JPH11302314A - Catalyst for olefin polymerization and olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization capable of producing a polyolefin having a wide molecular weight distribution, excellent moldability and high stereoregularity and to provide a method for polymerizing an olefin using the catalyst for olefin polymerization. SOLUTION: This catalyst for olefin polymerization comprises (A) a solid titanium catalytic component containing magnesium, titanium, a halogen and an electron donor, (B) an organoaluminum compound and (C) an organosilicon compound of the formula R<1> m R<2> n Si(OR<3> )4-m-n ((m) is, 2 or 3, (n is 0, 1 or 2 and 1<=m+n<4; R<1> is a cyclic amino group in which N is directly bonded to Si and contains at least one hetero atom except N directly bonded to Si; R<2> is a hydrocarbon group; R<3> is a hydrocarbon). The catalytic component may be prepolymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization capable of producing a polyolefin having a wide molecular weight distribution and excellent moldability, in particular, a highly stereoregular polyolefin with high polymerization activity, and a method for polymerizing olefin.

[0002]

BACKGROUND OF THE INVENTION As a catalyst for polyolefin production, a Ziegler-Natta catalyst comprising a titanium catalyst component and an organoaluminum compound has been widely used. In particular, a carrier-supported solid titanium catalyst component has been used as the titanium catalyst component. It is known that a catalyst containing the compound exhibits high polymerization activity. Particularly, a catalyst containing a magnesium chloride-supported titanium catalyst component among solid titanium catalyst components exhibits high polymerization activity and can produce a polyolefin having high stereoregularity when an olefin such as propylene is polymerized. Known as a catalyst.

[0003] In particular, when producing a highly stereoregular polyolefin such as polypropylene, a solid titanium catalyst component containing an internal donor (internal electron donor), an organoaluminum compound, and an external donor (external electron donor) are usually used. ) Is used.

[0004] For example, the present applicant has also disclosed
No. 006, it is possible to produce a highly stereoregular polyolefin in a high yield, and at least a carboxylic acid ester as an internal donor is used as a catalyst for producing a polyolefin excellent in particle size, particle size distribution, particle properties and bulk density. And an organosilicon compound having a Si-NC bond such as Si-OC or phenyldiethoxydiethylaminosilane as an external donor (external electron donor), together with an organoaluminum compound. A catalyst for olefin polymerization was proposed.

[0005] JP-8-143621 and JP-A No. 8-120021, as external donor, as described above, an organic silicon compound having two cyclic amino groups such as piperidino group, or R ¹ _n Si (OR ² ) _3-n
R ³ (R ³ : cyclic amino group, R ¹ : having 1 to 2 carbon atoms)
It has also been proposed that the use of an organosilicon compound represented by the hydrocarbon group of No. 4 and n is 0 to 2) can increase the melt flowability (MFR) without lowering the stereoregularity of the obtained polyolefin. .

The present inventor has continued his research on such olefin polymerization catalysts. As a result, together with the solid titanium catalyst component and the organoaluminum compound, among the organosilicon compounds as external donors, N was substituted by Si as a substituent.
An olefin polymerization catalyst formed by using an organosilicon compound having a cyclic amino group directly bonded to Si and having at least one hetero atom other than N directly bonded to Si is required to polymerize an olefin with high activity. It has been found that a polyolefin having a wide molecular weight distribution and excellent moldability, particularly a highly stereoregular polyolefin, can be obtained.

[0007]

An object of the present invention is to provide an olefin polymerization catalyst capable of producing a polyolefin having a wide molecular weight distribution and excellent moldability, especially a polyolefin having a high stereoregularity, with high polymerization activity.
And an olefin polymerization method using the olefin polymerization catalyst.

[0008]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
(A) a solid titanium catalyst component containing magnesium, titanium, a halogen, and an electron donor; (B) an organoaluminum compound; and (C) an organosilicon compound represented by the following formula (1). Features.

R ¹ _m R ² _n Si (OR ³ ) _4-mn (1) (wherein m is 1, 2 or 3, n is 0, 1 or 2 and 1 ≦ m + n < 4, R ¹ is N for Si
Is a cyclic amino group directly bonded to Si and has at least one hetero atom other than N directly bonded to Si, and when m is 2 or 3, a plurality of groups represented by R ¹ may be the same as each other. R ² is a hydrocarbon group, and when n is 2, the two groups represented by R ² may be the same or different, and R ³ is a hydrocarbon;
A plurality of groups represented by R ³ when -m-n is 2 or 3 may be the same or different from each other. In addition, the olefin polymerization catalyst according to the present invention provides an olefin polymerization catalyst comprising [I] the (A) solid titanium catalyst component described above, (B) an organoaluminum compound, and, if necessary, (D) an electron donor. The catalyst for use may be formed from a prepolymerized catalyst in which an olefin is prepolymerized, [II] an organosilicon compound represented by the above formula (1), and [III] an organoaluminum compound as required.

