JP2950168B2 - α-olefin polymerization catalyst and method for producing α-olefin polymer - Google Patents

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 a very high catalytic activity per solid catalyst and per titanium atom, the amount of catalyst residue and amorphous polymer is extremely small, and a highly stereoregular α-olefin having excellent mechanical properties and processability. The present invention relates to a polymerization catalyst and a method for producing a highly stereoregular α-olefin polymer.

[0002]

2. Description of the Related Art As a method for producing an .alpha.-olefin polymer such as propylene and butene-1, there are known methods IV to VI of the periodic table.
It is well known to use so-called Ziegler-Natta catalysts consisting of Group III transition metal compounds and Group I-III organometallic compounds.

[0003] In producing an α-olefin polymer,
An amorphous polymer is produced as a by-product 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, resulting in an extremely disadvantageous industrial view. Therefore,
The catalyst for producing the .alpha.-olefin polymer must have no or very little such amorphous formation. Further, a catalyst residue composed of a transition metal compound and an organometallic compound remains in the obtained α-olefin polymer. Since this catalyst residue causes problems in various points such as the stability and processability of the α-olefin polymer, equipment for removing and stabilizing the catalyst residue is required.

[0004] This disadvantage is attributed to the formation α per unit weight of the catalyst.
-It can be improved by increasing the catalytic activity expressed by the weight of the olefin polymer, the equipment for removing the catalyst residue is not required, and the production cost of the α-olefin polymer can be reduced.

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] In each case, although there is a certain level of realization of a non-extraction and decalcification-free process, 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 high rigidity of the polymer is desired, such as in the molding field, a highly stereoregular polymer directly produces high rigidity quality, and therefore has high stereoregular polymerization ability. However, the appearance of a catalyst having a good particle size distribution is urgently desired.

[0007]

Under such circumstances,
The problem to be solved by the present invention, that is, an object of the present invention is to provide an α-olefin polymerization having a good particle size distribution and having sufficiently high catalytic activity and stereoregularity so that removal of catalyst residues and amorphous polymer is not required. It is an object of the present invention to provide a catalyst for use as well as a method for producing a high-quality, high stereoregularity α-olefin polymer.

[0008]

According to the present invention, there is provided a compound of the general formula Ti (OR ¹ ) _a X _{4-a in} the presence of (A) an organosilicon compound having an Si—O bond and an ester compound.
(R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a represents a number satisfying 0 <a ≦ 4.) A solid obtained by reducing a titanium compound with an organomagnesium compound The product is treated with an ester compound and then treated with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound to obtain a trivalent titanium compound-containing solid catalyst component (B ) Organoaluminum compound (C) An α-olefin polymerization catalyst comprising an electron donating compound, and a method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using the catalyst. Things.

The use of the present catalyst achieves the above-mentioned object, in particular, high stereoregular polymerization of α-olefin.

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 carbon having 1 to 20 carbon atoms). A hydrogen group, X is a halogen atom, a is 0
≦ a ≦ 4). Specific examples of R ¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl,
Examples thereof include alkyl groups such as hexyl, heptyl, octyl, decyl, and dodecyl; cycloalkyl groups such as phenyl, cresyl, xyler, and naphthyl; allyl groups such as propenyl; and aralkyl groups such as benzyl. Among them, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. 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 chlorine, bromine and iodine. Among them, chlorine gives particularly favorable results.

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

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 and TiX ₄ at a predetermined ratio, or a method of reacting TiX ₄ and a corresponding alcohol in a predetermined amount can be used. Also,
These titanium compounds may be used after being diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Specifically, titanium tetrahalide compounds such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide;
Trihalogenated alkoxytitanium compounds such as methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium Dichloride, dihalogenated dialkoxytitanium compounds such as diethoxytitanium dibromide, monomethoxytrialkoxytitanium compounds such as trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, Tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetraphenoxytita Tetraalkoxy titanium compounds such can be mentioned.

(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, those represented by the following general formula are used. it can. _{^{Si (OR 2) m R 3}} 4-m R 4 (R 5 2 SiO) p SiR 6 3 or, here _{^{(R 7 2 SiO) q,}} R 2 is a hydrocarbon group having a carbon number of 1 to 20, R ³ ,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, m is a number satisfying 0 <m ≦ 4, p is an integer of 1 to 1000, q is 2 to 100
It is an integer of 0.

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.

Preferred among these organosilicon compounds
Are of the general formula Si (OR^Two )_mR ^Three _4-mAl represented by
Coxysilane compound, preferably 1 ≦ m ≦ 4
In particular, a tetraalkoxysilane compound having m = 4 is preferred.
New

(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, olefin carboxylic esters and alicyclic carboxylic esters. Acid esters and aromatic carboxylic 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, di-isopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-octyl phthalate, diphenyl phthalate, and the like.

