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, Trihalogenated alkoxytitanium compounds such as ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, diethoxytitanium dibromide and other dihalogenated dialkoxytitanium compounds, trimethoxytitanium chloride , Triethoxy titanium chloride,
Monohalogenated trialkoxy titanium compounds such as tributoxy titanium chloride, triphenoxy titanium chloride and triethoxy titanium bromide, and tetraalkoxy titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetrabutoxy titanium and tetraphenoxy titanium can be exemplified. .

(B) Organosilicon compound having a Si—O bond As the organosilicon compound having a Si—O bond used in the synthesis of the solid catalyst component of the present invention, for example, those represented by the following general formula: Can be used. _{^{Si (OR 2) m R 3}} 4-m R 4 (R 5 2 SiO) p R 6 3 or (R ⁷ ₂ SiO) _q Here,, R ² is a hydrocarbon group having carbon atoms 1 to 20,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and m is 0 <
It is a number that satisfies m ≦ 4, p is an integer of 1 to 1000, and q is an integer of 2 to 1000.

Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxydiisopropyl. Silane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane,
Examples include tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, and phenylhydropolysiloxane. be able to.

[0017] Preferred among these organic silicon compounds are the formula Si (OR ²⁾ alkoxysilane compound represented by _m R ³ _{4 -m,} in which case m is preferably 1 ≦
The number satisfies m ≦ 4, and a tetraalkoxysilane compound in which m = 4 is particularly preferable.

(C) Ester compound As the ester compound used in the present invention, mono- and polyvalent carboxylic esters are used, and examples thereof include aliphatic carboxylic esters, alicyclic carboxylic esters, and aromatic carboxylic esters. Carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, ethyl benzoate, butyl benzoate, toluyl Methyl acrylate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate,
Diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, phthalate Examples thereof include diisopropyl acid, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic dicarboxylic acid diesters are preferred, and phthalic acid diesters are particularly preferred.

(D) Organomagnesium compound Next, the organomagnesium compound used in the present invention is:
Any type of organomagnesium containing Mg-carbon bond
Compounds can be used. In particular, the general formula R ⁸MgX
(Where R⁸Represents a hydrocarbon group having 1 to 20 carbon atoms;
Represents a halogen atom. Grignard compound represented by)
Object or general formula R⁹R^TenMg (where R⁹And R^TenIs charcoal
Represents a hydrocarbon group having 1 to 20 elementary atoms. )
Hydrocarbyl magnesium compounds are preferably used
You. Where R⁸, R⁹, And R^TenAre the same but different
Methyl, ethyl, propyl, isopropyl
Pill, butyl, sec-butyl, amyl, iso
Amyl group, hexyl group, octyl group, 2-ethylhexyl
1-20 carbon atoms such as phenyl, phenyl and benzyl
Alkyl group, aryl group, aralkyl group, alkenyl
Groups are exemplified.

Specifically, as the Grignard compound,
Methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, se
c-butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, amylmagnesium chloride, isoamylmagnesium chloride, hexylmagnesium chloride,
Phenylmagnesium chloride, phenylmagnesium bromide and the like, as compounds represented by the general formula R ⁹ R ¹⁰ Mg, include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-sec-butyl magnesium, di- tert-butylmagnesium, butyl-sec-butylmagnesium, diamylmagnesium, dihexylmagnesium, diphenylmagnesium, butylethylmagnesium and the like.

As a solvent for synthesizing the above-mentioned organomagnesium compound, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, Ether solvents such as phenetole, anisole, tetrahydrofuran, tetrahydropyran and the like are commonly used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent is also used.

In the present invention, the organic magnesium compound is preferably used in the form of an ether solution.
As the ether compound in this case, an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure is used. It is particularly preferable to use a Grignard compound represented by the general formula R ⁸ MgX in an ether solution from the viewpoint of catalytic performance.

A hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and organometallic compound can also be used. Examples of such organometallic compounds include Li,
Organic compounds of Be, B, Al or Zn can be mentioned.

(E) Ether compound Next, ether compounds used in the present invention include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl Ether, dioctyl ether,
Examples thereof include dialkyl ethers such as methyl butyl ether, methyl isoamyl ether, and ethyl isobutyl ether. Of these, dibutyl ether or diisoamyl ether is particularly preferably used.

(F) Organic acid halide compound As the organic acid halide compound used in the present invention, mono- and polyvalent carboxylic acid halides are used, and examples thereof include aliphatic carboxylic acid halide and alicyclic carboxylic acid. Halides and aromatic carboxylic acid halides. Specific examples include acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride,
Examples thereof include benzoyl chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride, itaconic acid chloride and phthalic acid chloride.