As the (D) electron donor at the time of prepolymerization,
The organosilicon compound represented by the above formula (1) can also be used. In the organosilicon compound represented by the formula (1), in the formula, R ³ is preferably a cyclic hydrocarbon group having 3 to 10 carbon atoms.

The method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized in the presence of an olefin polymerization catalyst as described above.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization. The term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

First, the solid titanium catalyst component (A) used in preparing the olefin polymerization catalyst according to the present invention will be described. The solid titanium catalyst component (A) used in the present invention contains at least magnesium, titanium, halogen, and an electron donor as essential components. The preparation method of the solid titanium catalyst component is not limited as long as it contains these components, and (i) a magnesium compound, (ii) a titanium compound, and (iii) an electron donor are contacted by various methods. Can be prepared. The components used for preparing the solid titanium catalyst component (A) are shown below.

(I) Magnesium Compound The magnesium compound (i) used in the present invention includes 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 an organic magnesium compound represented by the following general formula. During X _n MgR _2-n wherein, n = 0 ≦ n <2, R is hydrogen or an alkyl group 1 to 20 carbon atoms, an aryl group or a cycloalkyl group, when n is 0 2 R may be the same or different. X is a halogen atom or an alkoxy group.

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

Specific examples of the magnesium compound having no reducing ability include magnesium chloride, magnesium bromide,
Magnesium halides such as magnesium iodide and magnesium fluoride; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; ants such as phenoxymagnesium chloride and methylphenoxymagnesium chloride Roxy magnesium halide; alkoxymagnesium such as diethoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, di-n-octoxymagnesium, di-2-ethylhexoxymagnesium, ethoxymethoxymagnesium; ants such as diphenoxymagnesium, dimethylphenoxymagnesium Roxy magnesium; magnesium laurate, magnesium stearate And the like. Other magnesium metal,
Magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order 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 converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

The above-mentioned magnesium compound having a reducing ability and the magnesium compound having no reducing ability form complex compounds and complex compounds with other metals such as aluminum, zinc, boron, beryllium, sodium and potassium. Or a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more of the above compounds may be used in combination.

As the magnesium compound used for preparing the solid titanium catalyst component, any magnesium compound other than those described above can be used. However, in the finally obtained solid titanium catalyst component, a magnesium compound containing halogen is present. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with a halogen-containing compound during the preparation.

Of these, magnesium compounds having no reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferred.

In the present invention, when preparing the solid titanium catalyst component, the above magnesium compound is preferably used in a liquid state. The solid magnesium compound can be made into a liquid state using an electron donor (iv) such as alcohols, phenols, ketones, aldehydes, ethers, amines, and pyridines.

The compound used as the electron donor (iv) may be the same as the electron donor (iii) used in preparing the solid titanium catalyst component. In order to make a solid magnesium compound into a liquid state,
Solid magnesium compound and metal salts such as tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, tetraethoxyzirconium, etc. It may be performed by contact.

Of these, alcohols and metal acid esters are particularly preferably used. The reaction between the solid magnesium compound and the electron donor (iv) (or metal acid ester) is carried out by bringing the solid magnesium compound into contact with the electron donor (iv) (or metal acid ester), if necessary. The method of heating is common. This contact
The reaction is usually performed at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.

The above reaction may be carried out in the presence of a hydrocarbon solvent or the like. Specific examples of such hydrocarbon solvents include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, and aliphatic hydrocarbons such as kerosene; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane,
Alicyclic hydrocarbons such as cyclohexene, halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, and chlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene are used.

(Ii) Titanium Compound In the present invention, a liquid titanium compound is preferably used as the titanium compound (ii), and a tetravalent titanium compound is particularly preferably used. As such a tetravalent titanium compound,
Examples include compounds represented by the following general formula.

[0028] During _{Ti (OR) g X 4-} g formulas, R is a hydrocarbon group, X is a halogen atom, a 0 ≦ g ≦ 4. Specific examples of such a tetravalent titanium compound include TiCl ₄ , TiBr ₄ , and TiI.
Titanium tetrahalide such as ₄ , Ti (OCH ₃ ) Cl
_{3, Ti (OC 2 H 5} ) Cl 3, Ti (On-C 4 H 9) Cl 3,
Trihalogenated alkoxytitanium such as Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ )
₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) _{2
Cl 2, Ti (OC 2 H} 5) dihalogenated dialkoxy titanium, such as _{2 Br 2, Ti (OCH 3} ) 3 Cl, Ti (OC
_{2 H 5) 3 Cl, Ti} (On-C 4 H 9) 3 Cl, Ti (OC 2
Monohalogenated trialkoxy titanium such as H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On
And tetraalkoxy titanium such as -C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds can be used in combination of two or more. The above titanium compound may be used after being diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon.

(Iii) Electron Donor In the present invention, when preparing the solid titanium catalyst component, it is preferable to use a polyvalent carboxylic acid ester as the electron donor (iii).

