JPH11116615A - Preparation of solid titanium catalyst component, olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst capable of polymerizing an olefin in high activity by contacting a liquid magnesium compound with a liquid titanium compound, adding a polybasic carboxylic acid ester and/or a polyether compound as an electron donor in the period from the start to the end of the precipitation of solid and contacting the obtained product with the above electron donor. SOLUTION: The objective catalyst is produced by (A) contacting a liquid magnesium compound with a liquid titanium compound and adding a polybasic carboxylic acid ester as an electrondonor [e.g. a compound of the formula (R is a 3-12C branched hydrocarbon group) (e.g. diheptyl phthalate) and/or a polyether compound to the contacted liquid in the period from the start to the end of the precipitation of solid from the contacted liquid to form a solid product containing titanium, etc., and (B) contacting the solid product obtained after the precipitation of the solid with the above electron donor (e.g. diisobutyl phthalate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for preparing a solid titanium catalyst component capable of polymerizing an olefin with high activity and producing a highly stereoregular olefin polymer. The present invention relates to a catalyst for olefin polymerization containing a titanium catalyst component and a method for polymerizing olefin.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a catalyst formed from a titanium catalyst component and an organoaluminum compound has been widely used as a catalyst for polyolefin production, and a solid titanium catalyst component supported on a carrier is used as the titanium catalyst component. These catalysts are known to exhibit high polymerization activity.

[0003] Among such solid titanium catalyst components, a catalyst comprising a solid titanium catalyst component containing titanium, magnesium, halogen and an electron donor (internal donor) and an organoaluminum compound exhibits high polymerization activity. In addition, it is known that when an α-olefin having 3 or more carbon atoms such as propylene is polymerized, a polyolefin having high stereoregularity can be produced.

Among the compounds proposed as electron donors (internal donors) as described above, compounds having a polyvalent carboxylic acid ester or a compound having two or more ether bonds existing through a plurality of atoms are particularly preferred. It is known that a solid titanium catalyst component containing (polyether compound) has high activity.

[0005] The present applicant has previously described titanium, magnesium,
A number of solid titanium catalyst components containing a polycarboxylic acid ester or a polyether compound as a halogen and an electron donor have been proposed.

Specifically, the solid titanium catalyst component (solid) as described above is produced by contacting a liquid magnesium compound, a liquid titanium compound, and a polycarboxylic acid ester or polyether compound. It is proposed that a highly active solid titanium catalyst component can be obtained by doing so.

For example, in the example of Japanese Patent Application Laid-Open No. 8-34813, when a liquid magnesium compound, a liquid titanium compound and a polyvalent carboxylic acid ester as an electron donor are brought into contact with each other to prepare a solid titanium catalyst component. Then, after contacting the liquid magnesium compound with the liquid titanium compound to precipitate a solid titanium catalyst component, the solid titanium catalyst component is contacted with a polyvalent carboxylic acid ester.

The present inventor has further studied the solid titanium catalyst component and the olefin polymerization catalyst as described above. As a result, a liquid magnesium compound, a liquid titanium compound, a polycarboxylic acid ester and / or a polyvalent carboxylic acid ester as the electron donor are used. Or, when preparing a solid titanium catalyst component by contacting with a polyether compound, the above-mentioned electron donor, from the start of the precipitation of solid by the contact of the liquid magnesium compound and the liquid titanium compound until the end thereof, By adding the above-mentioned electron donor to the resulting solid product again, thereby obtaining a solid titanium catalyst component capable of producing a polyolefin having higher activity and higher stereoregularity. The inventors have found that the present invention can be performed, and have completed the present invention.

[0009]

An object of the present invention is to provide a method for preparing a solid titanium catalyst component capable of polymerizing an olefin with high activity and producing an olefin polymer having a high stereoregularity. An object of the present invention is to provide an olefin polymerization catalyst containing a titanium catalyst component and a method for polymerizing olefins.

[0010]

SUMMARY OF THE INVENTION The method for preparing a solid titanium catalyst component according to the present invention comprises: [I] bringing a liquid magnesium compound into contact with a liquid titanium compound, and starting after the solid starts to precipitate in the contact liquid (β). In the meantime, in the contact liquid (β),
An electron donor (di) selected from the group consisting of a polyvalent carboxylic acid ester and a compound having two or more ether bonds present through a plurality of atoms is added, and titanium, magnesium, a halogen and an electron donor ( di) is formed, and then [II] the solid product (α) obtained after the completion of the solid precipitation is added to the polycarboxylic acid ester and the two compounds present through a plurality of atoms. A solid containing titanium, magnesium, halogen, an electron donor (di) and an electron donor (d-ii) by contacting an electron donor (d-ii) selected from the group consisting of compounds having an ether bond described above. And preparing a titanium-like catalyst component.

The contact liquid (β) is usually composed of a monocarboxylic acid ester, an aliphatic carboxylic acid, an acid anhydride, a ketone, a monoether, an aliphatic carbonate, an alcohol containing an alkoxy group, an alcohol containing an aryloxy group, Si—O
An electron donor (d-iii) selected from the group consisting of an organosilicon compound having a —C bond and an organic phosphorus compound having a P—O—C bond is contained before the addition of the electron donor (di).

Among the above electron donors (di) and electron donors (d-ii), the polycarboxylic acid ester is preferably a phthalic acid diester represented by the following formula.

[0013]

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In the present invention, when the electron donor (di) and the electron donor (d-ii) are both polycarboxylic acid esters, the electron donor (di) used in the above [I] is phthalic acid. It is preferably diheptyl, and the electron donor (d-ii) used in the above [II] is diisobutyl phthalate.

Further, the compound having two or more ether bonds existing through a plurality of atoms is preferably represented by the following formula.

[0016]

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(Where n is an integer of 2 ≦ n ≦ 10,
R ¹ to R ²⁶ is a substituent having carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, at least one element selected from boron and silicon, any of R ¹ ~
R ²⁶ , preferably R ^{1 to} R ^2n, may together form a ring other than a benzene ring, and the main chain may contain atoms other than carbon. ).

In the present invention, the electron donor (di) used in [I] and the electron donor (d-ii) used in [II] are used.
Is preferably 10/90 to 90/10.

The olefin polymerization catalyst according to the present invention comprises (A) a solid titanium catalyst component prepared as described above;
(B) an organoaluminum compound and, if necessary, (C)
And an electron donor.

In the present invention, the olefin is polymerized or copolymerized in the presence of such an olefin polymerization catalyst.

[0021]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for preparing a solid titanium catalyst component according to the present invention, an olefin polymerization catalyst containing the solid titanium catalyst component obtained by the method, and a method for polymerizing an olefin will be specifically described.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It is sometimes used in a sense that includes polymers.

(A) Preparation of Solid Titanium Catalyst Component FIG. 1 shows a step of preparing a solid tin catalyst component and a step of preparing a catalyst for olefin polymerization according to the present invention.

In the present invention, [I] the liquid magnesium compound is brought into contact with the liquid titanium compound, and the contact liquid (β) An electron donor (di) selected from the group consisting of a polyvalent carboxylic acid ester and a compound having two or more ether bonds existing through a plurality of atoms is added thereto to obtain titanium, magnesium, halogen and electron. Donor
to form a solid product (α) containing (di) and then [I
I] An electron donor selected from the group consisting of a polyvalent carboxylic acid ester and a compound having two or more ether bonds existing via a plurality of atoms in the solid product (α) obtained after the completion of solid deposition ( d-ii) is contacted to prepare a solid titanium catalyst component containing titanium, magnesium, halogen, an electron donor (di) and an electron donor (d-ii).

First, each component used in preparing this solid titanium catalyst component will be described.

Liquid magnesium compound In the present invention, examples of the magnesium compound 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 an organic magnesium compound represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
20 to 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different. X is a halogen or an alkoxy group.

Specific examples of the organomagnesium compound having such a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, and the like.
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium; alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halide, butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium, and other butyl magnesium hydrides.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, magnesium methoxy chloride, ethoxy magnesium chloride, and isopropoxy magnesium chloride. , Butoxy magnesium chloride, alkoxy magnesium halide such as octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halide such as methylphenoxy magnesium chloride, diethoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, di n-octoxy magnesium, di
2-ethylhexoxymagnesium, alkoxymagnesium such as ethoxymethoxymagnesium, diphenoxymagnesium, allyloxymagnesium such as dimethylphenoxymagnesium, magnesium laurate,
Examples thereof include magnesium carboxylate such as magnesium stearate. In addition, magnesium metal and magnesium hydride can 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, the magnesium compound is present in the form of a halogen-containing magnesium compound. 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 used in a liquid state (solution). The solid magnesium compound can be liquefied using an electron donor (d-iv). As the electron donor (d-iv), alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines, metal acid esters and the like can be used. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol C1-C18 alcohols such as trichloromethanol, trichloroethanol, and C1-C18 halogen-containing alcohols such as trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, C6-20 phenols which may have a lower alkyl group such as naphthol, acetone, methyl ethyl ketone Methyl isobutyl ketone, ethyl n- butyl ketone, acetophenone, benzophenone, benzoquinone, ketones having 3 to 15 carbon atoms such as cyclohexanone, acetaldehyde, propionaldehyde, 2 carbon atoms such as octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde
To 15 aldehydes, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, ethyl benzyl ether, ethylene glycol dibutyl ether, anisole, diphenyl ether and other ethers having 2 to 20 carbon atoms, methylamine, ethylamine, Dimethylamine,
Amines such as diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine, pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzyl Pyridines such as pyridine and pyridine chloride; metal acid esters such as tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium; Is mentioned.