Among these organic acid halide compounds, aromatic carboxylic acid chlorides such as benzoyl chloride, toluic acid chloride and phthalic acid chloride are preferred, and aromatic dicarboxylic acid dichloride is more preferred.
Particularly, phthalic acid chloride is preferably used.

(G) Synthesis of Solid Catalyst Component The solid catalyst component (A) of the present invention is a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and / or an ester compound. , An ether compound, titanium tetrachloride and an organic acid halide compound, and then treating the treated solid with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. All of these synthesis reactions are usually performed in an atmosphere of an inert gas such as nitrogen or argon.

As a method of the reduction reaction of the titanium compound with the organomagnesium compound, it is preferable to reduce the titanium compound with the organomagnesium compound in the presence of the organosilicon compound and the ester compound. More specifically, the titanium compound (a ), A method in which an organomagnesium compound (d) is added to a mixture of an organosilicon compound (b) and an ester compound (c), or conversely, a titanium compound (a) and an organosilicon compound (b) are added to the organomagnesium compound (d). ) And an ester compound (c). Among them, a method of adding an organomagnesium compound (d) to a mixture of a titanium compound (a), an organosilicon compound (b) and an ester compound (c) is preferable from the viewpoint of catalytic activity.

The titanium compound, the organosilicon compound and the ester compound are preferably used by dissolving or diluting in a suitable solvent. Such solvents include hexane,
Heptane, octane, aliphatic hydrocarbons such as decane, toluene, aromatic hydrocarbons such as xylene, cyclohexane,
Alicyclic hydrocarbons such as methylcyclohexane and decalin,
Examples include ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, and tetrahydrofuran.

The temperature of the reduction reaction is usually from -50 to 70 ° C, preferably from -30 to 50 ° C, particularly preferably from -25 to 3 ° C.
The temperature range is 5 ° C. If the reduction reaction temperature is too high, the catalytic activity decreases.

At the time of the reduction reaction, it is also possible to coexist a porous substance such as an inorganic oxide or an organic polymer to impregnate a solid product into the porous substance. Such a porous substance has a pore volume of 0.3 ml / g or more at a pore radius of 20 to 200 nm and an average particle diameter of 5 to 300 μm.
m is preferred.

As the porous inorganic oxide, SiO ₂ , A
l ₂ O ₃ , MgO, TiO ₂ , ZrO ₂ , SiO ₂ · Al ₂ O
₃ composite oxide, MgO-Al ₂ O ₃ composite oxide, MgO
SiO ₂ / Al ₂ O ₃ composite oxide and the like can be mentioned. As the porous polymer, polystyrene, styrene-divinylbenzene copolymer, styrene-n,
n'-alkylene dimethacrylamide copolymer, styrene-ethylene glycol dimethyl methacrylate copolymer, polyacrylate, methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethacryl Methyl acrylate, methyl methacrylate-divinylbenzene copolymer, polyethylene glycol methyl dimethacrylate, polyacrylonitrile,
Acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methyl acrylate copolymer, polystyrene such as polypropylene, polyacrylic Examples thereof include acid ester-based, polyacrylonitrile-based, polyvinyl chloride-based, and polyolefin-based polymers. Of these porous materials, SiO ₂ ,
Al ₂ O ₃ and a styrene-divinylbenzene copolymer are preferably used.

The dropping time is not particularly limited, but is usually about 30 minutes to 12 hours. After the reduction reaction is completed,
The post-reaction may be performed at a temperature of 120 ° C.

The amount of the organosilicon compound (b) used is usually Si / Ti = 10 to 300, preferably 20 in terms of the atomic ratio of silicon atoms to titanium atoms in the titanium compound (a).
To 200, particularly preferably 25 to 150.
The amount of the ester compound (c) to be used is usually an ester compound / Ti = 0.5 to 100, preferably 1 to 60, particularly preferably 2 to 2 in a molar ratio of the ester compound to the titanium atom of the titanium compound (a). -30. Further, the amount of the organomagnesium compound (d) used is usually Ti + Si / Mg = 0.1 to 10, preferably 0.2 to 5.0 in terms of the atomic ratio of the sum of titanium atoms and silicon atoms to the magnesium atoms. Particularly preferably, 0.5 to
2.0.