The polycarboxylic acid ester is represented by the following general formula, for example.

[0032]

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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 hydrocarbon group. Or 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 cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, and is, for example, C—O—C, COOR, COOH, OH, SO
_It has groups such as ₃ H, —C—N—C—, and NH ₂ .

Specific examples of such polycarboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, and isopropyl malonate. Diethyl acrylate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, β-methyl glutar Polycarboxylic acid esters such as diisopropyl acrylate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate and dioctyl citraconic acid; diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexyl Alicyclic polycarboxylic acid esters such as diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate; Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; heterogeneous groups such as 3,4-furandicarboxylic acid Cyclic polycarboxylic acid esters and the like.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Long chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate can also be mentioned.

Of these, phthalic esters are particularly preferred. In addition, as the electron donor (iii), a polyether compound having two or more ether bonds existing through a plurality of atoms 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. Among these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in an atom existing between two or more ether bonds is preferable. For example, a compound represented by the following formula: Polyethers are preferred.

[0038]

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(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 arbitrary R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and atoms other than carbon may be contained in the main chain. Specific examples of the compound of the polyether represented by the above formula are described in, for example, JP-A-6-279517, and the description of the publication can also be used in the present invention.

Among the above polyethers, for example, 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 1,3-diethers such as 1,2-diphenyl-1,3-dimethoxypropane and 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane are preferably used.

In the present invention, as the electron donor (iii), alcohol, phenol, ketone, aldehyde, ether, amine, carboxylic acid, organic acid halide, ester of organic or inorganic acid, acid amide, acid anhydride, ammonia, Nitriles, isocyanates, nitrogen-containing cyclic compounds, oxygen-containing cyclic compounds, and the like can also be used. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol,
Alcohols having 1 to 18 carbon atoms such as phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol; acetone, methylethylketone, methylisobutylketone, acetophenone , Benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde and naphthaldehyde; and 2 to 15 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether.
20 ethers; amines such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine; acetic acid N, N-dimethylamide, benzoic acid N,
Acid amides such as N-diethylamide, toluic acid N, N-dimethylamide; 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, benzoic acid Ethyl, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 18 carbon atoms such as ethyl carbonate; 2 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride
To 15 acid halides; nitriles such as acetonitrile, benzonitrile, and trinitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; pyrroles such as pyrrole, methylpyrrole, and dimethylpyrrole; pyrroline; Indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine,
Pyridines such as phenylpyridine, benzylpyridine and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines and isoquinolines; tetrahydrofuran;
1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran,
Cyclic oxygen-containing compounds such as pyran and ditedropyran;

Further, as the electron donor (iii), an organosilicon compound as described later as the catalyst component (D), or water, an anionic, cationic or nonionic surfactant can be used.

In the present invention, as the electron donor (iii),
Among the above, polycarboxylic acid esters are particularly preferably used. The electron donor (iii) can be used alone or in combination of two or more.

Preparation of Solid Titanium Catalyst Component (A) In preparing the solid titanium catalyst component, in addition to the above compounds, an organic material containing silicon, phosphorus, aluminum and the like used as a carrier and a reaction aid, etc. A compound or an inorganic compound may be used.

As such a carrier, Al ₂ O ₃ , S
iO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Zn
Resins such as O, SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are exemplified. Among them, Al ₂ O ₃ , SiO ₂ and styrene-divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (A) includes the magnesium compound (i) and the titanium compound (i) as described above.
i) and an electron donor (iii), and can be prepared by any method including a known method. The preparation method is not particularly limited. Magnesium compound (i), liquid titanium compound (ii) and electron donor (ii)
Preferably, i) is contacted.

When the compounds (i) to (iii) are brought into contact with each other to prepare a solid titanium catalyst component, a hydrocarbon solvent can be used if necessary, and the hydrocarbon may be a magnesium compound (i). ) Is similar to the hydrocarbon solvent shown in the liquefaction.

Hereinafter, a specific method for preparing a solid titanium catalyst component will be briefly described with reference to several examples. In the following method, as the organoaluminum compound, those described below as the organoaluminum compound (B) are used. (1) A magnesium compound (i) in a liquid state comprising a magnesium compound, an electron donor (iv) and a hydrocarbon solvent is brought into contact with an organoaluminum compound to precipitate a solid, or a titanium compound (i)
contact with i).

In this step, the electron donor (iii) is brought into contact with the contact product at least once. (2) A titanium compound (ii) and an electron donor (iii) are added to a contact product of an inorganic carrier and an organomagnesium compound (i).
Contact.

At this time, the contact product between the inorganic carrier and the organomagnesium compound (i) is previously converted to a halogen-containing compound and / or
Or you may contact with an organoaluminum compound. (3) From a mixture of a magnesium compound, an electron donor (iv), and optionally a liquid state magnesium compound (i) comprising a hydrocarbon solvent and an inorganic carrier or an organic carrier, an inorganic carrier carrying a magnesium compound is prepared. Alternatively, an organic carrier is prepared and then a titanium compound (ii)
Contact.