Among these, alcohols and metal acid esters are preferable, and alcohols having 6 or more carbon atoms are particularly preferably used. For example, when liquefying a magnesium compound using an alcohol having 6 or more carbon atoms, it is preferable to use the compound in an amount of about 1 mol or more, preferably 1.5 mol or more per 1 mol of the magnesium compound,
Although there is no particular upper limit, it is economically preferable that the amount is not too large, and it is desirable that the amount is not more than 40 mol per mol of the magnesium compound.

When liquefying a magnesium compound using an alcohol having 5 or less carbon atoms, usually about 15 mol or more is required per 1 mol of the magnesium compound.
The reaction between the solid magnesium compound and the electron donor (d-iv) is generally carried out by bringing the solid magnesium compound into contact with the electron donor (d-iv) and heating as necessary.
This contact is usually performed at 0 to 200 ° C, preferably 20 to 180 ° C.
C., more preferably at a temperature of 50 to 150.degree.

The above reaction may be carried out in the presence of a hydrocarbon solvent or the like. Such hydrocarbon solvents include:
For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, kerosene, cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, dichloroethane, dichloroethane Halogenated hydrocarbons such as chloropropane, trichloroethylene, and chlorobenzene, and aromatic hydrocarbons such as benzene, toluene, and xylene are used.

Liquid Titanium Compound In the present invention, a tetravalent titanium compound is preferably used as the liquid titanium compound. Examples of the tetravalent titanium compound include a compound represented by the following formula.

Ti (OR) _g X _{4-g In the} formula, R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. Specific examples of such a compound include titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Cl.
_{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 Cl 2, Ti (On
-Dialkoxytitanium dihalides such as -C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) 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 H 5)
Monohalogenated trialkoxy titanium such as ₃ Br, T
i (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ ,
Tetraalkoxy titanium such as 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.

(Di) Electron Donor In the present invention, when the above liquid magnesium compound is brought into contact with the liquid titanium compound, the electron donor (d-
As i), a polyvalent carboxylic acid ester and / or a compound having two or more ether bonds existing through a plurality of atoms is used.

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

[0043]

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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 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 a polycarboxylic acid ester 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 Aliphatic polycarboxylates such as diisopropyl acrylate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexane Hexane carboxylic acid diisobutyl, tetrahydrophthalic acid diethyl, alicyclic polycarboxylic acid esters such as nadic diethyl, diisopropyl phthalate, diisobutyl phthalate, dineopentyl phthalate, diheptyl phthalate, di-2
Ethylhexyl, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate,
Diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, didecyl phthalate, benzyl phthalate, diphenyl phthalate, Examples include aromatic polycarboxylic acid esters such as diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

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 represented by the following formula are particularly preferred.

[0048]

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In the formula, R is a branched hydrocarbon group having 3 to 12 carbon atoms, and the two Rs may be the same or different. In the formula, the benzene nucleus may be substituted with a halogen atom or a lower hydrocarbon group.

Specific examples include diisopropyl phthalate, diisobutyl phthalate, dineopentyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate and the like. As diheptyl phthalate, more specifically, di (2-methylhexyl) phthalate, di (3-methylhexyl) phthalate, di (4-methylhexyl) phthalate, di (5-methylhexyl) phthalate Di (2,4 dimethylpentyl) phthalate, di (3,4-dimethylpentyl) phthalate, di (2,2-dimethylpentyl) phthalate, di (2,3 dimethylpentyl) phthalate
Phthalic acid having a branched heptyl group such as -dimethylpentyl), di (3,3-dimethylpentyl) phthalate, di (3-ethylpentyl) phthalate, di (2,2,3-trimethylbutyl) phthalate Diheptyl.

Further, there may be mentioned, for example, compounds having different R groups from each other and, for example, a combination of different branched alkyl groups one by one among the branched alkyl groups contained in the compounds exemplified above.

A phthalic acid diester obtained by combining two or more of these may be used. Specifically, for example, 2 in the above formula
R groups are a 3-methylhexyl group (a%), a 5-methylhexyl group (b%) and a 2,4-dimethylpentyl group (c
%) (Where a + b + c = 100%). A diheptyl phthalate mixture is also preferably used.

In the compound having two or more ether bonds existing through a plurality of atoms (hereinafter sometimes referred to as a polyether compound) used in the present invention, the atoms existing between these ether bonds may be carbon, silicon or silicon. , Oxygen, sulfur, phosphorus, and boron, and has 2 or more atoms. Of these, relatively bulky substituents on the atoms between the ether bonds, specifically 2 carbon atoms
The above is preferable, and those having three or more substituents having a linear, branched or cyclic structure, more preferably those having a branched or cyclic structure bonded thereto are desirable. Further, a compound in which an atom existing between two or more ether bonds contains a plurality of, preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms is preferable.

When using such polyethers,
The Al / Ti ratio in the prepolymerization described below is 0.5 to 2.5 mol /
When the content is mol, the particle properties such as the bulk density of the obtained polymer particles can be improved.

As such a polyether compound,
For example, a compound represented by the following formula can be mentioned.

[0056]

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In the formula, n is an integer of 2 ≦ n ≦ 10;
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ^2n, may form a ring other than a benzene ring together, and may have an atom other than carbon in the main chain. May be included.

As the above polyether compounds, specifically, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2
-Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1 , 3-Dimethoxypropane, 2- (2-phenylethyl)-
1,3-dimethoxypropane, 2- (2-cyclohexylethyl)
-1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-
Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-
Diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,
3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-
Methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl
2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl- 1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2- Isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3 -Dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2, 2-diisobutyl-1,3-dibutoxypropane, 2-
Isobutyl-2-isopropyl-1,3-dimethoxypropane,
2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di-s-butyl- 1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy Propane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2
-Isopropyl-1,3-dimethoxypropane, 2-benzyl-2
-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-
Isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl -1,3-dimethoxypropane, 2-
Isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-
Cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1, 4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p -Fluorophenyl) -1,4-
Dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4
-Diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,
5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane , 1,
3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2 -Hexamethylene-1,3-dimethoxypropane, 1,2
-Bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] Octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxy Methyl) bicyclo [2,2,1]
Heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2- Methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3 -Dimethoxycyclohexane, 2-isopropyl-2-
Methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxy Methyl-1,3-dimethoxycyclohexane, 2-isopropyl-
2-ethoxymethyl-1,3-diethoxycyclohexane, 2-
Isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-
1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) ) Silane, cyclohexyl-t-butylbis (methoxymethyl) silane, i
-Propyl-t-butylbis (methoxymethyl) silane and the like.

Of these, 1,3-diethers are preferably used, and in particular, 2-isopropyl-2-isobutyl-1,2
3-dimethoxypropane, 2-isopropyl-2-sec-butyl-
1,3-dimethoxypropane, 2,2-diisobutyl-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, 2,2-diphenyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-
1,3-dimethoxypropane and the like are preferably used.

Preparation of Solid Titanium Catalyst Component In the present invention, a liquid magnesium compound as described above,
In preparing a solid titanium catalyst component from a liquid titanium compound and an electron donor (di), first, [I] a liquid magnesium compound is brought into contact with a liquid titanium compound, and a solid precipitates in a contact liquid (β). From the start to the end, an electron donor (di) selected from the group consisting of a polycarboxylic acid ester and a polyether compound is added to the contact liquid (β), and titanium, magnesium, A solid product (α) comprising a halogen and an electron donor (di) is formed.

The above-mentioned contact liquid (β) is usually composed of a monocarboxylic acid ester, an aliphatic carboxylic acid, an acid anhydride, a ketone, a monoether, an aliphatic carbonate, an alkoxy group-containing alcohol, an aryloxy group-containing alcohol,
Organosilicon compound having Si-OC bond, PO-
An electron donor (d-iii) selected from the group consisting of organic phosphorus compounds having a C bond is included before the addition of the electron donor (di).

