JP2003026719A - Method for producing solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, prepolymerization catalyst for olefin polymerization, and method for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a solid titanium catalyst component which gives in high activity a highly stereoregular polyolefin small in a lowly stereoregular polyolefin by-product, to provide a prepolymerization catalyst containing the component, and to provide a method for polymerizing an olefin by using the catalyst. SOLUTION: The method for producing a solid titanium catalyst component comprises bringing (i)a solid titanium component containing magnesium, titanium, a halogen, and an electron donor (c) and does not release titanium when washed with hexane at room temperature, (ii) a polar compound having a dipole moment of 0.50-4.00 D, and (iii) a liquid titanium component(d) and/or an electron donor (e) into contact with each other at 40 deg.C or higher to decrease the titanium content of the solid titanium (i) by at least 25 wt. % to produce a solid titanium catalyst component (A) having a weight ratio of the electron donors (c+e) to the titanium of at least 7.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a solid titanium catalyst component capable of producing a polyolefin having high stereoregularity, an olefin polymerization catalyst containing the solid titanium catalyst component obtained by this method, The present invention relates to a prepolymerization catalyst for olefin polymerization and a method for polymerizing olefins.

[0002]

BACKGROUND OF THE INVENTION Ziegler-Natta catalysts composed of a titanium catalyst component and an organoaluminum compound have been widely used as a catalyst for producing polyolefins. Particularly, a carrier-supported solid titanium catalyst component is used as the titanium catalyst component. It is known that the obtained catalyst has high polymerization activity.

Among such solid titanium catalyst components, a catalyst using a magnesium chloride-supported titanium catalyst component exhibits high polymerization activity and exhibits stereoregularity when olefins such as propylene and butene are polymerized. It is known that high polyolefins can be produced. Various catalysts capable of producing polyolefins having higher stereoregularity have been proposed. For example, a solid titanium catalyst component carrying magnesium chloride and an electron donating compound (electron donor) as a third component together with an organoaluminum compound. The catalyst used has been proposed.

However, when olefins are polymerized by using the catalyst containing the solid titanium catalyst component, there is a problem that a highly stereoregular polyolefin and a low stereoregular polyolefin are by-produced. Even with the catalyst for producing highly stereoregular polyolefin using the electron donor as the third component as described above, there is a limit in reducing the production amount of low stereoregular polyolefin.

The solid titanium catalyst component as described above is prepared by bringing a titanium compound, a magnesium compound and an electron donor into contact with each other. In the solid titanium catalyst component thus prepared, A titanium compound (hereinafter also referred to as “residual titanium compound”) that causes by-product of low stereoregular polyolefin is also included. In order to produce a highly stereoregular polyolefin,
It is preferred that the solid titanium catalyst component does not contain this excess titanium compound.

It is known that a part of the surplus titanium compound is released when the solid titanium catalyst component is washed with hexane at room temperature, but the titanium compound, the magnesium compound and the electron donor are contacted with each other. A method of preparing a solid titanium catalyst component by removing the excess titanium compound with a solvent from the solid thus obtained is also proposed. For example, JP-A-59-124909 discloses aromatic carbonization such as toluene. It is described that washing the surplus titanium compound with hydrogen is effective as a method for removing the surplus titanium compound.

However, when the solid titanium catalyst component is washed with the aromatic hydrocarbon as described above, the electron donor is removed together with the excess titanium compound, so that the resulting solid titanium catalyst component results in low stereoregularity. The effect of reducing the amount of polyolefin cannot be sufficiently expressed. Further, JP-A-9-31119 discloses that a solid titanium catalyst component obtained by washing a solid titanium catalyst component with a halogen-containing aromatic hydrocarbon such as o-dichlorobenzene and removing a residual titanium compound is , It is described that it is possible to effectively reduce by-products of low stereoregular polyolefin.
Japanese Patent Laid-Open Publication No. 04-04 proposes an olefin polymerization catalyst composed of a solid titanium catalyst component obtained by removing the excess titanium compound, an organoaluminum compound component, and a specific organosilicon compound. However,
When the solid titanium catalyst component is washed with a halogen-containing aromatic hydrocarbon, there is a problem that the activity per unit weight of the obtained solid titanium catalyst component is lowered due to the decrease in the amount of titanium supported.

Therefore, it has been desired to develop a solid titanium catalyst component and a catalyst capable of producing a highly stereoregular polyolefin with a high activity by producing a small amount of a low stereoregular polyolefin by-product.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is capable of producing a highly stereoregular polyolefin with a high activity, in which the amount of a low stereoregular polyolefin produced as a by-product is small. It is an object of the present invention to provide a method for producing such a solid titanium catalyst component, a prepolymerization catalyst containing the solid titanium catalyst component, an olefin polymerization catalyst, and an olefin polymerization method using these catalysts.

[0010]

SUMMARY OF THE INVENTION The method for producing a solid titanium catalyst component according to the present invention comprises (i) magnesium, titanium, a halogen and an electron donor (c), and titanium is eliminated by washing with hexane at room temperature. Solid titanium and (ii) dipole moment of 0.50 to 4.00 Deby
the polar compound of e and (iii) liquid titanium (d) and / or electron donor (e) are contacted at 40 ° C. or higher,
The titanium content in the solid titanium (i) is reduced by 25% by weight or more, and the weight ratio of the total amount of the electron donor (c) and the electron donor (e) to titanium (electron donor (c +
e) / titanium) is 7 or more, and a solid titanium catalyst component (A) is produced.

In the present invention, the above-mentioned (ii) polar compound having a dipole moment of 0.50 to 4.00 Debye is preferably a halogen-containing aromatic hydrocarbon, and in the solid titanium (i), The weight ratio of the electron donor (c) and titanium (electron donor (c) / titanium) is preferably 6 or less, and the solid titanium (i) is (a) a magnesium compound in a liquid state, It is preferable that (b) the titanium compound in a liquid state and (c) the solid substance (1) obtained by contacting with an electron donor, wherein the solid titanium (i) is (a) a magnesium compound in a liquid state. ,
(B) a titanium compound in a liquid state, and (c) a solid (1) obtained by contacting an electron donor, and (b)
It may be a solid (2) obtained by contacting a liquid titanium compound.

The olefin polymerization catalyst according to the present invention comprises the above-mentioned (A) solid titanium catalyst component, (B) organometallic compound, (C) organosilane compound having at least one alkoxy group, or (D). And a compound having two or more ether bonds existing through a plurality of atoms. The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

The prepolymerization catalyst for olefin polymerization according to the present invention comprises a solid titanium catalyst component (A), an organometallic compound (B), and optionally an organosilane compound (C) having at least one alkoxy group. ) Or a compound (D) having two or more ether bonds existing through a plurality of atoms, the olefin is prepolymerized.

A method for olefin polymerization according to another aspect of the present invention comprises a prepolymerization catalyst for olefin polymerization, (B) an organometallic compound, and (C) an organosilane having at least one alkoxy group. Olefin polymerization or copolymerization in the presence of an olefin polymerization catalyst consisting of the compound and (D) at least one compound selected from compounds having two or more ether bonds existing through a plurality of atoms. It is characterized by that.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a solid titanium catalyst component according to the present invention, an olefin polymerization catalyst containing the solid titanium catalyst component obtained by this method, a prepolymerization catalyst and these catalysts were used. The olefin polymerization method will be described. In the present specification, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” means not only homopolymer but also copolymerization. It may be used in the sense of including coalescence.

FIG. 1 shows an example of a step of preparing a solid titanium catalyst component and a step of preparing an olefin polymerization catalyst containing this solid titanium catalyst component. (A) Method for producing solid titanium catalyst component In the method for producing a solid titanium catalyst component according to the present invention, titanium is desorbed by containing magnesium, titanium, halogen and an electron donor and washing with hexane at room temperature. Solid titanium (i) and a polar compound (ii) having a dipole moment of 0.50 to 4.00 Debye,
(Iii) contacting liquid titanium (d) and / or electron donor (e) at 40 ° C. or higher to reduce the titanium content in the solid titanium (i) by 25% by weight or more,
The weight ratio of the total amount of the electron donor (c) and the electron donor (e) to titanium (electron donor (c + e) / titanium) is 7
The solid titanium catalyst component described above is manufactured.

The above solid titanium (i) can be prepared by contacting a magnesium compound, a titanium compound, an electron donor and the like by various methods,
The preparation method is not limited, but in the present invention, (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor are brought into contact with each other to obtain solid titanium (i). It is preferred to produce

First, each component used for preparing the solid titanium (i) will be specifically described below. (A) Magnesium compound In the present invention, when preparing solid titanium (i),
The magnesium compound is preferably used in a liquid state. The magnesium compound in the liquid state may be one in which the magnesium compound itself is in a liquid state,
Alternatively, it may be a solid magnesium compound, or the compound formed into a magnesium compound solution by a solvent.