In this process, the electron donor (iii) is brought into contact with the contact product at least once. (4) Magnesium compound (i), titanium compound (i
i) contacting an electron donor (iv), optionally a solution further containing a hydrocarbon solvent, with an inorganic or organic carrier and an electron donor (iii). (5) The organomagnesium compound (i) in a liquid state is converted into a halogen-containing titanium compound (ii) and an electron donor (ii).
contact with i). (6) After bringing the organomagnesium compound (i) in a liquid state into contact with a halogen-containing compound, the titanium compound (ii) is brought into contact.

In this step, the electron donor (iii) is used at least once. (7) The halogen-containing magnesium compound (i) is brought into contact with the titanium compound (ii) and the electron donor (iii) in a solid state. (8) An alkoxy group-containing magnesium compound (i)
A halogen-containing titanium compound (ii) and an electron donor (ii
contact with i). (9) A liquid state magnesium compound (i) comprising an alkoxy group-containing magnesium compound and an electron donor (iv) is brought into contact with a titanium compound (ii) and an electron donor (iii). (10) A magnesium compound (i) in a liquid state comprising an alkoxy group-containing magnesium compound and an electron donor (iv) is brought into contact with an organoaluminum compound and then with a titanium compound (ii).

In this process, the electron donor (iii) is brought into contact with the contact product at least once. (11) A liquid magnesium compound (i) having no reducing ability and a titanium compound (ii) are converted into an electron donor (iii)
In the presence or absence of.

In this process, the electron donor (iii) is brought into contact with the contact product at least once. (12) The reaction product obtained in (1) to (11) is further contacted with a titanium compound (ii). (13) The reaction product obtained in (1) to (12) is further contacted with an electron donor (iii) and a titanium compound (ii).

The contact of each component as described above is usually carried out at -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 preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally. For example, the electron donor (iii)
Is in an amount of 0.01 to 10 mol, preferably 0.1 to 5 mol, and the titanium compound (ii) in a liquid state is 0.01 to 100 mol.
It can be used in an amount of 0 mol, preferably 0.1 to 200 mol.

In the present invention, the solid titanium catalyst component thus obtained is preferably washed with a hydrocarbon solvent at 0 to 150 ° C. As the hydrocarbon solvent, the hydrocarbon solvents as described above when liquefying the magnesium compound can be used, and among these, aliphatic hydrocarbon solvents or halogen-free aromatic hydrocarbon solvents include It is preferably used.

In washing the solid titanium catalyst component,
The hydrocarbon solvent is usually from 10 to 500 per gram of the solid.
It can be used in an amount of about ml. The solid titanium catalyst component (A) thus obtained contains magnesium,
It contains titanium, a halogen and an electron donor (iii), and contains titanium in an amount of 0.1 to 10% by weight, preferably 0.2 to 10% by weight.
An electron donor (iii) in a proportion of 95 to 30% by weight in total with magnesium and halogen at a rate of about 7.0% by weight.
In a proportion of 0.5 to 30% by weight.

(B) Organoaluminum Compound In the present invention, examples of the organoaluminum compound used for preparing the catalyst for olefin polymerization include compounds represented by the following general formula.

[0059] R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, n represents a 1 to 3.) R ^a Is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group,
Isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; and isoprenylaluminum. Alkenyl aluminum such as; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide such as dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, Ethyl aluminum Alkylaluminum sesquihalide such as Musesukiburomido; methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

As the organoaluminum compound, the following
The compound represented by the formula can also be mentioned. R^a _nAlY_3-n In the above formula, R^aIs the same as above, and Y is -OR
^bGroup, -OSiR^c _ThreeGroup, -OAlR^d _TwoGroup, -NR
^e _TwoGroup, -SiR^f _ThreeGroup or -N (R^g) AlR^h _TwoBase
And n is 1-2, and R^b, R^c, R^dAnd R
^hIs methyl, ethyl, isopropyl, isobutyl
Group, cyclohexyl group, phenyl group, etc.^eIs
Hydrogen, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc.^fAnd R^gIs
Examples include a methyl group and an ethyl group.

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, and (ii) R ^a _n Al (OSiR ^c ) _3-n For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ A
_{l (OSiMe 3), (iso} -Bu) 2 Al (OSiEt 3) , _{^{etc., (iii) R a n Al}} (OAlR d 2) a compound represented by the _3-n, e.g., _{Et 2 AlOAlEt 2, (iso-} Bu) ₂ A
lOAl etc. _{(iso-Bu) 2, (} iv) R a n Al (NR e 2)
Compounds represented by _3-n , for example, Me ₂ AlNEt ₂ , Et ₂
AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (Me ₃ S
i) _2, (such as _{iso-Bu) 2 AlN (Me} 3 Si) 2, (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] a compound represented by the _3-n, e.g., Et
_{2 AlN (Me) -AlEt 2,} (iso-Bu) 2 AlN (Et)
Al (iso-Bu) ₂ etc.