The solid product obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane and heptane. The reduced solid product thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally shows amorphous or extremely weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable. In the present invention, the titanium content of the solid product obtained by such a reduction reaction is 1.5% by weight or less, more preferably 1.4 to 0.01% by weight, particularly preferably 1.3 to 0.1%. % By weight. If the titanium content exceeds 1.5% by weight, the amount of the cold xylene-soluble portion, which is an amorphous polymer having little industrial value, may increase. At the same time, the polymerization activity may decrease, and the productivity may also deteriorate. Here, the titanium content refers to the amount of titanium atoms contained in the solid product.

In the present invention, the reduced solid product is treated with a mixture of an ether compound, titanium tetrachloride and an organic acid halide compound. By reducing the titanium content of the solid product obtained by the reduction reaction to a specific value and using an organic acid halide compound, the amount of the cold xylene-soluble portion, which is an amorphous polymer of low industrial value, is reduced. I do. At the same time, the polymerization activity and the bulk density of the polymer powder are improved, and the productivity is also improved.

As a method of this treatment, it is preferable to add a mixture of an ether compound and titanium tetrachloride to the reduced solid product, and then add an organic acid halide compound, followed by treatment.

The amount of the ether compound used is usually 1 to 1 with respect to 1 mol of titanium atom contained in the reduced solid product.
000 mol, preferably 5 to 500 mol, particularly preferably 10 to 200 mol. The amount of titanium tetrachloride used is
Usually, 10 to 10000 mol, preferably 30 to 50 mol, per 1 mol of titanium atom contained in the reduced solid product.
00 mol, particularly preferably 100 to 3000 mol. The addition amount of titanium tetrachloride to 1 mol of the ether compound is usually 1 to 100 mol, preferably 1.5 to 100 mol.
It is 75 mol, particularly preferably 2 to 50 mol. The amount of the organic acid halide compound to be used is generally 1 to 500 mol, more preferably 3 to 200 mol, particularly preferably 5 to 100 mol, per 1 mol of titanium atoms in the reduced solid product. The amount of the organic acid halide compound used per mole of magnesium atom in the solid product is usually 0.01%.
To 1.0 mol, preferably 0.03 to 0.5 mol. If the amount of the organic acid halide compound is excessively large, the particles may be disintegrated.

The treatment of the reduced solid product with the ether compound, titanium tetrachloride and the organic acid halide compound can be carried out by any known method such as a slurry method or a mechanical pulverizing means such as a ball mill, which can bring the two into contact with each other. And a slurry method in which the two are brought into contact in the presence of a diluent.

Examples of the diluent include aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; cyclohexane;
Alicyclic hydrocarbons such as cyclopentane, and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used. Among them, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferred.

The amount of the diluent to be used is generally 0.1 ml to 1000 ml, preferably 1 ml to 100 ml, per 1 g of the reduced solid product. The processing temperature is usually -50
To 150 ° C, preferably 0 to 120 ° C, more preferably 60 to 120 ° C, and particularly preferably 100 to 120 ° C. The processing time is usually 30 minutes or more, but preferably 1 to 10 hours. After the normal treatment, the mixture is allowed to stand, separated into a solid and a liquid, and then washed several times with an inert hydrocarbon solvent to obtain an organic acid halide treated solid.

Next, the obtained solid treated with an organic acid halide is treated with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. This treatment is preferably performed in a slurry state. As the solvent used for slurrying, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, toluene, aromatic hydrocarbons such as xylene, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, Dichloroethane, trichloroethylene,
Examples thereof include halogens and hydrocarbons such as monochlorobenzene, dichlorobenzene, and trichlorobenzene, and among them, halogenated hydrocarbons and aromatic hydrocarbons are preferable.

The slurry concentration is usually 0.05 to 0.7 g
Solid / ml solvents, especially 0.1-0.5 g solid / ml solvent are preferred. The processing temperature is usually 30 to 150 ° C, preferably 45 to 135 ° C, and more preferably 60 to 120 ° C.
And particularly preferably 100 to 120 ° C. The reaction time is not particularly limited, but is preferably about 30 minutes to 6 hours.

As a method of supplying the solid treated with an organic acid halide, an ester compound, an ether compound and titanium tetrachloride, a method of adding an ester compound, an ether compound and titanium tetrachloride to a solid treated with an organic acid halide, and conversely, a method of supplying an ester compound and an ether Any method such as a method of adding a solid treated with an organic acid halide to a solution of the compound and titanium tetrachloride may be used. In the method of adding an ester compound, an ether compound and titanium tetrachloride to an organic acid halide-treated solid, a method of adding an ester compound, an ether compound and then adding titanium tetrachloride, and simultaneously adding an ester compound, an ether compound and titanium tetrachloride. A method is preferable, and a method in which a mixture of an ester compound, an ether compound and titanium tetrachloride previously prepared is added to a solid treated with an organic acid halide is particularly preferable.