As such a magnesium compound,
Examples thereof include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability. Examples of the magnesium compound having a reducing ability include organomagnesium compounds represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an alkyl group having 5 to 20 carbon atoms. When R is a cycloalkyl group and n is 0, two Rs may be the same or different. X is halogen.

Specific examples of the organomagnesium compound having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, octylbutylmagnesium, ethylbutylmagnesium. Alkyl magnesium halides such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride; alkyl magnesium alkoxides such as butyl ethoxy magnesium, ethyl butoxy magnesium, octyl butoxy magnesium; and other butyl compounds Examples include magnesium hydride.

Specific examples of the magnesium compound having no reducing ability include magnesium chloride, magnesium bromide,
Magnesium halides such as magnesium iodide and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride; ants such as phenoxy magnesium chloride and methylphenoxy magnesium chloride Roxymagnesium halide; Alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; Aryloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, magnesium laurate, magnesium stearate. Examples include magnesium carboxylates such as To be In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparing the catalyst component. To derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is
Polysiloxane compound, halogen-containing silane compound, halogen-containing aluminum compound, ester, alcohol, halogen-containing compound, or OH group or active carbon-
It may be brought into contact with a compound having an oxygen bond.

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability described above are organometallic compounds described later, for example, complex compounds with other metals such as aluminum, zinc, boron, beryllium, sodium and potassium. , May form a double compound, or may be a mixture with another metal compound. further,
The magnesium compound may be used alone or in combination of two or more kinds.

As the magnesium compound used for preparing the solid titanium (i), magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium (i), the form of the halogen-containing magnesium compound is used. Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Of these, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferable. Among the above magnesium compounds, when the magnesium compound is a solid, it can be made into a liquid state by using an electron donor (ci). Examples of the electron donor (ci) include alcohols, phenols, ketones, aldehydes, ethers, amines, which will be described later as the electron donor (c).
Pyridines and the like can be used.

Further, metal acid esters such as tetraethoxy titanium, tetra-n-propoxy titanium, tetra-i-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium and tetraethoxy zirconium can be used. . Among these, alcohols and metal acid esters are particularly preferably used.

The solubilization reaction of the solid magnesium compound with the electron donor (ci) is generally carried out by bringing the solid magnesium compound and the electron donor (ci) into contact with each other and heating them as necessary. This contact is usually 0-20
0 ° C, preferably 20 to 180 ° C, more preferably 50 to 1
It is carried out at a temperature of 50 ° C. Further, in the above-mentioned solubilization reaction, a hydrocarbon solvent (f) and the like may coexist. Specific examples of such a hydrocarbon solvent include pentane, hexane, heptane, octane, decane, dodecane, tetradecane,
Aliphatic hydrocarbons such as kerosene; cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclohexene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene and chlorobenzene Aromatic hydrocarbons such as benzene, toluene and xylene are used.

(B) Titanium Compound In the present invention, a tetravalent titanium compound is particularly preferably used as the liquid state titanium compound (b). Examples of such a tetravalent titanium compound include compounds represented by the following formula. Ti (OR) _g X _{4-g In the} formula, R is a hydrocarbon group having 1 to 15 carbon atoms, and X is
Is a halogen atom and 0 ≦ g ≦ 4.

Specific examples of such a compound include:
Tetrahalogenated titanium such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) C
l ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ ,
_{Ti (O-iso-C 4} H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 C
_{l 2, Ti (On-C} 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2 Br 2
Dihalogenated dialkoxy titanium such as; Ti (OC
_{H 3) 3 Cl, Ti (} OC 2 H 5) 3 Cl, Ti (On-C 4 H 9) 3
Cl, Ti (OC ₂ H ₅ ) ₃ Br and other monohalogenated trialkoxy titanium; Ti (OCH ₃ ) ₄ , Ti (OC
_{2 H 5) 4, Ti (} On-C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4,
Examples thereof include tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used in combination of two or more. The titanium compound may be diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon before use. (C) Electron Donor Examples of the electron donor (c) used in the preparation of solid titanium (i) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acids or inorganic acids. Ester, ether, acid amide, acid anhydride, ammonia, amine, nitrile, isocyanate,
Examples thereof include nitrogen-containing cyclic compounds and oxygen-containing cyclic compounds.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; 1 to 1 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol
8 halogen-containing alcohols; 6 to 6 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol
20 phenols; acetone, methyl ethyl ketone,
Methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, and other ketones having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms; methyl formate , Methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, dimethyl carbonate, carbonic acid C2 to C30 organic acid esters such as ethyl; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; methyl ether, ethyl ether, isopropyl Ether, butyl ether,
Ethers having 2 to 20 carbon atoms such as amyl ether, anisole and diphenyl ether; acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-
Acid amides such as dimethylamide, amines such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine, nitriles such as acetonitrile, benzonitrile, tolunitrile Class; acetic anhydride,
Acid anhydrides such as phthalic anhydride and benzoic anhydride, pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline, pyrrolidine, ndol, pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethyl Pyridines such as pyridine, phenylpyridine, benzylpyridine and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines and isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, Examples thereof include cyclic oxygen-containing compounds such as dimethylfuran, diphenylfuran, benzofuran, coumarane, phthalane, tetrahydropyran, pyran and dihydropyran.

As the electron donor (c), polyhydric hydroxy compound ethers such as 1-methoxyethanol, 2-methoxyethanol, 4-methoxybutanol and 2-butoxyethanol can be mentioned as particularly preferable examples. Further, as the above organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0033]

[Chemical 1]

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted group. Alternatively, it is an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a ring structure. The hydrocarbon radicals R ^{1 to} R ⁶ are generally 1 to 1
Substituents having 5 carbon atoms, which are substituted, include heteroatoms such as N, O, and S, for example, C—O
-C, COOR, COOH, OH, SO 3 H, -C-N
It has a group such as —C— and NH ₂ .

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate, and isopropyl malonate. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl allyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylic acid esters such as diethyl itaconate and dioctyl citraconic acid; alicyclic polycarboxylic acids such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Ester; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate , Di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate,
Aromatic polycarboxylic acid esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; 3,4-furandicarboxylic acid and ethanol, n-butanol, i-butanol , Heterocyclic polycarboxylic acid esters such as esters with 2-ethylhexanol and the like.

Other examples of polycarboxylic acid esters include diethyl adipate, diisobutyl adipate,
Mention may also be made of long-chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate and di-2-ethylhexyl sebacate. Further, in the present invention, as the electron donor (c),
A compound having two or more ether bonds existing via a plurality of atoms (hereinafter also referred to as “polyether”) can be used. Examples of the polyether include carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur, and compounds in which two or more kinds of atoms are present between ether bonds. Of these, a compound having a relatively bulky substituent bonded to the atom between the ether bonds and having a plurality of carbon atoms in the atom existing between two or more ether bonds is preferable, for example, represented by the following formula. Polyethers are preferred.

[0037]

[Chemical 2]

(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) Of these, 1,3-diethers are preferably used,
In particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-
Isopropyl-2-isobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2 , 2-Diphenyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane and the like are preferably used.

Further, as the electron donor (c), an organic silane compound (C) having at least one alkoxy group as described below, water, or an anionic, cationic or nonionic surfactant is used. It can also be used. In the present invention, it is preferable to use a carboxylic acid ester among the above as the electron donor (c), particularly polyvalent carboxylic acid esters, polyvalent hydroxy compound esters, especially phthalic acid esters, and aliphatic polyvalent hydroxy compounds. Preference is given to using the compound ethers and acid anhydrides.

Two or more of these electron donors (c) can be used in combination. Preparation of solid titanium (i) In the present invention, the solid titanium (i) is contacted with the liquid magnesium compound (a), the liquid titanium compound (b) and the electron donor (c) as described above. i) can be prepared. When these components are brought into contact with each other, the titanium compound (b) in the liquid state may be used once to generate the solid matter (1), and the titanium compound (b) in the liquid state is further added to the solid matter (1). May be contacted with each other to form a solid (2).

When the solids are prepared by bringing the components (a) to (c) into contact with each other, the hydrocarbon solvent (f) as shown in the liquid magnesium compound (a) preparation may be used, if necessary. Can be used. In the present invention, the solid matter (1) or (2) obtained by bringing these (a) to (c) into contact has a dipole moment of 0.50 to 4.00 De.
It can be directly used as the solid titanium (i) to be contacted with the polar compound (ii) which is bye, but the solid titanium (i) or (2) is washed with a hydrocarbon solvent if necessary, and the solid titanium (i) is then used. It is preferable to prepare (i).