Further, there may be mentioned similar compounds, for example, organic aluminum compounds in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. 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 Al
Aluminoxanes such as N (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and methylaluminoxane can be mentioned.

As the organoaluminum compound, M ¹
A complex alkyl compound represented by AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms) can also be used. Specifically, Li
_{Al (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like.

[0065] Among the organoaluminum compounds mentioned _{^{above, R a 3 Al, R a}} n Al (OR b) 3-n, R a n A
l organoaluminum compound represented by (OAlR ^d _{2) 3-n} is preferably used.

The organoaluminum compounds can be used alone or in combination of two or more. (C) Organosilicon compound In the present invention, the organosilicon compound represented by the following general formula (1) together with the solid titanium catalyst component (A) and the organoaluminum compound (B) as the catalyst component for olefin polymerization. (C) is used.

R ¹ _m R ² _n Si (OR ³ ) _4-mn (1) In the formula, m is 1, 2 or 3, and preferably 1. n is 0, 1 or 2, and preferably 1.

Further, m and n satisfy 1 ≦ m + n <4. R ¹ is a cyclic amino group in which N is directly bonded to Si, and has at least one hetero atom other than N which is directly bonded to Si. Heteroatoms other than N directly bonded to Si include N, O, B, S, P and the like.

Specific examples of such a cyclic amino group include the following groups.

[0070]

Embedded image

When m is 2 or 3, a plurality of groups represented by R ¹ may be the same or different. R ²
Is a hydrocarbon group, specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl,
a linear or branched C1-C10 hydrocarbon group such as n-pentyl, n-amyl, i-amyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl; 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc.
Alicyclic hydrocarbon groups having 10 to 10 carbon atoms; and aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl, o-tolyl, p-tolyl, and naphthyl. Among these, a cyclic hydrocarbon group having 3 to 10 carbon atoms is preferable, and cyclopentyl, cyclohexyl and the like are preferable.

When n is 2, the two groups represented by R ² may be the same or different. R ³ is a hydrocarbon, specifically having 1 carbon atom as in R ^2.
10 to 10 linear or branched hydrocarbon groups, alicyclic hydrocarbon groups having 3 to 10 carbon atoms, 6 to 10 carbon atoms
Aromatic hydrocarbon group. Of these,
A linear or branched hydrocarbon group having 1 to 10 carbon atoms is preferable, and methyl, ethyl and the like are particularly preferable.

When (4-mn) is 2 or 3, a plurality of groups represented by R ³ may be the same or different. As the organosilicon compound represented by the formula (1), more specifically, for example,

[0074]

Embedded image

And the like. As the organosilicon compound used in the present invention, in the general formula (I), m =
1, n = 1 are preferred, m = 1, n = 1 and R ² is a cyclic hydrocarbon group, for example,

[0076]

Embedded image

More preferably, m = 1 and n =
1. R ² is a cyclic hydrocarbon group, and a hetero atom not directly bonded to Si of R ¹ is substituted by a secondary or tertiary hydrocarbon group, preferably a cyclohydrocarbon group or an aromatic hydrocarbon group. Compounds, such as

[0078]

Embedded image

And the like are preferably used. Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises (A) a solid titanium catalyst component, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the general formula (1). And a compound.

FIG. 1 shows a process for preparing such an olefin polymerization catalyst. In the present invention, a prepolymerized catalyst [I] can be formed by preliminarily (co) polymerizing an olefin with the above catalyst component, and specifically, [I] the solid titanium catalyst (A) described above. A prepolymerized catalyst obtained by prepolymerizing an olefin into a catalyst for olefin polymerization comprising a component, (B) an organoaluminum compound and, if necessary, (D) an electron donor, and [II] the organosilicon compound (C). )
And [III] an organoaluminum compound (B), if necessary, to form an olefin polymerization catalyst.

At the time of the prepolymerization, an electron donor (D) can be used if necessary. As the electron donor (D), the above-mentioned organosilicon compound (C) can be specifically used. Other electron donors can also be used.

Other electron donors include, for example, the aforementioned polyether compounds; 2,6-substituted piperidines, 2,5-substituted piperidines; N, N, N ', N'-tetramethylmethylenediamine, Substituted methylenediamines such as N, N, N ', N'-tetraethylmethylenediamine; nitrogen-containing electrons such as substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine Donor; phosphites such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite, etc. Phosphorus-containing electron donors; oxygen-containing electron donors such as 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans may also be used. Can; it may be further used an organic silicon compound other than the above (C) Other electron donor. As other organic silicon compounds, specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane,
Diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-
Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, Phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxy (allyloxy) silane, vinyltris (β-methoxyethoxysilane) , Vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, ethyl silicate, butyl silicate and the like.