The treatment of the solid treated with an organic acid halide with an ether compound and titanium tetrachloride or the treatment with a mixture of an ester compound, an ether compound and titanium tetrachloride may be repeated one or more times. This treatment is preferably repeated at least twice from the viewpoint of catalytic activity and stereoregularity.

The amount of the ether compound to be used is generally 0.1 to 100 mol, preferably 0.5 to 50 mol, per 1 mol of titanium atom contained in the solid treated with the organic acid halide.
Particularly preferably, it is 1 to 20 mol. The amount of titanium tetrachloride to be used is generally 1 to 1000 mol, preferably 3 to 500 mol, particularly preferably 10 to 300 mol, per 1 mol of titanium atoms contained in the solid treated with an organic acid halide. The amount of titanium tetrachloride used is generally 1 to 100 mol, preferably 1.5 to 100 mol per mol of the ether compound.
It is 75 mol, particularly preferably 2 to 50 mol.

When the ester compound is used, the amount of the ester compound used is 30 mol or less, preferably 15 mol or less, particularly preferably 5 mol or less, based on 1 mol of the titanium atom contained in the solid treated with the organic acid halide. It is.

The solid catalyst component (A) obtained by the above method
Is usually used for polymerization after solid-liquid separation, washing several times with an inert hydrocarbon solvent such as hexane and heptane. After solid-liquid separation, with a large amount of a halogenated hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent such as toluene,
After washing at least once at a temperature of 50 to 120 ° C. and repeating several times with an aliphatic hydrocarbon solvent such as hexane, it is preferable to use for polymerization in view of catalytic activity and stereoregularity.

(H) Organoaluminum Compound The organoaluminum compound (B) used in the present invention has at least one Al-carbon bond in the molecule. Typical examples are shown below by a general formula. ¹⁴ R ¹⁵ (wherein _{^{R 11 r AlY 3-r R}} 12 R 13 Al-O-AlR, R 11 ~R 15 is 1-20 hydrocarbon group carbon atoms, Y is a halogen atom, a hydrogen atom or Represents an alkoxy group, and r is a number satisfying 2 ≦ r ≦ 3.) Specific examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, diethylaluminum hydride, and diisobutyl. Dialkylaluminum hydride such as aluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, trialkylaluminum and dialkylaluminum halide mixture such as a mixture of triethylaluminum and diethylaluminum chloride, tetraethyl Alumoxane, an alkyl alumoxane such as tetrabutyl di alumoxane can be exemplified.

Of these organoaluminum compounds,
Trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, and an alkylalumoxane are preferable, and particularly, triethylaluminum, triisobutylaluminum, a mixture of a triethylaluminum and diethylaluminum chloride or tetraethyldialumoxane is preferable.

The amount of the organoaluminum compound used is usually from 0.5 to 1000 per mole of titanium atom in the solid catalyst.
It can be selected from a wide range such as moles,
A range of 00 moles is preferred.

(I) Electron Donating Compound The electron donating compound (C) used at the time of polymerization in the present invention.
As oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, ammonia, amines , Nitriles,
Examples include nitrogen-containing electron donors such as isocyanates. Of these electron donors, esters and ethers of inorganic acids are preferably used.

The esters of inorganic acids are preferably represented by the general formula R ¹⁶ _n Si (OR ¹⁷ ) _4-n (where R ¹⁶ is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and R ¹⁷ is a carbon atom It is a hydrocarbon group having 1 to 20 atoms, R ¹⁶ and R ¹⁷ may each have a different substituent in the same molecule, and n is a number satisfying 0 ≦ n <4. )). Specific examples include tetramethoxysilane, tetraethoxysilane,
Tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, isopropyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, Vinyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, butylmethyldimethoxysilane, butylethyl Dimethoxysilane, tert-butylmethyldimethoxysilane, isobutylisopro Rudimethoxysilane, tert-butylisopropyldimethoxysilane, hexylmethyldimethoxysilane, hexylethyldimethoxysilane, dodecylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane , Cyclopentyl-ter
t-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,
Cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-
Butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, vinylmethyldimethoxysilane , Methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, tert-butyltriethoxysilane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, dimethyldi Ethoxysilane,
Diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, butylmethyldiethoxysilane, butylethyldi Ethoxysilane, tert-butylmethyldiethoxysilane, hexylmethyldiethoxysilane, hexylethyldiethoxysilane, dodecylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane Silane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane, ethyltriisopropoxy Orchids, vinyltributoxysilane, phenyltri-tert-butoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, trimethylphenoxysilane, methyltriaryloxysilane, and the like. it can.