Of these ester compounds, olefin carboxylic esters such as methacrylic esters and maleic esters and phthalic esters are preferred, and diesters of phthalic acid are particularly preferred.

(D) Organomagnesium compound Next, the organomagnesium used in the present invention is Mg-
Any type of organomagnesium compound containing a carbon bond can be used. In particular, a Grignard compound represented by the general formula R ⁸ MgX (wherein R ⁸ represents a hydrocarbon group having 1 to 20 carbon atoms and X represents a halogen), and a general formula R ⁹ R ¹⁰ Mg (wherein R ⁹ and R ¹⁰ have 1 to 2 carbon atoms
Represents a hydrocarbon group of 0. The dialkylmagnesium compound or the diarylmagnesium compound represented by the formula (1) is preferably used. Here, R ⁸ , R ⁹ and R ¹⁰ may be the same or different and include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, isoamyl, hexyl, octyl, 2-ethylhexyl, phenyl, benzyl and the like. Examples thereof include an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and an alkenyl group.

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 the 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, and tetrahydropyran can be 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 may be used.

The organic magnesium compound is preferably used in the form of an ether solution. In this case, the ether compound includes an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure. 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.

Further, 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 and diisoamyl ether are particularly preferably used.

(F) Synthesis of solid catalyst The solid catalyst of the present invention is obtained by treating a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound, with an ester compound, And 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 performed under an atmosphere of an inert gas such as nitrogen or argon.

The method of reducing the titanium compound with the organomagnesium compound may be a method of adding the organomagnesium compound to a mixture of the titanium compound, the organosilicon compound and the ester compound, or conversely, adding the titanium compound to a solution of the organomagnesium compound. Any method of adding a mixture of an organosilicon compound and an ester compound may be used. Among them, a method of adding an organomagnesium compound to a mixture of a titanium compound, an organosilicon compound and an ester compound is preferred from the viewpoint of catalytic activity.

The titanium compound, the organosilicon compound and the ester compound are preferably dissolved or diluted in an appropriate solvent before use. 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 reduction reaction temperature is -50 to 70 ° C, preferably -30 to 50 ° C, particularly preferably -25 to 35 ° C.
Temperature range. If the reduction reaction temperature is too high, the catalytic activity decreases.

When a solid product is synthesized by a reduction reaction, a porous material such as an inorganic oxide or an organic polymer may coexist, and the solid product may be impregnated into the porous material. As such a porous substance, a pore radius of 20 to 2 is used.
It is preferable that the pore volume at 00 nm is 0.3 ml / g or more.

As the porous inorganic oxide, SiO ₂ , A
l ₂ O ₃ , MgO, TiO ₂ , ZrO ₂ , SiO ₂ · A
l ₂ O ₃ composite oxide, MgO · Al ₂ O ₃ composite oxide,
_{MgO · SiO 2 · Al 2 O} 3 composite oxide and the like. Examples of the porous polymer include polystyrene, styrene-divinylbenzene copolymer, styrene-n, n'-alkylene dimethacrylamide copolymer,
Styrene-ethylene glycol dimethyl methacrylate copolymer, polyethyl acrylate, methyl acrylate-divinyl benzene copolymer, ethyl acrylate-divinyl benzene copolymer, polymethyl methacrylate, methyl methacrylate-divinyl benzene copolymer Coalescence, polyethylene glycol methyl methacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methyl acrylate copolymer And polystyrene-based, polyacrylate-based, polyacrylonitrile-based, polyvinyl chloride-based, and polyolefin-based polymers represented by polypropylene and the like. Among 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 used is represented by the atomic ratio of silicon atoms to titanium atoms in the titanium compound,
Ti = 1 to 50, preferably 3 to 30, particularly preferably 5 to 25. The amount of the ester compound used is the molar ratio of the ester compound to the titanium atom of the titanium compound, and the ester compound / Ti = 0.05 to 10,
It is preferably in the range of 0.1 to 6, particularly preferably 0.2 to 3. Further, the amount of the organic magnesium compound used is Ti + Si / Mg = 0.1 to 10, preferably 0.2 to 5.0, particularly preferably 0.2 to 5.0 in terms of the atomic ratio of the sum of titanium atoms and silicon atoms to the magnesium atom. 0.5-2.0
Range.

The solid product obtained by the reduction reaction is subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane and heptane. The solid product thus obtained contains trivalent titanium, magnesium and hydrocarbyloxy groups and generally exhibits amorphous or very weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.