As such an electron donor (d-iii),
Specifically, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, i-butyl acetate, t-butyl acetate, octyl acetate, cyclohexyl acetate, methyl chloroacetate, ethyl dichloroacetate, ethyl propionate, pyruvate Ethyl, ethyl pivalate, methyl butyrate, ethyl valerate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, Monocarboxylic acid esters such as phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, and ethyl ethoxy benzoate; formic acid, acetic acid, and propionic acid , Butyric acid, valeric acid Fatty acid carboxylic acids such as acetic anhydride, phthalic anhydride, maleic anhydride, benzoic anhydride,
Trimellitic anhydride, acid anhydrides such as tetrahydrophthalic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl n-butyl ketone, acetophenone, benzophenone, benzoquinone, ketones such as cyclohexanone, methyl ether, ethyl ether, isopropyl ether, butyl ether, Amyl ether,
Monoethers such as ethylbenzyl ether and anisole; aliphatic carbonates such as dimethyl carbonate, diethyl carbonate and ethylene carbonate; alcohols containing alkoxy groups such as butyl cellosolve and ethyl cellosolve; Si such as methyl silicate, ethyl silicate and diphenyldimethoxysilane Organic silicon compounds having an -OC bond, preferably R ¹ xR ² ySi (OR ³ ) z (where R ¹ and R ² are each independently a hydrocarbon group or halogen, and R ³ is a hydrocarbon 0 ≦ x <2, 0 ≦ y <2, 0 <z ≦ 4
It is. ), And organic phosphorus compounds having a POC bond, such as trimethyl phosphite and triethyl phosphite.

These electron donors (d-iii) can be used in combination of two or more kinds. An electron donor as described above (d-ii
i) Before adding the electron donor (di) to the contact liquid (β) between the liquid magnesium compound and the liquid titanium compound,
It is sufficient that it is contained in the contact liquid (β). For example, one or both of the liquid magnesium compound and the liquid titanium compound are contacted with an electron donor (d-iii). Or an electron donor
Before the addition of (di), the electron donor (d-iii) may be added to the contact liquid (β) between the liquid magnesium compound and the liquid titanium compound.

When the liquid magnesium compound is brought into contact with the liquid titanium compound in the presence of the electron donor (d-iii), a solid product (α) having an excellent particle shape can be obtained. Further, in the present invention, when the liquid magnesium compound and the liquid titanium compound are brought into contact with each other, in addition to (di) an electron donor (di) selected from the group consisting of a polycarboxylic acid ester and a polyether compound, Other electron donors (dv) as long as the object of the invention is not impaired.
May be used.

Examples of such other electron donors (dv) include an electron donor (d-iv) and an electron donor (C) described below when the magnesium compound is liquefied. Organosilicon compounds such as acetic acid N, N-
Acid amides such as dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, acetyl chloride, benzoyl chloride, toluic acid chloride, and C2-15 acid halides such as anisic acid chloride;
Nitriles such as acetonitrile, benzonitrile, trinitrile, pyrroles such as pyrrole, methylpyrrole, dimethylpyrrole, pyrroline; pyrrolidine; indole; piperidines, quinolines, nitrogen-containing cyclic compounds such as isoquinolines; tetrahydrofuran; And cyclic oxygen-containing compounds such as cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran.

In the step [I] of forming the solid product (α),
The liquid magnesium compound is brought into contact with the liquid titanium compound as described above, and a polyvalent carboxylic acid is contained in the contact liquid (β) during a period from the start to the end of precipitation of the solid in the contact liquid (β). An electron donor (di) selected from the group consisting of acid esters and polyether compounds is added.

Specifically, a liquid magnesium compound and
The liquid titanium compound is usually used in the presence of an electron donor (d-iii) in the presence of -70 ° C to 200 ° C, preferably -50 ° C to 15 ° C.
The solid is deposited by contact at a temperature of 0 ° C, more preferably at a temperature of -30 to 130 ° C. The liquid temperature of the liquid magnesium compound used for this contact may be different from the liquid temperature of the liquid titanium compound.

According to the present invention, a liquid magnesium compound and a liquid titanium compound are prepared in the presence of an electron donor (d-iii).
Initially, it is preferable to contact at a low temperature and gradually raise the temperature to precipitate a solid. The electron donor (di) is preferably added in such a heating process. Specifically, when the amount of the solid finally precipitated is 100% by weight, the solid in the contact liquid (β) is added. It is preferable to add at an amount of 20% by weight or more and less than 100% by weight, preferably 50-99% by weight, more preferably 70-95% by weight. As described above, the electron donor (di) may be added in a plurality of portions from the start of the precipitation of the solid in the contact liquid (β) to the end thereof.

Although the solid deposition rate can be evaluated by actual measurement according to the evaluation method described in the examples, the deposition time, the deposition temperature, and the like can be determined by a model experiment, and the determination can be made based on the determined results.

The amount of each component used for preparing the solid product (α) differs depending on the preparation method and cannot be specified unconditionally. For example, the titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0 to 1000 mol per mol of the magnesium compound. .1-2
It can be used in an amount of 00 mol. The electron donor (d
-iii) is 0.01 to 0.01 mol per mol of the magnesium compound.
It is desirable to use it in an amount of 1 mol, preferably 0.02 to 0.7 mol, more preferably 0.05 to 0.5 mol.

The electron donor (di) can be used in an amount of usually 0.005 to 9.995 mol, preferably 0.01 to 4.99 mol, per 1 mol of the magnesium compound. In the present invention, the total amount of the electron donor (di) and the electron donor (d-ii) as described below is usually 0.01 to 10 mol, preferably 0.1 to 5 mol. The total amount is preferably an amount corresponding to the amount of an electron donor conventionally generally used in preparing a solid titanium catalyst component.

The molar ratio of the electron donor (di) to the electron donor (d-ii) used in [II] described later is 10
/ 90 to 90/10, but more preferably
(di) / (d-ii) <1, and particularly preferably (di) / (d-ii)
<0.5.

In this step [I], two or more compounds selected from the group consisting of polyvalent carboxylic acid esters and polyether compounds may be used as the electron donor (di).

At the time of the above-mentioned contact, a hydrocarbon solvent can be used if necessary. As the hydrocarbon solvent, the same hydrocarbon solvents as those used in the preparation of the liquid magnesium compound can be used. .

At the time of contact, in addition to the above components,
Silicon, phosphorus,
Organic or inorganic compounds containing luminium
Any may be used. Such carriers include Al
_TwoO_Three, SiO_Two, B_TwoO_Three, MgO, CaO, TiO_Two,
ZnO, SnO_Two, BaO, ThO, styrene-divinyl vinyl
Resins such as benzene copolymer are exemplified. these
At home, Al_TwoO_Three, SiO_Two , Styrene-divinylben
Zen copolymers are preferably used.

By such contact, a solid product (α) containing titanium, magnesium, halogen and electron donor (di) is obtained. In the present invention, [II] the solid product (α) obtained after the completion of the solid deposition is further contacted with an electron donor (d-ii) selected from the group consisting of a polycarboxylic acid ester and a polyether compound. Let me.

For example, by adding the electron donor (d-ii) to the contact liquid (β) containing the solid product (α) after the solid precipitation is completed in the above [I], the solid product ( α)
And the electron donor (d-ii). At this time, the contact liquid (β) on which the solid deposition has been completed is brought to the temperature at which the solid deposition has been completed, specifically 70 to 150 ° C., preferably 80 ° C.
It is preferable to add the electron donor (d-ii) to the contact liquid (β) while maintaining the temperature at −140 ° C.

The above-mentioned solid product (α) may be once removed from the contact liquid (β) by filtration or the like, and then the electron donor (d-ii) may be added. In the present invention, the electron donor (d) is contained in the contact liquid (β) containing the solid product (α).
It is preferable to add -ii).

When the solid product (α) is once filtered as described above, the solid product (α) is resuspended again in an inert medium such as hexane or a liquid catalyst component such as titanium tetrachloride. And an electron donor (d-ii).

In the present invention, as described above, the electron donor (d
-i) and the electron donor (d-ii) in a molar ratio of 10/90 to 90/10
Is preferably, more preferably (di) / (di
i) <1, and particularly preferably (di) / (d-ii) <0.5. The electron donor (d-ii) is usually used in an amount of 0.005 to 9.9 per mole of the magnesium compound in the solid product (α).
It is desirable to use 75 moles, preferably 0.01 to 4.99 moles. The electron donor (d-ii) can be added in two or more portions.

As the electron donor (d-ii), specifically, the compounds exemplified as the electron donor (di) are used. Two or more of these compounds can be used as the electron donor (d-ii).

The electron donor (d-ii) as described above may be the same as or different from the electron donor (di). For example, both (di) and (d-ii) may be polycarboxylic acid esters, or both may be polyether compounds. (Di) may be a polycarboxylic acid ester, and (d-ii) may be a polyether compound or vice versa. In particular, it is desirable to use a combination of different compounds as the electron donors (di) and (d-ii).