As another organosilicon compound, the following
Organosilicon having a bulky group represented by the general formula (2)
Element compounds. R^a _nSi (OR^b)_4-n ... (2) (where n is 1, 2 or 3 and n is 1)
Come, R^aIs a secondary or tertiary hydrocarbon group, and n is 2
Or when 3,^aAt least one of
Is a tertiary hydrocarbon group;^aAre the same but different
May be R ^bIs a hydrocarbon having 1 to 4 carbon atoms
And when (4-n) is 2 or 3, OR
^bMay be the same or different. ) Having a bulky group represented by the general formula (2)
Secondary or tertiary hydrocarbon groups in organic silicon compounds
Are cyclopentyl, cyclopentenyl,
Clopentadienyl group, those groups having a substituent and
And secondary or tertiary hydrocarbons adjacent to Si and Si
Groups.

Specific examples include dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, and di-t-amyldimethoxysilane. Can be

These can be used in combination of two or more.
Examples of the olefin used at the time of the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, and 1-pentene.
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-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Α-olefins having 20 or less carbon atoms are exemplified. Further, other vinyl compounds and polyene compounds as described later can also be used at the time of preliminary polymerization. These are 2
More than one species may be used in combination.

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 below. In the present invention, there is no particular limitation on the method of performing the prepolymerization, for example, olefins, polyene compound can be performed in a liquid state,
Further, the reaction can be carried out in the presence of an inert solvent, and furthermore, can be carried out under gas phase conditions. Of these, it is preferable to add olefins and various catalyst components to the inert solvent in the presence of an inert solvent, and to carry out prepolymerization under relatively mild conditions. At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium or under a condition in which the prepolymer is not dissolved, but it is preferably carried out under a condition in which the prepolymer is not dissolved.

The prepolymerization is usually carried out at about -20 to + 100 ° C.
Preferably about -20 to + 80 ° C, more preferably -1.
It is desirable to carry out at 0 to + 40 ° C. The prepolymerization can be performed in any of a batch system, a semi-continuous system, and a 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. Although the concentration of the catalyst component in the prepolymerization varies depending on the type of the catalyst component, the concentration of the solid titanium catalyst component (A) is as follows.
Per liter of polymerization volume, usually about 0.001 to 5000 mmol, preferably about 0.01
It is desirable that the amount be from 1000 to 1000 mmol, particularly preferably from 0.1 to 500 mmol.

The organoaluminum compound (B) is usually used in an amount of about 0.1 to about 0.1 mol per mol of titanium in the solid titanium catalyst component.
It can be used in an amount of 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol.

In the prepolymerization, the electron donor (D)
Is usually 0.01 to 50 mol, preferably 0.05 to 3 mol per mol of titanium atom in the solid titanium catalyst component (A).
0 mol, more preferably 0.1 to 10 mol, can be used as needed.

At the time of prepolymerization, a molecular weight regulator such as hydrogen may be used. In the prepolymerization as described above, 0.01 to 2000 per 1 g of the solid titanium catalyst component (A).
g, preferably 0.03 to 1000 g, more preferably 0.05 to 200 g of the preliminary (co) polymer.

When the prepolymerized catalyst is obtained in a suspended state, in the subsequent (main) polymerization, the prepolymerized catalyst can be used as it is in a suspended state, or the prepolymerized catalyst formed from the suspension can be used. The polymerization catalyst can be used separately.

The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization, in addition to the above components. Olefin Polymerization Method In the olefin polymerization method according to the present invention, (A) a solid titanium catalyst component, (B) an organoaluminum compound and (C) a cyclic amino group represented by the general formula (1) are used. An olefin polymerization catalyst comprising an organosilicon compound having, or [I] a prepolymerization catalyst, [II] an organosilicon compound having a cyclic amino group represented by the general formula (1) and, if necessary, [III] an organoaluminum compound (B) in the presence of an olefin polymerization catalyst comprising
Olefin is polymerized or copolymerized.

When an olefin is polymerized using such an olefin polymerization catalyst, a polyolefin having a wide molecular weight distribution and excellent moldability can be obtained. Examples of the olefin to be polymerized in the present invention include α-olefins having 20 or less carbon atoms as specifically shown in the preliminary polymerization.

Further, cyclopentene, cycloheptene,
Norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,
Cycloolefins such as 5,8,8a-octahydronaphthalene; styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclopentane,
Vinyl compounds such as vinylcyclohexane, vinylcycloheptane, and allyltrialkylsilanes can also be used.

Among them, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, Allyl naphthalene and the like are preferably used. In particular, it is desirable to carry out (co) polymerization of propylene.

In the present invention, a small amount of a diene compound may be copolymerized with an olefin as long as the effects of the present invention are not impaired. Specific examples of such a diene compound include 1,3-butadiene, 1,3-pentadiene,
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-1,
Examples include 6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. These two
More than one species may be used in combination.