Next, the solid product obtained by the above method is
The treatment is performed with an ester compound. The amount of the ester compound used is 0.1 to 0.1 mol per mol of titanium atom in the solid product.
It is 50 mol, more preferably 0.3 to 20 mol, particularly preferably 0.5 to 10 mol. The amount of the ester compound used per mole of magnesium atom in the solid product is 0.01 to 1.0 mole, preferably 0.03 to 1.0 mole.
0.5 mole. If the amount of the ester compound is excessively large, the particles will be disintegrated.

The treatment of the solid product with the ester compound can be carried out by any known method capable of bringing both into contact, such as a slurry method or a mechanical grinding means such as a ball mill. In addition, a large amount of fine powder is generated and the particle size distribution is widened, which is not preferable from an industrial point of view.

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 used is 0.1 ml to 1000 ml per gram of the solid product, preferably 1 ml to 1000 ml.
100 ml. The treatment temperature is -50 to 150C, preferably 0 to 120C. The processing time is 5 minutes or more, preferably 15 minutes to 3 hours. After the treatment, the mixture is allowed to stand, separated into solid and liquid, and washed with an inert hydrocarbon solvent several times to obtain an ester-treated solid.

Next, the ester-treated solid is treated with a mixture of an ether compound and titanium tetrachloride. This treatment is preferably performed in a slurry state. Solvents used for slurrying include pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, toluene,
Aromatic hydrocarbons such as xylene, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, dichloroethane, trichloroethylene, monochlorobenzene,
Halogen such as dichlorobenzene and trichlorobenzene and hydrocarbons are mentioned, and among them, halogenated hydrocarbons and aromatic hydrocarbons are preferable.

The slurry concentration is preferably from 0.05 to 0.7 g solid / ml solvent, particularly preferably from 0.1 to 0.5 g solid / ml solvent. The reaction temperature is 30-150 ° C., preferably 45
To 135 ° C, particularly preferably 60 to 120 ° C. The reaction time is not particularly limited, but is preferably about 30 minutes to 6 hours.

As a method for supplying the ester-treated solid, the ether compound and titanium tetrachloride, a method of adding the ether compound and titanium tetrachloride to the ester-treated solid, and conversely, the method of supplying the ester-treated solid in a solution of the ether compound and titanium tetrachloride. Any of the adding methods may be used. In the method of adding an ether compound and titanium tetrachloride to an ester-treated solid, a method of adding an ether compound and then adding titanium tetrachloride, or a method of simultaneously adding an ether compound and titanium tetrachloride is preferable. A method of adding a mixture of an ether compound prepared in advance and titanium tetrachloride is preferred.

The reaction of the ester-treated solid with the ether compound and titanium tetrachloride may be repeated twice or more. From the viewpoint of catalytic activity and stereoregularity, it is preferable to repeat the reaction with the mixture of the ether compound and titanium tetrachloride at least twice or more.

The amount of the ether compound used is 0.1 to 100 with respect to 1 mol of titanium atom contained in the solid product.
Mol, preferably 0.5 to 50 mol, particularly preferably 1
２０20 mol. The addition amount of titanium tetrachloride is 1 to 100 with respect to 1 mol of titanium atoms contained in the solid product.
0 mol, preferably 3 to 500 mol, particularly preferably 1 mol
0 to 300 mol. The amount of titanium tetrachloride added is 1 to 100 moles, preferably 1.5 to 75 moles, and particularly preferably 2 to 50 moles per mole of the ether compound.

When treating the ester-treated solid with a mixture of the ether compound and titanium tetrachloride, the ester compound may be allowed to coexist. The amount of the ester compound used at that time is 30 mol or less, preferably 15 mol or less, particularly preferably 5 mol or less, based on 1 mol of titanium atoms contained in the solid product.

The solid catalyst containing a trivalent titanium compound obtained by the above method is subjected to solid-liquid separation, washed several times with an inert hydrocarbon solvent such as hexane or heptane, and then used for polymerization. After solid-liquid separation, wash with a large amount of a halogenated hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent such as toluene at a temperature of 50 to 120 ° C. at least once, and further wash with an aliphatic hydrocarbon solvent such as hexane. After repeated washing, it is preferable to use for polymerization in view of catalytic activity and stereoregularity.

(G) Organoaluminum Compound The organoaluminum compound used in the present invention has at least one Al-carbon bond in the molecule.
Typical examples are shown below by a general formula. _{^{R 11 γAlY 3- γ R 12 R}} 13 Al-O-AlR 14 R 15 (R 11 ~R 15 has 1-20 hydrocarbon group having carbon atoms, Y represents halogen, hydrogen or an alkoxy group, gamma is 2 ≦ γ
Specific examples of the organoaluminum compound include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and diethylaluminum. Examples thereof include a dialkylaluminum halide such as chloride, a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of triethylaluminum and diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

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

The amount of the organoaluminum compound used can be selected from a wide range such as 0.5 to 1000 mol per mol of titanium atom in the solid catalyst.
A molar range is preferred.