In the present invention, the electron donor (di) used for forming the solid product (α) with the above [I] and the electron donor (d-ii) used in the [II] are both polyvalent. When the carboxylic acid ester is used, when the electron donor (di) is diheptyl phthalate and the electron donor (d-ii) is diisobutyl phthalate, a highly active solid titanium catalyst component can be obtained. it can.

In this step [II], the solid product (α) can be further contacted with a titanium compound. The contact between the titanium compound and the solid product (α) may be simultaneous with the contact between the electron donor (d-ii) and the solid product (α), or before or after the contact. Is also good. As the titanium compound, the above-mentioned liquid titanium compound can be used, and may be the same as or different from the titanium compound used in the step [I].

The titanium compound can be used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol, per 1 mol of the magnesium compound in the solid product (α). The solid titanium catalyst component (A) thus obtained contains magnesium, titanium, halogen, and electron donors ((di) and (d-ii)).
Titanium in an amount of 0.1 to 10% by weight, preferably 0.2 to 7.0% by weight, and a total of 95 to
It is desirable to contain the electron donor (total of (di) and (d-ii)) in an amount of 0.5 to 30% by weight in an amount of 30% by weight.

The solid titanium catalyst component (A) obtained above can be used for polymerization as it is, but it is preferable to wash the solid titanium catalyst component with a hydrocarbon solvent at 0 to 200 ° C. before use.

As the washing solvent, there may be used a hydrocarbon solvent as shown in the preparation of the liquid magnesium compound, and among these, an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent is preferably used.

At the time of washing, the hydrocarbon solvent is generally used in an amount of 1 to 10 g per 1 g of the solid titanium catalyst component (solid).
It is used in an amount of 000 ml, preferably 5 to 5000 ml, more preferably 10 to 1000 ml.

This washing is preferably performed until the titanium is no longer desorbed by washing with hexane at room temperature. The olefin polymerization catalyst containing the solid titanium catalyst component prepared as described above can polymerize olefin with extremely high activity.

The olefin polymerization catalyst according to the present invention is formed from the above (A) solid titanium catalyst component, (B) an organoaluminum compound, and, if necessary, (C) an electron donor. .

(B) Organoaluminum Compound The organoaluminum compound (B) used in the present invention is:
For example, it is represented by the following equation.

[0092] In R ^a _n AlX _3-n (wherein, 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 hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum 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, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

Further, as the organoaluminum compound, a compound represented by the following formula can also be mentioned. In R ^a _n AlY _3-n the above formulas, R ^a is as defined above, Y is -OR
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
A SiR ^f ₃ group or a —N (R ^g ) AlR ^h ₂ group, wherein n is 1
, 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, an isopropyl group. Group, phenyl group, trimethylsilyl group, etc., and R ^f and R ^g are methyl group, ethyl group, etc.

Specific examples of such an organoaluminum compound include the following compounds. _{^{(i) R a n Al (}} OR b) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R a n Al}} (OSiR c) 3-n Et 2 Al (OSiMe 3 ), (Iso-Bu) ₂ Al (OSiM
_{e 3), (iso-Bu} ) 2 Al (OSiEt 3) , _{^{etc., (iii) R a n Al}} (OAlR d 2) 3-n Et 2 AlOAlEt 2, (iso-Bu) 2 AlOAl (iso-Bu)
Such as ^{_{2, (iv) R a n}} Al (NR e 2) 3-n Me 2 AlNEt 2, Et 2 AlNHMe, Me 2 AlNHEt,
Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si) _{2
^{Etc., (v) R a n Al}} (SiR f 3) 3-n (iso-Bu) such as _{2 AlSiMe 3, (vi) R} a n Al [N (R ^g) -AlR ^h _{2] 3-n} Et ₂ AlN (Me) -AlEt ₂ (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

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
AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 1 carbon atoms.
15 hydrocarbon group) can also be used. Specifically, LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 and the like.

Among the above-mentioned organoaluminum compounds, ^Ra 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.

In the present invention, the organoaluminum compound is
More than one species may be used in combination.

(C) Electron Donor In forming the olefin polymerization catalyst, the (C) electron donor can be used as necessary. Examples of the electron donor (C) include an organosilicon compound represented by the following formula (i).

R _n Si (OR ′) _4-n (i) (wherein R and R ′ are hydrocarbon groups, and n is 1, 2
Or 3. Specific examples of the organic silane compound represented by the above formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-
Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bism-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxy Silane,
Decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltri Ethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxy (all
yloxy) silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like. Ethyl silicate, butyl silicate and the like can also be used.

In the present invention, the organosilane compound represented by the above formula (i) is particularly preferably represented by the following formula (ii). R ^a _n Si (OR ^b ) _4-n ( _n ) wherein n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary hydrocarbon group , N is 2
Or when 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When (4-n) is 2 or 3, OR ^b may be the same or different. In the organosilane compound having a bulky group represented by the formula (ii), the secondary or tertiary hydrocarbon group has a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and a substituent These groups and Si
And a hydrocarbon group in which the carbon adjacent to 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-dimethyl Cyclopentyl group, 2,5-dimethylcyclopentyl group,
2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,
Examples thereof include cyclopentyl groups having an alkyl group such as a 3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

Examples of the substituted cyclopentenyl group include 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 Cyclopentenyl groups 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 are exemplified.

As the substituted cyclopentadienyl group, 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,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Cyclopentadienyl groups having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group are exemplified.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include an i-propyl group, an s-butyl group, an s-amyl group and an α-methylbenzyl group. Examples of the hydrocarbon group having a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group and an admantyl group.

When n is 1, the organosilane compound represented by the formula (ii) may be cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, or 2,3-dimethylcyclopentyltrimethoxysilane. , Cyclopentyl triethoxy silane, iso-butyl triethoxy silane, t-butyl triethoxy silane,
Trialkoxysilanes such as cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, and 2-norbornanetriethoxysilane. When n is 2, dicyclopentyldiethoxysilane, t- Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,
And dialkoxysilanes such as cyclohexylmethyldiethoxysilane and 2-norbornanemethyldimethoxysilane.

When n is 2 among the organic silane compounds represented by the formula (ii), particularly, the following formula (ii)
The dimethoxysilane compound represented by i) can be preferably exemplified.

[0109]

Embedded image

In the formula, R ^a and R ^c 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
A hydrocarbon group in which carbon adjacent to Si is a secondary or tertiary carbon.

Examples of the organic silane compound represented by the formula (iii) include, for example, dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, di (2 -Methylcyclopentyl) 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-triethylsi Lopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclo Pentenyl) 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) dimethoxy Silane, di (tetramethylcyclopenteni ) Dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxy Silane, di (2-
n-butylcyclopentenyl) dimethoxysilane, di (2,
3-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,4-dimethylcyclopentadienyl) dimethoxysilane, 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 (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, di-s-butyldimethoxysilane, di-s-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

When n is 3 as the electron donor represented by the formula (ii), tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethyl Monoalkoxysilanes such as ethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are exemplified.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and represented by the formula (iii) Dimethoxysilanes, specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane, etc. Is preferably used.

Examples of the electron donor (C) include the above-mentioned polyether compounds, 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, Nitrogen-containing compounds such as substituted methylenediamines such as N, N, N ', N'-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine Phosphorous esters such as electron donors, triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite It is also possible to use oxygen-containing electron donors such as phosphorus-containing electron donors, 2,6-substituted tetrahydropyrans, and 2,5-substituted tetrahydropyrans. That.

Two or more of these may be used in combination. In the present invention, when forming an olefin polymerization catalyst from each of these components (A) and (B) and, if necessary, (C), other components can be used as necessary.

In the present invention, a prepolymerization catalyst may be formed from each of the above components. The prepolymerized catalyst includes the solid titanium catalyst component (A), the organoaluminum compound (B) and, if necessary, the electron donor (C).
Is formed by preliminary (co) polymerizing an olefin or the like in the presence of

The olefins used in the prepolymerization include, for example, ethylene, propylene, 1-butene,
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-tetradecene, 1-hexadecene, 1-octadecene, Α-olefins having 2 or more carbon atoms, such as 1-eicosene. Also other vinyl compounds as described below,
Polyene compounds can also be used during prepolymerization. These may be used in combination of two or more.

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, the method of performing the prepolymerization is not particularly limited, for example, the prepolymerization can be performed in a liquid state, or can be performed in the co-presence of a polymerization inert organic solvent. Can be performed under gas phase conditions. Of these, it is preferable to add a prepolymerized monomer and each catalyst component to the inert solvent in the presence of an inert solvent, and to carry out the 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 solvent, or may be carried out under a condition in which the polymer is not dissolved.