Further, as the ethers, dialkyl ethers and general formulas (Wherein, R ^{18 to} R ²¹ each represent a linear or branched alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group,
An aryl group or an aralkyl group, R ¹⁸ or R
¹⁹ may be a hydrogen atom. )). As a specific example,
Diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, ethyl isobutyl ether, 2,2-diisobutyl-1 , 3-Dimethoxypropane, 2-isopropyl-2-isopentyl-1,3
-Dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3 -Dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2, 2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-
Dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane and the like are mentioned. Can be.

Of these electron donating compounds, the compounds represented by the general formula R
²² organosilicon compound represented by R ²³ Si (OR ²⁴⁾ ₂ are particularly preferably used. Here, in the formula, R ²² is a carbon atom having a secondary or tertiary carbon atom adjacent to Si and having 3 carbon atoms.
To 20 hydrocarbon groups, specifically, an isopropyl group, a sec-butyl group, a tert-butyl group, a tert-butyl group.
-A branched alkyl group such as amyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; cycloalkenyl group such as cyclopentenyl group; aryl group such as phenyl group and tolyl group. In the formula, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, and specifically,
Linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and pentyl group; branched chain alkyl groups such as isopropyl group, sec-butyl group, tert-butyl group and tert-amyl group; cyclopentyl group And cycloalkyl groups such as cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, and aryl groups such as phenyl group and tolyl group. In the formula, R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
To 5 hydrocarbon groups.

Specific examples of the organosilicon compound used as such an electron donating compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane,
Di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert -Amylethyldimethoxysilane, ter
t-amyl-n-propyldimethoxysilane, tert
-Amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyl Dimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane,
Cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, Phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, te
rt-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyl Diethoxysilane,
tert-amyl-n-propyldiethoxysilane, t
ert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane,
Cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2
-Norbornanemethyldimethoxysilane.

(J) Olefin Polymerization Method The α-olefin applicable to the present invention is an α-olefin having 3 or more carbon atoms, and preferably has 3 to 3 carbon atoms.
10 α-olefins. Specific examples include linear monoolefins such as propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and decene-1, 3-methylbutene-1, and 3-methylpentene-1. , 4-methylpentene-1, and the like, and vinylcyclohexane. One type of these α-olefins may be used, or two or more types may be used in combination. Among these α-olefins, it is preferable to perform homopolymerization using propylene or butene-1, or to perform copolymerization using a mixed olefin containing propylene or butene-1 as a main component. It is particularly preferable to carry out homopolymerization by use of propylene or to carry out copolymerization using a mixed olefin containing propylene as a main component. In the copolymerization in the present invention, two types selected from ethylene and the above-mentioned α-olefin, or
More types of olefins can be used in admixture. Further, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. Then, heteroblock copolymerization in which polymerization is carried out in two or more stages can be easily performed.

The method for supplying each catalyst component to the polymerization tank is not particularly limited except that it is supplied in an inert gas such as nitrogen or argon without moisture.

The solid catalyst component (A), the organoaluminum compound (B), and the electron donating compound (C) may be supplied individually, or may be supplied by contacting any two of them in advance. .

In the present invention, the olefin can be polymerized in the presence of the above-mentioned catalyst, but the prepolymerization described below may be performed before the polymerization (main polymerization) is performed.

The prepolymerization is carried out by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), and is preferably carried out in a slurry state. Examples of the solvent used for slurrying include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, in forming the slurry, a liquid olefin can be used instead of part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound used in the prepolymerization can be selected from a wide range, usually from 0.5 to 700 mol, per mol of titanium atom in the solid catalyst component. Preferably, 1 to 200 mol is particularly preferred.

The amount of the olefin to be prepolymerized is
Usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 1000 g per 1 g of the solid catalyst component.
200 g.

