JP2001329012A - Sold catalyst component for olefin polymerization and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid catalyst component for olefin polymerization, and a catalyst which can produce an olefinic polymer in an extremely high yield and particularly a propylene polymer with maintaining a high stereoregularity. SOLUTION: There are provided a solid catalytic component for olefin polymerization and a catalyst, which comprise (a) a magnesium compound, (b) titanium tetrachloride, (c) a phthalic acid diester, and (d) a phenol that may be substituted by a 1-10C alkyl or a 1-3C cycloalkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst component and a catalyst for olefin polymerization which can be obtained in high yield while maintaining a high stereoregularity of the olefin polymer.

[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.
Further, many olefin polymerization methods for polymerizing or copolymerizing olefins 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
2-98045 discloses a magnesium halide,
A method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination of a solid catalyst component containing an electron donor of a diester compound such as a titanium halide and an organic carboxylic acid ester and an organic aluminum compound is disclosed. Have been.

JP-A-53-19395 discloses an acyl halide, a magnesium dihalide, a halogen-containing titanium compound and an alcohol compound and / or
Alternatively, a solid catalyst component for polymerizing olefins containing a phenolic compound is disclosed, and by polymerizing an olefin in the presence of the solid catalyst component, a polymer having both excellent mechanical properties and moldability can be obtained. It is obtained in a yield, and the effect is improved to some extent.

However, in order to reduce the cost of olefin polymers in recent years, to improve processes, and to produce high-performance polymers such as copolymers at a high rate, further activation of catalysts is strongly desired. Therefore, it is not always sufficient to satisfy this demand, and further improvement has been desired.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problems left in the prior art, and to obtain an olefin polymer in an extremely high yield. An object of the present invention is to provide a solid catalyst component for olefin polymerization which can be obtained in an extremely high yield while maintaining high stereoregularity, and a catalyst.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the problems remaining in the above prior art, and as a result, have found that solids composed of magnesium compounds, titanium tetrachloride, phthalic acid diester and phenols are obtained. The catalyst component exhibits high activity when subjected to the polymerization of olefins, particularly exhibits high activity when subjected to the polymerization of propylene, and can provide a propylene polymer having high stereoregularity in high yield. As a result, the present invention has been completed.

[0007] That is, the present invention relates to a method comprising the steps of (a) magnesium compound, (b) titanium tetrachloride, (c) phthalic acid diester, and (d) alkyl or cycloalkyl group having 1 to 10 carbon atoms. A solid catalyst component for the polymerization of olefins, characterized by being formed by phenol.

Further, the present invention, (A) above olefin polymerization solid catalyst component, (B) the general formula _{^{(1); R 1 p AlQ}} 3-p (1) ( wherein, R ¹ is the number of carbon atoms Represents an alkyl group of 1 to 4, Q represents a hydrogen atom or a halogen atom, p is an integer of 0 <p ≦ 3), and (C) a general formula (2); R ² _q Si (OR ³ ) _4-q (2) (wherein R ² 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, and is the same R ³ 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, and may be the same or different, and q is 0 ≦ wherein q is an integer of 3 or less.) Olefin polymerization catalyst.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The magnesium compound (hereinafter sometimes simply referred to as “component (a)”) used for preparing the solid catalyst component (A) for olefin polymerization of the present invention includes magnesium dihalide and dialkyl. Examples include magnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide, and fatty acid magnesium.

Specific examples of magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride and the like.