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

The esters of inorganic acids are preferably
General formula R¹⁶ _nSi (OR¹⁷)_4-n(R ¹⁶Has 1 to 20 carbon atoms
A hydrocarbon group or a hydrogen atom, R¹⁷Has 1 to 20 carbon atoms
A hydrocarbon group;¹⁶, R¹⁷Are in the same molecule
May have a different substituent, and n is 0 ≦ n <4
Which is a silicon compound represented by
it can. Specific examples include tetramethoxysilane, tet
Laethoxysilane, tetrabutoxysilane, tetrafe
Nonoxysilane, methyltrimethoxysilane, ethyltri
Methoxy silane, butyl trimethoxy silane, isobutyl
Rutrimethoxysilane, tbutyltrimethoxysilane,
Isopropyltrimethoxysilane, cyclohexyltri
Methoxysilane, phenyltrimethoxysilane, vinyl
Trimethoxysilane, dimethyldimethoxysilane, die
Tildimethoxysilane, dipropyldimethoxysilane,
Propylmethyldimethoxysilane, diisopropyldimene
Toxic silane, dibutyl dimethoxy silane, diisobuty
Rudimethoxysilane, di-t-butyldimethoxysila
Butylmethyldimethoxysilane, butylethyldimethyl
Toxisilane, t-butylmethyldimethoxysilane, t-
Butylethyldimethoxysilane, t-butyl-n-pro
Pildimethoxysilane, isobutyl isopropyl dimethoate
Xysilane, t-butylisopropyldimethoxysila
T-butyl-n-butyldimethoxysilane, t-butyl
Tyl-iso-butyldimethoxysilane, t-butyl-
sec-butyldimethoxysilane, hexylmethyldim
Toxysilane, hexylethyldimethoxysilane, dode
Silmethyl dimethoxysilane, dicyclopentyl dimethoate
Xysilane, cyclopentylmethyldimethoxysilane,
Cyclopentylethyldimethoxysilane, cyclopenty
Leisopropyldimethoxysilane, cyclopentyliso
Butyldimethoxysilane, cyclopentyl-t-butyl
Dimethoxysilane, dicyclohexyldimethoxysila
, Cyclohexylmethyldimethoxysilane, cyclohexane
Xylethyldimethoxysilane, cyclohexyl isop
Ropyldimethoxysilane, cyclohexylisobutyldi
Methoxysilane, cyclohexyl-t-butyldimethoxy
Sisilane, cyclohexylcyclopentyldimethoxysi
Orchid, cyclohexylphenyldimethoxysilane, diph
Phenyldimethoxysilane, phenylmethyldimethoxysilane
Orchid, phenylisopropyldimethoxysilane, phenyl
Lysobutyldimethoxysilane, phenyl-t-butyl
Dimethoxysilane, phenylcyclopentyldimethoxy
Silane, vinylmethyldimethoxysilane, methyltrier
Toxic silane, ethyl triethoxy silane, butyl tri
Ethoxysilane, isobutyltriethoxysilane, t-
Butyltriethoxysilane, isopropyltriethoxy
Silane, cyclohexyltriethoxysilane, phenyl
Triethoxysilane, vinyltriethoxysilane,
Tildiethoxysilane, diethyldiethoxysilane, di
Propyldiethoxysilane, propylmethyldiethoxy
Silane, diisopropyldiethoxysilane, dibutyldi
Ethoxysilane, diisobutyldiethoxysilane, di-
t-butyldiethoxysilane, butylmethyldiethoxy
Silane, butylethyldiethoxysilane, t-butylmeth
Tyldiethoxysilane, hexylmethyldiethoxysila
, Hexylethyldiethoxysilane, dodecylmethyl
Diethoxysilane, dicyclopentyldiethoxysila
, Dicyclohexyldiethoxysilane, cyclohexyl
Methyldiethoxysilane, cyclohexylethyldie
Toxysilane, diphenyldiethoxysilane, phenyl
Methyldiethoxysilane, vinylmethyldiethoxysila
, Ethyl triisopropoxy silane, vinyl tributane
Xysilane, phenyltri-t-butoxysilane, 2-
Norbornane trimethoxysilane, 2-norbornant
Liethoxysilane, 2-norbornanemethyldimethoxy
Silane, trimethylphenoxysilane, methyltriaryl
Roxysilane and the like can be mentioned.