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 a reaction form of slurry polymerization, the above-mentioned inert organic solvent can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can be used.

In the polymerization, the solid titanium catalyst component (A) or the prepolymerized catalyst [I] is usually used in an amount of about 0.001 to 1 in terms of titanium atom per liter of polymerization volume.
It can be used in an amount of 00 mmol, preferably about 0.005 to 20 mmol.

The organoaluminum compound (B) (or [III]) has a metal atom in the compound (B) of usually about 1 to 2000 mol per 1 mol of titanium atom in the polymerization system.
Preferably, it can be used in an amount of about 2 to 500 mol.

When the prepolymerized catalyst [I] is used, the organoaluminum compound [III] may not be used in some cases. Organosilicon compound (C) (or [I
I]) is a metal atom 1 of the organoaluminum compound (B).
It can be used in an amount of usually about 0.001-10 mol, preferably 0.01-5 mol, per mol.

When hydrogen is used at the time of 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, the polymerization is usually carried out at a temperature of usually about 20 to 300 ° C, preferably about 50 to 150 ° C,
g / cm ² , preferably under a pressure of about ² to 50 kg / cm ² .

In the polymerization method of the present invention, the polymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization was conducted by changing the reaction conditions.
It can also be performed in multiple stages.

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 olefins. In the present invention as described above, for example, when propylene is polymerized, polypropylene having a molecular weight distribution (Mw / Mn) of 5 or more, preferably 5 to 10 can be obtained.

[0105]

According to the olefin polymerization catalyst and olefin polymerization method of the present invention using the above specific organosilicon compound as an external donor, a polyolefin having a wide molecular weight distribution and excellent moldability can be obtained with high polymerization activity. Obtainable. In particular, when used for the polymerization of α-olefins having 3 or more carbon atoms, a highly stereoregular polyolefin having a wide molecular weight distribution and excellent moldability can be obtained with high polymerization activity.

[0106]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. (1) Boiling heptane extraction residual ratio (II) (stereoregularity index): Polyolefin was determined by Soxhlet extraction with boiling heptane until the extraction residue became a constant weight. (2) Amount of n-decane-soluble component (the smaller the soluble amount, the narrower the composition distribution); The amount of n-decane-soluble component is determined by adding about 3 g of the copolymer to 450 ml of n-decane and adding 145 ° C. After dissolution, the temperature was measured by cooling to 23 ° C., removing the n-decane insoluble portion by filtration, and collecting the n-decane soluble portion from the filtrate. (3) Melt flow rate (MFR); ASTM D1
It was measured at 230 ° C. under a load of 2.16 kg in accordance with 238. (4) Molecular Weight Distribution (Mw / Mn) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyolefin were determined by GPC.

[0107]

Example 1 Preparation of solid titanium catalyst component (A) 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were added to 130 parts of a catalyst.
C. for 2 hours to form a homogeneous solution. To this solution, 21.3 g of phthalic anhydride was added.
Stir and mix for hours to dissolve.

After cooling the thus obtained homogeneous solution to room temperature, 30 ml of this homogeneous solution was added to 80 ml of titanium tetrachloride (TiCl ₄ ) maintained at -20 ° C.
Charged dropwise over time. The temperature of the liquid was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 2.1 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred and maintained at the same temperature for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
This solid part is mixed with 110 ml of TiCl _Four Resuspended in
Thereafter, the resulting suspension was heated again at 110 ° C. for 2 hours.
After completion of the reaction, the solid portion was collected again by hot filtration, and
Using decane and hexane, free
Washing was conducted until no compound was detected.

The solid titanium catalyst component obtained as described above was stored as a decane slurry. A part of this slurry was collected and dried, and the composition of the solid titanium catalyst component was analyzed.

As the solid titanium catalyst component (A), 2.2% by weight of titanium, 19.0% by weight of magnesium, DIB
It contained 19.8% by weight of P. Preparation of Preliminary Polymerization Catalyst Component [I] In a 200-ml four-necked glass reactor equipped with a stirrer, 100 ml of purified hexane and 3 mmol of triethylaluminum were added under nitrogen atmosphere to the solid titanium catalyst component (A) obtained above. After adding 1.0 mmol in conversion,
At 20 ° C., propylene was supplied at a rate of 3.2 Nl / h for 1 hour.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and a washing operation comprising removing the supernatant and adding purified hexane was performed twice, and the obtained prepolymerized catalyst component [I] was removed. It was resuspended in purified hexane and transferred to a catalyst bottle in its entirety.

[0113] to a heavy case 1-liter autoclave, purified heptane 4
00 ml, 60 ° C., propylene atmosphere, triethylaluminum 0.4 mmol, cyclopentyl-N
0.08 mmol of -methylpiperazinodimethoxysilane and 0.008 mmol of the prepolymerized catalyst component [I] obtained above were charged in terms of titanium atoms.

After 100 ml of hydrogen was introduced and the temperature was raised to 70 ° C., the temperature was maintained for 1 hour to polymerize propylene. The pressure during the polymerization was kept at 5 kg / cm ² -G. After completion of the polymerization, the slurry containing the produced solid was filtered to separate into a white powder and a liquid phase.

The yield of the polymer obtained as a white powder after drying was 92.0 g. The boiling heptane extraction residual ratio (II) of this white powdery polymer was 97.4% by weight, and n-
The decane-soluble component amount (DS) is 3.72% by weight, the melt flow rate (MFR) is 3.0 g / 10 minutes,
The weight average molecular weight Mw measured by GPC is 41.2 × 10
^{4. The} molecular weight distribution scale Mw / Mn was 8.3.

The liquid phase was concentrated to obtain 0.4 g of a solvent-soluble polymer. Therefore, the polymerization activity is 11600g-PP
/ Mmol-Ti, 3590 g / g-catalyst, boiling heptane extraction residue (tI.I.) of all polymers is 96.9% by weight, and n-decane soluble component of all polymers (T-DS)
Was 4.1% by weight. Table 1 shows the results.

[0117]

Example 2 The procedure of Example 1 was repeated, except that cyclopentyl-N-methylpiperazinodimethoxysilane was used instead of cyclopentyl-N-methylpiperazinodimethoxysilane in the “polymerization” of Example 1. Propylene was polymerized. Table 1 shows the results.

[0118]

Example 3 The procedure of Example 1 was repeated, except that bis (N-phenylpiperazino) dimethoxysilane was used instead of cyclopentyl-N-methylpiperazinodimethoxysilane in the “polymerization” of Example 1. To polymerize propylene. Table 1 shows the results.

[0119]

[Table 1]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of a preparation process of an olefin polymerization catalyst according to the present invention.

Claims (5)

[Claims] 1. A solid titanium catalyst component containing (A) magnesium, titanium, a halogen and an electron donor;
(B) an organoaluminum compound, (C) an organosilicon compound represented by the following general formula (1), and R ¹ _m R ² _n Si (OR ³ ) _4-mn (1) (where m is 1 , 2 or 3, n is 0, 1 or 2, and 1 ≦ m + n <4, and R ¹ is N
Is a cyclic amino group directly bonded to Si and has at least one hetero atom other than N directly bonded to Si, and when m is 2 or 3, a plurality of groups represented by R ¹ may be the same as R ² is a hydrocarbon group, and when n is 2, the two groups represented by R ² may be the same or different from each other, and R ³ is a hydrocarbon;
A plurality of groups represented by R ³ when -m-n is 2 or 3 may be the same or different from each other. A catalyst for olefin polymerization, characterized by comprising: 2. A method comprising: (I) a solid titanium catalyst component containing (A) magnesium, titanium, a halogen and an electron donor; (B) an organoaluminum compound; and, if necessary, (D) an electron donor. A prepolymerized catalyst in which an olefin is prepolymerized as an olefin polymerization catalyst, [II] an organosilicon compound represented by the following general formula (1), and R ¹ _m R ² _n Si (OR ³ ) _4-mn . 1) (wherein, m is 1, 2 or 3, n is 0, 1 or 2, and is 1 ≦ m + n <4, R 1 is n is Si
Is a cyclic amino group directly bonded to Si and has at least one hetero atom other than N directly bonded to Si, and when m is 2 or 3, a plurality of groups represented by R ¹ may be the same as each other. R ² is a hydrocarbon group, and when n is 2, the two groups represented by R ² may be the same or different, and R ³ is a hydrocarbon;
A plurality of groups represented by R ³ when -m-n is 2 or 3 may be the same or different from each other. [III] An olefin polymerization catalyst, which comprises an organic aluminum compound as required. 3. The method according to claim 1, wherein (D) the electron donor is represented by the following general formula (1): R ¹ _m R ² _n Si (OR ³ ) _4-mn (1) (where m is 1, 2 or 3) And n is 0, 1 or 2, and 1 ≦ m + n <4, and R ¹ is N
Is a cyclic amino group directly bonded to Si and has at least one hetero atom other than N directly bonded to Si, and when m is 2 or 3, a plurality of groups represented by R ¹ may be the same as R ² is a hydrocarbon group, and when n is 2, the two groups represented by R ² may be the same or different, and R ³ is a hydrocarbon;
A plurality of groups represented by R ³ when -m-n is 2 or 3 may be the same or different from each other. 3. The olefin polymerization catalyst according to claim 2, which is an organosilicon compound represented by the formula: 4. In the organosilicon compound represented by the general formula (1), in the general formula, R ² has 3 to 1 carbon atoms.
The catalyst for olefin polymerization according to any one of claims 1 to 3, which is a cyclic hydrocarbon group of 0. 5. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.