When the solid titanium (i) is prepared, in addition to these compounds, an organic compound or inorganic compound containing silicon, phosphorus, aluminum, etc. used as a carrier and a reaction aid is used. Good. Examples of such carriers include Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , and M.
gO, CaO, TiO ₂ , ZnO, SnO ₂ , BaO, T
Examples thereof include resins such as hO and styrene-divinylbenzene copolymer. Among these, TiO ₂ , Al ₂
O ₃ , SiO ₂ , and a styrene-divinylbenzene copolymer are preferably used.

As a method for preparing the solid (1) or (2) (or the direct solid titanium (i)) from the above components, the following methods can be exemplified. In addition, the method of preparing a solid material described below also includes a step of preparing a magnesium compound (a) in a liquid state. Further, in the following method, as the organoaluminum compound, an organoaluminum compound as described below as the organometallic compound (B) is used. (1) A liquid magnesium compound (a) consisting of a magnesium compound, the above electron donor (ci) and a hydrocarbon solvent is contact-reacted with an organoaluminum compound to precipitate a solid, or a liquid while being precipitated. And react with the titanium compound (b) in the state.

In this process, the electron donor (c) is contacted with the contact product at least once. (2) The titanium compound (b) and the electron donor (c) in a liquid state are contact-reacted with the contact product of the inorganic carrier and the liquid organomagnesium compound (a). At this time, the contact product of the inorganic carrier and the liquid organomagnesium compound (a) may be previously contact-reacted with the halogen-containing compound and / or the organoaluminum compound. (3) A mixture of a magnesium compound, an electron donor (ci) and, in some cases, a hydrocarbon solvent in a liquid state, with a magnesium compound (a) and an inorganic carrier or an organic carrier. Alternatively, an organic carrier is prepared, and then the titanium compound (b) in a liquid state is brought into contact with it. In this process, the electron donor (c) is contacted with the contact product at least once. (4) A solution containing a magnesium compound, a titanium compound (b) in a liquid state, and optionally an electron donor (ci) and / or a hydrocarbon solvent, an inorganic carrier or an organic carrier, and an electron donor (c). To contact. (5) After bringing the liquid state organomagnesium compound (a) into contact with the liquid state titanium compound (b), it is brought into contact with the electron donor (c). (6) The organomagnesium compound (a) in the liquid state is contact-reacted with the halogen-containing compound, and then the titanium compound (b) in the liquid state is brought into contact. In this process, the electron donor (c) is used at least once. (7) The alkoxy-containing magnesium compound (a) is catalytically reacted with the liquid titanium compound (b) and the electron donor (c). (8) Catalytic reaction of a hydrocarbon solution of a complex of a magnesium compound and an electron donor (ci) (a liquid magnesium compound (a)) with a liquid titanium compound (b) and an electron donor (c) Let (9) A liquid complex composed of a magnesium compound and an electron donor (ci) (a magnesium compound (a) in a liquid state) is brought into contact with an organoaluminum compound, and then a titanium compound (b) in a liquid state is subjected to a contact reaction. In this process, the electron donor (c) is contacted with the contact product at least once. (10) Liquid magnesium compound (a) having no reducing ability
And the titanium compound (b) in a liquid state are brought into contact with each other in the presence or absence of the electron donor (c). In this process, the electron donor (c) is contacted with the contact product at least once. (11) The reaction product (solid (1)) obtained in (1) to (10) is further contacted with a titanium compound (b) in a liquid state. (12) The electron donor (c) and the liquid titanium compound (b) are brought into contact with the reaction product (solid (1)) obtained in (1) to (10).

The contact of each component as described above is usually -70.
C. to + 200.degree. C., preferably -50.degree. C. to + 150.degree. C., more preferably -30 to + 130.degree. The amount of each component used in the preparation of solid titanium (i) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is 0.0
The titanium compound is present in an amount of 1 to 10 moles, preferably 0.1 to 5 moles, 0.01 to 1000 moles, preferably 0.1 to 1000 moles.
It can be used in an amount of 200 mol.

In the present invention, among the above, the solid (1) is produced by the contact method (8), or the solid (2) is produced by the contact method (11) or (12) including the contact method (8). Is preferably generated, and it is particularly preferable to generate the solid (1) by the contacting method (8). The olefin polymerization catalyst containing the solid (1) is preferable because it shows high activity in propylene homopolymerization and gives a propylene random copolymer having a low decane-soluble content.

Further, in such a method, the liquid state magnesium compound (a) prepared from the magnesium compound and the electron donor (ci) is brought into contact with the liquid state titanium compound (b), and then the electron donating is carried out. When contacting the body (c), it is preferable to use polyvalent carboxylic acid esters and / or polyvalent hydroxy compound ethers as the electron donor (c).

In the present invention, the solid matter (1) or (2) thus obtained can be used as it is as the solid titanium (i), and the solid matter is 0 to 150 ° C.
It is preferable to wash with the hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, and cetane, non-halogen aromatic hydrocarbon solvents such as toluene, xylene, and benzene, and halogen-containing solvents as described below. An aromatic hydrocarbon solvent or the like is used. Of these, an aliphatic hydrocarbon solvent or a halogen-free aromatic hydrocarbon solvent is preferably used.

In washing the solid matter, the hydrocarbon solvent is usually used in an amount of 10 to 500 ml, preferably 20 to 100 ml, based on 1 g of the solid matter. The solid titanium (i) thus obtained contains magnesium, titanium, halogen and an electron donor. In this solid titanium (i), electron donor / titanium (weight ratio)
Is preferably 6 or less.

This solid titanium (i) is not desorbed by washing with hexane at room temperature. Polar compound (ii) and liquid titanium (d) and / or electricity
In the present invention, solid titanium (i) as described above, a polar compound (ii) having a dipole moment of 0.50 to 4.00 Debye, and liquid titanium (d) are used in the present invention. And / or the electron donor (e) is contacted to prepare the solid titanium catalyst component (A).

Specifically, the polar compound (ii) having a dipole moment of 0.50 to 4.00 Debye used for contact with the solid titanium (i) (hereinafter, also simply referred to as "polar compound"), Chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, trichlorobenzene, α, α,
Aromatic hydrocarbon containing halogen such as α-trichlorotoluene, o-chlorotoluene, 2,4-dichlorotoluene, benzyl chloride, 2-chlorobenzyl chloride; 1,2-dichloroethane, 1,1,2,2-tetrachloroethane , 1-chloropropane,
2-chloropropane, 1,2-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2
Examples thereof include halogen-containing aliphatic hydrocarbons such as -chloro-2-methylpropane and 1-chloropentane; and halogen-containing Si compounds such as diphenyldichlorosilane and methyltrichlorosilane. Of these, halogen-containing aromatic hydrocarbons are preferable.

The liquid titanium (d) used for contact with the solid titanium (i) includes the above-mentioned titanium compound (b).
Can be the same as. Among them, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. Examples of the electron donor (e) used for contact with the solid titanium (i) include the same electron donors (c) as described above. Among them, it is preferable to use the same electron donor as that used for preparing the solid titanium (i) to be contacted.

Solid titanium (i) and polar compound (ii)
And liquid titanium (d) and / or electron donor (e)
The contact with is usually 40 to 200 ° C., preferably 50 to 18
It is carried out at a temperature of 0 ° C., more preferably 60 to 160 ° C., for 1 minute to 10 hours, preferably 10 minutes to 5 hours. In this contact, the polar compound (ii) becomes solid titanium (i).
Usually 1 to 10,000 ml, preferably 5 to 1 g
It is used in an amount of 5000 ml, preferably 10 to 1000 ml. Liquid titanium (d) is a polar compound (ii) 1
The amount is usually 0.1 to 50 ml, preferably 0.2 to 20 ml, and particularly preferably 0.3 to 10 ml with respect to 00 ml. The electron donor (e) is generally 0.01 to 10 ml, preferably 0.02 to 5 ml, particularly preferably 0.03 to 100 ml of the polar compound (ii).
Used in a volume of 3 ml.

Solid titanium (i) and polar compound (ii)
And liquid titanium (d) and / or electron donor (e)
The order of contact with is not particularly limited, and they can be contacted simultaneously or sequentially. In the present invention, it is preferable that the polar compound (ii) is brought into contact with the liquid titanium (d) and / or the electron donor (e), and then the contact product is brought into contact with the solid titanium (i). .