Further, as the ethers, preferred are dialkyl ethers and general formulas (R ^{18 to} R ²¹ are a linear or branched alkyl, alicyclic, aryl, alkylaryl, arylalkyl group having 1 to 20 carbon atoms, and R ¹⁸ or R ¹⁹ may be hydrogen) And a diether compound represented by the following formula: Specific examples include 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 can be mentioned.

Of these electron donating compounds, a compound 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 hydrocarbon group having 3 to 20 carbon atoms in which the carbon adjacent to Si is secondary or tertiary, and specifically, an isopropyl group, se
a branched alkyl group such as a c-butyl group, a t-butyl group, a t-amyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group such as a cyclopentenyl group, a phenyl group, a tolyl group; And an aryl group. In the formula, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, a sec group. -Butyl group, t-butyl group, t-amyl group, etc., branched alkyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group,
Examples thereof include a cycloalkenyl group such as a cyclopentenyl group and an aryl group such as a phenyl group and a tolyl group. Further, in the formula, R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of the organosilicon compound used as such an electron donating compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane,
Di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane,
t-butyl-n-propyldimethoxysilane, isobutylisopropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyl-n-butyldimethoxysila, t-butyl-iso-butyldimethoxysilane, t-butyl-sec-butyldimethoxysilane Silane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl -T-butyldimethoxysilane, cyclohexyl Black pentyl dimethoxy silane,
Cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane,
Phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-t-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldiethoxysilane, t
-Butylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane,
Examples thereof include cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

(I) Olefin polymerization method The α-olefin applicable to the present invention is an α-olefin having 3 or more carbon atoms. Specific examples of the α-olefin that can be used include propylene, butene-1, and pentene-1. ,
Hexene-1, heptene-1, octene-1, decene-
Linear monoolefins such as 1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-
And branched monoolefins such as 1, 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,
Preferably, homopolymerization is performed using propylene or butene-1, or copolymerization is performed using a mixed olefin containing propylene or butene-1 as a main component. It is particularly preferable to carry out the copolymerization using a mixed olefin containing as a main component. Further, at the time of copolymerization in the present invention, two or more olefins selected from ethylene and the above-mentioned α-olefin can be mixed and used. 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. However, 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 is determined per mole of titanium atom in the solid catalyst component.
Although it can be selected from a wide range such as 0.5 to 700 mol, 0.8 to 500 mol is preferable, and 1 to 200 mol is particularly preferable.

The amount of the olefin to be prepolymerized is
0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 20 g per gram of the solid catalyst component.
0 g.

The concentration of the slurry used in the prepolymerization is 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 be used.
May coexist. The electron donating compound used is
Part or all of the above electron donating compound (C). The used amount is 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 1 mol of titanium atom contained in the solid catalyst component (A).
To 100 mol, and 0.003 to 5 mol, preferably 0.005 to 3 mol, based on the organoaluminum compound (B).
Mol, particularly preferably 0.01 to 2 mol.

The method of supplying the electron donating compound (C) at the time of the prepolymerization is not particularly limited, and it may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with the organic aluminum compound 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 prepolymerization as described above or without the prepolymerization, the α-constituting agent 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, such as 1 to 1000 mol, per mol of titanium atom in the solid catalyst component (A). Is preferred.

The electron-donating compound (C) used in the main polymerization is used in an amount of 0.1 to 2000 mol, preferably 0.3 to 2000 mol, per 1 mol of titanium atom contained in the solid catalyst component (A). 1000 mol, particularly preferably 0.5 to 80
0 mol, and 0.0 mol
The amount is from 0.01 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 1 mol.

The main polymerization can be carried out at a temperature of -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 /
A pressure of about ² cm ² , preferably about ² to 50 kg / cm ² is employed. 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.

[0071]

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)
After dissolving 1 g of the polymerized powder in 200 ml of boiling xylene, the solution was gradually cooled to 50 ° C., then cooled to 20 ° C. while being immersed in ice water and stirred, and allowed to stand at 20 ° C. for 3 hours. Is filtered off. Xylene is evaporated from the filtrate and dried under reduced pressure at 60 ° C. to recover a polymer soluble in xylene at 20 ° C.

(2) Intrinsic viscosity (hereinafter abbreviated as [η]): Measured at 135 ° C. in a tetralin solvent.