The dialkylmagnesium has the general formula
A compound represented by R ⁴ R ⁵ Mg (wherein, R ⁴ and R ⁵ each represent an alkyl group having 1 to 10 carbon atoms, which may be the same or different from each other) is preferable, and 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. 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 ⁶ MgD ¹ (wherein R ⁶ represents an alkyl group having 1 to 10 carbon atoms and D ¹ represents a halogen atom) is preferable. 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 ⁷ ) (OR ⁸ )
(Wherein, R ⁷ and R ⁸ each represent an alkyl group or an aryl group having 1 to 10 carbon atoms, which may be the same or different), and more specifically, dimethoxy. Magnesium, 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 the alkoxymagnesium halide, a compound represented by the general formula Mg (OR ⁹ ) D ² (wherein R ⁹ is an alkyl group having 1 to 10 carbon atoms, and D ² is a halogen atom such as chlorine, bromine, iodine or fluorine) Are preferable, and more specifically, magnesium methoxychloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride and the like can be mentioned.

As the fatty acid magnesium, the general formula Mg (R
¹⁰ COO) ₂ (wherein, R ¹⁰ 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 a dialkoxymagnesium is used as the component (a) in the present invention, the dialkoxymagnesium may be in the form of granules or powder, and the shape 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 dialkoxymagnesium 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 a 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.

The solid catalyst component for olefin polymerization of the present invention
In the preparation of (A), titanium tetrachloride (hereinafter simply referred to as “component
(B) ". ), But using titanium tetrachloride
Other titanium halide compounds besides
Can be. Titanium halide that can be used with titanium tetrachloride
The compound represented by the general formula Ti (OR¹¹)_nCl_4-n(Where R¹¹
Represents an alkyl group having 1 to 4 carbon atoms, and n represents 1 ≦ n ≦ 3
It is an integer. ) Alkoxytitanium chloride
Is exemplified. In addition, the above-mentioned titanium halide compound
May be used alone or in combination of two or more. Concrete
Typically, Ti (OCH_Three) Cl_Three, Ti (OC_TwoH_Five) Cl_Three, Ti (OC_ThreeH₇) Cl_Three,
Ti (O-n-C_FourH₉) Cl_Three, Ti (OCH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoCl _Two, Ti
(OC_ThreeH₇)_TwoCl_Two, Ti (O-n-C_FourH₉)_TwoCl_Two, Ti (OCH_Three)_ThreeCl, Ti (O
C_TwoH_Five)_ThreeCl, Ti (OC_ThreeH₇)_ThreeCl, Ti (O-n-C_FourH₉)_ThreeCl is an example
It is.

The phthalic acid diester used in the preparation of the solid catalyst component (A) for olefin polymerization according to the present invention (hereinafter referred to as "the phthalic acid diester")
It may simply be referred to as “component (c)”. Examples of) include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate,
Di-n-butyl phthalate, 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-is phthalate
o-pentyl, dihexyl phthalate, di-n-phthalate
Heptyl, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-iso-decyl phthalate, bis-phthalate (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), i-phthalic acid
so-pentyl (n-decyl), n-pentyl undecyl phthalate, iso-pentyl phthalate (iso-hexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (2-ethylhexyl),
N-hexyl phthalate (iso-nonyl), n-phthalate
-Hexyl (n-decyl), n-heptyl phthalate (2
-Ethylhexyl), n-heptyl phthalate (iso-
Nonyl), n-heptyl phthalate (neo-decyl),
Examples thereof include 2-ethylhexyl phthalate (iso-nonyl), and one or more of these are used.

Of the above, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate,
Di-n-butyl phthalate, di-iso-butyl phthalate, di-n-octyl phthalate, bis (2-ethylhexyl) phthalate, and di-iso-decyl phthalate are preferably used.

The phenol which may be substituted with an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group used for preparing the component (A) in the present invention is phenol and an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group. Phenol substituted with a group. The number of the substituents is 1 or 2, and the substituent may be substituted at any of the 2- to 6-positions. When the number of substituents is 2,
The substituents may be the same or different. Preferred substituents include methyl, ethyl, n-propyl, is
o-propyl group, n-butyl group, iso-butyl group, t
-A butyl group, a cyclopentyl group and a cyclohexyl group. The number of substituents of the substituted phenol is preferably 1.

The phenols of component (d) are specifically phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol,
-N-propylphenol, 2-iso-propylphenol, 3-n-propylphenol, 3-iso-propylphenol, 4-n-propylphenol, 4-
iso-propylphenol, 2-n-butylphenol, 2-iso-butylphenol, 2-t-butylphenol, 3-n-butylphenol, 3-iso-butylphenol, 3-t-butylphenol, 4-n-
Butylphenol, 4-iso-butylphenol, 4
-T-butylphenol, 2,4-dimethylphenol, 2,4-diethylphenol, 3-cyclopentylphenol, 3-cyclohexylphenol, 4-cyclopentylphenol, 4-cyclohexylphenol and the like.

Among these, phenols which are preferred as one component (d) of the catalyst for olefin polymerization are phenol, 3-methylphenol, 4-methylphenol, and phenol.
-Ethylphenol, 4-ethylphenol, 4-n-
Propylphenol, 4-iso-propylphenol, 4-n-butylphenol, 4-iso-butylphenol and 4-t-butylphenol. These phenols can be used alone or in combination of two or more.

In the preparation of the solid catalyst component (A) for olefin polymerization in the present invention, in addition to the above essential components,
Furthermore, aluminum compounds, metal salts of organic acids or polysiloxanes can be used, and their use is effective in controlling the crystallinity of the resulting polymer.

As the aluminum compound, aluminum trichloride, diethoxyaluminum chloride, di-iso-propoxyaluminum chloride,
Examples thereof include ethoxyaluminum dichloride, iso-propoxyaluminum dichloride, butoxyaluminum dichloride, and triethoxyaluminum.

Examples of the metal salt of an organic acid include sodium stearate, magnesium stearate, aluminum stearate and the like.

Examples of the polysiloxane include a chain, partially hydrogenated, cyclic or modified polysiloxane which is liquid or viscous at ordinary temperature. Examples of the linear polysiloxane include dimethyl polysiloxane and methylphenyl polysiloxane, examples of the partially hydrogenated polysiloxane include methyl hydrogen polysiloxane having a hydrogenation ratio of 10 to 80%, and examples of the cyclic polysiloxane include hexamethylcyclopentane. Siloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, Oxyalkylene group-substituted dimethylsiloxane is exemplified.

The olefin polymerization catalyst component (A)
Can be prepared by contacting component (a), component (b), component (c), and component (d) as described above, wherein the contact is effected in the absence of an inert organic solvent. Although it is possible to carry out the treatment, it is preferable to carry out the treatment in the presence of the solvent in consideration 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. And the like, of which the boiling point is 90 to 1
Aromatic hydrocarbon compounds that are liquid at room temperature at about 50 ° C., specifically, toluene, xylene, and ethylbenzene are preferably used.

As a method for preparing the solid catalyst component (A) for olefin polymerization according to the present invention, the magnesium compound as the component (a) is dissolved in an alcohol, a titanium compound, or the like, and this solution is mixed with the component (A). b) or component (b) and component (c) are brought into contact with each other to precipitate a solid substance by heat treatment or the like, and then further contacted with component (b);
A method of obtaining a solid component by bringing the component (d) into contact with the component (d) in any one of the above steps, and suspending the component (a) in the component (b) or an inert hydrocarbon solvent, and further adding the component (c) or the component A method of contacting the component (b) with the component (c), further contacting the component (b), and contacting the component (d) at any stage to obtain the component (A).

Among these, 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.

In the present invention, when the solid catalyst component (A) for olefin polymerization is prepared, the order of contact of the components (a) to (d) is arbitrary. ), And then contacting with the component (a) and / or the component (c) are preferable for improving the activity of the solid catalyst component. Here, when the component (d) is brought into contact with the component (b) in advance, after forming a complex compound of a phenol and a titanium compound such as titanium tetrachloride, the component (a) and / or the component (c) are formed. Contacting is also one of the preferred embodiments.

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.

The method for preparing the solid catalyst component (A) for olefin polymerization is described below. (1) After dissolving magnesium chloride (a) in tetraalkoxytitanium, a polysiloxane is contacted to obtain a solid product. The solid product, titanium tetrachloride (b), and titanium tetrachloride (b) And then reacting the component (d) with the component (c), and then contacting the component (c) with the component (A).
How to prepare. At this time, the component (A) may be preliminarily polymerized with an organoaluminum compound, an organosilicon compound and an olefin.

(2) Anhydrous magnesium chloride (a) and 2
After reacting ethylhexyl alcohol to form a homogeneous solution, phthalic anhydride is brought into contact with the homogeneous solution, and then titanium tetrachloride (b) and the component (c) are brought into contact with the solution to obtain a solid product. A method of preparing component (A) by further contacting titanium tetrachloride (b) and component (d) previously contacted with titanium tetrachloride (b) to the solid product.

(3) An organomagnesium compound (a) is synthesized by reacting magnesium metal, butyl chloride and dibutyl ether, and tetrabutoxytitanium and tetraethoxytitanium are contact-reacted with the organomagnesium compound (a). A solid product is obtained, and the solid product is contact-reacted with component (c), dibutyl ether, titanium tetrachloride (b) and component (d) previously contacted with titanium tetrachloride (b) to give component (A) How to prepare. At this time, the component (A) can also be prepared by preliminarily polymerizing the solid component with an organoaluminum compound, an organosilicon compound and an olefin.

(4) An organomagnesium compound (a) such as dibutylmagnesium and an organoaluminum compound are
In the presence of a hydrocarbon solvent, for example, a contact reaction with an alcohol such as butanol or 2-ethylhexyl alcohol is carried out to form a homogeneous solution, and this solution is contacted with a silicon compound such as SiCl ₄ , HSiCl ₃ or polysiloxane to produce a solid product. And then reacting the solid product with titanium tetrachloride (b), component (c) and component (d) previously contacted with titanium tetrachloride (b) in the presence of an aromatic hydrocarbon solvent. And then contacting titanium tetrachloride to obtain the component (A).

(5) Magnesium chloride (a), tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to form a homogeneous solution, and titanium tetrachloride (b) is added to the solution. Thereafter, the temperature is raised to precipitate a solid product, and the component (c) is brought into contact with the solid product,
Further reacting with titanium tetrachloride (b) and component (d) previously contacted with titanium tetrachloride (b), component (A)
How to get.

(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. (A), titanium tetrachloride (b) was added to the solution, and the temperature was raised to precipitate a solid product. The component (c) was brought into contact with the solid product, and titanium tetrachloride (b) and Component (d) previously contacted with titanium tetrachloride (b)
A component (A) is prepared by reacting

(7) Diethoxymagnesium (a) is suspended in an alkylbenzene or halogenated hydrocarbon solvent, then brought into contact with titanium tetrachloride (b), and then heated to contact with component (c). After washing the solid product with alkylbenzene, the solid product is contacted again with titanium tetrachloride (b) and the component (d) previously contacted with titanium tetrachloride (b) in the presence of alkylbenzene. A method for preparing the component (A). In this case, the solid component may be subjected to a heat treatment in the presence or absence of a hydrocarbon solvent to obtain the component (A).

(8) After suspending diethoxymagnesium (a) in alkylbenzene, titanium tetrachloride (b)
And a contact reaction with the component (c) to obtain a solid product. The solid product is washed with alkylbenzene, and then contacted again with titanium tetrachloride (b) and titanium tetrachloride (b) in the presence of alkylbenzene. A method of obtaining a component (A) by bringing the component (A) into contact with the component (d). At this time, the solid component and titanium tetrachloride (b) and titanium tetrachloride (b)
The component (A) can also be obtained by contacting the component (d) with the component (d) two or more times.

(9) Diethoxymagnesium (a), calcium chloride and a silicon compound represented by Si (OR ¹⁵ ) ₄ (wherein R ¹⁵ represents an alkyl group or an aryl group) are co-ground to obtain a mixture. After suspending the pulverized solid obtained in the aromatic hydrocarbon, it is contacted with titanium tetrachloride (b) and component (c), and then further reacted with titanium tetrachloride (b) and titanium tetrachloride (b). A method for preparing the component (A) by bringing the contacted component (d) into contact.

(10) Diethoxymagnesium (a) and component (c) are suspended in alkylbenzene, and the suspension is added to titanium tetrachloride (b) and reacted to obtain a solid product. A method of obtaining the component (A) by washing the solid product with an alkylbenzene and then contacting the titanium tetrachloride (b) and the component (d) previously contacted with the titanium tetrachloride (b) in the presence of the alkylbenzene. .

(11) Calcium halide and aliphatic magnesium such as magnesium stearate (a) are contacted with titanium tetrachloride (b) and component (c), and then further reacted with titanium tetrachloride (b) and A method of preparing component (A) by contacting component (d) which has been brought into contact with titanium tetrachloride (b).

(12) Diethoxymagnesium (a) is suspended in an alkylbenzene or halogenated hydrocarbon solvent, then brought into contact with titanium tetrachloride (b), and then heated to contact reaction with component (c). A solid product is obtained by washing the solid product with alkylbenzene and then contacting again with titanium tetrachloride (b) and the component (d) previously contacted with titanium tetrachloride (b) in the presence of alkylbenzene. Wherein the component (A) is prepared by
A method of preparing component (A) by contacting aluminum chloride at any stage of the contact and the contact reaction.

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

(14) Magnesium chloride (a), an organic epoxy compound and a phosphoric acid compound are suspended in a hydrocarbon solvent such as toluene, and then heated to form a homogeneous solution. Titanium chloride is contact-reacted to obtain a solid product, the component (c) is brought into contact with the solid product and reacted, and the obtained reaction product is washed with alkylbenzene, and then tetrachloride is again added in the presence of alkylbenzene. A method of obtaining component (A) by contacting titanium (b) and component (d) previously contacted with titanium tetrachloride (b).

(15) The dialkoxymagnesium (a), the titanium compound and the component (c) are contact-reacted in the presence of toluene, and the resulting reaction product is contact-reacted with a silicon compound such as polysiloxane. After the contact reaction of titanium chloride (b) and the contact reaction of the metal salt of the organic acid, the titanium tetrachloride (b) and the component (d) previously contacted with titanium tetrachloride (b) are brought into contact again. A method for obtaining the component (A) by

Further, as a preferred method for preparing the solid catalyst component (A) for olefin polymerization used in the present invention based on the preparation methods described in the above (1) to (15), the following method is used. For example, a suspension is formed by suspending a dialkoxymagnesium as a component (a) at room temperature in a liquid aromatic hydrocarbon compound,
Then, titanium tetrachloride was added to the suspension as component (b).
The contact is carried out at 20 to 100C, preferably -10 to 70C, more preferably 0 to 30C, and the reaction is carried out at 40 to 130C, more preferably 70 to 120C. At this time, before or after contacting titanium tetrachloride with the above suspension,
Di-n-butyl phthalate as component (c), -20 to
Contact at 130 ° C. to obtain a solid reaction product. After washing the solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, titanium tetrachloride and phenol as the component (d) previously brought into contact with titanium tetrachloride are replaced with phenol and aromatic hydrocarbon compound such as toluene. In the presence, 40-130
C., more preferably 70-120.degree. C., and further washed with a liquid hydrocarbon compound at room temperature to obtain a solid catalyst component (A) for olefins polymerization.

The ratio of the amounts of the respective compounds varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the component (b) is 0.5 to 100 mol, preferably 0.5 to 100 mol per mol of the 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.
0.1 to 1 mol, more preferably 0.02 to 0.6 mol, and component (d) is 0.0005 to 1 mol, preferably 0.0005 to 0.5 mol, more preferably 0.001 to 1 mol.
０．１0.1 mol. When the component (d) is used in contact with the component (b) in advance, the amount of the component (b) used is from 0.00002 to 0.0 with respect to 1 mol of the component (b).
It is 5 mol, preferably 0.0001 to 0.01 mol.

The solid catalyst component (A) for olefin polymerization 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 0.05 to 2% of component (d). % By weight, and 40 to 70% by weight of halogen atoms.

The organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is represented by the general formula (1): R ⁴ _p AlQ _3-p (wherein, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3). Compounds can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, and tri-iso.
-Butyl aluminum, diethyl aluminum bromide, diethyl aluminum hydride, and 1
Species or two or more species can be used. Preferably, they are triethyl aluminum and tri-iso-butyl aluminum.

The organosilicon compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is represented by the general formula (2): R ⁵ _q Si (OR ⁶ ) _4-q (wherein, R ⁵ 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, and may be the same or different. R ⁶ 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, and q is an integer of 0 ≦ q ≦ 3. The compound represented by is used. Such organosilicon compounds include:
Examples thereof include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

Specific examples of the above-mentioned 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, di- 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-methylhexyl) dimethoxysilane 4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysila , Cyclohexyl cyclopentyl distearate propoxysilane, 3 - methylcyclohexyl cyclopentyl dimethoxysilane, 4 - methylcyclohexyl cyclopentyl dimethoxysilane, 3,5 - dimethyl cyclohexyl cyclopentyl dimethoxy silane, 3 - methylcyclohexyl cyclohexyl dimethoxysilane,
4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (is
o-propyl) dimethoxysilane, cyclopentyl (i
(so-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, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, n-propyltrimethoxysilane, i
so-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n
-Butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane,
Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxy Examples thereof include silane and tetrabutoxysilane. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n
-Butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n
-Butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane,
3-Methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) can be used alone or in combination of two or more. .

Next, the olefin polymerization catalyst of the present invention is:
It comprises the above-mentioned solid catalyst component for olefin polymerization (A), an organoaluminum compound (B), and an organosilicon compound (C), and performs polymerization or copolymerization of olefins in the presence of the catalyst. The olefins include ethylene, propylene, 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, propylene and 1-
Butene is 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,
-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 arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the component (B) is a 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 the solid catalyst component for the polymerization of olefins ( It is desirable to contact A).

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 state of gas and 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 olefin is polymerized using a catalyst for olefin polymerization (also referred to as main polymerization), in order to further improve the catalytic activity, stereoregularity, and the particle properties of the produced polymer, etc. It is desirable to carry out preliminary polymerization prior to 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 organoaluminum compound (B) is first charged in a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere. And then contacted with the solid catalyst component (A) for olefin polymerization, and then the olefin such as propylene and / or 1
Contacting one or more other olefins.
When the prepolymerization is performed by combining the organosilicon compound (C), the organoaluminum compound (B) is first charged into the prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then the organosilicon compound (C) ), And further contacting the solid catalyst component (A) for olefin polymerization, and then contacting an olefin such as propylene and / or one or other two or more olefins.

When olefins are polymerized in the presence of the olefin polymerization catalyst formed according to the present invention, higher yields can be obtained while maintaining high stereoregularity as compared with the case where a conventional catalyst is used. An olefin polymer can be obtained.

[0063]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. Example 1 [Preparation of solid catalyst component (A)] 10 g of diethoxymagnesium and 80 ml of toluene were charged into a 500 ml round bottom flask which was sufficiently substituted with nitrogen gas and equipped with a stirrer. did. Next, 20 ml of titanium tetrachloride was added to the suspension, and the temperature was raised. When the temperature reached 80 ° C., a solution in which 3.4 ml of di-n-butyl phthalate was dissolved was added.
The temperature was further raised to 110 ° C. Thereafter, the reaction was carried out with stirring at 110 ° C. for 1 hour. After the completion of the reaction, the mixture was washed three times with 100 ml of toluene at 90 ° C.
0.094 g of phenol was added to ml, and a solution stirred at room temperature for 1 hour was added. The temperature was raised to 110 ° C., and the mixture was reacted with stirring for 1 hour. After the reaction, n-heptane 1 at 40 ° C.
After washing 7 times with 00 ml, a solid catalyst component (A) was obtained. In addition, the solid-liquid in this solid catalyst component was separated, and the titanium content in the solid content was measured and found to be 2.8% by weight.

[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,
2.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and after preliminarily polymerizing at 20 ° C. for 5 minutes, the temperature was raised and the polymerization reaction was performed at 70 ° C. for 1 hour. The polymerization activity per gram of the solid catalyst component was 46,200 g-PP / g-cat.
Met. Melt index value of polymer (a) (M
I) (Measurement method conforms to ASTM D 1238, JIS K 7210)
Was 3.2 g / 10 minutes. The polymerization activity per solid catalyst component used here was calculated by the following equation. Polymerization activity = (a) 206.0 (g) / solid catalyst component 0.
[00446] (g) When this polymer was extracted with boiling n-heptane for 6 hours, the polymer (b) insoluble in n-heptane was 203.7.
g, and the ratio of boiling n-heptane insolubles in the polymer was 98.9% by weight.

Comparative Example 1 An experiment was performed in the same manner as in Example 1 except that phenol was not added. As a result, the titanium content in the solid catalyst component was 2.9% by weight. The polymerization activity per 1 g of the solid catalyst component was 42,400 g-PP / g-cat. The ratio of boiling n-heptane insolubles in the polymer is 98.
7% by weight, and the value of the melt index is 6.6 g /
10 minutes.

From the above results, 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 an extremely high yield.

[0067]

Industrial Applicability The olefin polymerization catalyst of the present invention can obtain an olefin polymer in an extremely high yield while maintaining high stereoregularity at a high level. 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 (72) Inventor Takuma Yoshida 3-3-5 Chigasaki, Chigasaki-shi, Kanagawa Toho Titanium Co., Ltd. (72) Inventor Maki Sato 3-3-5 Chigasaki, Chigasaki-shi, Kanagawa Toho Titanium Co., Ltd. the internal F-term (reference) 4J028 AA01A AA02A AB01A AB02A AC05A AC06A BA00A BA01B BA02B BB00A BB01B BC05A BC06A BC15B BC16B BC18B BC26B BC34B CA15A CA16A CA19A CB25A CB33C CB35A CB36A CB37A CB38A CB39C CB44A CB55A CB56A CB91A DA01 DA02 DA03 DA04 DA05 EA01 EB02 EB04 EB05 EB07 EB08 EB10 EC01 EC02 EC04 EC06 FA01 FA02 FA04 FA07 GA12 GB01

Claims (3)

[Claims] 1. A method comprising: (a) a magnesium compound, (b) titanium tetrachloride, (c) phthalic acid diester, and (d) phenol optionally substituted with an alkyl or cycloalkyl group having 1 to 10 carbon atoms. A solid catalyst component for olefin polymerization, which is formed. 2. The solid catalyst component for olefin polymerization according to claim 1, wherein the magnesium compound is a dialkoxymagnesium. 3. A solid catalyst component for olefin polymerization according to claim 1 or 2; (B) a general formula (1); R ¹ _p AlQ _3-p (1) wherein R ¹ is An alkyl group having 1 to 4 carbon atoms; Q represents a hydrogen atom or a halogen atom; p is an integer of 0 <p ≦ 3); and (C) a general formula (2) R ² _q Si (OR ³ ) _4-q (2) (wherein, R ² 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; R ³ 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, and may be the same or different, and q is 0 ≦ q is an integer of 3 or less.) Catalyst for polymerization of refins.