Solid titanium (i) and polar compound (ii)
And liquid titanium (d) and / or electron donor (e)
Is preferably brought into contact with stirring under an inert gas atmosphere. For example, a slurry of solid titanium (i), polar compound (ii), and liquid titanium (d) and / or electron donor (e) in a glass flask equipped with a stirrer, which has been sufficiently replaced with nitrogen, is added as described above. Stirrer at 100-
The solid titanium (i), the polar compound (ii), the liquid titanium (d) and / or the electron donor (e) are brought into contact with each other by stirring at 1000 rpm, preferably at a rotation speed of 200 to 800 rpm, for the above time. It is desirable to let

After contact, the solid titanium (i) and the polar compound (ii) can be separated by filtration. By contacting such solid titanium (i) with the polar compound (ii), a solid titanium catalyst component having a titanium content lower than that of the solid titanium (i) can be obtained. Specifically, the titanium content is 25% by weight or more, preferably 30 to 95% by weight, more preferably 40 to 40% by weight, as compared with the solid titanium (i).
90% by weight less solid titanium catalyst component (A) is obtained.

The solid titanium catalyst component (A) according to the present invention obtained as above is magnesium, titanium,
It contains a halogen and an electron donor, and (1) to
(4) is satisfied. (1) The titanium content of the solid titanium catalyst component (A) is 2.5% by weight or less, preferably 2.2 to 0.1% by weight, more preferably 2.0 to 0.2% by weight, It is particularly preferably 1.8 to 0.3% by weight, and most preferably 1.4 to 0.4% by weight. (2) The electron donor content is 8 to 30% by weight. (3) The electron donor / titanium (weight ratio) is 7 or more, preferably 7.5 to 35, more preferably 8 to 30, and particularly preferably 8.5 to 25. (4) In the solid titanium catalyst component (A), titanium is not substantially desorbed by washing with hexane at room temperature. The hexane washing of the solid titanium catalyst component is usually 10 to 500 m with respect to 1 g of the solid titanium catalyst component.
1, preferably 20 to 100 ml of hexane for 5 minutes. Room temperature is 15 to 25 ° C.
Further, the fact that titanium is not substantially desorbed means that the titanium concentration in the hexane cleaning liquid is 0.1 g / liter or less.

Here, the amounts of magnesium, halogen, titanium and electron donor are respectively% by weight per unit weight of the solid titanium catalyst component (A), and magnesium, halogen and titanium are measured by plasma emission spectroscopy (I
(CP method), the electron donor is quantified by gas chromatography. When the solid titanium catalyst component (A) according to the present invention as described above is used as a catalyst component for olefin polymerization, olefin can be polymerized with high activity, and the production amount of polyolefin having low stereoregularity is small. It is possible to produce a highly stereoregular polyolefin. The solid titanium catalyst component (A) according to the present invention includes, for example, the following organometallic compounds (B) and organosilane compounds (C) having at least one alkoxy group.
Alternatively, it is used as a catalyst for olefin polymerization in combination with a compound (D) having two or more ether bonds existing via a plurality of atoms.

(B) Organometallic Compound As the organometallic compound used in the present invention, those containing a metal selected from Groups 1, 2 and 13 of the periodic table are preferable, and specifically, an organoaluminum compound ,
Complex Alkyl Compounds of Group 1 Metals with Aluminum, Second
Examples thereof include organic metal compounds of group metals.

The organoaluminum compound is represented by the following formula, for example. R ^a _n AlX _3-n (In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to _3. ) R ^a is a carbon atom A hydrocarbon group of formulas 1 to 12, such as an alkyl group, a cycloalkyl group or an aryl group,
Specific examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl group, cyclohexyl, phenyl, tolyl and the like.

Specific examples of such an organoaluminum compound include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri 2-.
Trialkylaluminums such as ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum, dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide and other dialkylaluminum halides; methylaluminum sesquichloride, ethylaluminum sesquichloride. Alkyl aluminum sesquihalides such as chloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide Umujiharaido diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

As the organoaluminum compound, compounds represented by the following formula can also be mentioned. R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is —OR ^b.
Group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
SiR ^f ₃ group or —N (R ^g ) AlR ^h ₂ group, n is 1
To R 2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like, and ^Re is hydrogen, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ^f and R ^g are methyl group, ethyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds. (I) A compound represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide. (Ii) ^a compound represented by R ^a _n Al (OSiR ^c ) _3-n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OS
iMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), and the like. (Iii) R ^a _n Al (OAlR ^d ₂ ) _3-n Et ₂ AlOAlEt
₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _{2, and the} like. (Iv) Compounds represented by R ^a _n Al (NR ^e ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlN
HEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN
(Me ₃ Si) ₂ etc. _{^{(V) R a n Al (}} SiR f 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} . (Vi) R ^a _n Al [N (R ^g) -AlR ^h _{2] 3-n} compound represented by, for example _{Et 2 AlN (Me) -AlEt 2} (iso-
Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Further, a compound similar to this, for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. More _{specifically, (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 4 H 9)
_{2 AlOAl (C 4 H 9)} 2, (C 2 H 5) 2 AlN (C 2 H 5) Al
(C ₂ H ₅ ) ₂ and the like, as well as aluminoxanes such as methylaluminoxane.

Among the above organoaluminum compounds, R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n and R ^a _n Al (O
An organoaluminum compound represented by AlR ^d ₂ ) _3-n is preferably used. A complex alkyl compound of a Group 1 metal and aluminum is represented by the following general formula.

M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 1 carbon atoms.
Specifically, LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄
And so on. The organometallic compound of Group 2 metal is represented by the following general formula. R ^k R ^l M ² (R ^k and R ^l are a hydrocarbon group having 1 to 15 carbon atoms or halogen, and may be the same or different from each other.
Except when both are halogen. M ² is Mg, Z
Specific examples include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like.

Two or more of these organometallic compounds can be used in combination. (C) Organosilane Compound The organosilane compound having at least one alkoxy group used in the present invention is represented by the following general formula (c). R _n Si (OR ′) _4-n (c) (In the formula, R and R ′ are hydrocarbon groups having 1 to 20 carbon atoms, and n is 1, 2 or 3.) Specific examples of the organic silane compound represented by the formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-
Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane , Trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisilo And San. Further, ethyl silicate, butyl silicate and the like can also be used.

In the present invention, the organosilane compound represented by the above formula (c) is particularly preferably a compound represented by the following formula (ci). R ^a _n Si (OR ^b ) _4-n ... (ci) (where n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary carbon atom number 1 to 20 hydrocarbon groups, and when n is 2 or 3, at least one R ^a is a secondary or tertiary hydrocarbon group, and R ^a
R ^b may be the same or different, R ^b is a hydrocarbon group having 1 to 4 carbon atoms, and (4-n) is 2 or 3
And OR ^b may be the same or different. ) In the organosilane compound having a bulky group represented by the formula (ci), the secondary or tertiary hydrocarbon group has a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and a substituent. Examples of these groups and hydrocarbon groups in which carbon adjacent to Si is secondary or tertiary.

More specifically, as the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2, 4-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,3,4-triethylcyclopentyl group Group, and a cyclopentyl group having an alkyl group such as a tetramethylcyclopentyl group and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes a 2-methylcyclopentenyl group, a 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Examples thereof include a cyclopentenyl group having an alkyl group such as a cyclopentenyl group, a 2,3,5-trimethylcyclopentenyl group, a 2,3,4-triethylcyclopentenyl group, a tetramethylcyclopentenyl group and a tetraethylcyclopentenyl group.

The substituted cyclopentadienyl group is 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Examples thereof include a cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl group, s-butyl group, s-amyl group, α-methylbenzyl group and the like, which are adjacent to Si. As a hydrocarbon group whose carbon is a tertiary carbon, te
Examples include rt-butyl group, tert-amyl group, α, α′-dimethylbenzyl group, and admantyl group. In such an organosilane compound represented by the formula (ci), n is 1
And cyclopentyltrimethoxysilane,
2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, tert-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornane Examples thereof include trialkoxysilanes such as trimethoxysilane and 2-norbornanetriethoxysilane. When n is 2, dicyclopentyldiethoxysilane, tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, Dialcohols such as tert-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane Shishiran acids and the like.

When n is 2 among the organic silane compounds represented by the formula (ci), dimethoxysilane compounds represented by the following formula (c-ii) are particularly preferable.