Example 1 (a) Synthesis of an organomagnesium compound 10 equipped with a stirrer, reflux condenser, dropping funnel and thermometer
After the 00 ml flask was replaced with argon, 32.0 g of milled magnesium for Grignard was charged. 120 g of butyl chloride and dibutyl ether 5 were added to the dropping funnel.
Of the magnesium in the flask.
The reaction was started by dropping ml. After the start of the reaction, the dropwise addition was continued at 50 ° C. for 4 hours.
The reaction was continued for hours. Thereafter, the reaction solution is cooled to room temperature,
The solid was filtered off. The butylmagnesium chloride in the sampled reaction solution is hydrolyzed with 1 N sulfuric acid,
When the concentration was determined by back titration with a normal aqueous sodium hydroxide solution (phenolphthalein was used as an indicator), the concentration was 2.1 mol / l.

(B) Synthesis of solid product After a 500 ml flask equipped with a stirrer and a dropping funnel was replaced with argon, 290 ml of hexane, 9.3 ml (9.3 g, 27 mmol) of tetrabutoxytitanium, and diisobutyl phthalate 8 were added. 0.5 ml (8.8 g, 32 mmol) and 79.1 ml tetraethoxysilane (74.
(4 g, 357 mmol) to give a homogeneous solution. Next, the organic magnesium compound solution 18 synthesized in (a)
9 ml was gradually dropped from the dropping funnel over 2 hours while maintaining the temperature in the flask at 5 ° C. After dropping,
After further stirring at room temperature for 1 hour, solid-liquid separation was performed at room temperature. Washing was repeated three times with 300 ml of hexane and three times with 300 ml of toluene, and then 270 ml of toluene was added.

A portion of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.8% by weight of titanium atoms, 0.5% by weight of phthalate,
It contained 30.7% by weight of ethoxy groups and 3.3% by weight of butoxy groups. The slurry concentration is 0.140g
/ Ml.

(C) 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 (b) was introduced, and Further, 12.1 ml of the supernatant was withdrawn, 7.8 ml (29 mmol) of diisobutyl phthalate was added, and the mixture was reacted at 95 ° C. for 30 minutes. After the reaction, solid-liquid separation was performed, and washing was performed twice with 59 ml of toluene.

(D) Synthesis of solid catalyst component (activation treatment) After the washing in the above (c), toluene.
3 ml, 0.66 ml (2.5 mmol) of diisobutyl phthalate, 1.2 ml (6.9 mmol) of butyl ether, and 23.4 ml (0.213 mol) of titanium tetrachloride were added and reacted at 95 ° C. for 3 hours. Was. After completion of the reaction, solid-liquid separation was performed at the same temperature.
Washing was performed twice with l. Then, toluene 12.0m
1, 1.2 ml (6.9 mmol) of butyl ether and 11.7 ml (0.106 mol) of titanium tetrachloride were added and reacted at 95 ° C. for 1 hour. After the completion of the reaction, solid-liquid separation was carried out at the same temperature, followed by washing three times with 59 ml of toluene at the same temperature, followed by washing three times with 59 ml of hexane, and further drying under reduced pressure to obtain 8.1 g of a solid catalyst component.

[0079] In the solid catalyst component, titanium atom is 1.4.
% Of phthalic acid ester, 0.5% by weight of ethoxy group and 0.1% by weight of 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.

(E) 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 4.0 mg of a solid catalyst component synthesized with (d). 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,
5 g of polypropylene powder were obtained.

Accordingly, the yield of polypropylene per gram of the solid catalyst component (hereinafter abbreviated as PP / Cat) is
/ Cat = 26,300 (g / g). The ratio of the component soluble in xylene at 20 ° C. in the total polymer yield was CXS = 0.72 (wt%), and the intrinsic viscosity of the polymer was [η] = 1.91. Table 1 shows the polymerization conditions and the polymerization results.

Comparative Example 1 (a) Synthesis of Solid Product After a 500 ml flask equipped with a stirrer and a dropping funnel was purged with argon, 240 ml of hexane, 5.4 g (15.8 mmol) of tetrabutoxytitanium and tetraethoxysilane 61.4 g (295 mmol) was charged to obtain a homogeneous solution. Next, 150 ml of the organomagnesium compound synthesized in (a) of Example 1 was gradually dropped from the dropping funnel over 4 hours while maintaining the temperature in the flask at 5 ° C. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, separated into solid and liquid at room temperature, washed repeatedly with 240 ml of hexane three times, and dried under reduced pressure to obtain 45.0 g of a brown solid product.

The solid product contained 1.7% by weight of titanium atoms, 33.8% by weight of ethoxy groups, and 2.9% of butoxy groups.
% By weight.

The solid product was found to have an amorphous structure without any clear diffraction peak in the wide-angle X-ray diffraction diagram by Cu-Kα radiation.

(B) Synthesis of ester-treated solid After replacing a 100 ml flask with argon, (a)
6.5 g of solid product synthesized in 16.2 ml of toluene
Then, 4.3 ml (16 mmol) of diisobutyl phthalate was added, and the mixture was reacted at 95 ° C. for 1 hour. After the reaction, solid-liquid separation was performed, and washing was performed three times with 33 ml of toluene.

(C) Synthesis of solid catalyst component (activation treatment) After completion of the washing in (b), toluene was added to the flask.
2 ml, 0.36 ml (1.3 mmol) of diisobutyl phthalate, 2.2 ml (13 mmol) of butyl ether and 38.0 ml (346 mmol) of titanium tetrachloride were added and reacted at 95 ° C. for 3 hours. After completion of the reaction, 95 ° C
, And washed twice with 33 ml of toluene at the same temperature. The above treatment with a mixture of diisobutyl phthalate, butyl ether and titanium tetrachloride was repeated once more under the same conditions, and washed three times with 33 ml of hexane to obtain 5.0 g of an ocher solid catalyst.

The solid catalyst contained 2.1% by weight of titanium atoms, 19.9% by weight of magnesium atoms, and 12.7% by weight of phthalic acid esters.

(D) Polymerization of Propylene The polymerization of propylene was carried out in the same manner as in the polymerization of propylene in Example 1 (e), except that the solid catalyst component obtained in the above (c) was used.

The polymerization result was as follows: PP / Cat = 24,100
(G / g), CXS = 0.94 (wt%), [η] =
1.95. Table 1 shows the polymerization conditions and the polymerization results. This comparative example is inferior in stereoregularity to the present invention because polymerization was not performed using the solid catalyst component of the present invention.

Example 2 (a) Synthesis of solid product The amount of the reagent used was 7.5 ml of tetrabutoxytitanium.
(7.5 g, 22 mmol), diisobutyl phthalate 2.5 ml (2.6 g, 9.3 mmol) and tetraethoxysilane 74.8 ml (70.3 g, 338 mmol) except for 173 ml of the organomagnesium compound solution. A solid product was synthesized in the same manner as in Example 1 (b).

A portion of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.8% by weight of titanium atoms, 0.1% by weight of phthalate,
It contained 35.0% by weight of ethoxy groups and 3.2% by weight of butoxy groups.

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

(C) Synthesis of solid catalyst component (activation treatment) Synthesis of solid catalyst component was carried out in the same manner as in (d) of Example 1 except that activation treatment and washing with toluene were carried out at 105 ° C. Was.

In the solid catalyst component, titanium atom is contained in 1.5 parts.
% By weight, 8.9% by weight of phthalic acid ester, 0.4% by weight of ethoxy group and 0.1% by weight of 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 (e), except that the solid catalyst component obtained in the above (c) was used.

The polymerization result was as follows: PP / Cat = 30,000
(G / g), CXS = 0.74 (wt%), [η] =
2.01. Table 1 shows the polymerization conditions and the polymerization results.

Example 3 (a) Synthesis of solid product The amount of the reagent used was 7.5 ml of tetrabutoxytitanium.
(7.5 g, 22 mmol), 3.8 ml (4.0 g, 14 mmol) of diisobutyl phthalate and 174 ml of an organic magnesium compound solution (74.8 g, 70.3 g, 338 mmol) of tetraethoxysilane. A solid product was synthesized in the same manner as in 1 (b).

A portion of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.7% by weight of titanium atoms, 0.1% by weight of phthalate,
It contained 34.2% by weight of ethoxy groups and 3.2% by weight of butoxy groups.

(B) Synthesis of ester-treated solid A ester-treated solid was synthesized under the same conditions as in (c) of Example 1.

(C) Synthesis of solid catalyst component (activation treatment) The synthesis of the solid catalyst component was carried out in the same manner as in (d) of Example 1 except that the activation treatment and the washing with toluene were performed at 105 ° C. Was.

The solid catalyst component contains 1.7 titanium atoms.
% By weight, phthalic acid ester 10.0% by weight, ethoxy group 0.4% by weight, and butoxy group 0.1% by weight. 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 (e), except that the solid catalyst component obtained in the above (c) was used.

The polymerization result was as follows: PP / Cat = 37,200
(G / g), CXS = 0.73 (wt%), [η] =
2.02. Table 1 shows the polymerization conditions and the polymerization results.

Example 4 (a) Synthesis of solid product The amount of the reagent used was changed to 9.9 ml of tetrabutoxytitanium.
(9.9 g, 29 mmol), 8.5 ml (8.8 g, 32 mmol) of diisobutyl phthalate and 78.7 ml (74.0 g, 355 mmol) of tetraethoxysilane in 189 ml of an organic magnesium compound solution. A solid product was synthesized in the same manner as in 1 (b).

A part of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.9% by weight of titanium atoms, 0.4% by weight of phthalic acid ester,
It contained 31.3% by weight of ethoxy groups and 3.5% by weight of butoxy groups.

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

(C) Synthesis of solid catalyst component (activation treatment) Except that the amount of diisobutyl phthalate to be used was 0.1 ml per 1 g of solid product, and the activation treatment and washing with toluene were performed at 105 ° C. Is (d) of Example 1.
The solid catalyst component was synthesized in the same manner as described above.

[0108] In the solid catalyst component, 1.3 atoms of titanium were contained.
% By weight, 10.2% by weight of a phthalate, 0.3% by weight of an ethoxy group, and 0.1% 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 (e), except that the solid catalyst component obtained in the above (c) was used.

The polymerization result was as follows: PP / Cat = 32,700
(G / g), CXS = 0.52 (wt%), [η] =
It was 1.83. Table 1 shows the polymerization conditions and the polymerization results.

Example 5 (a) Synthesis of solid product The amount of the reagent used was 7.5 ml of tetrabutoxysilane.
(7.5 g, 22 mmol), diisobutyl phthalate 2.5 ml (2.6 g, 9.3 mmol) and tetraethoxysilane 73.8 ml (68.9 g, 331 mmol) except for 168 ml of the organomagnesium compound solution. After synthesizing a solid product in the same manner as in (b) of Example 1, the product was heated at 105 ° C. for 1 hour. A part of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.9% by weight of titanium atoms, 0.2% by weight of phthalic acid esters, and 35.6% by weight of ethoxy groups. , Butoxy groups in an amount of 2.7% by weight. (B) Synthesis of ester-treated solid After replacing a 100 ml flask with argon, (a)
6.5 g of solid product synthesized in 16.2 ml of toluene
And 5.5 ml (21 mmol) of diisobutyl phthalate were added and reacted at 95 ° C. for 1 hour. After the reaction, solid-liquid separation was performed, and washing was performed three times with 33 ml of toluene. (C) Synthesis of solid catalyst component (activation treatment) A solid catalyst component was synthesized in the same manner as in (d) of Example 1 except that the activation treatment and the washing with toluene were performed at 105 ° C. The solid catalyst component contained 1.9% by weight of a titanium atom, 12.3% by weight of a phthalate, 0.4% by weight of an ethoxy group, and 0.2% by weight of a butoxy group. Further, when the solid catalyst component was observed with a stereoscopic microscope, the solid catalyst component had good particle properties without fine powder. (D) Polymerization of propylene In the polymerization of propylene in Example 1 (e), the procedure was the same except that tert-butylmethyldimethoxysilane was used instead of the solid catalyst component obtained in (c) and cyclohexylethyldimethoxysilane. Propylene was polymerized. The polymerization result was PP / Cat = 36,300
(G / g), CXS = 0.72 (wt%), [η] =
2.11. Table 1 shows the polymerization conditions and the polymerization results.

Example 6 The polymerization of propylene was carried out in the same manner as in Example 5, except that tert-butyl-n-propyldimethoxysilane was used instead of tert-butylmethyldimethoxysilane. The polymerization result was PP / C
at = 45,000 (g / g), CXS = 0.61 (w
t%), [η] = 2.42. Table 1 shows the polymerization conditions and the polymerization results.

[0113]

[Table 1]

[0114]

EFFECT OF THE INVENTION A catalyst for the polymerization of .alpha.-olefins which has a good particle size distribution and has sufficiently high catalytic activity and stereoregularity so that removal of catalyst residues and amorphous polymers is not necessary, and high quality, high stereoregularity Provided is a method for producing a hydrophilic α-olefin polymer.

[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.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-283703 (JP, A) JP-A-2-163104 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] (1) In the presence of (A) an organosilicon compound having an Si-O bond and an ester compound, 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 represents a halogen atom, and a represents a number 0 <a ≦ 4. ) Is treated with an ester compound, and then treated with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. An α-olefin polymerization catalyst comprising a trivalent titanium compound-containing solid catalyst component obtained by the treatment, (B) an organoaluminum compound, and (C) an electron donating compound. 2. In the presence of (A) an organosilicon compound having an Si--O bond and an ester compound, 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 represents a halogen atom, and a represents a number 0 <a ≦ 4. ) Is treated with an ester compound, and then treated with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. By the treatment, the obtained trivalent titanium compound-containing solid catalyst component (B) an organoaluminum compound (C) an α-olefin is homopolymerized or copolymerized using an α-olefin polymerization catalyst comprising an electron-donating compound. Α-
A method for producing an olefin polymer.