The concentration of the slurry during the prepolymerization is from 1 to
500 g-solid catalyst component / liter-solvent is preferred,
Particularly, 3 to 300 g-solid catalyst component / liter-solvent is preferable. The prepolymerization temperature is preferably from -20 to 100C, particularly preferably from 0 to 80C. The partial pressure of the olefin in the gas phase during the prepolymerization is 0.01 to 20 kg / c.
m ² is preferred, and particularly preferably 0.1 to 10 kg / cm ^2, but not limited to olefins which are liquid at the pressure and temperature of the prepolymerization. Further, the prepolymerization time is not particularly limited, but is usually preferably from 2 minutes to 15 hours.

In carrying out the prepolymerization, the solid catalyst component (A), the organoaluminum compound (B) and the olefin are supplied by bringing the solid catalyst component (A) into contact with the organoaluminum compound (B). Any of the following methods may be used: a method of supplying an olefin after the contact, and a method of supplying the organoaluminum compound (B) after the solid catalyst component (A) is brought into contact with the olefin. As a method for supplying the olefin, either a method of sequentially supplying the olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of initially supplying a predetermined amount of the olefin at all is used. good. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the obtained polymer.

Further, when the solid catalyst component (A) is preliminarily polymerized with a small amount of olefin in the presence of the organoaluminum compound (B), if necessary, the electron donating compound (C)
May coexist. The electron donating compound used is
Part or all of the above electron donating compound (C). The amount used is generally 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.1 to 400 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A).
The amount is usually from 0.003 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 2 mol, based on the organoaluminum compound (B).

The method of supplying the electron donating compound (C) at the time of the prepolymerization is not particularly limited, and may be supplied separately from the organoaluminum compound (B) or may be supplied in contact with the organic aluminum compound (B) in advance. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

After the pre-polymerization as described above or without the pre-polymerization, the α-polymer comprising the solid catalyst component (A), the organoaluminum compound (B) and the electron donating compound (C) is used. The main polymerization of α-olefin can be carried out in the presence of an olefin polymerization catalyst.

The amount of the organoaluminum compound used in the main polymerization can be selected from a wide range, usually from 1 to 1000 mol, per mol of titanium atom in the solid catalyst component (A). A range is preferred.

The electron-donating compound (C) used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 2000 mol, per 1 mol of titanium atom contained in the solid catalyst component (A). To 1000 mol, particularly preferably 0.5 to
The amount is 800 mol, usually 0.001 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to 1 mol, based on the organic aluminum compound.

The main polymerization can be carried out usually at -30 to 300 ° C., preferably at 20 to 180 ° C. The polymerization pressure is not particularly limited, but is generally from normal pressure to 100 kg in that it is industrial and economical.
/ Cm ² , preferably about ² to 50 kg / cm ² . As a polymerization system, any of a batch system and a continuous system can be used. In addition, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, bulk polymerization using a liquid olefin as a medium at the polymerization temperature, or gas phase polymerization is also possible.

At the time of the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

[0074]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not particularly limited by the following Examples. In the examples, methods for evaluating various physical properties of the polymer are as follows.

(1) Xylene soluble part at 20 ° C. (hereinafter CXS)
1 g of polymerized powder was dissolved in 200 ml of boiling xylene, cooled slowly to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and left at 20 ° C. for 3 hours. Is filtered off. Xylene is evaporated from the filtrate, dried at 60 ° C. under reduced pressure, and a polymer soluble in xylene at 20 ° C. is recovered and weighed, and the weight% of the total polymer is determined. The smaller the value of CXS, the smaller the amount of the amorphous polymer and the higher the stereoregularity.

(2) Intrinsic viscosity (hereinafter abbreviated as [η]): a tetralin solvent at 135 ° C. using an Ubbelohde viscometer.
Was measured.

Example 1 (a) Synthesis of reduced solid product After replacing a 500 ml flask equipped with a stirrer and a dropping funnel with nitrogen, 270 ml of hexane and 3.0 ml of tetrabutoxytitanium (3.0 g, 8.8) Mmol), 2.5 ml of diisobutyl phthalate (2.6 g, 9.3 mmol) and 70.7 ml of tetraethoxysilane (66.
0 g, 317 mmol) to give a homogeneous solution. Next, 170 m of a di-n-butyl ether solution of n-butylmagnesium chloride (manufactured by Organic Synthetic Chemicals, n-butylmagnesium chloride concentration 2.1 mmol / ml)
1 was gradually dropped from the dropping funnel over 4 hours while maintaining the temperature in the flask at 5 ° C. After dropping, 5 ° C
And further stirred at room temperature for 1 hour. Thereafter, solid-liquid separation was performed, and washing was repeated three times with 185 ml of toluene, followed by washing with hexane and drying to obtain a solid product. When the composition of the solid product was analyzed, the solid product contained 0.72% by weight of titanium atoms, no phthalate ester was detected, 35.5% by weight of ethoxy groups and 1.9% by weight of butoxy groups. It was contained.