[0075]

[Chemical 3]

In the formula, R ^a and R ^b are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or S
A hydrocarbon group in which the carbon adjacent to i is a secondary carbon or a tertiary carbon. Examples of the organosilane compound represented by the formula (c-ii) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, ditert-butyldimethoxysilane, and di (2-methyl). Cyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane, di (2,3-dimethylcyclopentyl) dimethoxysilane, di (2,4-dimethylcyclopentyl) dimethoxysilane, di (2,5-Dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane , Di (2,3,4-triethylcyclopentyl )
Dimethoxysilane, di (tetramethylcyclopentyl)
Dimethoxysilane, di (tetraethylcyclopentyl)
Dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-Dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl)
Dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di ( Tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-
Ethylcyclopentadienyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxy Silane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,
4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetramethylcyclopentadienyl)
Dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentamethylcyclopentadienyl) dimethoxysilane, di (1,2, 3,4,5-Pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α,
α'-Dimethylbenzyl) dimethoxysilane, di (adamantyl) dimethoxysilane, adamantyl-t-butyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, Examples include isopropyl-s-butyldimethoxysilane and the like.

Further, as the organosilane compound represented by the formula (ci), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentyl Examples thereof include monoalkoxysilanes such as methylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, tert-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane Preferred are silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and dimethoxysilanes represented by formula (c-ii). Good Especially the formula (c-ii)
The dimethoxysilanes represented by are preferable, specifically,
Dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-tert-amyldimethoxysilane and the like are preferable.

These may be used in combination of two or more kinds. (D) Two or more ethers existing through a plurality of atoms
Compound Having Bonds Examples of the compound (D) having two or more ether bonds existing through a plurality of atoms used in the present invention include the polyethers described as the electron donor (c).

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention has the above-mentioned (A) solid titanium catalyst component, (B) organometallic compound, and (C) at least one alkoxy group. It is formed from an organic silane compound or a compound (D) having two or more ether bonds existing through a plurality of atoms.

In the present invention, each of these components (A),
When forming the olefin polymerization catalyst from (B), (C) and (D), other components may be used as required. For example, the above-mentioned polyether compound and 2,6-substituted piperidines may be used. Substituted methylenediamines such as 2,2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine; 1,3-dibenzyl Nitrogen-containing electron donors such as imidazolidine, substituted imidazolidines such as 1,3-dibenzyl-2-phenylimidazolidine; triethylphosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butylphosphite , Triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite and other phosphorous acid-containing electron donors; 2,6-substituted tetrahydropyrans, 2,5 An oxygen-containing electron donor such as -substituted tetrahydropyrans can be used, and two or more kinds of them can be used in combination.

Further, in the present invention, a prepolymerization catalyst may be formed from each of the above components. The prepolymerization catalyst is the solid titanium catalyst component (A), the organometallic compound (B), and, if necessary, the organosilane compound (C).
Alternatively, it is formed by prepolymerizing olefins and the like in the presence of the compound (D) having two or more ether bonds existing via a plurality of atoms.

Examples of the olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl- 1-pentene, 4-methyl-1-pentene,
4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-
Dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl
-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Examples thereof include α-olefins having 2 or more carbon atoms such as tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Also, other vinyl compounds and polyene compounds as described below can be used during the prepolymerization. You may use these 2 or more types together.

The α-olefin used in the prepolymerization is
It may be the same as or different from the α-olefin used in the main polymerization described later. In the present invention, the method for carrying out the prepolymerization is not particularly limited, and for example, it can be carried out in a state in which the olefins and the polyene compound are in a liquid state, or can be carried out in the coexistence of an inert solvent, and further, in a gas phase. It is also possible to carry out under conditions. Of these, it is preferable to carry out prepolymerization under relatively mild conditions by adding olefins and respective catalyst components to the inert solvent in the presence of an inert solvent.

The prepolymerization is usually about -20 to + 80 ° C, preferably about -20 to + 60 ° C, more preferably -10.
It is desirable to carry out at + 40 ° C. Further, the prepolymerization can be carried out in any of batch system, semi-continuous system and continuous system. In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used and the like, but the concentration of the solid titanium catalyst component (A) is usually about 0.01 to 500 millimoles in terms of titanium atom per 1 liter of the polymerization volume. , Preferably 0.1-10
It is desirable that the amount is 0 millimole, particularly preferably 1 to 50 millimole.

The organometallic compound (B) is used in an amount of 0.01 to 2000 g, preferably 0.03 to 1000 g, and more preferably 0.05 to 1000 g per 1 g of the solid titanium catalyst component (A).
Used in an amount such that 200 g of prepolymer is produced,
It is usually about 0.1 to 1000 mol, preferably about 0.5 to 50, per 1 mol of titanium in the solid titanium catalyst component (A).
It is used in an amount of 0 mol, particularly preferably 1 to 100 mol.

During the prepolymerization, the organosilane compound (C) is usually added in an amount of 0.01 to 50 mol, preferably 0.05, per mol of titanium atom in the solid titanium catalyst component (A).
To 30 moles, more preferably 0.1 to 10 moles, which can be optionally used, and a compound (D) having two or more ether bonds existing through a plurality of atoms.
Is usually 0.01 to 50 mol, preferably 0.05 to 30 mol per mol of titanium atom in the solid titanium catalyst component (A).
It can be optionally used in an amount of 0.1 to 10 mol, more preferably 0.1 to 10 mol.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. When the prepolymerized catalyst is obtained in a suspension state as described above, the prepolymerized catalyst can be used in the suspended state in the (main) polymerization of the next step, or can be produced from the suspension. It is also possible to separate and use the prepared prepolymerization catalyst. The above-mentioned prepolymerization catalyst is usually an olefin polymerization catalyst together with an organometallic compound (B), an organosilane compound (C) or a compound (D) having two or more ether bonds existing through a plurality of atoms. In some cases, only the prepolymerization catalyst can be used as the olefin polymerization catalyst although it is formed.
When the organosilane compound (C) or the compound (D) having two or more ether bonds existing through a plurality of atoms is not used in the prepolymerization, the organosilane compound (C) together with the prepolymerization catalyst in the main polymerization Alternatively, the olefin polymerization catalyst may be formed by using the compound (D) having two or more ether bonds existing through a plurality of atoms.

The olefin polymerization catalyst according to the present invention may contain other components useful for the polymerization of olefins, in addition to the above components. Olefin Polymerization Method In the olefin polymerization method according to the present invention, the solid titanium catalyst component (A) as described above and the organometallic compound (B) are used.
And an organic silane compound (C) or a compound (D) having two or more ether bonds existing through a plurality of atoms as necessary, or a solid titanium catalyst component (A) and an organic compound. The metal compound (B) and the organosilane compound (C) having at least one alkoxy group as necessary, or the compound (D) having two or more ether bonds existing through a plurality of atoms, an olefin The olefin is polymerized or copolymerized in the presence of a catalyst containing a prepolymerized catalyst having been prepolymerized. When using a prepolymerization catalyst, (B) an organometallic compound, (C) an organosilane compound having at least one alkoxy group, and (D) two or more existing through a plurality of atoms, if necessary. It is possible to use at least one compound selected from the above-mentioned compounds having an ether bond.

As such an olefin, specifically, an α-olefin having 2 or more carbon atoms similar to that used in the prepolymerization can be used, and further, cyclopentene, cycloheptene, norbornene, 5-ethyl-2.
-Norbornene, tetracyclododecene, 2-ethyl-1,4,
Cycloolefins such as 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, styrene, dimethylstyrene, allylnaphthalene, allylnorbornane, vinylnaphthalene, allyltoluene, allylbenzene, Vinyl compounds such as vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and allyltrialkylsilanes can also be used.

Of these, ethylene, propylene, 1-
Butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-
Methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene and the like are preferably used. Further, a small amount of diene compound may be copolymerized with the olefin. Specific examples of such a diene compound include 1,3-butadiene and 1,3-butadiene.
Pentadiene, 1,4-pentadiene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-
1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl- 1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl- Examples thereof include 1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. You may use these in combination of 2 or more types.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the polymerization takes the reaction form of slurry polymerization, the above-mentioned inert organic solvent can be used as the reaction solvent, or a liquid olefin at the reaction temperature can be used. In the polymerization, the solid titanium catalyst component (A) or the prepolymerization catalyst is usually converted into titanium atoms per 1 liter of the polymerization volume and is usually about 1 × 10 ^−5.
~ 1 mmol, preferably about 1 x 10 ^{-4 to} 0.1 mmol.

The organometallic compound (B) is the compound (B)
It is used in an amount such that the metal atom therein is usually about 1-2000 mol, preferably about 2-500 mol, per 1 mol of titanium atom in the polymerization system. Organosilane compound (C)
Is usually used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the metal atom of the organometallic compound (B).