The prepolymerization is usually carried out at about -20 to + 100 ° C, preferably at about -20 to + 80 ° C, more preferably at -10 to + 80 ° C.
It is desirable to carry out at + 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. The concentration of the catalyst component in the pre-polymerization varies depending on the catalyst component used, etc., but the concentration of the solid titanium catalyst component (A) is expressed in terms of titanium atoms per liter of polymerization volume.
Usually about 0.001 to 5000 mmol, preferably about 0.0
It is preferably from 1 to 1000 mmol, particularly preferably from 0.1 to 500 mmol.

The organoaluminum compound (B) is used in an amount of 0.01 to 2,000 g, preferably 0.03 to 1000 g, more preferably 0.05 to 2,000 g of the solid titanium catalyst component (A).
Used in an amount such that ~ 200 g of the preliminary (co) polymer is produced, and per mole of titanium in the solid titanium catalyst component,
Usually about 0.1-1000 mol, preferably about 0.2-500
Moles, particularly preferably 0.5 to 100 moles.

In the prepolymerization, the electron donor (C)
Is used as needed in an amount of usually 0.01 to 50 mol, preferably 0.05 to 30 mol, more preferably 0.1 to 10 mol, per 1 mol of titanium atoms in the solid titanium catalyst component (A). Can be.

In the preliminary polymerization, a molecular weight regulator such as hydrogen can be used. When the prepolymerized catalyst is obtained in a suspended state as described above, in the next step (main) polymerization, the prepolymerized catalyst can be used as it is in a suspended state or can be produced from the suspension. The pre-polymerized catalyst may be used separately.

The above-mentioned prepolymerized catalyst is usually used together with the organoaluminum compound (B) and the electron donor (C). In some cases, only the prepolymerized catalyst can be used as a catalyst for olefin polymerization. Preliminary polymerization can be performed without using the electron donor (C), and the electron donor (C) can be used together with the prepolymerization catalyst.
May not be required.

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, the olefin comprising the solid titanium catalyst component (A), the organoaluminum compound (B) and, if necessary, the electron donor (C) is used. An olefin is polymerized or copolymerized in the presence of a catalyst including a polymerization catalyst or a prepolymerization catalyst.

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

Among 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 a diene compound may be copolymerized with an olefin. As such a diene compound, specifically, 1,3-butadiene, 1,3-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-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 are 2
It may be used in combination of more than one kind.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. When the polymerization takes a reaction mode of slurry polymerization, the above-mentioned polymerization-inactive 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 is usually used in an amount of about 0.001 to 100 mmol, preferably about 0.005 to 100 mmol, in terms of titanium atom per liter of polymerization volume. Used in an amount of 20 mmol.

The organoaluminum compound (B) has a metal atom in the compound (B) of usually about 1 to 2000 mol, preferably about 2 to 500 mol per mol of titanium atom in the polymerization system.
It is used in a molar amount.

Although the electron donor (C) may or may not be used, the metal atom 1 of the organoaluminum compound (B) may be used.
It is used in an amount of usually about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, per mol, if necessary.

When a prepolymerization catalyst is used in this polymerization, neither the organoaluminum compound (B) nor the electron donor (C) may be used in some cases. When an olefin polymerization catalyst is formed from the component (B) and / or (C) together with the prepolymerization catalyst, these components (B) and (C) can be used in the amounts described above.

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., and normal pressure to 100 kg / l, although it varies depending on the type of the olefin, the form of the polymerization, and the like.
cm ² preferably carried out at a pressure of about to 50 kg / cm ^2.

In the polymerization method of the present invention, the polymerization can be carried out in 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.

[0138]

According to the olefin polymerization catalyst containing the solid titanium catalyst component prepared in the present invention as described above, olefins can be polymerized with extremely high activity, and the α-olefin having 3 or more carbon atoms can be polymerized. When an olefin is polymerized, a polyolefin having high stereoregularity can be produced.

[0139]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The methods for measuring the physical properties of the polypropylene obtained in the following examples will be described. (1) Bulk density (BD): Measured according to ASTM D1895. (2) Melt flow rate (MFR); ASTM D12
Measured at 230 ° C under a load of 2.16 kg in accordance with No.38. (3) 23 ° C. n-decane-soluble component amount (t-DS): The 23 ° C. n-decane-soluble component amount (t-DS) of the polymer is calculated as 23 ° C. n in the powdery polymer obtained after polymerization. -The ratio of the total amount of the decane-soluble component and the solvent-soluble polymer to the whole polymer was determined as follows.

A 1 liter flask was charged with 3 g of the sample (powder polymer), 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500 ml of n-decane, and dissolved by heating at 145 ° C. Was. Cool to 23 ° C. over 8 hours after dissolution and maintain at 23 ° C. for 8 hours. The precipitated solid polymer and the n-decane solution containing the dissolved polymer were separated by filtration through a glass filter.

The liquid phase is dried under reduced pressure at 150 ° C. until a constant weight is obtained, and its weight is measured. The obtained polymer dissolution amount was calculated as a percentage (p-DS) based on the weight of the sample. From the p-DS obtained as described above, the weight of the powdery polymer obtained after the polymerization, and the weight of the solvent-soluble polymer, the decane-soluble component amount (t-DS) of polypropylene at 23 ° C. was determined by the following formula.

[0143]

(Equation 1)

Solid deposition rate In the following Examples and Comparative Examples, the solid deposition rate in the contact liquid (β) between the liquid magnesium compound and the liquid titanium compound at the time of preparing the solid titanium catalyst component was determined as follows. Was.

7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexyl alcohol were added to 130
C. for 2 hours to form a homogeneous solution, into which 1.67 g (11.3 mmol) of phthalic anhydride was added.
The mixture was further stirred and mixed at 0 ° C. for 1 hour to dissolve.

After the homogeneous solution thus obtained was cooled to room temperature, 200 ml (1.
(8 mol) of titanium tetrachloride (TiCl ₄ ).

The temperature of the resulting mixture (contact liquid (β)) was raised to 20 ° C. (the temperature at which the electron donor (di) was added in the following examples), and the slurry in the system was The mixture was filtered while maintaining the temperature.

By measuring the amount of Mg contained in the solid part and the amount of Mg contained in the liquid part with a plasma emission spectrometer, the solid (MgCl ₂ ) deposition rate of Mg was determined.
This was defined as the solid deposition rate in the contact liquid (β).

With the above contact liquid (β), the solid deposition rate at 20 ° C. was 82%. Similarly, the solid deposition rates at 92 ° C and 110 ° C were 100%.

[0150]

Example 1 Preparation of Solid Titanium Catalyst Component (A-1) (1) 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexyl alcohol were added to 130 parts of C. for 2 hours to form a homogeneous solution, into which 1.67 g (11.3 mmol) of phthalic anhydride was added.
And further stirred for 1 hour to dissolve. (2) After cooling the thus obtained homogeneous solution to room temperature, it was dropped into 200 ml (1.8 mol) of titanium tetrachloride (TiCl ₄ ) maintained at -20 ° C. over 1 hour. did. (3) The temperature of the obtained mixture was raised to 20 ° C, 3.01 ml (11.25 mmol) of diisobutyl phthalate (DIBP) was added, and then the temperature was raised to 110 ° C. Stirring was maintained at the same temperature for 2 hours. (4) Next, a solid portion was collected by hot filtration, and the solid portion was suspended in 275 ml of TiCl ₄ , heated to 110 ° C., and added with 2.01 ml (7.5 mmol) of DIBP. Heated at 110 ° C. for 2 hours. (5) The solid portion was collected by hot filtration, and
The operation of resuspending in 5 ml of TiCl ₄ and heating at 110 ° C. for 2 hours was performed twice. (6) After completion of the reaction, the solid portion was collected again by hot filtration, and
Washing was sufficiently performed using decane at 10 ° C. and hexane at room temperature until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component (A-1) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-1) contained 3.7% by weight of titanium, 16% by weight of magnesium and 18.5% by weight of DIBP.

Preparation of Prepolymerization Catalyst (1) 68.2 ml of purified hexane was charged into a 200-ml glass reactor purged with nitrogen, cooled to 18 ° C.
1.2 mmol of triethylaluminum (TEA)
After charging the solid titanium catalyst component (A-1) obtained above in an amount of 0.4 mmol in terms of titanium atoms, propylene gas was supplied to the reactor at 1.39 l / h, and the mixture was stirred at 20 ° C.
For 1 hour.

After completion of the polymerization, the reaction mixture was taken out under a nitrogen atmosphere, and the liquid part was removed to obtain a solid part (preliminary polymerization catalyst).
Was isolated and resuspended in decane. The prepolymerization amount was 3.0 g per 1 g of the solid titanium catalyst component.

[0155] in Polymerization nitrogen substituted one liter autoclave was charged with purified heptane 400 ml, 60 ° C., under a propylene atmosphere, triethyl aluminum (TEA) 0.4 mmol of dicyclopentyl Shi silane (DCPM
0.08 mmol of S) and 0.004 mmol of the prepolymerized catalyst (1) obtained above in terms of titanium atom were charged.

