JP2002249507A - Solid catalyst component for olefin polymerization and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid catalyst component for olefin polymerization capable of obtaining an olefin polymer in an extremely high yield, especially a propylene polymer in a high yield while keeping high stereoregularity, and having a high response capacity to hydrogen, and a catalyst. SOLUTION: This solid catalyst component for olefin polymerization and this catalyst contain magnesium, titanium, a halogen, an electron donor compound, and a dibenzofuran and its derivative represented by a specified structural formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a solid catalyst for olefin polymerization capable of obtaining an olefin polymer at an extremely high yield while maintaining a high stereoregularity and having a high hydrogen response ability. It relates to components and catalysts.

[0002]

2. Description of the Related Art Heretofore, in the polymerization of olefins, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components have been known.
In addition, many olefin polymerization methods for polymerizing or copolymerizing propylene in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organic aluminum compound and an organic silicon compound have been proposed. For example, JP
JP-A-7-63310 and JP-A-57-63311 disclose a solid catalyst component containing an electron donor of a diester compound such as a magnesium compound, a titanium compound and a phthalic acid diester, an organoaluminum compound and Si-O. A method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination with an organosilicon compound having a -C bond is disclosed.

[0003] Japanese Patent Application Laid-Open No. 1-6006 discloses a solid catalyst component for the polymerization of olefins containing alkoxymagnesium, titanium tetrachloride and dibutyl phthalate. Propylene is added in the presence of this solid catalyst component. By the polymerization, a stereoregular polymer is obtained in a high yield, and the effect is improved to some extent. By the way, polymers obtained by using the above-mentioned catalysts are used for various uses such as containers and films in addition to molded products such as automobiles and home electric appliances. These are obtained by melting polymer powder produced by polymerization and molding by various molding machines. In particular, when manufacturing large molded products by injection molding, etc., the fluidity (melt flow rate) of the molten polymer is increased. Higher values may be required, and much work has been done to increase the melt flow rate of the polymer.

[0004] Melt flow rate is highly dependent on the molecular weight of the polymer. In the art, during the polymerization of olefins, it is common to add hydrogen as a molecular weight regulator for the resulting polymer. At this time, when producing a polymer having a low molecular weight, that is, in order to produce a polymer having a high melt flow rate, usually a large amount of hydrogen is added. However, the pressure resistance of the reactor is limited due to its safety. There is also a limit on the amount. In order to add more hydrogen, the partial pressure of the monomer to be polymerized must be reduced, and in this case, the productivity is reduced. Also,
Since a large amount of hydrogen is used, a problem of cost arises. Therefore, there has been a demand for the development of a catalyst capable of producing a polymer having a high melt flow rate with a smaller amount of hydrogen and having a high so-called hydrogen activity or response to hydrogen and a high stereoregular polymer in a high yield. However, the above prior art was not sufficient to solve the problem.

[0005]

That is, an object of the present invention is to solve the problems remaining in the prior art and to obtain an olefin polymer in an extremely high yield. Is to obtain a very high yield while maintaining high stereoregularity, and further provides a solid catalyst component and a catalyst for olefins polymerization having a high ability to respond to hydrogen.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the problems left in the prior art, and as a result, have found that magnesium, titanium, halogen, an electron donating compound, dibenzofuran, and the like. And a derivative thereof and a solid catalyst component for the polymerization of olefins exhibit extremely high activity when subjected to the polymerization of olefins, and particularly when subjected to the polymerization of propylene, extremely high activity while maintaining high stereoregularity. It has been found that propylene can be polymerized in a high yield, and that it has high hydrogen response ability, and the present invention has been completed.

That is, the present invention provides magnesium, titanium, halogen, an electron donating compound, and the following general formula (1):

[0008]

Embedded image (1)

(Wherein R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom, and even if R ¹ and R ² are the same, X and y are 0 or an integer of 1 to 4, and x and y may be the same or different.) And a dibenzofuran and a derivative thereof. An object of the present invention is to provide a solid catalyst component for olefin polymerization (hereinafter, may be simply referred to as “component (A)”).

The olefin polymerization catalyst of the present invention comprises (A) the olefin polymerization solid catalyst component,
(B) The following general formula (2): R ³ _p AlQ _3-p (2) (wherein, R ³ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p represents And an organoaluminum compound represented by the following formula (3): R ⁴ _qSi (OR ⁵ ) _4-q (3) (wherein R ⁴ is an integer of 0 <p ≦ 3). Represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms, And represents an alkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3.) It is intended to provide an olefin polymerization catalyst characterized by the above.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The solid catalyst component for polymerization of olefins of the present invention (hereinafter sometimes simply referred to as "component (A)") comprises magnesium, titanium, halogen, an electron donating compound, It is characterized by containing the dibenzofuran represented by the general formula (1) and a derivative thereof. For example, a magnesium compound, a tetravalent titanium halide compound, an electron-donating compound, It is prepared by contacting the dibenzofuran represented by 1) and its derivative.

The magnesium compound used for preparing the above component (A) (hereinafter sometimes simply referred to as “component (a)”) includes magnesium dihalide,
Examples include dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium and fatty acid magnesium.

Specific examples of the magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride and the like.
As the dialkylmagnesium, a compound represented by the general formula R ⁶ R ⁷ Mg (wherein R ⁶ and R ⁷ each represent an alkyl group having 1 to 10 carbon atoms and may be the same or different) is preferable. More specifically, dimethyl magnesium, diethyl magnesium, methyl ethyl magnesium, dipropyl magnesium, methyl propyl magnesium, ethyl propyl magnesium, dibutyl magnesium, methyl butyl magnesium, ethyl butyl magnesium and the like can be mentioned. These dialkylmagnesiums can be obtained by reacting metal magnesium with a halogenated hydrocarbon or alcohol.

As the alkylmagnesium halide, a compound represented by the general formula R ⁸ MgD ¹ (wherein R ⁸ represents an alkyl group having 1 to 10 carbon atoms, and D ¹ represents a halogen atom such as chlorine, bromine, iodine and fluorine) Is preferred, and
More specifically, examples thereof include ethyl magnesium chloride, propyl magnesium chloride, and butyl magnesium chloride. These magnesium halides can be obtained by reacting metal magnesium with a halogenated hydrocarbon or alcohol.

The dialkoxymagnesium or diaryloxymagnesium may be represented by the general formula Mg (OR ⁹ ) (OR ¹⁰ )
(Wherein, R ⁹ and R ¹⁰ represent an alkyl group or an aryl group having 1 to ¹⁰ carbon atoms and may be the same or different). More specifically, dimethoxymagnesium , Diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like. These dialkoxymagnesium or diaryloxymagnesium can be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

As an alkoxymagnesium halide
Is the general formula Mg (OR¹¹) D²(Where R ¹¹ Is carbon number 1 to 1
An alkyl group of 0, D²Is chlorine, bromine, iodine, fluorine, etc.
Represents a halogen atom. ) Is preferred.
More specifically, methoxymagnesium chloride, eth
Magnesium oxychloride, propoxy magnesium chloride,
Butoxy magnesium chloride and the like.

The fatty acid magnesium is represented by the general formula Mg (R
¹² COO) ₂ (wherein R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms), and more specifically, magnesium laurate, magnesium stearate, magnesium octoate and And magnesium decanoate.

Of these magnesium compounds in the present invention, dialkoxymagnesium is preferred, and among them, diethoxymagnesium and dipropoxymagnesium are particularly preferred. The above magnesium compounds can be used alone or in combination of two or more.

When dialkoxymagnesium is used as the component (a) in the present invention, the alkoxymagnesium is in the form of granules or powder, and the shape thereof may be irregular or spherical. For example, when a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer powder is used. Problems such as clogging caused by the contained fine powder are eliminated.

The above-mentioned spherical dialkoxy magnesium is
It is not always necessary to have a true spherical shape, and an elliptical or potato-shaped one is used. Specifically, the shape of the particles is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is usually 3 or less, preferably 1 to 2, and more preferably 1 to 2.
From 1.5. Methods for producing such spherical dialkoxymagnesium are described, for example, in JP-A-58-41832, JP-A-62-51633, and JP-A-3-7434.
No. 1, No. 4-368391, No. 8-73338
No. 8, for example.

The average particle size of the dialkoxymagnesium is usually 1 to 200 μm, preferably 5 to 1 μm.
50 μm. In the case of spherical dialkoxymagnesium, the average particle size is usually 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm.
m. Further, as for the particle size, it is desirable to use a fine particle and coarse powder having a small particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, particles having a size of 100 μm or more are 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the particle size at 90% in integrated particle size, and D10 is the particle size at 10% in integrated particle size), it is 3 or less, and preferably 3 or less. 2 or less.

In the present invention, the component (A)
Tetravalent titanium halide compound (hereinafter simply referred to as “component
(B) ". ) Is represented by the general formula Ti (OR
¹³) _nCl_4-n(Where R¹³Is an alk having 1 to 4 carbon atoms
And n is an integer of 0 or 1-3. )
Are exemplified. In addition, the halogenated
The tan compounds may be used alone or in combination of two or more.
Wear. Specifically, TiCl_Four, Ti (OCH₃) Cl₃ , Ti (OC₂H
₅) Cl₃, Ti (OC₃H₇) Cl₃, Ti (O-n-C₄H₉) Cl ₃ , Ti
(OCH₃)₂Cl₂, Ti (OC₂H₅)₂Cl₂ , Ti (OC₃H₇)₂C
l₂ , Ti (O-n-C₄H₉)₂Cl₂, Ti (OCH₃)₃Cl, Ti (OC
₂H₅)₃Cl, Ti (OC₃H₇)₃Cl, Ti (O-n-C₄H₉)₃Cl etc.
Among them, especially TiCl_FourIs preferably used
You. These tetravalent titanium halide compounds may be used alone.
Alternatively, two or more kinds can be used in combination.

The electron donating compound (hereinafter referred to simply as component (c)) used in the preparation of the solid catalyst component (A) in the present invention.
There is that. ) Is an organic compound containing oxygen or nitrogen, for example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles,
Examples include isocyanates and organosilicon compounds containing a Si—O—C bond.

Specifically, methanol, ethanol, n
Alcohols such as propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and diphenyl ether;
Ethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid Ethyl, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, anise Monocarboxylic acid esters such as ethyl acrylate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate , Dipropyl phthalate, dibutyl phthalate, dipentyl, dihexyl phthalate,
Dicarboxylic esters such as diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, and benzophenone; and acid halides such as phthalic dichloride and terephthalic dichloride. Aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde and benzaldehyde; amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine; amides such as oleic amide and stearamide; acetonitrile and benzonitrile; Examples thereof include nitriles such as tolunitrile and isocyanates such as methyl isocyanate and ethyl isocyanate.

Examples of the organosilicon compound containing a Si—O—C bond include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

Among the above electron-donating compounds, esters, particularly aromatic dicarboxylic diesters, are preferably used, and phthalic diester is particularly preferred. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, and di-n-phthalate.
Butyl, di-iso-butyl phthalate, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl) Di-n-pentyl phthalate, di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis-phthalic acid (2 , 2-dimethylhexyl), bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate,
Di-iso-decyl phthalate, bis (2,2-
Dimethylheptyl), n-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate ( Heptyl), n-pentyl phthalate (2-ethylhexyl), n-pentyl phthalate (iso-nonyl),
Iso-pentyl phthalate (n-decyl), n-phthalic acid
-Pentylundecyl, iso-pentyl phthalate (i
(so-hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl) ), N-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (iso-nonyl), n-heptyl phthalate (n
eo-decyl), 2-ethylhexyl phthalate (iso
-Nonyl) and one or more of these are used.

The above-mentioned esters are preferably used in combination of two or more. In this case, the total number of carbon atoms in the alkyl group of the ester used is at least 4 as compared with that of the other esters. It is desirable to combine the esters. Further, those obtained by substituting one or two alkyl groups having 1 to 5 carbon atoms or halogen atoms such as chlorine, bromine and fluorine on the aromatic ring of these phthalic acid diesters are also preferably used. Specifically, 4-
Dineopentyl methyl phthalate, Dineopentyl 4-ethylphthalate, Dineopentyl 4,5-dimethylphthalate, Dineopentyl 4,5-diethylphthalate, Diethyl 4-chlorophthalate, Di-n-butyl 4-chlorophthalate, Diisobutyl 4-chlorophthalate, Diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate,
Diisohexyl 4-bromophthalate, diisooctyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, 4,5
-Diisohexyl dichlorophthalate and diisooctyl 4,5-dichlorophthalate.

The dibenzofuran represented by the general formula (1) and a derivative thereof (hereinafter sometimes simply referred to as “component (d)”) used for the preparation of the component (A) in the present invention include the above-mentioned general compounds. In the formula (1), R ¹ and R ²
Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Those having 4 alkoxy groups, bromine atoms and fluorine atoms are preferred, and those having methyl groups and bromine atoms are particularly preferred. As described above, the derivative of dibenzofuran in the present invention includes a compound in which a hydrogen atom is added to a part or all of positions 1 to 8 of dibenzofuran.

Specific examples of the compound (d) include dibenzofuran, 1,4-dihydrodibenzofuran, 3,4-dihydrodibenzofuran, 1,2,3,4
-Tetrahydrodibenzofuran, 3,4,5,6-tetrahydrodibenzofuran, octahydrodibenzofuran, 2-methyldibenzofuran, 3-methyldibenzofuran, 4-methyldibenzofuran, 2,7-dimethyldibenzofuran, 3,6-dimethyldibenzofuran, 2,
3,7-trimethyldibenzofuran, 2,3,6-trimethyldibenzofuran, 2,3,6,7-tetramethyldibenzofuran, 2-ethyldibenzofuran, 3-ethyldibenzofuran, 4-ethyldibenzofuran, 2,7
-Diethyldibenzofuran, 3,6-diethyldibenzofuran, 2,3,7-triethyldibenzofuran, 2,
3,6-trimethyldibenzofuran, 2,3,6,7-
Tetraethyldibenzofuran, 2-methoxydibenzofuran, 3-methoxydibenzofuran, 4-methoxydibenzofuran, 2,7-dimethoxydibenzofuran, 3,
6-dimethoxydibenzofuran, 2-ethoxydibenzofuran, 3-ethoxydibenzofuran, 4-ethoxydibenzofuran, 2,7-diethoxydibenzofuran,
3,6-diethoxydibenzofuran, 2-chlorodibenzofuran, 3-chlorodibenzofuran, 4-chlorodibenzofuran, 2,7-dichlorodibenzofuran, 3,6
-Dichlorodibenzofuran, 2-bromodibenzofuran, 3-bromodibenzofuran, 4-bromodibenzofuran, 2,7-dibromodibenzofuran, 3,6-dibromodibenzofuran, 2-fluorodibenzofuran,
-Fluorodibenzofuran, 4-fluorodibenzofuran, 2,7-difluorodibenzofuran, 3,6-difluorodibenzofuran, 2-iododibenzofuran, 3
-Iododibenzofuran, 4-iododibenzofuran,
Examples thereof include 2,7-diiododibenzofuran and 3,6-diiododibenzofuran.

Among the compounds exemplified as component (d), dibenzofuran, 1,4-dihydrodibenzofuran,
2,3,4-tetrahydrodibenzofuran, 3,4
5,6-tetrahydrodibenzofuran, octahydrodibenzofuran, 3-methyldibenzofuran, 3,6-dimethyldibenzofuran, 3-bromodibenzofuran, 3
-Fluorodibenzofuran, 3,6-dibromodibenzofuran, and 3,6-difluorodibenzofuran are preferable, and dibenzofuran, 3-methyldibenzofuran, and 3-bromodibenzofuran are particularly preferably used. These dibenzofurans and their derivatives can be used alone or in combination of two or more.

The component (A) can be prepared by bringing the components (a), (b), (c) and (d) into contact with each other as described above.
Although it is possible to carry out the treatment in the absence of an inert organic solvent, it is preferable to carry out the treatment in the presence of the solvent in view of the ease of operation. Examples of the inert organic solvent used include saturated hydrocarbon compounds such as hexane, heptane, and cyclohexane; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; ortho-dichlorobenzene, methylene chloride, carbon tetrachloride, and dichloroethane. Among them, the aromatic hydrocarbon compounds having a boiling point of about 90 to 150 ° C. and in a liquid state at room temperature, specifically, toluene, xylene,
Ethylbenzene is preferably used.

As a method for preparing the component (A), the magnesium compound of the component (a) is dissolved in an alcohol or a titanium compound, and the component (b) or the component (b) and the component (c) are dissolved. A method of obtaining a component (A) by contacting the component (c) or the component (c) and the component (b) with the solid, or contacting the component (c) with the component (b). A method of suspending in the component (b) or an inert hydrocarbon solvent or the like, and contacting the component (c) or the component (c) with the component (b) to obtain the component (A) can be mentioned.

Among them, the particles of the solid catalyst component obtained by the former method are almost spherical, and the particle size distribution is sharp. Also, in the latter method, a spherical and sharp particle size distribution solid catalyst component can be obtained by using a spherical magnesium compound, and even without using a spherical magnesium compound, for example, by using a spray device. By spraying and drying the solution or suspension to form particles by a so-called spray drying method, a solid catalyst component which is similarly spherical and has a sharp particle size distribution can be obtained.

The contact of each component is carried out in a container equipped with a stirrer under an inert gas atmosphere under a condition where moisture and the like are removed.
This is performed while stirring. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact and stirred or mixed or dispersed or suspended for denaturation treatment. If you get
A temperature range of 40 to 130C is preferred. Reaction temperature is 4
When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and as a result, the performance of the solid catalyst component prepared becomes insufficient,
When it exceeds, the evaporation of the solvent used becomes remarkable,
It becomes difficult to control the reaction. The reaction time is 1 minute or more,
It is preferably at least 10 minutes, more preferably at least 30 minutes.

Hereinafter, a method for preparing the component (A) will be exemplified. (1) After dissolving magnesium chloride in tetraalkoxytitanium, contact a polysiloxane to obtain a solid product, react the solid product with titanium tetrachloride, and then convert component (c) and component (d). A method of preparing component (A) by contact reaction. At this time, the component (A) may be preliminarily polymerized with an organoaluminum compound, an organosilicon compound and an olefin.

(2) After reacting anhydrous magnesium chloride and 2-ethylhexyl alcohol to form a homogeneous solution,
The homogeneous solution is contacted with phthalic anhydride, and then the titanium tetrachloride and the component (c) are contact-reacted with the solution to obtain a solid product. The solid product is further treated with titanium tetrachloride and the component (d). A method of preparing component (A) by contact.

(3) An organomagnesium compound is synthesized by reacting metallic magnesium, butyl chloride and dibutyl ether, and the organomagnesium compound is contacted with tetrabutoxytitanium and tetraethoxytitanium to obtain a solid product. A method of preparing component (A) by contacting component (c), dibutyl ether, component (d) and titanium tetrachloride with the solid product. At this time, an organic aluminum compound,
Preliminary polymerization treatment with an organosilicon compound and an olefin can also be performed.

(4) An organomagnesium compound such as dibutylmagnesium and an organoaluminum compound are contact-reacted with an alcohol such as butanol and 2-ethylhexyl alcohol in the presence of a hydrocarbon solvent to form a homogeneous solution. For example, a solid product was obtained by contacting a silicon compound such as SiCl 4, HSiCl 3 or polysiloxane, and then the solid product was contact-reacted with titanium tetrachloride and the component (c) in the presence of an aromatic hydrocarbon solvent. rear,
A method of obtaining component (A) by further contacting titanium tetrachloride and component (d).

(5) Magnesium chloride, tetraalkoxytitanium and an aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to form a homogeneous solution. Titanium tetrachloride is added to the solution, and the temperature is raised to a solid. A method in which the product is precipitated, the component (c) is brought into contact with the solid product, and further reacted with titanium tetrachloride and the component (d) to obtain the component (A).

(6) A metal magnesium powder, an alkyl monohalogen compound and iodine are contact-reacted, and then a tetraalkoxytitanium, an acid halide and an aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon to obtain a homogeneous solution. After adding titanium tetrachloride to the solution, the temperature is raised to precipitate a solid product, and the component (c) is added to the solid product.
And then reacting with titanium tetrachloride and component (d) to prepare component (A).

(7) After suspending diethoxymagnesium in an alkylbenzene or halogenated hydrocarbon solvent, the suspension is brought into contact with titanium tetrachloride, and then heated to contact with component (c) to obtain a solid product. Washing the solid product with alkylbenzene and then contacting it again with titanium tetrachloride and component (d) in the presence of alkylbenzene to prepare component (A). At this time, the component (A) can be obtained by heat-treating the component (A) in the presence or absence of a hydrocarbon solvent.

(8) Diethoxymagnesium is suspended in alkylbenzene, and then reacted with titanium tetrachloride and the component (c) to obtain a solid product. The solid product is washed with alkylbenzene, and then washed with alkylbenzene. A method of obtaining a component (A) by contacting titanium tetrachloride and the component (d) again in the presence of In this case, the component (A) can be obtained by further contacting the component (A) with titanium tetrachloride two or more times.

(9) Diethoxymagnesium and component (c) are suspended in alkylbenzene, and the suspension is added to titanium tetrachloride and reacted to obtain a solid product.
After washing the solid product with alkylbenzene, titanium tetrachloride and component (d) are again added in the presence of alkylbenzene.
To obtain the component (A).

(10) Aliphatic magnesium such as magnesium stearate is added to titanium tetrachloride and component (c).
And then contacting with titanium tetrachloride and component (d) to prepare component (A).

(11) Diethoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of toluene to form a homogeneous solution, and titanium tetrachloride and the component (c) are contact-reacted with the solution to form a solid. The solid product is further dissolved in tetrahydrofuran, and then the solid product is further precipitated. The solid product is contact-reacted with titanium tetrachloride and the component (d). A method of preparing the component (A) by repeating the reaction. In this case, a silicon compound such as tetrabutoxysilane can be used in any of the contact, contact reaction, and dissolution steps.

(12) Magnesium chloride, an organic epoxy compound and a phosphoric acid compound are suspended in a hydrocarbon solvent such as toluene, and then heated to make a homogeneous solution, and phthalic anhydride and titanium tetrachloride are added to this solution. A contact reaction is carried out to obtain a solid product, the component (c) is brought into contact with the solid product to cause a reaction, and the obtained reaction product is washed with alkylbenzene, and then in the presence of alkylbenzene, titanium tetrachloride and the component are reacted again. A method of obtaining component (A) by contacting (d).

Preferred methods for preparing the component (A) used in the present invention include the following methods. For example, a suspension is formed by suspending a dialkoxymagnesium in a liquid aromatic hydrocarbon compound at room temperature, and then adding a tetravalent titanium halide to the suspension at -20 to 100 ° C, preferably-. The contact is performed at 10 to 70 ° C, more preferably 0 to 30 ° C, and the reaction is performed at 40 to 130 ° C, more preferably 70 to 120 ° C. At this time, before or after the titanium halide is brought into contact with the suspension, phthalic acid diester is added as component (c), and -2.
Contact at 0-130 ° C. to obtain a solid reaction product. After washing the solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, tetravalent titanium halide is added in the presence of the aromatic hydrocarbon compound, and the temperature is 40 to 130 ° C, more preferably 70 to 120 ° C. React at ° C. Further, a tetravalent titanium halide is added in the presence of an aromatic hydrocarbon compound, and then dibenzofuran and a derivative thereof are added as a component (d) to 40 to 130 ° C, more preferably 70 to 130 ° C.
A contact reaction is performed at 120 ° C., and the mixture is further washed with a hydrocarbon compound which is liquid at ordinary temperature to obtain the component (A).

The amount ratio of each compound varies depending on the preparation method and cannot be specified unconditionally. For example, 0.5 to 100 mol, preferably 0.5 to 100 mol of component (b) per mol of component (a). 50 mol, more preferably 1 to 10 mol, and component (c) is 0.01 to 10 mol, preferably 0.1 to 10 mol.
01 to 1 mol, more preferably 0.02 to 0.6 mol,
Component (d) is 0.01 to 10 mol, preferably 0.1 to 10 mol
It is 5.0 mol, more preferably 0.3 to 2.0 mol.

The component (A) prepared as described above contains magnesium, titanium, component (c), component (d), and a halogen atom. The content of each component is not particularly limited, but preferably 10 to 30% by weight of magnesium, 1 to 5% by weight of titanium, 1 to 20% by weight of component (c), and 0.1 to 10% of component (d). Weight%, halogen atom is 40 ~
70% by weight.

The organoaluminum compound (B) (hereinafter, referred to as "B") used in forming the propylene polymerization catalyst of the present invention.
It may be referred to as “component (B)”. ) May be a compound represented by the above general formula (2). Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more kinds can be used. Preferably, triethyl aluminum, tri-is
o-Butyl aluminum.

The organosilicon compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the propylene polymerization catalyst of the present invention is represented by the above general formula (3). Compounds are used. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

Specific examples of the above organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n
-Propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxysilane, tri-
t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n
-Propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane,
Di-iso-propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane 4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxy Silane, cyclohexyl cyclopentyl distearate propoxysilane, 3-methyl-cyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxysilane, 3,5-dimethyl-cyclohexyl cyclopentyl dimethoxy silane, 3
-Methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane Cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, Cyclohexyl (n-propyl ) Diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Silane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane , Iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, Examples thereof include cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane,
Dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentyl Ethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used. Object (C) may be used in combination singly or in combination.

Next, the olefin polymerization catalyst of the present invention is
It comprises the above-mentioned component (A), component (B) and component (C), and performs polymerization or copolymerization of olefins in the presence of the catalyst. As the olefins, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-
Penten, vinylcyclohexane and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene.
In the case of polymerization of propylene, copolymerization with other olefins can also be performed. The olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like, and these olefins can be used alone or in combination of two or more. . In particular, ethylene and 1-butene are preferably used.

The use ratio of each component is not particularly limited as long as it does not affect the effect of the present invention, and the component (B) is usually titanium atom in the component (A). 1 to 2000 mol, preferably 50, per mol
It is used in the range of ~ 1000 mol. Component (C) is
0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 2 mol, per 1 mol of the component (B).
It is used in a range of 0.5 mol.

The order of contact of each component is arbitrary, but first, the organoaluminum compound (B) is charged into the polymerization system, then the organosilicon compound (C) is brought into contact, and then the solid catalyst component (A) is brought into contact. It is desirable to make it.

The polymerization method of the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any of a gas and a liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Further, any of a continuous polymerization method and a batch polymerization method can be used. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

Further, in the present invention, when the olefin is polymerized using the catalyst comprising the components (A), (B) and (C) (also referred to as main polymerization), the catalytic activity, stereoregularity, and formation In order to further improve the particle properties and the like of the resulting polymer, it is desirable to carry out preliminary polymerization prior to the main polymerization. In the prepolymerization, the same monomers as olefins or styrene used in the main polymerization can be used.

In carrying out the prepolymerization, the order of contact of each component and the monomer is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set in an inert gas atmosphere or a gas atmosphere for carrying out polymerization such as propylene. )
Next, after contacting the component (A), an olefin such as propylene and / or one or more other olefins are contacted. When prepolymerization is performed by combining component (C), component (B) is first charged into a prepolymerization system set in an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene, and then component (C) And then contacting the solid catalyst component (A) with an olefin such as propylene and / or one or more other olefins.
A method of contacting more than one olefin is desirable.

When polymerization of olefins is carried out in the presence of the catalyst for polymerization of olefins formed according to the present invention, an extremely high yield can be obtained while maintaining high stereoregularity as compared with the case where a conventional catalyst is used. To obtain an olefin polymer. Furthermore, high hydrogen response can be realized.

[0060]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. In the following examples,
In the following Examples, the composition of the solid catalyst component (A) for olefin polymerization was analyzed by the following method. The magnesium content was measured by EDTA titration. The content of titanium was measured by a redox titration method. The chlorine content was measured by potentiometry. The content of the phthalic acid diester was measured by hydrolyzing the component (A), extracting with an organic solvent, and quantifying by gas chromatography. The content of dibenzofuran was measured by hydrolyzing the component (A), extracting with an organic solvent, and quantifying by gas chromatography.

Example 1 [Preparation of solid catalyst component (A)] A 500-ml round-bottomed flask sufficiently purged with nitrogen gas and equipped with a stirrer was charged with 10 g of diethoxymagnesium and 80 ml of toluene. It was turbid. Next, 20 ml of titanium tetrachloride was added to the suspension, and the temperature was raised. When the temperature reached 80 ° C., 2.7 ml of di-n-butyl phthalate was added, and the temperature was further raised to 110 ° C. Thereafter, the reaction was carried out with stirring at 110 ° C. for 1 hour. After the reaction, 9
After washing three times with 100 ml of toluene at 0 ° C., 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 1 hour. 20 ml of titanium tetrachloride and 80 ml of toluene were further added, and then 10.3 g of dibenzofuran was added and dissolved by stirring.
The temperature was raised to 100 ° C., and the reaction was performed with stirring for 2 hours. After completion of the reaction, the solid was washed seven times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. Incidentally, the solid-liquid in the solid catalyst component is separated, the content of magnesium in the solid content, the content of titanium, the content of chlorine, the content of di-n-butyl phthalate, and the content of dibenzofuran, In the above way,
As a result of measurement, magnesium was 23.2% by weight, titanium was 3.3% by weight, chlorine was 61.1% by weight, di-n-butyl phthalate was 11.4% by weight, and dibenzofuran was 1.0% by weight. Met.

[Formation and Polymerization of Polymerization Catalyst] In a 2.0-liter autoclave equipped with a stirrer completely purged with nitrogen gas, 1.32 mmol of triethylaluminum was added.
Cyclohexylcyclopentyldimethoxysilane 0.1
3 mmol and 0.1% of the solid catalyst component as titanium atom.
0026 mmol was charged to form a polymerization catalyst. afterwards,
After charging 6.0 liters of hydrogen gas and 1.4 liters of liquefied propylene, the mixture was preliminarily polymerized at 20 ° C. for 5 minutes, then heated, and polymerized at 70 ° C. for 1 hour. The polymerization activity per gram of the solid catalyst component is 110,900-pp / g-c.
at. The melt index value (MI) of the polymer (a) (measurement method was according to ASTM D 1238, JIS K 7210) was 81 g / 10 min. The polymerization activity per solid catalyst component used here was calculated by the following equation. Polymerization activity = (a) 428.9 (g) / solid catalyst component 0.
00387 (g) Further, when the polymer was extracted with boiling n-heptane for 6 hours, the polymer (b) insoluble in n-heptane was measured, and the boiling n-heptane-insoluble matter (HI) in the polymer was measured. The ratio was calculated by the following equation. HI = (b) 413.9 (g) / (a) 428.9
(G) The polymerization activity, heptane insoluble matter (HI), and melt index (MI) are also shown in Table 1.

Example 2 A solid component was prepared in the same manner as in Example 1 except that 11.2 g of 3-methyldibenzofuran was used instead of dibenzofuran, and a polymerization catalyst was formed and polymerization was carried out. The solid-liquid in the solid catalyst component was separated, and the magnesium content, titanium content, chlorine content, di-n-butyl phthalate content, and 3-methyldibenzofuran content in the solid component were separated. Was measured by the above-mentioned method, magnesium was 23.0% by weight, and titanium was 3.1% by weight.
%, Chlorine is 61.5% by weight, di-n-butyl phthalate is 11.6% by weight, and 3-methyldibenzofuran is 0.1% by weight.
It was 8% by weight. The polymerization results are shown in Table 1.

Example 3 A solid component was prepared in the same manner as in Example 1 except that 15.1 g of 3-bromodibenzofuran was used instead of dibenzofuran, and a polymerization catalyst was formed and polymerization was carried out. The solid-liquid in the solid catalyst component was separated, and the magnesium content, titanium content, chlorine content, di-n-butyl phthalate content, and 3-bromodibenzofuran content in the solid content were separated. Was measured by the above-described methods, and it was found that magnesium was 23.5% by weight and titanium was 3.4% by weight.
% By weight, 60.8% by weight of chlorine, 11.3% by weight of di-n-butyl phthalate, and 1.30% by weight of 3-bromodibenzofuran.
It was 1% by weight. Table 1 shows the polymerization results.

Comparative Example 1 A solid component was prepared in the same manner as in Example 1 except that dibenzofuran was not added, and a polymerization catalyst was formed and polymerization was carried out. As a result, the titanium content in the solid catalyst component was 2.2% by weight. Table 1 shows the polymerization results.

[0066]

[Table 1]

From the results shown in Table 1, it can be seen that the polymerization of olefins using the solid catalyst component and the catalyst of the present invention can provide an olefin polymer in extremely high yield. Also, it can be seen that the response to hydrogen is extremely excellent.

[0068]

Industrial Applicability The olefin polymerization catalyst of the present invention can obtain an olefin polymer in an extremely high yield while maintaining a high stereoregularity at a high level, and has a high hydrogen response. It is a catalyst. Accordingly, general-purpose polyolefins can be provided at low cost, and are expected to be useful in the production of olefin copolymers having high functionality.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the steps for preparing a polymerization catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J028 AA01A AB01A AC03A AC06A BA01A BA01B BB00A BB01B BC04A BC05A BC06A BC14B BC18B CA14A CA15A CA16A CB22A CB27A CB42A CB46A CB50A CB52A CB52A CB52A CB53A CB53A CB52A CB52A CB53A 4J128 AA01 AB01 AC03 AC06 BA01A BA01B BB00A BB01B BC04A BC05A BC06A BC14B BC18B CA14A CA15A CA16A CB22A CB27A CB42A CB46A CB50A CB52A CB53A CB62A CB66A CB68A EB91 CB91A EB91 CB91A CB91A CB79A CB91A

Claims (3)

[Claims] 1. A magnesium, titanium, halogen, electron donating compound, and a compound represented by the following general formula (1): (1) (wherein, R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom, and even if R ¹ and R ² are the same, X and y may be 0 or an integer from 1 to 4, x and y
May be the same or different. A solid catalyst component for the polymerization of olefins, comprising dibenzofuran and a derivative thereof represented by the following formula: 2. A method comprising preparing a magnesium compound, a tetravalent titanium halide compound, an electron-donating compound, and a dibenzofuran represented by the general formula (1) and a derivative thereof by contacting the compound. The solid catalyst component for olefin polymerization according to claim 1. Wherein (A) an olefin polymerization solid catalyst component according to claim 1 or 2, (B) the following general formula _{^{(2); R 3 p AlQ}} 3-p (2) ( wherein, R ³ Represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer satisfying 0 <p ≦ 3), and (C) the following general formula: (3); R ⁴ _q Si (OR ⁵ ) _4-q (3) (wherein, R ⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group) ^May be the same or different, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different; q is an integer of 0 ≦ q ≦ 3). Olefin polymerization catalyst characterized in that it is.