If a prepolymerization catalyst is used during this polymerization, it may not be necessary to add the organometallic compound (B) and the organosilane compound (C). When the olefin polymerization catalyst is formed from the components (B) and / or (C) together with the prepolymerization catalyst, these respective components (B) and (C) can be used in the amounts as described above. If hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained.

In the olefin polymerization method according to the present invention,
Depending on the type of olefin, the form of polymerization, etc.,
The polymerization is usually about 20 to 150 ° C., preferably about 50 to 1
It is carried out at a temperature of 00 ° C. and under atmospheric pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . In the polymerization method of the present invention, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In the present invention, an olefin homopolymer may be produced, or a random copolymer or a block copolymer may be produced from two or more kinds of olefins. The method of the present invention is a process for producing a highly stereoregular propylene homopolymer, a random copolymer of propylene and at least one monomer selected from ethylene and an olefin having 4 to 20 carbon atoms, which is decane-capable. It is particularly suitable for the production of low soluble copolymers. In the production of the random copolymer, the amount of the comonomer to be reacted with propylene is 0 to 500 g, preferably 0.5 to 100 g, and more preferably 5 to 10 g of ethylene per 1 kg of propylene, and the number of carbon atoms is The olefin having 4 or more is 0 to 2000 g, preferably 10 to 1000 g, and more preferably 50 to 500 g. The obtained random copolymer contains the propylene unit in an amount of 85 mol% or more, preferably 90 mol% or more, more preferably 93 mol% or more.

The ethylene content of the copolymer of propylene and at least one monomer selected from ethylene and α-olefins having 4 to 20 carbon atoms or the α-olefin content having 4 to 20 carbon atoms is It can be measured as follows. The ethylene having an ethylene content means isolated ethylene. The term "isolated ethylene" means an ethylene unit in a portion where three or more ethylene units are continuously polymerized in the polymer chain, and the isolated ethylene content (C ₂ ) is measured as follows. That is,
Using a hydraulic molding machine manufactured by Toho Press Co., Ltd., 0.5 g of the sample is heated for 2 minutes and 30 seconds, degassed at 20 atm, and then pressed at 80 atm for 10 seconds. Subsequently, a film is obtained by pressing at 100 atm for 1 minute using a hydraulic molding machine in which cooling water is circulated. At this time, an iron spacer is used so that the obtained film has a thickness of about 0.3 mm. The obtained film was manufactured by JASCO D
800 using S-701G type diffraction grating infrared spectrophotometer
The infrared absorption spectrum in the region of ˜650 cm ⁻¹ is measured by the transmittance. Around 760 cm ^-1 in the chart obtained, and 7
A common tangent line of the maximum points near 00 cm ^-1 is drawn as a baseline. Transmittance (T%) at the minimum absorption point at 733 cm ^-1
And a perpendicular to the wavenumber line from the absorption minimum point at 733 cm ⁻¹ , and the transmittance (T _{0 at} the intersection of the perpendicular and the baseline).
%), And the absorbance at ₇₃₃ cm ⁻¹ (D ₇₃₃ = log
Calculate (T ₀ / T)). Next, the isolated ethylene content rate (C ₂ ) is determined from the absorbance (D ₇₃₃ ) at ₇₃₃ cm ⁻¹ and the thickness (L (mm)) of the film used for the measurement by the following formula.

Isolated ethylene content (%) = 6.17 × (D ₇₃₃ / L) The 1-butene content (C ₄ ) as a representative of C _{4 to} C ₂₀ α-olefin content is as follows. Can be measured. That is, a film is obtained from 0.5 g of the sample in the same manner as described above. At this time, an iron spacer is used so that the obtained film has a thickness of about 0.3 mm. About the obtained film, the infrared absorption spectrum of 800-700 cm < ^-1 > area | region is measured by the transmittance | permeability using the JASCO make A-302 type | mold diffraction grating infrared spectrophotometer. And around 775cm ^-1 of the resulting chart, drawing a common tangent of the maximum point in the vicinity of 750 cm ^-1, and baseline. 765c
The transmittance (T%) at the absorption minimum point of m ^{−1 and} the perpendicular to the wave number line are drawn from the absorption minimum point of 765 cm ⁻¹ , and the transmittance (T ₀ %) at the intersection of the perpendicular and the baseline is read, 7
The absorbance at 65 cm ⁻¹ (D ₇₆₅ = log (T ₀ / T)) is calculated. Next, the 1-butene content (C ₄ ) was measured for the absorbance (D ₇₆₅ ) at 733 cm ⁻¹ and the thickness (L) of the film used for the measurement.
(Mm)) by the following formula.

1-Butene content (%) = 7.77 × (D ₇₆₅ / L)

[0100]

EFFECT OF THE INVENTION By using the olefin polymerization catalyst containing the solid titanium catalyst component according to the present invention, a polyolefin having a high stereoregularity can be produced with an extremely high polymerization activity, and a polyolefin having a low stereoregularity can be produced. The amount produced is small.

[0101]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0102]

Example 1 Preparation of solid titanium (i-1) 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 2-ethylhexyl alcohol 3
5.1 ml (225 mmol) were mixed and the mixture was mixed at 130 ° C. for 2 minutes.
Heated for a period of time to give a homogeneous solution. Thereafter, 1.67 g (11.25 mmol) of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride 20 kept at -20 ° C was used.
The total amount was dropped into 0 ml (1.8 mol) over 1 hour. After dropping, the temperature was raised to 110 ° C over 4 hours, and 110 ° C
Diisobutyl phthalate 5.03ml
(18.8 mmol) and 2-isopropyl-2-isobutyl-
0.043 ml (0.188 mmol) of 1,3-dimethoxypropane was added. The mixture was subsequently stirred for 1.5 hours at 110 ° C.

After completion of the reaction for 1.5 hours, the solid substance was collected by hot filtration and washed with decane at 90 ° C. and hexane at room temperature until titanium was not detected in the filtrate. Solid titanium (i-1) thus obtained
Is titanium 6.3% by weight, magnesium 12% by weight, chlorine 49% by weight, diisobutyl phthalate 2%.
It contained 5.1% by weight and 0.1% by weight of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane. Therefore,
The electron donor / titanium (weight ratio) was 3.98.

Preparation of solid titanium catalyst component (A-1) (pole
Treatment with a polar compound) In a 200 ml glass reactor sufficiently replaced with nitrogen,
2,4-dichlorotoluene 150ml, titanium tetrachloride 5ml
Then, 0.61 ml of diisobutyl phthalate was added, and then 6.1 g of the solid titanium (i-1) obtained above was charged. Then, the temperature in the reactor was raised to 130 ° C., and the mixture was stirred at that temperature for 1 hour. After the contact treatment for 1 hour, solid-liquid separation was performed by hot filtration, and the obtained solid part was separated into 9
With decane at 0 ° C. and hexane at room temperature in the catalyst
It was washed until the content of 2,4-dichlorotoluene was 1% by weight or less. As a result, 1.2% by weight of titanium, 20% by weight of magnesium, 14.1% by weight of diisobutyl phthalate, and 0.1% by weight of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane were included in a solid state. Titanium catalyst component (A-
1) got. Therefore, electron donor / titanium (weight ratio)
Was 11.8, and the titanium content was 81% by weight lower than that before the contact treatment.

Preparation of Prepolymerization Catalyst (P-1) 50 ml of hexane was placed in a 200 ml glass reactor purged with nitrogen, 2.5 mmol of triethylaluminum and 2-isopropyl-2-isobutyl-1,3-dimethoxy were added. After charging 0.5 mmol of propane and 0.25 mmol of the solid titanium catalyst component (A-1) obtained above in terms of titanium atom, while maintaining the temperature in the system at 20 ° C.
Propylene was fed in an amount of 1.6 l / h for 1 hour. By the operation, solid titanium catalyst component (A-1) 1
3 g of propylene was prepolymerized per g.

Main Polymerization Propylene was added to an autoclave having an internal volume of 2 liters in an amount of 50
0 g and 7.5 N-liter of hydrogen were charged and the temperature in the system was raised to 60 ° C. Thereafter, 0.5 mmol of triethylaluminum, 0.5 mmol of dicyclopentyldimethoxysilane and the prepolymerization catalyst (P-
Polymerization was initiated by adding 0.002 mmol of 1) in terms of titanium atom. Polymerization was carried out for 1 hour while maintaining the temperature in the system at 70 ° C. After 1 hour, the polymerization was stopped by adding ethanol and the unreacted propylene was purged to obtain an MFR of 99 g / 10 minutes, a decane-soluble component amount of 0.62% by weight, and a ¹³ C- NMR
The pentad fraction (mmmm) measured by
%, And 302.6 g of polypropylene having a bulk specific gravity of 0.405 g / cc was obtained.