After 240 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 polymer was filtered to separate into a white powder and a liquid phase.

The yield of the polymer obtained in the form of a white powder was 7
It was 6.4 g. The liquid phase was concentrated to obtain 0.1 g of a solvent-soluble polymer. Polymerization activity, MFR, apparent bulk specific gravity (BD), and 23 ° C. n-decane soluble determined as the ratio of the total amount of the solvent-soluble polymer to the powdery polymer at 23 ° C. n-decane soluble component Table 1 shows the component amounts (t-DS).

[0158]

Example 2 Preparation of Solid Titanium Catalyst Component (A-2) The same operation as in (1) to (4) of Example 1 was performed. That is, a homogeneous solution of anhydrous magnesium chloride and titanium tetrachloride are mixed, the mixture is heated to 20 ° C, 3.01 ml (11.25 mmol) of diisobutyl phthalate (DIBP) is added, and then the temperature is raised to 110 ° C. When the temperature reached 110 ° C., the mixture was kept stirred at the same temperature for 2 hours. Next, a solid portion was collected by hot filtration, and this solid portion was separated by 275.
After suspending in 110 ml of TiCl ₄ , the temperature was raised to 110 ° C.
2.01 ml (7.5 mmol) of IBP was added and 11
Heat at 0 ° C. for 2 hours. (5) Then, the solid portion was collected by hot filtration, and the solid portion was collected by 55 ml of TiCl ₄ and
After suspending in 20 ml of toluene, the operation of heating at 115 ° C. for 2 hours was performed twice.

The same washing operation as in (6) of Example 1 was performed. Solid titanium catalyst component obtained as described above
(A-2) was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-2) contained 1.7% by weight of titanium, 22% by weight of magnesium, and 13.7% by weight of DIBP.

Preparation of Prepolymerized Catalyst (2) The procedure of Example 1 was repeated, except that the solid titanium catalyst component (A-2) obtained above was used in place of the solid titanium catalyst component (A-1). Prepolymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (2).

[0162] In Polymerization Example 1, except for using the prepolymerized catalyst (2) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0163]

Example 3 Preparation of Solid Titanium Catalyst Component (A-3) The same operation as in (1) and (2) of Example 1 was performed.
(3) The mixture containing magnesium chloride and titanium tetrachloride obtained above was heated to 20 ° C., and 4.13 ml of a diheptyl phthalate mixture (DHP) as shown below was added.
(11.25 mmol), and then heated to 92 ° C.
When the temperature reached 92 ° C., stirring was maintained for 2 hours at the same temperature.

[0164]

Embedded image

(4) Then, a solid portion was collected by hot filtration, and the solid portion was suspended in 275 ml of TiCl ₄ , heated to 92 ° C., and 2.75 ml (7.5 mmol) of DHP was added. And heated at 92 ° C. for 2 hours. (5) The solid portion was collected by hot filtration, and
After suspending in 5 ml of TiCl ₄ , the operation of heating at 92 ° C. for 2 hours was performed twice. (6) After completion of the reaction, a solid portion was collected again by hot filtration,
Washing was performed sufficiently using decane at 2 ° C. and hexane at room temperature until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component (A-3) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-3) contained 2.0% by weight of titanium, 19% by weight of magnesium, and 1% of DHP.
It contained 3.6% by weight.

Preparation of Prepolymerized Catalyst (3) The procedure of Example 1 was repeated except that the solid titanium catalyst component (A-3) obtained above was used in place of the solid titanium catalyst component (A-1). Prepolymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (3).

[0169] In Polymerization Example 1, except for using the prepolymerized catalyst (3) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0170]

Example 4 Preparation of Solid Titanium Catalyst Component (A-4) The procedure of Example 1 was repeated, except that the procedure (3) was carried out as follows. (3) A mixture containing magnesium chloride and titanium tetrachloride obtained by the same operation as in (1) and (2) of Example 1 was heated to 20 ° C., and diheptyl phthalate (DHP) was added to the mixture. After adding .51 ml (15.0 mmol), the temperature was raised to 92 ° C., and when the temperature reached 92 ° C., stirring was maintained at the same temperature for 2 hours.

The same operations as in (4) and (5) of Example 1 were performed. That is, (4) Then, a solid portion was collected by hot filtration, and the solid portion was suspended in 275 ml of TiCl ₄ , heated to 110 ° C., and added with 2.01 ml (7.5 mmol) of DIBP. At 110 ° C. for 2 hours. (5) The solid portion was collected by hot filtration, and
After suspending in 5 ml of TiCl ₄ , the operation of heating at 110 ° C. for 2 hours was performed twice.

The same washing operation as in (6) of Example 1 was performed.

The solid titanium catalyst component (A-4) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-4) contained 3.4% by weight of titanium, 16% by weight of magnesium, and 4.4% by weight of DHP.
It contained 0% by weight and 14.8% by weight of DIBP.

Preparation of Prepolymerized Catalyst (4) The procedure of Example 1 was repeated, except that the solid titanium catalyst component (A-4) obtained above was used instead of the solid titanium catalyst component (A-1). Prepolymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (4).

[0176] In Polymerization Example 1, except for using the prepolymerized catalyst (4) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0177]

Example 5 Preparation of Solid Titanium Catalyst Component (A-5) The same operation as in Example 1 was performed, except that operations (3) and (5) were performed as described below. . (3) A mixture containing magnesium chloride and titanium tetrachloride obtained by the same operation as in (1) and (2) of Example 1 was heated to 20 ° C., and diheptyl phthalate (DHP) was added to the mixture. After addition of .13 ml (11.25 mmol), 92 ° C
When the temperature reached 92 ° C., the mixture was stirred and maintained at the same temperature for 2 hours. (4) The same operation as (4) in Example 1 was performed. That is, a solid portion was collected by hot filtration, and this solid portion was 275 m
of TiCl ₄ and then heated to 110 ° C.
2.01 ml (7.5 mmol) of BP was added and 110
Heated at ° C for 2 hours. (5) The same operation as in (5) of Example 2 was performed. That is, the solid portion was collected by hot filtration, and the solid portion was 55 m
After suspending in 1 l of TiCl ₄ and 220 ml of toluene, the operation of heating at 115 ° C. for 2 hours was performed twice.

The same washing operation as in (6) of Example 1 was performed. Solid titanium catalyst component obtained as described above
(A-5) was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-5) contained 1.5% by weight of titanium, 20% by weight of magnesium, and 2.5% by weight of DHP.
It contained 7% by weight and 10.5% by weight of DIBP.

Preparation of Prepolymerized Catalyst (5) The procedure of Example 1 was repeated except that the solid titanium catalyst component (A-5) obtained above was used in place of the solid titanium catalyst component (A-1). Preliminary polymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (5).

[0181] In Polymerization Example 1, except for using the prepolymerized catalyst (5) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0182]

Example 6 Preparation of Solid Titanium Catalyst Component (A-6) The procedure of Example 1 was repeated, except that the operation (5) was not performed, and the operations (3) and (4) were performed as follows. The same operation as in Example 1 was performed. (3) The same operation as in (3) of Example 2 was performed. That is, the magnesium chloride obtained in the operations (1) and (2),
The temperature of the mixed solution containing titanium tetrachloride was raised to 20 ° C., and 4.13 ml (11.25 mmol) of diheptyl phthalate (DHP) was added. Then, the temperature was raised to 92 ° C., and when the temperature reached 92 ° C., From this, stirring was maintained at the same temperature for 2 hours. (4) Then the solid portion was collected by hot filtration, and thereafter the solid portion was suspended in TiCl ₄ in 275 ml, and DIBP was 0.60 ml (2.25 mmol) added heated to 110 ° C., 110 The operation of heating at 2 ° C. for 2 hours was performed three times.

The same washing operation as in (6) of Example 1 was performed.

The solid titanium catalyst component (A-6) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-6) contained 2.5% by weight of titanium, 18% by weight of magnesium, and 3.5% of DHP.
It contained 6% by weight and 12% by weight of DIBP.

Preparation of Prepolymerized Catalyst (6) The procedure of Example 1 was repeated, except that the solid titanium catalyst component (A-6) obtained above was used in place of the solid titanium catalyst component (A-1). Prepolymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (6).

[0187] In Polymerization Example 1, except for using the prepolymerized catalyst (6) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0188]

Example 7 Preparation of solid titanium catalyst component (A-7) The same operation as in Example 1 was performed, except that operations (3) to (5) were performed as described below. . (3) The mixture containing the magnesium chloride obtained in the operations (1) and (2) and titanium tetrachloride is heated to 20 ° C.
After adding 4.33 ml (18.75 mmol) of isopropyl-2-isobutyl-1,3 dimethoxypropane (PBDME), the temperature was raised to 110 ° C., and when it reached 110 ° C., it was kept at the same temperature for 2 hours. Stirring was maintained. (4) Then the solid portion was collected by hot filtration, and thereafter the solid portion was suspended in TiCl ₄ in 275 ml, and PBDME was 0.43 ml (1.88 mmol) added heated to 110 ° C., 110 Heated at 150C for 1.5 hours. (5) The solid portion was collected by hot filtration, and
After suspended in 5 ml TiCl ₄ in the PBDME 0.4
3 ml (1.88 mmol) were added and heated at 110 ° C. for 1.5 hours.