(B) Synthesis of solid catalyst component After a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen, 5.61 g of the solid product obtained in the above (a) was charged. 14.0 ml of toluene was added, and 0.56 ml (4.52 mmol) of butyl ether was added.
And a mixture of 11.2 ml (0.102 mol) of titanium tetrachloride, and then 1.12 ml of phthalic chloride.
(7.78 mmol: 0.20 ml / 1 g solid product)
Was added, and the mixture was heated to 115 ° C. and stirred for 3 hours.
After completion, solid-liquid separation is performed at the same temperature, and toluene 2
Washing was performed twice with 8 ml. Then, toluene 7.0m
1, 0.31 ml (1.16 mmol) of diisobutyl phthalate, 0.56 ml (4.52 mmol) of butyl ether, and 5.6 ml (0.051 mol) of titanium tetrachloride
And the mixture was treated at 115 ° C. for 1 hour. After the treatment, solid-liquid separation is performed at the same temperature, and toluene 2
Washing was performed twice with 8 ml. Then, toluene 7.0m
l, butyl ether 0.56 ml (4.52 mmol)
And 5.6 ml (0.051 mol) of titanium tetrachloride, and the mixture was treated at 115 ° C. for 1 hour. After completion of the treatment, solid-liquid separation was performed at the same temperature, and the solid was washed three times with 28 ml of toluene at the same temperature, washed three times with 28 ml of hexane, and dried under reduced pressure to obtain 5.02 g of a solid catalyst component. The solid catalyst component contained 1.84% by weight of a titanium atom, 9.79% by weight of a phthalate, 0.08% by weight of an ethoxy group, and 0.11% by weight of a butoxy group. Further, when the solid catalyst component was observed with a stereoscopic microscope, it was found that the solid catalyst component had good particle properties without fine powder.

(C) Polymerization of Propylene A 3-liter stirred autoclave made of stainless steel was replaced with argon, 2.6 mmol of triethylaluminum, 0.26 mmol of cyclohexylethyldimethoxysilane, and 5.5 mg of a solid catalyst component synthesized with (b). And hydrogen corresponding to a partial pressure of 0.33 kg / cm ² was added. Next, 780 g of liquefied propylene was charged, the temperature of the autoclave was raised to 80 ° C., and polymerization was carried out at 80 ° C. for 1 hour. After completion of the polymerization, unreacted monomers were purged. The resulting polymer was dried under reduced pressure at 60 ° C. for 2 hours,
7 g of polypropylene powder were obtained. Therefore, the yield of polypropylene per gram of solid catalyst component (hereinafter referred to as PP
/ Cat) is PP / Cat = 61,300 (g
/ G). The ratio of the component soluble in xylene at 20 ° C. in the total polymer yield was CXS = 0.38 (wt.
%), The intrinsic viscosity of the polymer is [η] = 2.05, bulk density =
It was 0.372 g / ml. Table 1 shows the polymerization conditions and the polymerization results.
Shown in

Comparative Example 1 (a) Synthesis of Reduced Solid Product The amount of the reagent used was 7.5 ml of tetrabutoxytitanium.
(7.5 g, 22 mmol), 2.5 ml (2.6 g, 9.3 mmol) of diisobutyl phthalate and 74.8 ml (70.3 g, 338 mmol) of tetraethoxysilane, n-butylmagnesium chloride solution 173
The reaction was carried out in the same manner as in Example 1 (a), except that the amount was changed to ml. The solid product obtained by solid-liquid separation is hexane 3
Washing was repeated three times with 00 ml and three times with 300 ml of toluene, and then 270 ml of toluene was added. A part of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.80% by weight of titanium atoms, 0.1% by weight of phthalic acid esters, and 35.0% by weight of ethoxy groups. , Butoxy groups in an amount of 3.2% by weight.

(B) Synthesis of ester-treated solid After a 200 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with argon, 84 ml of the slurry containing the solid product obtained in the above (a) was charged, and Further, 12.1 ml of the supernatant was extracted, 7.8 ml (29 mmol) of diisobutyl phthalate was added, and the mixture was stirred at 95 ° C. for 30 minutes. After the reaction, solid-liquid separation was performed, and washing was performed twice with 59 ml of toluene.

(C) Synthesis of solid catalyst component In a flask, 15.3 ml of toluene, 0.66 ml (2.5 mmol) of diisobutyl phthalate, 1.2 ml (6.9 mmol) of butyl ether, and titanium tetrachloride 2
3.4 ml (0.213 mol) of the mixture are added and 105
The treatment was performed at 3 ° C. for 3 hours. After the completion of the treatment, solid-liquid separation was performed at the same temperature, and then washing was performed twice at the same temperature with 59 ml of toluene. Then, 12.0 ml of toluene, 1.2 ml (6.9 mmol) of butyl ether and titanium tetrachloride 1
1.7 ml (0.106 mol) of the mixture are added and 105
The treatment was performed at ℃ for 1 hour. After the treatment, solid-liquid separation was performed at the same temperature. After washing three times with 59 ml of toluene at the same temperature, washing three times with 59 ml of hexane and drying under reduced pressure, 8.1 g of a solid catalyst component was obtained. The solid catalyst component contained 1.5% by weight of a titanium atom, 8.9% by weight of a phthalate, 0.4% by weight of an ethoxy group, and 0.1% by weight of a butoxy group.

(D) Polymerization of Propylene The polymerization of propylene was carried out in the same manner as in the polymerization of propylene in Example 1 (c) except that 4.0 mg of the solid catalyst component obtained in the above (c) was used. The polymerization result is PP
/ Cat = 30,000 (g / g) and low polymerization activity,
CXS = 0.74 (wt%), indicating low stereoregularity.
The bulk density was 0.360 g / ml and [η] was 2.01. Table 1 shows the polymerization conditions and the polymerization results.

Comparative Example 2 (a) Synthesis of Solid Product The amounts of the reagents used were 267 ml of hexane, 3.0 ml (3.0 g, 8.8 mmol) of tetrabutoxytitanium, 2.5 ml of diisobutyl phthalate (2.6 g). , 9.3 mmol) and 71.6 ml of tetraethoxysilane (6
(6.9 g, 321 mmol), and a solid product was synthesized in the same manner as in Example 1 (a) except that a solution of n-butylmagnesium chloride in 170 ml of di-n-butyl ether was used. A part of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 0.74% by weight of titanium atoms and 0.09% by weight of phthalate.
It contained 9% by weight, 33.9% by weight of an ethoxy group, and 1.67% by weight of a butoxy group.

(B) Synthesis of Ester-Treated Solid An ester-treated solid was synthesized under the same conditions as in (b) of Comparative Example 1.

(C) Synthesis of solid catalyst component A solid catalyst component was synthesized in the same manner as in (c) of Comparative Example 1. The solid catalyst component contained 1.40% by weight of a titanium atom, 9.13% by weight of a phthalate, 0.59% by weight of an ethoxy group, and 0.15% by weight of a butoxy group. Further, when the solid catalyst component was observed with a stereoscopic microscope, it was found that the solid catalyst component had good particle properties without fine powder.

(D) Polymerization of Propylene The polymerization of propylene was carried out in the same manner as in the polymerization of propylene in Example 1 (c) except that the solid catalyst component obtained in the above (c) was used. The polymerization result is PP / Cat =
43,800 (g / g), CXS = 0.58 (wt
%), [Η] = 1.70 (dl / g), bulk density = 0.3
75 (g / ml). Table 1 shows the polymerization conditions and the polymerization results.

[0088]

[Table 1] cHEDMS: cyclohexylethyldimethoxysilane

[0089]

According to the present invention, an α-olefin polymerization catalyst having sufficiently high catalytic activity and stereoregular polymerization ability so that the removal of the catalyst residue and the amorphous polymer is unnecessary, and a high-quality high steric polymer A method for producing a regular α-olefin polymer is provided.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (2)

[Claims] (1) In the presence of (A) an organosilicon compound and / or an ester compound having a Si—O bond, a compound of the general formula T
i (OR ¹ ) _a X _4-a (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is a number satisfying 0 <a ≦ 4). A titanium product obtained by reducing a titanium compound with an organomagnesium compound has a titanium content of 1.5% by weight or less, and after treating the solid product with an ether compound, titanium tetrachloride and an organic acid halide compound, A titanium compound-containing solid catalyst component obtained by treating the treated solid with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound, (B) an organoaluminum compound, and (C) An α-olefin polymerization catalyst comprising an electron-donating compound. 2. An α-olefin characterized by homopolymerizing an α-olefin or copolymerizing an α-olefin with ethylene or another α-olefin using the α-olefin polymerization catalyst according to claim 1. A method for producing a polymer.