[0108]

[Comparative Example 1] Preparation of solid titanium catalyst component (A-1 ratio)
(Contact Treatment with Polar Compound) The same procedure as in Example 1 was performed except that titanium tetrachloride and diisobutyl phthalate were not used, and 1.1% by weight of titanium, 20% by weight of magnesium and diisobutyl were used. Phthalate 13.2% by weight, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane 0.1.
A solid titanium catalyst component (A-1 ratio) containing 1% by weight was obtained.

Preparation of Prepolymerization (P-1 Ratio) Example except that solid titanium catalyst component (A-1 ratio) was used in place of solid titanium catalyst component (A-1) in Example 1. The same procedure as in 1 was carried out to obtain a prepolymerized (P-1 ratio). Main Polymerization The same procedure as in Example 1 was carried out except that in Example 1, a preliminary polymerization (P-1 ratio) was used instead of the preliminary polymerization (P-1). As a result, the MFR was 150 g / 10 min, the amount of decane-soluble component was 0.61% by weight, the pentad fraction (mmmm) measured by ¹³ C-NMR was 98.0%, and the bulk specific gravity was 112.5 g of a polypropylene having an N of 0.392 g / cc was obtained.

[0110]

Example 2 Preparation of Solid Titanium (i-2) In Example 1, 2-isopropyl-2-isobutyl-1,3-
A solid form containing 5.7% by weight of titanium, 13% by weight of magnesium, 53% by weight of chlorine, and 20.6% by weight of diisobutyl phthalate was performed in the same manner as in Example 1 except that dimethoxypropane was not used. Titanium (i-2) was obtained. Therefore, the electron donor / titanium (weight ratio) is 3.
It was 61.

Preparation of solid titanium catalyst component (A-2) (pole
Treatment with a polymerizable compound) In Example 1, except that solid titanium (i-2) was used instead of solid titanium (i-1), and the amount of solid titanium charged was 5.6 g. Was carried out in the same manner as in Example 1 to obtain a solid titanium catalyst component (A-2) containing 1.2% by weight of titanium, 21% by weight of magnesium and 14.6% by weight of diisobutylphthalate. Therefore, the electron donor / titanium (weight ratio) was 12.2, and the titanium content was 79% by weight lower than that before the contact treatment.

Preparation of Prepolymerization (P-2) Example 1 was repeated except that the solid titanium catalyst component (A-2) was used in place of the solid titanium catalyst component (A-1). The same procedure was followed to obtain a prepolymerized (P-2). Main Polymerization The same procedure as in Example 1 was carried out except that the solid titanium catalyst component (A-2) was used in place of the solid titanium catalyst component (A-1). As a result, MFR is 110g
/ 10 min, decane-soluble component is 0.68% by weight, pentad fraction measured by ¹³ C-NMR (mm
mm) is 98.1% and the bulk specific gravity is 0.402 g / c.
232.2 g of polypropylene, which is c, was obtained.

[0113]

Example 3 Preparation of Solid Titanium (i-3) In Example 1, 2-isopropyl-2-isobutyl-1,3-
The amount of dimethoxypropane added was 0.217 ml (0.9
4 mmol) except that the same procedure as in Example 1 was performed,
Titanium is 6.1% by weight, magnesium is 12% by weight, chlorine is 50% by weight, diisobutylphthalate is 23.5% by weight, and 2-isopropyl-1,3-dimethoxypropane is 0.1% by weight.
Solid titanium (i-3) containing 5% by weight was obtained. Therefore, the electron donor / titanium (weight ratio) was 3.85.

Preparation of solid titanium catalyst component (A-3) (pole
Treatment with a polar compound) In a 200 ml glass reactor sufficiently replaced with nitrogen,
2,4-dichlorotoluene 150ml, titanium tetrachloride 0.6
5 ml, diisobutyl phthalate 0.052 ml, and 2-ethylhexyl alcohol 0.039 ml were charged, and the mixture was kept at 110 ° C. for 1.5 hours while stirring. After holding for 1.5 hours, the temperature was cooled to room temperature, and then 6.1 g of the solid titanium (i-3) obtained above was charged. Then, the temperature in the reactor was raised to 130 ° C., and the mixture was stirred at that temperature for 1 hour. After the contact treatment for 1 hour, solid-liquid separation is performed by hot filtration, and the obtained solid part is washed with decane at 90 ° C and hexane at room temperature until 2,4-dichlorotoluene in the catalyst becomes 1% by weight or less. did. As a result, 1.2% by weight of titanium, 20% by weight of magnesium, 13.3% by weight of diisobutylphthalate, 2-isopropyl-2-isobutyl-1,
A solid titanium catalyst component (A-3) containing 0.6% by weight of 3-dimethoxypropane was obtained. Therefore, the electron donor / titanium (weight ratio) was 11.1, and the titanium content was reduced by 80% by weight as compared with that before the contact treatment.

Preparation of prepolymerization catalyst (P-3) Example 1 except that the solid titanium catalyst component (A-3) was used in place of the solid titanium catalyst component (A-1) in Example 1. The same procedure was followed to obtain a prepolymerized catalyst (P-3). Main Polymerization The same procedure as in Example 1 was carried out except that the prepolymerization catalyst (P-3) was used in place of the prepolymerization catalyst (P-1). As a result, MFR was 120 g / 10 minutes, the amount of decane-soluble component was 0.52% by weight, and ¹³ C-NMR
The pentad fraction (mmmm) measured by
%, And 194.0 g of polypropylene having a bulk specific gravity of 0.382 g / cc was obtained.

[0116]

Example 4 Preparation of solid titanium catalyst component (A-4) (pole
Treatment with a polar compound) The procedure of Example 3 was repeated except that the solid titanium (i-1) was used in place of the solid titanium (i-3), and titanium was added to 1.0 % By weight, 21% by weight of magnesium, 12.3% by weight of diisobutyl phthalate and 0.2% of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane.
A solid titanium catalyst component (A-4) containing 1% by weight was obtained.
Therefore, the electron donor / titanium (weight ratio) was 12.3, and the titanium content was 84% by weight lower than that before the contact treatment.

Preparation of prepolymerization catalyst (P-4) Same as Example 1 except that solid titanium catalyst component (A-4) was used in place of solid titanium catalyst component (A-1). The prepolymerization catalyst (P-4) was obtained. Main Polymerization Example 1 was repeated except that the prepolymerization catalyst (P-4) was used in place of the prepolymerization catalyst (P-1). As a result, the MFR was 99 g / 10 min, the amount of decane-soluble component was 0.52% by weight, and the pentad fraction (mmmm) measured by ¹³ C-NMR was 98.7%.
Thus, 236.2 g of polypropylene having a bulk specific gravity of 0.388 g / cc was obtained.

[0118]

Example 5 Main Polymerization Example 4 except that the amount of dicyclopentyldimethoxysilane added was 0.15 mmol.
I went the same way. As a result, the MFR was 115 g / 10 minutes, the amount of decane-soluble components was 0.68% by weight, and ¹³ C
-284.0 g of polypropylene having a pentad fraction (mmmm) measured by NMR of 97.8% and a bulk specific gravity of 0.402 g / cc was obtained.

[0119]

Example 6 Main Polymerization The same procedure as in Example 5 was repeated except that cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane in Example 5. As a result, MFR is 2
35 g / 10 min, the amount of decane-soluble component was 0.82% by weight, the pentad fraction (mmmm) measured by ¹³ C-NMR was 96.6%, and the bulk specific gravity was 0.394.
193.6 g of polypropylene having g / cc was obtained.

[0120]

[Example 7] The same as Example 4 except that the amount of the prepolymerized catalyst (P-4) added was 0.0015 mmol in terms of titanium atom and no dicyclopentyldimethoxysilane was added. I went the same way. As a result, MFR is 470g /
10 min, decane-soluble component is 1.58% by weight, pentad fraction measured by ¹³ C-NMR (mm
mm) is 95.9%, and the bulk specific gravity is 0.400 g / c.
229.4 g of polypropylene, which is c, was obtained.

[0121]

Example 8 Preparation of Prepolymerization Catalyst (P-5) In Example 4, the amount of triethylaluminum added was 0.75 mmol, and 2-isopropyl-2-isobutyl-
A prepolymerization catalyst (P-5) was obtained in the same manner as in Example 4 except that 1,3-dimethoxypropane was not added.