The same washing operation as in (6) of Example 1 was performed.

The solid titanium catalyst component (A-7) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-7) was composed of 2.2% by weight of titanium, 19% by weight of magnesium, and DBDME.
Was contained at 15.0% by weight.

Preparation of Prepolymerized Catalyst (7) The procedure of Example 1 was repeated, except that the solid titanium catalyst component (A-7) obtained above was used in place of the solid titanium catalyst component (A-1). Prepolymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (7).

[0193] In Polymerization Example 1, using the prepolymerized catalyst obtained above in place of the prepolymerized catalyst (1) (7), cyclohexylmethyl dimethoxy silane in place of DCPMS (CMMS)
And the polymerization was carried out in the same manner as in Example 1 except that the amount of hydrogenation was changed to 100 ml. Table 1 shows the results.

[0194]

Example 8 except that Polymerization CMMS was not used was subjected to the polymerization in the same manner as in Example 7. Table 1 shows the results.

[0195]

Comparative Example 1 Preparation of Solid Titanium Catalyst Component (A-8) The same operation as in (1) and (2) of Example 1 was performed. (2
The operation (3) of Example 1 in which DIBP was added at 0 ° C. was not performed. (4) The mixed solution containing the magnesium chloride obtained in the operations (1) and (2) and titanium tetrachloride was added to the mixture for 110 hours over 4 hours.
The temperature was raised to 110 ° C., and when the temperature reached 110 ° C., 5.03 ml (18.8 mmol) of DIBP was added, and the mixture was stirred and maintained at the same temperature for 2 hours. (5) The solid portion was collected by hot filtration, and
The operation of suspending in 5 ml of TiCl ₄ and heating at 110 ° C. for 2 hours was repeated three times.

The same washing operation as in (6) of Example 1 was performed.

The solid titanium catalyst component (A-8) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-8) contained 2.1% by weight of titanium, 18% by weight of magnesium, and 58% of chlorine.
% Of DIBP and 10.9% by weight of DIBP.

Preparation of Prepolymerized Catalyst (8) The procedure of Example 1 was repeated except that the solid titanium catalyst component (A-8) obtained above was used in place of the solid titanium catalyst component (A-1). Preliminary polymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (8).

[0200] In Polymerization Example 1, except for using the prepolymerized catalyst (8) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0201]

Comparative Example 2 Preparation of Solid Titanium Catalyst Component (A-9) The same operation as (1) to (2) and (4) of Comparative Example 1 was performed. (Operation (3) of Example 1 was not performed.) Next, in addition to operation (5) of Comparative Example 1, the same operation as operation (5) of Example 2 was performed. That is, (5) In the same manner as in the operation (5) of Comparative Example 1, a solid portion was collected by hot filtration, and the solid portion was suspended in 275 ml of TiCl ₄ and heated at 110 ° C. for 2 hours. Then, in the same manner as in the operation (5) of Example 2, a solid portion was collected by hot filtration, and the solid portion was suspended in 55 ml of TiCl ₄ and 220 ml of toluene, followed by heating at 115 ° C. for 2 hours. 2
Performed times.

The same washing operation as in (6) of Example 1 was performed.

The solid titanium catalyst component (A-9) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-9) contained 1.9% by weight of titanium, 24% by weight of magnesium, and 6.3% by weight of DIBP.

Preparation of Prepolymerized Catalyst (9) The procedure of Example 1 was repeated, except that the solid titanium catalyst component (A-9) obtained above was used in place of the solid titanium catalyst component (A-1). Preliminary polymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (9).

[0206] In Polymerization Example 1, except for using the prepolymerized catalyst (9) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0207]

Comparative Example 3 Preparation of Solid Titanium Catalyst Component (A-10) In Example 3, the operation (3) of adding DHP at 20 ° C. was not performed, and the operations (4) and (5) were performed as follows. The same operation as in Example 3 was performed except that the operation was performed. (4) The mixture containing the magnesium chloride and titanium tetrachloride obtained in the operations (1) and (2) was heated to 92 ° C, and when the temperature reached 92 ° C, 6.88 ml of DHP was added.
(18.8 mmol), and the mixture was stirred and maintained at the same temperature for 2 hours. (5) The solid portion was collected by hot filtration, and
The operation of suspending in 5 ml of TiCl ₄ and heating at 92 ° C. for 2 hours was repeated three times.

The same cleaning operation as in (6) of Example 3 was performed.

The solid titanium catalyst component (A-10) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-10) contained 2.2% by weight of titanium, 19% by weight of magnesium, and 1% of DHP.
It contained 1.0% by weight.

Preparation of Prepolymerized Catalyst (10) In Example 1, except that the solid titanium catalyst component (A-10) obtained above was used in place of the solid titanium catalyst component (A-1), Preliminary polymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (10).

[0212] In Polymerization Example 1, except for using the prepolymerized catalyst (10) obtained above in place of the prepolymerized catalyst (1) is Example 1
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0213]

Comparative Example 4 Preparation of Solid Titanium Catalyst Component (A-11) In Example 7, the operation (3) of adding PBDME at 20 ° C. was not performed, and the operations (4) and (5) were performed as follows. The same operation as in Example 7 was performed except that the operation was performed. (4) The mixture containing the magnesium chloride obtained in the operations (1) and (2) and titanium tetrachloride was heated to 110 ° C., and when the temperature reached 110 ° C., PBDME was added to 5.19.
ml (22.51 mmol), and the mixture was kept stirring at the same temperature for 2 hours. (5) The solid portion was collected by hot filtration, and
After suspended in 5 ml TiCl ₄ was heated 110 for 2 hours. (PBDME was not added.) The same washing operation as in (6) of Example 7 was performed.

The solid titanium catalyst component (A-11) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-11) was composed of 2.3% by weight of titanium, 19% by weight of magnesium, and PBDME.
Was 10.0% by weight.

Preparation of Prepolymerized Catalyst (11) Except that the solid titanium catalyst component (A-11) obtained above was used in place of the solid titanium catalyst component (A-1) in Example 1, Preliminary polymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (11).

[0217] In Polymerization Example 7, except for using the prepolymerized catalyst (12) obtained above in place of the prepolymerized catalyst (7) is Example 7
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0218]

Comparative Example 5 Preparation of Solid Titanium Catalyst Component (A-12) In Example 7, the operation (3) of adding PBDME at 20 ° C. was not performed, and the operations (4) and (5) were performed as follows. The same operation as in Example 7 was performed except that the operation was performed. (4) The mixture containing magnesium chloride and titanium tetrachloride obtained in the operations (1) and (2) was heated to 110 ° C., and when the temperature reached 110 ° C., PBDME was added to 2.59.
ml (11.25 mmol) was added, and the mixture was stirred and maintained at the same temperature for 2 hours. (5) Then, a solid portion was collected by hot filtration, and the solid portion was suspended in 275 ml of TiCl ₄ , heated to 110 ° C., and 1.73 ml (7.5 mmol) of PBDME was added thereto. Heated at ° C for 2 hours.

The same washing operation as in (6) of Example 7 was performed.

The solid titanium catalyst component (A-12) obtained as described above was stored as a hexane slurry. A part of this hexane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-12) was composed of 1.8% by weight of titanium, 20% by weight of magnesium, and PBDME.
Was contained at 17.7% by weight.

Preparation of Prepolymerized Catalyst (12) In Example 1, except that the solid titanium catalyst component (A-12) obtained above was used in place of the solid titanium catalyst component (A-1), Preliminary polymerization was carried out in the same manner as in Example 1 to prepare a prepolymerized catalyst (12).

[0223] In Polymerization Example 7, except for using the prepolymerized catalyst (12) obtained above in place of the prepolymerized catalyst (7) is Example 7
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0224]

[Table 1]

[0225]

Example 9 Preparation of solid titanium catalyst component (A-13) (1) 140 mg (90 mmol) of 2.88 g (30 mmol) of anhydrous magnesium chloride, 15.0 ml of decane and 14.0 ml (90 mmol) of 2-ethylhexyl alcohol The mixture was heated at a temperature of 4 ° C. for 4 hours to obtain a homogeneous solution. 0.667 g (4.5 mmol) of phthalic anhydride was added to the solution, and the mixture was further stirred at 130 ° C. for 1 hour to be dissolved. (2) After cooling the homogeneous solution thus obtained to room temperature, 80 ml (0.72 mol) kept at -20 ° C.
Of titanium tetrachloride (TiCl ₄ ) was added dropwise over 45 minutes. (3) The temperature of the obtained mixed solution was raised to 20 ° C, and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane (PBDM
After addition of 1.04 ml (4.5 mmol) of E), 110
The temperature was raised to 110 ° C., and when the temperature reached 110 ° C., stirring was maintained at the same temperature for 2 hours. (4) Then, a solid portion was collected by hot filtration, and the solid portion was suspended in 100 ml of TiCl ₄ and then heated to 110 ° C. to remove diisobutyl phthalate (DIBP) from 0.24.
0 ml (0.9 mmol) was added and heated at 110 ° C. for 1 hour. (5) A solid portion was collected by hot filtration, and this solid portion was
After suspending in 0 ml TiCl ₄ , DIBP was added to 0.24
The operation of adding 0 ml (0.9 mmol) and heating at 110 ° C. for 30 minutes was performed twice. (6) After completion of the reaction, a solid portion was collected again by hot filtration,
Washing was carried out sufficiently using decane at 0 ° C. and hexane at room temperature until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component (A-13) obtained as described above was stored as a decane slurry. A part of this decane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-13) was composed of 2.9% by weight of titanium, 17% by weight of magnesium, PBDME
Was contained at 5.5% by weight and DIBP was contained at 12.6% by weight. Preparation of Prepolymerized Catalyst (13) Example 1 was repeated except that the solid titanium catalyst component (A-13) obtained above was used in place of the solid titanium catalyst component (A-1). Preliminary polymerization was carried out in the same manner as in to prepare a prepolymerized catalyst (13).

[0228] In Polymerization Example 1, using the prepolymerized catalyst (13) obtained above in place of the prepolymerized catalyst (1), the amount of hydrogen addition 100ml
Polymerization was performed in the same manner as in Example 1 except that Table 2 shows the results.

[0229]

Example 10 Preparation of Solid Titanium Catalyst Component (A-14) The same operation as (1) and (2) of Example 9 was performed. (3) Magnesium chloride obtained above and TiCl ₄
Is heated to 20 ° C., and PBDME is adjusted to 0.5.
After the addition of 18 ml (2.25 mmol), the temperature was raised to 110 ° C., and when the temperature reached 110 ° C., stirring was maintained for 2 hours at the same temperature. (4) Then, a solid portion was collected by hot filtration, and the solid portion was suspended in 100 ml of TiCl ₄ , heated to 110 ° C., and added with 0.801 ml (3 mmol) of DIBP.
Heated at 110 ° C. for 1 hour. (5) A solid portion was collected by hot filtration, and this solid portion was
After suspending in 0 ml of TiCl ₄ , PBDME was added to 0.5 ml.
18 ml (2.25 mmol) were added and heated at 110 ° C. for 30 minutes. (6) A solid portion is collected by hot filtration, and
After suspending in 0 ml of TiCl ₄ , it was heated at 110 ° C. for 30 minutes.

The same washing operation as in (6) of Example 9 was performed. The solid titanium catalyst component (A
-14) was stored as a decane slurry. A part of this decane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-14) was composed of 4.0% by weight of titanium, 15% by weight of magnesium, PBDME
6.5% by weight and DIBP 16.4% by weight. Preparation of Prepolymerized Catalyst (14) Example 1 was repeated except that the solid titanium catalyst component (A-14) obtained above was used in place of the solid titanium catalyst component (A-1). Preliminary polymerization was carried out in the same manner as in to prepare a prepolymerized catalyst (14). In Polymerization Example 9, except for using the prepolymerized catalyst (14) obtained above in place of the prepolymerized catalyst (13) was polymerized in the same manner as in Example 9. Table 2 shows the results.

[0232]

Example 11 Preparation of Solid Titanium Catalyst Component (A-15) The same operation as in Example 9 (1) and (2) was performed. (3) Magnesium chloride obtained above and TiCl ₄
Was heated to 20 ° C., and DIBP was reduced to 0.80.
After adding 1 ml (3 mmol), the temperature was raised to 110 ° C.
When the temperature reached 10 ° C., stirring was maintained for 2 hours at the same temperature. (4) Next, a solid portion was collected by hot filtration, and the solid portion was suspended in 100 ml of TiCl ₄ , heated to 110 ° C., and 0.345 ml (1.5 mmol) of PBDME was added thereto. Heated at 0 ° C. for 1 hour. (5) A solid portion was collected by hot filtration, and this solid portion was
After suspending in 0 ml of TiCl ₄ , PBDME was added to 0.3 ml.
An operation of adding 45 ml (1.5 mmol) and heating at 110 ° C. for 30 minutes was performed twice.

The same washing operation as in (6) of Example 9 was performed. The solid titanium catalyst component (A
-15) was stored as a decane slurry. A part of this decane slurry was dried, and the composition of the solid titanium catalyst component was analyzed.

The solid titanium catalyst component (A-15) contained 1.4% by weight of titanium, 22% by weight of magnesium, and PBDME.
8.9% by weight and DIBP 1.2% by weight. Preparation of Prepolymerized Catalyst (15) Example 1 was repeated except that the solid titanium catalyst component (A-15) obtained above was used in place of the solid titanium catalyst component (A-1). Prepolymerization was carried out in the same manner as in to prepare a prepolymerization catalyst (15). In Polymerization Example 9, except for using the prepolymerized catalyst (15) obtained above in place of the prepolymerized catalyst (13) was polymerized in the same manner as in Example 9. Table 2 shows the results.

[0235]

[Table 2]

[0236]

In Example 12 Polymerization Example 7, except that the amount of hydrogen addition and 500 ml, polymerization was performed in the same manner as in Example 7. Table 3 shows the results.

[0237]

In Example 13 Polymerization Example 12, except that the TEA addition amount of the preliminary polymerization catalyst prepared as 0.4 mmole, was polymerized in the same manner as in Example 12. Table 3 shows the results.

[0238]

In Example 14 Polymerization Example 13, except that was polymerized for 3 hours under 20 ° C. stirred by supplying propylene gas to the reactor 0.46 l / h during prepolymerization catalyst preparation, Example Polymerization was carried out in the same manner as in Example 13. Table 3 shows the results.

[0239]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a diagram showing a process for preparing a solid titanium catalyst component and a process for preparing an olefin polymerization catalyst according to the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masao Nakano 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Sadahiko Matsuura Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Mitsui Chemicals, Inc.

Claims (8)

[Claims] [I] A liquid magnesium compound and a liquid titanium compound are brought into contact with each other, and during the period from the start of precipitation of solids in the contact liquid (β) to the end thereof, the contact liquid (β) Adding an electron donor (di) selected from the group consisting of a polyvalent carboxylic acid ester and a compound having two or more ether bonds present through a plurality of atoms, to obtain titanium, magnesium, a halogen and an electron donor. (d-
i) to form a solid product (α) containing
The solid product (α) obtained after the completion of the solid deposition is added to an electron donor (d-) selected from the group consisting of a polyvalent carboxylic acid ester and a compound having two or more ether bonds existing through a plurality of atoms. ii) is contacted to prepare a solid titanium catalyst component comprising titanium, magnesium, halogen, an electron donor (di) and an electron donor (d-ii); Method. 2. The contact liquid (β) comprises a monocarboxylic acid ester, an aliphatic carboxylic acid, an acid anhydride, a ketone, a monoether, an aliphatic carbonate, an alkoxy group-containing alcohol, an aryloxy group-containing alcohol, Si—O An organosilicon compound having a -C bond, P
The electron donor (d-iii) selected from the group consisting of organic phosphorus compounds having an -OC bond before the addition of the electron donor (di) is contained. A method for preparing a solid titanium catalyst component. 3. The method for preparing a solid titanium catalyst component according to claim 1, wherein the polycarboxylic acid ester is a phthalic acid diester represented by the following formula: 4. The electron donor (di) used in [I].
Is diheptyl phthalate, and the electron donor (d-ii) used in [II] is diisobutyl phthalate. Method. 5. The solid titanium catalyst according to claim 1, wherein the compound having two or more ether bonds existing through a plurality of atoms is represented by the following formula. Method for preparing components; (Wherein, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ have at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. A substituent, and any of R ^{1 to} R ²⁶ , preferably R
^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and an atom other than carbon may be contained in the main chain. ). 6. The electron donor (di) used in [I].
The solid titanium catalyst according to any one of claims 1 to 5, wherein a molar ratio of the titanium donor to the electron donor (d-ii) used in [II] is 10/90 to 90/10. How to prepare the components. 7. A solid titanium catalyst component obtained by the method for preparing a solid titanium catalyst component according to any one of claims 1 to 6, and (B) an organoaluminum compound. C) An olefin polymerization catalyst, comprising: an electron donor. 8. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 7.