Main Polymerization The same procedure as in Example 6 was carried out except that the prepolymerization catalyst (P-5) was used in place of the prepolymerization catalyst (P-4). As a result, the MFR was 82 g / 10 min, the amount of decane-soluble component was 0.92% by weight, and the pentad fraction (mmmm) measured by ¹³ C-NMR was 96.9%.
And 183.3 g of polypropylene having a bulk specific gravity of 0.399 g / cc was obtained.

[0123]

Example 9 Preparation of Prepolymerization Catalyst (P-6) Same as Example 4 except that 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was replaced by dicyclopentyldimethoxysilane in Example 4. went. In the present Polymerization Example 4, the prepolymerization catalyst (P-6) was used in place of the prepolymerization catalyst (P-5), the addition amount was 0.003 mmol in terms of titanium atom, and the addition amount of triethylaluminum was 0. The procedure of Example 4 was repeated, except that the amount of addition of 0.6 mmol and dicyclopentyldimethoxysilane was changed to 0.6 mmol. As a result, MFR is 13.5 g /
10 min, decane-soluble component is 0.27% by weight, pentad fraction measured by ¹³ C-NMR (mm
mm) is 98.8% and the bulk specific gravity is 0.389 g / c.
244.9 g of polypropylene, which is c, was obtained.

[0124]

Example 10 In the present Polymerization Example 9, the amount of triethylaluminum added was 0.4 mmol, cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane, and the amount added was 0.08 mmol. The procedure of Example 9 was repeated, except that the amount of the catalyst (P-6) added was 0.002 mmol in terms of titanium atom and the amount of hydrogen added was 3 N-liter. As a result, MFR is 5.4g / 10
The amount of the decane-soluble component is 0.33% by weight,
Polypropylene with bulk specific gravity of 0.397 g / cc is 3
27.9 g was obtained.

[0125]

Example 11 Main Polymerization Propylene was added to an autoclave having an internal volume of 2 liters in an amount of 50.
After charging 0 g of hydrogen and 7.5 N-liter of hydrogen, 0.5 mmol of triethylaluminum, 0.05 mmol of dicyclopentyldimethoxysilane, and the solid titanium catalyst component (A-4) prepared in Example 4 were added. 0.002 mmol of titanium atom was added. Then, the temperature in the system was raised to 60 ° C. in 7 to 9 minutes to start the polymerization. Polymerization was carried out for 1 hour while maintaining the temperature in the system at 70 ° C. After 1 hour, the polymerization was stopped by adding ethanol, and the unreacted propylene was purged to make the MFR 1
364.5 g of polypropylene having 9.5 g / 10 minutes, a decane-soluble component amount of 0.33% by weight, and a bulk specific gravity of 0.422 g / cc were obtained.

[0126]

Example 12 Main Polymerization Example 11 was repeated except that cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane. as a result,
The MFR is 88 g / 10 minutes, and the decane-soluble component amount is 1.
235.4 g of polypropylene having 11% by weight and a bulk specific gravity of 0.422 g / cc was obtained.

[0127]

Example 13 Main Polymerization The same procedure as in Example 11 was repeated except that 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was used instead of dicyclopentyldimethoxysilane. As a result, the MFR was 350 g / 10 minutes, the decane-soluble component amount was 0.85% by weight, and the bulk specific gravity was 0.42.
223.9 g of polypropylene having 8 g / cc was obtained.

[0128]

Example 14 Preparation of solid titanium catalyst component (A-5)
(Contact Treatment with Polar Compound) In Example 3, solid titanium (i-1) was used instead of solid titanium (i-3), and the addition amount of titanium tetrachloride was set to 0.
Add 49 ml of diisobutyl phthalate to 0.01
The same procedure as in Example 4 was carried out except that the amount was 4 ml. As a result, titanium was 1.3% by weight, magnesium was 21% by weight, diisobutylphthalate was 14.6% by weight, and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was 0.1% by weight.
A solid titanium catalyst component (A-5) containing 1% by weight was obtained. Therefore, the electron donor / titanium (weight ratio) is 11.2.
The titanium content was 79% by weight lower than that before the contact treatment.

Preparation of Prepolymerized Catalyst (P-7) Example 1 except that the solid titanium catalyst component (A-5) was used in place of the solid titanium catalyst component (A-1) in Example 1. I went the same way. Main Polymerization The same procedure as in Example 1 was carried out except that the prepolymerization catalyst (P-7) was used in place of the prepolymerization catalyst (P-1). As a result, MFR was 120 g / 10 min, the amount of decane-soluble component was 0.65% by weight, and ¹³ C-NMR
The pentad fraction (mmmm) measured by
%, And 177.1 g of polypropylene having a bulk specific gravity of 0.415 g / cc was obtained.

[0130]

Example 15 Main Polymerization Propylene was added to an autoclave having an internal volume of 2 liters by adding 40 parts of propylene.
0 g, ethylene 2.4 N-liter, 1-butene 40
After charging 7.5 g of hydrogen and 7.5 N-liter of hydrogen, 0.5 mmol of triethylaluminum, 0.15 mmol of dicyclopentyldimethoxysilane, and the solid titanium catalyst component (A-1) prepared in Example 1 were added. 0.004 mmol of titanium atom was added. Then, the temperature in the system was raised to 60 ° C. in about 10 minutes to start the polymerization. Polymerization was carried out for 40 minutes while maintaining the temperature in the system at 65 ° C. Subsequent operations were carried out in the same manner as in Example 1, so that the MFR was 1
1.5 g / 10 min, melting point 132 ° C., ethylene content 3.6 mol%, 1-butene content 2.2 mol%, decane soluble component amount 3.6 wt. % Of propylene / ethylene / 1-butene ternary random copolymer was obtained.

[0131]

Example 16 Main Polymerization In the polymerization of Example 11, 4 N-liter of hydrogen, 0.005 mmol of dicyclopentyldimethoxysilane, 0.045 mmol of propyltriethoxysilane and solid titanium catalyst prepared in Example 1 were used. Ingredient (A-
Example 1 was repeated except that 0.0015 mmol of 1) was added in terms of titanium atom. As a result, MF
R was 45 g / 10 min, the amount of decane-soluble component was 0.9% by weight, and 163 g of polypropylene having a bulk specific gravity of 0.438 g / cc was obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of a step of preparing a solid titanium catalyst component according to the present invention, and a step of preparing an olefin polymerization catalyst containing the solid titanium catalyst component.

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Claims (9)

[Claims] 1. A solid titanium containing (i) magnesium, titanium, a halogen and an electron donor (c), and titanium is not desorbed by hexane washing at room temperature, and (ii) a dipole moment. Is 0.50 to 4.00 Deby
the polar compound of e and (iii) liquid titanium (d) and / or electron donor (e) are contacted at 40 ° C. or higher,
The titanium content in the solid titanium (i) is reduced by 25% by weight or more, and the weight ratio of the total amount of the electron donor (c) and the electron donor (e) to titanium (electron donor (c +
e) / titanium) is a solid titanium catalyst component of 7 or more, and a solid titanium catalyst component (A) is produced.
Manufacturing method. 2. The method for producing a solid titanium catalyst component according to claim 1, wherein the polar compound (ii) is a halogen-containing aromatic hydrocarbon. 3. The solid titanium (i), wherein the weight ratio of the electron donor (c) and titanium (electron donor (c) / titanium) is 6 or less. 3. The method for producing a solid titanium catalyst component according to 1 or 2. 4. A solid (1) obtained by bringing the solid titanium (i) into contact with (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor. The method for producing a solid titanium catalyst component according to any one of claims 1 to 3, wherein 5. A solid (1) obtained by bringing the solid titanium (i) into contact with (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor. The method for producing a solid titanium catalyst component according to any one of claims 1 to 3, which is a solid (2) obtained by further contacting (b) a liquid titanium compound. . 6. A solid titanium catalyst component (A) produced by the method according to claim 1, (B) an organometallic compound, and (C) an organosilane compound having at least one alkoxy group, or ( D) A catalyst for olefin polymerization, which comprises a compound having two or more ether bonds existing through a plurality of atoms. 7. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 6. 8. The solid titanium catalyst component (A) according to claim 1, an organometallic compound (B), and, if necessary, an organosilane compound (C) having at least one alkoxy group or a plurality of atoms. A prepolymerization catalyst for olefin polymerization, wherein an olefin is prepolymerized with a compound (D) having two or more ether bonds present via 9. The prepolymerization catalyst for olefin polymerization according to claim 8, and optionally (B) an organometallic compound,
Olefin polymerization catalyst comprising (C) an organosilane compound having at least one alkoxy group and (D) at least one compound selected from compounds having two or more ether bonds existing through a plurality of atoms. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of: