JP2003201311A - Solid catalyst component for olefin polymerization, olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid catalyst for olefin polymerization having high polymerization activity and capable of obtaining excellent powder, an olefin polymerization catalyst and a method for producing an olefin polymer. <P>SOLUTION: The olefin polymerization solid catalyst component can be obtained by reacting (a) a halogen-containing titanium compound, (b) an alkoxy group-containing magnesium compound, and (c-1) a halogen-containing silicon compound having a molar ratio of the halogen to the alkoxy group in the above alkoxy group-containing magnesium compound (b) of ≥0.50 or the above components (a), (b), and (c-1), and (d) an electron-donating compound at a temperature of 120°C to 150°C, washing the reaction product with an inert solvent, reacting the obtained reaction product with the halogen-containing titanium compound (a) at a temperature of 120°C to 150°C at least once, and washing the reaction product with an inert solvent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization and a method for producing an olefin polymer for producing a homopolymer or a copolymer of α-olefin.

[0002]

2. Description of the Related Art Generally, an olefin polymer is polymerized by a Ziegler-Natta catalyst composed of a titanium compound and an organic aluminum compound. For example, in the production of polypropylene which is one of olefin polymers, a solid catalyst component mainly composed of titanium, magnesium, chlorine and an electron donating compound, an organoaluminum compound as a co-catalyst component, and a stereoregularity improving agent are used. By using a catalyst containing an organosilicon compound having an alkoxy group of
We have obtained isotactic polypropylene,
Attempts have been made to improve catalyst activity during polymerization, improve stereoregularity of olefin polymers, and improve powder form for stable production of olefin polymers.

For example, JP-A-63-280707 discloses a method of supporting a magnesium compound on an inorganic oxide such as silica for the purpose of improving the morphology of the olefin polymer such as particle size and shape. Also,
Japanese Patent Laid-Open No. 58-000811 discloses a method in which a magnesium compound is once dissolved in a solvent such as alcohol and then re-precipitated, which is used. However, these methods have a drawback in that the processes such as supporting, dissolution, and precipitation of the magnesium compound are indispensable, so that the process is extremely complicated and the performance stability of the catalyst is lacking. Further, these methods have a defect that the catalytic activity during polymerization and the stereoregularity of the olefin polymer are not sufficient.

Therefore, as a method for improving these drawbacks, Japanese Patent Application Laid-Open No. 02-413883 discloses a method of using a reaction product of metallic magnesium, an alcohol, and a specific amount of halogen as a catalyst carrier, and Japanese Patent Publication No. 07-257. −
No. 0,522,822 discloses an olefin polymer using a Ziegler-Natta catalyst containing a solid catalyst component obtained by adding an organic acid ester to a reaction product of alkoxymagnesium, a halogenating agent and an alkoxytitanium, and further reacting the titanium halide. A manufacturing method is disclosed.
However, these methods still have insufficient catalytic activity during polymerization and stereoregularity of the olefin polymer.

In JP-A-11-269218, a magnesium compound and a titanium compound are contacted in the presence of an electron-donating compound at a temperature of 120 ° C. or higher and 150 ° C. or lower, and then 100 ° C. or higher and 150 ° C. or lower. Disclosed is a solid catalyst component for olefin polymerization, which is obtained by washing with an inert solvent at a temperature, and is effective in suppressing a decrease in catalyst activity over time during polymerization and improving stereoregularity of an olefin polymer. There is. However, the polymerization activity of this catalyst was not always sufficiently satisfactory,
Further improvements were needed to improve this.

[0006]

Therefore, the present invention provides a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization and a method for producing an olefin polymer, which gives an olefin polymer having high polymerization activity and excellent powder form. The purpose is to provide.

[0007]

According to the present invention, the following compounds (a) to (c-1) (that is, compound (a), compound (b) and compound (c-1)), or the following compound (A)
To (d) (that is, compound (a), compound (b), compound (c-1) and compound (d)) at 120 ° C. or higher and 150 ° C. or higher.
The reaction is carried out at a temperature of ℃ or less, washed with an inert solvent, and further reacted once or more (for example, once or twice) with the halogen-containing titanium compound (a) at a temperature of 120 to 150 ° C. A solid catalyst component for olefin polymerization obtained by washing with an inert solvent is provided. (A) Halogen-containing titanium compound (b) Alkoxy group-containing magnesium compound (c-1) Halogen-containing silicon compound (d) in which the molar ratio of halogen to alkoxy group in the alkoxy group-containing magnesium compound (b) is 0.50 or more. ) Electron-donating compound

By preparing the solid catalyst component in this way, it is possible to reduce the residual amount of alkoxy groups, obtain an olefin polymer having a high polymerization activity and an excellent powder form.

According to another aspect of the present invention, the following compounds (a) to (c) (that is, compound (a), compound (b) and compound (c)) or the following compounds (a) to (d): ) (Ie, compound (a), compound (b), compound (c) and compound (d)), the amount of supported titanium (T
The molar ratio (RO) of the residual amount (RO) of the alkoxy groups to i) (RO
A solid catalyst component for olefin polymerization having / Ti) of 0.30 or less is provided. (A) Halogen-containing titanium compound (b) Alkoxy group-containing magnesium compound (c) Halogen-containing silicon compound (d) Electron-donating compound

By setting the molar ratio (RO / Ti) to 0.30 or less, an olefin polymer having a high polymerization activity and an excellent powder form can be obtained.

The compound (c) preferably has a molar ratio of halogen of the compound (c) to the alkoxy group in the compound (b) of 0.50 or more. Molar ratio 0.50
By the above, since the halogenation reaction of the compound (b) with the compound (c) effectively proceeds, the degree of halogenation of the compound (b) is finally improved, and an alkoxytitanium compound expected to be a by-product. Is considered to suppress the generation of. This increases the polymerization activity. Also, in some cases, the compound (b) by the compound (c)
The halogenation reaction of compound (b) with compound (a)
It is considered that the powder form is excellent because the halogenation rate of the compound (b) is decreased and the fineness of the catalyst is suppressed because the halogenation reaction proceeds preferentially to the halogenation reaction.

By such a preparation method, the compound (a)
It is considered that the halogenation reaction of the compound (b) by the compounds (c) and (c) is promoted, and the alkoxytitanium compound and the like expected to be by-produced are easily extracted from the solid surface.

The compound (b) is obtained by reacting metal magnesium, alcohol, and a halogen containing 0.0001 gram atom or more of halogen atom and / or a halogen-containing compound with 1 mol of the metal magnesium. Is preferred.

When the amount of the halogen and / or the halogen-containing compound is less than this amount, the particle size of the compound (b) becomes coarse, the halogenation degree of the compound (b) is suppressed, and the extraction efficiency of alkoxytitanium and the like decreases. There is a risk that By using such a compound (b), the morphology of the olefin polymer can be improved. The thus-produced compound (b) is nearly spherical and does not require a classification operation.

In the preparation of the solid catalyst component of the present invention, the electron-donating compound (d) is used, if necessary, but the solid catalyst component not using the electron-donating compound (d) is particularly preferably ethylene homopolymer. It is suitable as a catalyst for producing a polymer or an ethylene-based copolymer, and can obtain high polymerization activity.

Yet another aspect of the present invention is an olefin polymerization catalyst containing the following components [A], [B] or the following components [A], [B], [C]. [A] The above-mentioned solid catalyst component for olefin polymerization [B] Organoaluminum compound [C] Electron-donating compound By thus constituting the catalyst, an olefin polymer having high polymerization activity and excellent in powder form is obtained. You can The electron-donating compound [C] is optionally contained, but the inclusion of this compound may improve the stereoregularity and / or polymerization activity of the olefin polymer.

Yet another aspect of the present invention is a method for producing an olefin polymer in which an olefin is polymerized using the above-mentioned olefin polymerization catalyst.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Next, each catalyst component, production method, polymerization method and the like of the present invention will be described. The following are preferred examples and the present invention is not limited thereto. 1. Catalyst component [A] Solid catalyst component for olefin polymerization

(A) Halogen-Containing Titanium Compound The halogen-containing titanium compound has the following general formula (I):
The compound represented by can be preferably used. TiX ¹ _p (OR ¹ ) _4-p ... (I)

In the above general formula (I), X ¹ represents a halogen atom, of which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ¹ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear or branched one, or a cyclic one, and may be sulfur, nitrogen, It may contain a hetero atom such as oxygen, silicon, or phosphorus. Of these, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are preferable, and a linear or branched alkyl group is particularly preferable. When a plurality of OR ^1's are present, they may be the same or different from each other. Specific examples of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclo A hexenyl group,
Examples thereof include a phenyl group, a tolyl group, a benzyl group and a phenethyl group. p shows the integer of 1-4.

Specific examples of the halogen-containing titanium compound represented by the above general formula (I) include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium compounds;
Trihalogenated alkoxytitanium such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di Dihalogenated dialkoxytitanium such as -n-propoxytitanium dichloride and diethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, tri-
Examples include monohalogenated trialkoxytitanium such as n-butoxytitanium chloride. Of these, titanium compounds having a high halogen content, particularly titanium tetrachloride, are preferred from the viewpoint of polymerization activity. These halogen-containing titanium compounds may be used alone or in combination of two or more.

(B) Alkoxy group-containing magnesium compound As the alkoxy group-containing magnesium compound, a compound represented by the following general formula (II) can be preferably used. Mg (OR ² ) _q R ³ _2-q ... (II)

In the above general formula (II), R ² represents a hydrocarbon group and R ³ represents a hydrocarbon group or a halogen atom. Here, examples of the hydrocarbon group of R ² and R ³ include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and the like, which may be the same or different. Moreover, examples of the halogen atom of R ³ include chlorine, bromine, iodine, and fluorine. q is 1-2
Indicates an integer.

Specific examples of the alkoxy group-containing magnesium compound represented by the above general formula (II) include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium and diphenoxy. Dialkoxy magnesium and diaryloxy magnesium such as magnesium and dicyclohexyloxy magnesium; alkoxyalkyl magnesium such as ethoxyethyl magnesium, phenoxymethyl magnesium, ethoxyphenyl magnesium and cyclohexyloxyphenyl magnesium, allyloxyalkyl magnesium, alkoxyallyl magnesium and allyloxy Allyl magnesium; butoxy magnesium chloride, cyclohexyloxymag Shiumukurorido, phenoxy magnesium chloride, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide, etc. alkoxy magnesium halide and allyloxy magnesium halide, such as ethoxy magnesium iodide and the like. Among these, dialkoxy magnesium can be preferably used from the viewpoint of polymerization activity and stereoregularity, and diethoxy magnesium is particularly preferable.

From the viewpoint of the polymerization activity of the catalyst, the powder form of the olefin polymer and the stereoregularity, the alkoxy group-containing magnesium compound (b) is preferably 0. It can be obtained by reacting a halogen and / or a halogen-containing compound containing a halogen atom of 0001 gram atom or more.

In this case, the shape of metallic magnesium is not particularly limited. Therefore, it is possible to use metallic magnesium having an arbitrary particle diameter, for example, granular, ribbon-shaped or powdered metallic magnesium. Further, the surface state of the magnesium metal is not particularly limited, but it is preferable that the surface of the surface is not coated with magnesium hydroxide or the like.

As the alcohol, it is preferable to use a lower alcohol having 1 to 6 carbon atoms. In particular, use of ethanol is preferable because a solid product that significantly improves the expression of catalytic performance can be obtained. The purity and the water content of the alcohol are not particularly limited, however, when an alcohol having a high water content is used, magnesium hydroxide is produced on the surface of the metal magnesium, and therefore an alcohol having a water content of 1% or less, particularly 2,000 ppm or less is used. It is preferable. Furthermore, in order to obtain a better morphology, the smaller the water content, the more preferable, and generally 200 ppm or less is desirable.

As the halogen, chlorine, bromine or iodine, particularly iodine is preferably used. The halogen atom of the halogen-containing compound is preferably chlorine, bromine or iodine.
Further, among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. As the halogen-containing compound, specifically, MgCl ₂ , MgI ₂ , Mg (OEt) Cl, M
g (OEt) I, MgBr ₂ , CaCl ₂ , NaCl, K
Br etc. can be used conveniently. Among these, especially Mg
Cl ₂ is preferred. These states, shapes, particle sizes, etc. are not particularly limited and may be arbitrary, and for example, they can be used as a solution in an alcohol solvent (eg, ethanol).

The amount of alcohol used is preferably 2 to 100 mol, and particularly preferably 5 to 50 mol, per 1 mol of magnesium metal. If the amount of alcohol used is too large, the yield of the alkoxy group-containing magnesium compound (b) with good morphology may decrease, and if it is too small, stirring in the reaction tank may not be performed smoothly. . However, the molar ratio is not limited.

The amount of halogen used is 1 metal magnesium.
The halogen atom content is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more, based on mol. 0.000
When the amount is less than 1 gram atom, there is no great difference between when the halogen is not used as a reaction initiator and when the obtained alkoxy group-containing magnesium compound (b) is used as a catalyst carrier, the catalytic activity and the morphology of the olefin polymer are It may be defective.

The halogen-containing compound is used in an amount of 0.0001 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0. More than 001 gram atom. When the amount is less than 0.0001 gram atom, it is almost the same as when the halogen-containing compound is not used as a reaction initiator, and when the obtained alkoxy group-containing magnesium compound (b) is used as a catalyst carrier, the catalytic activity and the olefin polymer are May have poor morphology and the like.

In the present invention, the halogen and the halogen-containing compound may be used alone or in combination of two or more kinds. Further, halogen and a halogen-containing compound may be used in combination. When halogen and a halogen-containing compound are used in combination, the total amount of halogen atoms in the halogen and the halogen-containing compound is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 1 to 1 mol of magnesium metal. The amount is 0.001 gram atom or more.

The upper limit of the amount of halogen and / or halogen-containing compound to be used is not particularly limited, but may be appropriately selected within a range where the alkoxy group-containing magnesium compound (b) used in the present invention can be obtained, and generally, it is 0. It is preferably less than 06 gram atoms.

In the method for producing an olefin polymer of the present invention, the particle size of the alkoxy group-containing magnesium compound (b) can be freely controlled by appropriately selecting the amount of halogen and / or halogen-containing compound used. It is possible.

The production of the alkoxy group-containing magnesium compound (b) is carried out until generation of hydrogen gas is no longer observed (usually 1 to 30 hours). Specifically, when iodine is used as halogen, metal magnesium, a method of reacting by heating after adding solid iodine in alcohol, in metal magnesium and alcohol,
It can be produced by a method of dropping an alcohol solution of iodine and then reacting it by heating, or a method of dropping an alcohol solution of iodine while heating the magnesium magnesium and alcohol solutions to react.

Any of the methods may be carried out in an inert gas (eg, nitrogen gas, argon gas) atmosphere, optionally using an inert organic solvent (eg, saturated hydrocarbon such as n-hexane). preferable.

Regarding the addition of magnesium metal, alcohol and halogen, it is not necessary to add them all from the beginning, but they may be added separately. A particularly preferable form is a method in which the entire amount of alcohol is charged from the beginning, and metallic magnesium is charged in several times.
In such a case, it is possible to prevent the temporary generation of a large amount of hydrogen gas, which is highly desirable from the viewpoint of safety. Also,
The reaction tank can also be downsized. Furthermore, it becomes possible to prevent the entrainment of alcohol or halogen caused by the temporary large generation of hydrogen gas. The number of divisions may be determined in consideration of the scale of the reaction tank, and is not particularly limited, but it is usually preferably 5 to 10 times considering the complexity of the operation.

The reaction itself may be a batch type or a continuous type. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is added again. It is also possible to repeat.

Further, in view of catalytic activity during polymerization and powder form of the olefin polymer, metal magnesium, alcohol, and halogen and / or halogen-containing compound are reacted at 30 to 60 ° C., more preferably 40 to 55 ° C. The average particle diameter (D ₅₀ ) of the obtained alkoxy group-containing magnesium compound (b) is 50 μm or less, more preferably 40 μm or less. Further, D ₅₀ is preferably 1 μm or more. The average particle size (D ₅₀ ) is defined as the particle size corresponding to a weight cumulative fraction of 50%. That is, D
The total weight of the smaller particles than the particle size represented by ₅₀ is shown to be 50 percent of total grain total weight sum.

By setting the reaction temperature to 30 to 60 ° C., the particle size of the compound (b) is reduced and the halogenation of the compound (b) is promoted while maintaining the spherical property and the narrow particle size distribution. The residual amount of alkoxy groups in the component can be reduced.
If the reaction temperature is higher than this, the particle size reduction does not proceed efficiently, and if the reaction temperature is lower than this, the production rate of the compound (b) is remarkably reduced and the productivity is lowered. By reducing the average particle size (D ₅₀ ) to 50 μm or less, it is considered that the halogenation degree of the compound (b) is improved and the alkoxytitanium compound or the like expected to be a byproduct is easily extracted from the solid surface. To be

When the alkoxy group-containing magnesium compound (b) is used in the preparation of the solid catalyst component [A], it may be dried, or it may be filtered and washed with an inert solvent such as heptane. May be. In any case, the alkoxy group-containing magnesium compound (b) can be used in the following steps without pulverization or classification operation for adjusting the particle size distribution.
The alkoxy group-containing magnesium compound (b) is
It is almost spherical and has a sharp particle size distribution. Furthermore, even if each particle is taken, the variation in sphericity is small.

These alkoxy group-containing magnesium compounds (b) may be used alone or in combination of two or more. Further, it may be supported on a support such as silica, alumina, polystyrene or the like, or may be used as a mixture with halogen or the like.

(C) Halogen-containing silicon compound As the halogen-containing silicon compound, the following general formula (II
The compounds represented by I) can be used. Si (OR ⁴ ) _r X ² _4-r ... (III)

By using the halogen-containing silicon compound (c), it may be possible to improve the catalytic activity during polymerization, stereoregularity, and reduce the amount of fine powder contained in the olefin polymer.

In the above general formula (III), X ² represents a halogen atom, of which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ⁴ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be linear or branched, or cyclic, and may be sulfur, nitrogen, It may contain a hetero atom such as oxygen, silicon, or phosphorus. Among these, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group and the like are preferable. When there are a plurality of OR ^4's , they may be the same or different from each other. Specific examples of R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, Examples thereof include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group and phenethyl group. r represents an integer of 0 to 3.

Specific examples of the halogen-containing silicon compound represented by the above general formula (III) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane,
Examples thereof include diethoxydichlorosilane, triethoxychlorosilane, propoxytrichlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Of these, silicon tetrachloride is particularly preferable. It is considered that by using silicon tetrachloride, the rate and reaction rate of the halogenation reaction of compound (b) with silicon tetrachloride can be sufficiently controlled. These halogen-containing silicon compounds may be used alone or in combination of two or more.

The compound (c) is preferably a halogen-containing silicon compound (c-1) in which the molar ratio of halogen to the alkoxy group in the compound (b) is 0.50 or more. When such a halogen-containing silicon compound is used, the halogenation of the compound (b) proceeds, and the residual amount of alkoxy groups in the solid catalyst component can be reduced. More preferred is a halogen-containing silicon compound in which the molar ratio of halogen to the alkoxy group in compound (b) is 0.80 or more.

(D) Electron-donating compound In the preparation of the olefin polymerization catalyst of the present invention, the electron-donating compound (d) is optionally used. Examples of the electron-donating compound (d) include alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, esters of organic acids or inorganic acids, ethers such as monoethers, diethers or polyethers. Examples thereof include oxygen-containing compounds such as compounds, and nitrogen-containing compounds such as ammonia, amines, nitriles, and isocyanates. Among these, polycarboxylic acid esters are preferable, and aromatic polycarboxylic acid esters are more preferable. Of these, monoesters and / or diesters of aromatic dicarboxylic acids are particularly preferable from the viewpoint of catalytic activity during polymerization. Further, an aliphatic hydrocarbon in which the organic group of the ester portion is linear, branched or cyclic is preferable.

Specifically, phthalic acid, naphthalene-1,
2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2
-Methyl, ethyl, n- of dicarboxylic acids such as dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid and indane-5,6-dicarboxylic acid Propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Pentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl,
n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl,
3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl,
Examples include dialkyl esters such as 3-ethylpentyl. Among these, phthalic acid diesters are preferable, and linear or branched aliphatic hydrocarbons having an organic group in the ester portion having 4 or more carbon atoms are particularly preferable. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, diethyl phthalate and the like. Further, these compounds may be used alone or in combination of two or more kinds.

[B] Organoaluminum Compound The organoaluminum compound [B] used in the present invention is not particularly limited, but an alkyl group, a halogen atom,
Those having a hydrogen atom, an alkoxy group, aluminoxane and a mixture thereof can be preferably used. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and trioctylaluminum; dialkyls such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and dioctylaluminum monochloride. Examples include aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; and chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable. These organoaluminum compounds may be used alone or in combination of two or more.

[C] Electron-donating compound In the preparation of the olefin polymerization catalyst of the present invention, an electron-donating compound [C] is used, if necessary. As such an electron-donating compound [C], an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound can be used. Among these, it is particularly preferable to use an organosilicon compound having an alkoxy group.

Specific examples of the organosilicon compound having an alkoxy group include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane and propylisopropyldimethoxysilane. , Diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t
-Butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane, t-
Butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane , T
-Butyl (3,3,3-trifluoromethylpropyl)
Dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, Cyclopentyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, α-naphthyl-1,1,2- Trimethylpropyldimethoxysilane, n- Toradekaniru 1,1,2-methylpropyl di Mexico silane, 1,1,2-trimethyl propyl methyl dimethoxy silane, 1,1,2-trimethyl propyl ethyl dimethoxy silane, 1,1,2
-Trimethylpropylisopropyldimethoxysilane,
1,1,2-trimethylpropylcyclopentyldimethoxysilane, 1,1,2-trimethylpropylcyclohexyldimethoxysilane, 1,1,2-trimethylpropylmyristyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane Silane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclo Hexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, ethyltriisopropoxysilane, methylcyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t -Butyl (t
-Butoxy) dimethoxysilane, (isobutoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, chlorotriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane, 1,1,2-trimethylpropylisopropoxydimethoxysilane, 1,1,2-trimethylpropyl (t-butoxy) dimethoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyl tris (β-methoxyethoxy)
Examples thereof include silane, vinyltrisacetoxysilane, and dimethyltetraethoxydisiloxane. These organosilicon compounds may be used alone or in combination of two or more.

Examples of such an organosilicon compound include a silicon compound having no Si--O--C bond and an O--C compound.
A compound obtained by previously reacting an organic compound having a bond or by reacting it at the time of polymerization of α-olefin can also be mentioned. Specific examples include compounds obtained by reacting silicon tetrachloride with alcohol.

Specific examples of the nitrogen-containing compound include 2,6
-Diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl 2,2,6,6-
2,6-Substituted piperidines such as tetramethylpiperidine; 2,5-diisopropyl azolidine, N-methyl 2,2,5,5-tetramethyl azolidine such as 2,5-
Substituted azolidines; Substituted methylenediamines such as N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine; 1,3
-Dibenzyl imidazolidine, 1,3-dibenzyl-2
-Substituted imidazolidines such as phenylimidazolidine and the like can be mentioned.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite. Examples include phosphite esters such as fight.

Specific examples of the oxygen-containing compound include 2,
2,5,5-tetramethyltetrahydrofuran, 2,
2,5,5-tetraethyltetrahydrofuran, etc.
5-Substituted tetrahydrofurans; 1,1-dimethoxy-
2,3,4,5-tetrachlorocyclopentadiene,
Examples include dimethoxymethane derivatives such as 9,9-dimethoxyfluorene and diphenyldimethoxymethane.

2. [A] Method for preparing solid catalyst component [A] is prepared by using the above halogen-containing titanium compound (a), alkoxy group-containing magnesium compound (b) and halogen-containing silicon compound (c), or if necessary. Accordingly, the electron donating compound (d) is further reacted. A preferable preparation method is that the halogen-containing titanium compound (a), the alkoxy group-containing magnesium compound (b) and the halogen-containing silicon compound (c), or, if necessary, the electron-donating compound (d), at 120 ° C. or higher. The reaction is carried out at a temperature of 150 ° C. or lower, the product is washed with an inert solvent, and the halogen-containing titanium compound (a) is further washed once or more.
Is reacted at a temperature of 120 ° C. or higher and 150 ° C. or lower, and washed with an inert solvent. At this time, the compound (c) is a halogen-containing silicon compound (c-1) in which the molar ratio of halogen to the alkoxy group in the compound (b) is 0.50 or more. Thus, compounds (a) to (c), (a) to
After the catalytic reaction of (d) at a specific temperature, the halogen-containing titanium compound (a) may be catalytically reacted again (at least once) at a specific temperature to increase the polymer activity.

The other contact order is not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as hydrocarbon, or each component may be diluted in advance with an inert solvent such as hydrocarbon and contacted. Examples of the inert solvent include aliphatic hydrocarbons or alicyclic hydrocarbons such as octane, decane and ethylcyclohexane, aromatic hydrocarbons such as toluene, ethylbenzene and xylene, and chlorobenzene, tetrachloroethane and chlorofluorocarbons. And halogenated hydrocarbons such as or a mixture thereof. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferable, and aliphatic hydrocarbons are particularly preferable.

The compounds (a) to (c) and (a) to
The contact order of (d) is not particularly limited, but first, the alkoxy group-containing magnesium compound (b) and the halogen-containing silicon compound (c) are brought into contact, then the halogen-containing titanium compound (a) is brought into contact, and finally It is preferable that the electron-donating compound (d) is brought into contact with the reaction and the halogen-containing titanium compound (a) is brought into contact therewith, because the polymerization activity can be increased.

Here, the halogen-containing titanium compound (a)
Is usually 0.5 to 100 mol, relative to 1 mol of magnesium of the alkoxy group-containing magnesium compound (b),
Preferably, 1 to 50 mol is used. If this molar ratio deviates from the above range, the catalytic activity may become insufficient.

The electron-donating compound (d) is the magnesium 1 of the alkoxy group-containing magnesium compound (b).
The amount is usually 0.01 to 10 mol, preferably 0.05 to 1.0 mol, based on mol. If this molar ratio deviates from the above range, the catalytic activity and stereoregularity may become insufficient.

The halogen-containing silicon compound (c)
Is usually an alkoxy group-containing magnesium compound (b)
The molar ratio of halogen to the alkoxy group in is 0.50
The amount used is preferably 0.60 to 4.0, more preferably 1.0 to 2.5. If this amount is less than the above range, the catalytic activity, the effect of improving the stereoregularity are not sufficiently exhibited, and the amount of fine powder of the polymer produced is increased, and the bulk density is decreased. It never happens.

Further, the above compounds (a) to (c),
The catalytic reaction of (a) to (d) is as follows after adding all of them.
Preferably 120 to 150 ° C., particularly preferably 125 to 150 ° C.
It is performed in the temperature range of 140 ° C. If the contact temperature is out of the above range, the catalytic activity and the stereoregularity may not be sufficiently improved. The contact is usually performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. When a solvent is used, the pressure at this time varies depending on the type, contact temperature, etc., but is usually atmospheric pressure to 5 MPa, preferably atmospheric pressure to 1 MPa. Further, during the contact operation, it is preferable to perform stirring from the viewpoint of contact uniformity and contact efficiency. These contact conditions are the same for the second and subsequent contact reactions of the halogen-containing titanium compound (a).

When a solvent is used in the contact operation of the halogen-containing titanium compound (a), it is usually 5,000 ml or less, preferably 10 to 1, with respect to 1 mol of the halogen-containing titanium compound (a). Use 000 milliliters of solvent. If this ratio deviates from the above range, contact uniformity and contact efficiency may be deteriorated.

Further, the washing temperature with an inert solvent after the contact and reaction of the halogen-containing titanium compound (a) is
After the first contact and reaction of the halogen-containing titanium compound (a), 100 to 150 ° C., particularly preferably 120 to 140.
Washing with an inert solvent at a temperature of ℃ is preferable because the effect of improving the catalytic activity and stereoregularity may increase. Examples of the inert solvent include aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, chlorobenzene, tetrachloroethane, and the like. Examples thereof include halogenated hydrocarbons such as chlorofluorocarbons and mixtures thereof. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used.

The washing temperature after the second contact with the halogen-containing titanium compound (a) after the reaction is 100 to 150 ° C., particularly preferably 12 from the viewpoint of stereoregularity.
It may be better to wash with an inert solvent at a temperature of 0 to 140 ° C.

As the washing method, decantation, filtration and the like are preferable. The amount of the inert solvent used, the washing time, and the number of washings are not particularly limited, but usually 100 to 100,00 per 1 mol of the magnesium compound.
The solvent is used in 0 ml, preferably 500 to 50,000 ml, and is usually used for 1 minute to 24 hours, preferably 10 minutes to 6 hours. If this ratio deviates from the above range, cleaning may be incomplete.

The pressure at this time varies depending on the type of solvent, the washing temperature, etc., but is usually atmospheric pressure to 5 MPa, preferably atmospheric pressure to 1 MPa. Further, during the washing operation, it is preferable to perform stirring from the viewpoint of washing uniformity and washing efficiency. The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as hydrocarbon.

In the solid catalyst component [A] thus obtained, the molar ratio of the amount of remaining alkoxy groups to the amount of titanium supported is preferably 0.30 or less. The molar ratio is more preferably 0.20 or less, still more preferably 0.15 or less.

Further, the residual amount (RO) of the alkoxy group is 0.
It is preferably 13 mmol / g or less. The reason for this is that when the residual amount of alkoxy groups exceeds 0.13 mmol / g, the polymerization activity is low, and the cost of the catalyst may increase and the amount of residual catalyst such as Cl in the powder may increase, resulting in deterioration of the quality. Is. Further, the residual amount of alkoxy groups is more preferably 0.10 mmol / g or less, further preferably 0.08 mmol / g or less.

The amount of titanium supported is preferably 1.5% by weight or more. The reason for this is that the amount of titanium supported is 1.
This is because if it is less than 5% by weight, the activity per catalyst may be low even if the activity per titanium is high (RO / Ti is low). Also, the amount of titanium supported is 1.8.
The content is more preferably at least wt%, and even more preferably at least 2.0 wt%.

When the solid catalyst component [A] is prepared using the electron-donating compound (d), the molar ratio, the amount of remaining alkoxy groups, and the amount of titanium supported are likely to be the above preferable values. Furthermore, the residual amount of alkoxy groups can be controlled by selecting a specific carrier to be used or controlling the catalyst preparation conditions. The amount of titanium supported can be controlled by setting the catalyst preparation conditions, particularly the reaction temperature of the compound (a) and each component, and the washing temperature after the reaction of the compound (a) to a specific temperature.

3. Method for Producing Olefin Polymer The amount of each component of the catalyst for olefin polymerization of the present invention is not particularly limited, but the solid catalyst component [A] is usually converted into titanium atom per 1 liter of reaction volume and The amount used is in the range of 0.00005 to 1 mmol.

The organoaluminum compound [B] is used in such an amount that the aluminum / titanium atomic ratio is usually in the range of 1 to 1,000, preferably 10 to 500.
If this atomic ratio deviates from the above range, the catalytic activity may become insufficient.

When the electron-donating compound [C] is used, [C] / [B] (molar ratio) is usually 0.001 to
The amount used is in the range of 5.0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0.
If this molar ratio deviates from the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when performing prepolymerization, the amount of the electron-donating compound [C] used can be further reduced.

As the olefin used in the present invention,
Α-Olefin represented by the general formula (IV) is preferable. _{^{R 5 -CH = CH 2 ··· (}} IV)

In the above general formula (IV), R ⁵ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group, or may be a straight chain or branched chain. It may have or have an annular shape. Specifically, ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, butadiene, isoprene, piperylene and the like can be mentioned. These olefins may be used alone or in combination of two or more. Among the above olefins, ethylene and propylene are particularly preferable.

In the polymerization of the olefin in the present invention, the olefin is preliminarily prepolymerized and then the main polymerization is carried out, if desired, in view of the catalytic activity during the polymerization, the stereoregularity of the olefin polymer and the powder form. May be. In this case, 1 to 1 of the olefin is usually added in the presence of a catalyst prepared by mixing the solid catalyst component [A], the organoaluminum compound [B], and optionally the electron donating compound [C] at a predetermined ratio. At a temperature in the range of 100 ° C., prepolymerization is carried out at atmospheric pressure to a pressure of about 5 MPa, and then olefin is main polymerized in the presence of a catalyst and a prepolymerized product.

There are no particular restrictions on the type of polymerization in this main polymerization, and it can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, and the like, and can be applied to both batch polymerization and continuous polymerization. Applicable to two-step polymerization and multi-step polymerization under different conditions.

Regarding the reaction conditions, the polymerization pressure is not particularly limited, and from the viewpoint of polymerization activity, it is usually atmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa, and the polymerization temperature is usually 0 to 200. ° C, preferably 30-100 ° C
Is appropriately selected within the range. The polymerization time is usually 5 minutes to 20 hours, preferably 10 minutes to 10 hours, though it depends on the kind of the raw material olefin and the polymerization temperature.

The molecular weight of the olefin polymer can be adjusted by adding a chain transfer agent, preferably hydrogen. Further, an inert gas such as nitrogen may be present. Regarding the catalyst component in the present invention, the solid catalyst component [A], the organoaluminum compound [B] and the electron donating compound [C] are mixed at a predetermined ratio and contacted, and then the olefin is immediately introduced. Polymerization may be carried out, or after contacting, aging may be carried out for about 0.2 to 3 hours, and then olefin may be introduced to carry out polymerization. Further, this catalyst component can be supplied by suspending it in an inert solvent, olefin or the like. In the present invention, post-treatment after polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after the polymerization, the polymer powder derived from the polymerization vessel,
In order to remove the olefin and the like contained therein, it may be passed through a nitrogen stream or the like, and may be pelletized by an extruder as desired, in order to completely deactivate the catalyst at that time. It is also possible to add a small amount of water, alcohol or the like. Further, in the bulk polymerization method, after the polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

[0082]

EXAMPLES Next, the present invention will be illustrated concretely by examples, but the present invention is not limited to the following examples.
The average particle diameter (D ₅₀ ) of the alkoxy group-containing magnesium compound (b), the remaining amount of alkoxy groups in the solid catalyst component, Ti
The supported amount, the bulk density of the polymerized powder, the average particle size (D ₅₀ ), the amount of fine powder, the amount of coarse powder, the intrinsic viscosity [η], and the stereoregularity [mmmm] were determined as follows.

(1) Average particle size (D ₅₀ ) of the alkoxy group-containing magnesium compound (b): The compound (b) is suspended in a hydrocarbon solvent and measured by a light transmission method. The particle size distribution obtained by this method was plotted on a log-normal probability paper, and 50%
The particle size was determined as the average particle size.

(2) Remaining amount of alkoxy group: After the solid catalyst component is sufficiently dried, this is precisely weighed and tightly sealed in a vial bottle,
It was thoroughly decalcified using 1.2N hydrochloric acid. Then, the insoluble matter was filtered, the amount of alcohol in the filtrate was quantified by gas chromatography, and the corresponding residual amount of alkoxy groups was calculated.

(3) Ti supported amount: After the solid catalyst component was sufficiently dried, it was precisely weighed and thoroughly decalcified with 3N sulfuric acid. Then, the insoluble matter was filtered, phosphoric acid was added to the filtrate as a masking agent, and 3% hydrogen peroxide solution was further added to develop the color of the solution. The absorbance at 420 nm was measured using FT-IR to measure the Ti concentration. Then, the amount of supported Ti in the solid catalyst component was calculated.

(4) Bulk density: The polymer was measured according to JIS K672.
It measured based on 1.

(5) Average particle size (D ₅₀ ) of polymer, amount of fine powder, amount of coarse powder: The particle size distribution measured using a sieve was plotted on a lognormal probability paper, and the 50% particle size was calculated as the average particle size. Sought as. Further, the weight fraction with an opening size of 250 μm or less was defined as a fine powder amount, and the weight fraction with an opening size of 2830 μm or more was defined as a coarse powder amount, and these were obtained.

(6) Intrinsic viscosity of polymer [η]: The polymer was dissolved in decalin and measured at 135 ° C.

(7) Stereoregularity of polymer [mmmm]:
The polymer was dissolved in a 90:10 (volume ratio) mixed solution of 1,2,4-trichlorobenzene and heavy benzene, and ¹³ C-NM was added.
R (manufactured by JEOL Ltd., trade name: LA-500) was used to quantify using the signal of the methyl group measured by the proton complete decoupling method at 130 ° C.

The isotactic pentad fraction [m
mmm] means A. Zambell
i) etc. are Macromolecules (Macromolec)
ules) Vol. 6, page 925 (1973), and means the isotactic fraction in the pentad unit in the polypropylene molecular chain, which is determined from the ¹³ C-NMR spectrum. Further, the method for determining the attribution of the peak in the ¹³ C-NMR spectrum is described in A. Zambe (A. Zambe).
Macromolecules (Macromol)
ecules) Vol. 8, page 687 (1975).

Example 1 (1) Preparation of solid catalyst component A three-necked flask with an internal volume of 0.5 liter equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane and diethoxymagnesium (metal magnesium) were used. , Ethanol and iodine, iodine / Mg: 0.00
The reaction was carried out at an atomic ratio of 57 grams and a reaction temperature of 50 ° C., and 16 g of D ₅₀ : 35 μm) was added. After heating to 40 ° C., 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) was added and stirred for 4 hours, and then 3.4 ml of di-n-butyl phthalate was added. The temperature of this solution was raised to 65 ° C., and then titanium tetrachloride was added to 77
A milliliter was dropped, and the contact operation was performed at an internal temperature of 125 ° C. with stirring for 1 hour. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Add 100 ml of dehydrated octane and raise the temperature to 125 ° C with stirring and
After holding for a minute, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. After that, 122 ml of titanium tetrachloride was added, and the internal temperature was 12
After stirring at 5 ° C. for 2 hours and performing a contact operation, the above 1
Washing with dehydrated octane at 25 ° C. was performed 6 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene Polymerization A stainless steel autoclave with an internal volume of 1 liter equipped with a stirrer was sufficiently dried, and after nitrogen substitution, 400 ml of heptane dehydrated at room temperature was added. Triethylaluminum 2.0 mmol, dicyclopentyldimethoxysilane 0.25 mmol, 0.0025 mmol of the solid catalyst component prepared in (1) in terms of Ti atom was added, hydrogen was added at 0.1 MPa, and then propylene was introduced. 80 ° C, total pressure 0.8MPa
Polymerization was carried out for a time. Then, the temperature was lowered and the pressure was released, and the contents were taken out and put into 2 liters of methanol to deactivate the catalyst. It was filtered off and dried in vacuum to obtain a propylene polymer. The evaluation results are shown in Table 1.

Example 2 (1) Preparation of solid catalyst component In Example 1 (1), except that the washing temperature with octane after the second supporting reaction of titanium tetrachloride was room temperature,
A solid catalyst component was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Propylene Polymerization In Example 1 (2), 0.5 mmol of cyclohexylmethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane, and the solid catalyst component prepared in the above (1) was converted into Ti atom at 0. Polymerization of propylene was carried out in the same manner as in Example 1 except that 0.005 mmol was added and hydrogen was added at 0.05 MPa, and the obtained propylene polymer was evaluated. The results are shown in Table 1.

Example 3 (1) Preparation of solid catalyst component In Example 1 (1), the gram atom ratio of iodine / Mg was 0.00019, and the average particle size (D ₅₀ was produced at a reaction temperature of 50 ° C.). ) Was 10 μm, and a solid catalyst component was prepared and evaluated in the same manner as in Example 1 except that diethoxymagnesium was used. The results are shown in Table 1.

(2) Propylene Polymerization In Example 1 (2), propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (1) above was used to obtain the propylene polymer. Was evaluated. The results are shown in Table 1.

Example 4 (1) Preparation of solid catalyst component In Example 1 (1), the gram atom ratio of iodine / Mg was 0.019, and the average particle size (D ₅₀ was produced at a reaction temperature of 78 ° C.). ) Was 70 μm, and a solid catalyst component was prepared and evaluated in the same manner as in Example 1 except that diethoxymagnesium was used. The results are shown in Table 1.

(2) Propylene Polymerization Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (1) above was used in Example 1 (2) to obtain a propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

Example 5 (1) Preparation of solid catalyst component A three-necked flask with an internal volume of 0.5 liter equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane and diethoxymagnesium (metal magnesium) were used. , Ethanol and iodine, iodine / Mg: 0.01
9g atomic ratio, reaction temperature: manufactured by reacting at 78 ° C,
16 g of D ₅₀ : 70 μm) was added. After heating to 40 ° C., 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) was added and stirred for 4 hours, and then 47 ml of titanium tetrachloride was added dropwise. The temperature of this solution was raised to 65 ° C., 3.4 ml of di-n-butyl phthalate was added, and then the temperature was raised to 125 ° C., followed by an internal temperature of 125 ° C.
The mixture was stirred for 1 hour and contacted. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Add 100 ml of dehydrated octane and stir to 125
After the temperature was raised to 0 ° C. and the temperature was maintained for 1 minute, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Then, 77 ml of titanium tetrachloride was added, and a contact operation was carried out by stirring at an internal temperature of 125 ° C. for 2 hours. The stirring was stopped to settle the solid, and the supernatant was extracted. Further, 100 ml of dehydrated octane was added and the mixture was stirred at room temperature. The stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in the above (1) was used to obtain a propylene polymer obtained. The coalescence was evaluated. The results are shown in Table 1.

Example 6 (1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter equipped with a stirrer with nitrogen gas, 80 ml of dehydrated octane and diethoxymagnesium (metal magnesium) were replaced. , Ethanol and iodine, iodine / Mg: 0.01
9g atomic ratio, reaction temperature: manufactured by reacting at 78 ° C,
16 g of D ₅₀ : 70 μm) was added. The mixture was heated to 40 ° C., 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) was added, and the mixture was stirred for 4 hours.
3.4 ml of n-butyl was added. The temperature of this solution was raised to 65 ° C., 47 ml of titanium tetrachloride was subsequently added dropwise, and the mixture was stirred at an internal temperature of 125 ° C. for 1 hour to perform a contact operation. After that, stirring is stopped and the solid is allowed to settle,
The supernatant liquid was extracted. 100 ml of dehydrated octane was added, the temperature was raised to 125 ° C. with stirring, the temperature was maintained for 1 minute, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. After that, 77 ml of titanium tetrachloride was added, and the internal temperature was 125 ° C.
The mixture was stirred for 2 hours to carry out a contact operation, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Further, 100 ml of dehydrated octane was added and the mixture was stirred at room temperature. The stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in the above (1) was used to obtain a propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

Example 7 (1) Preparation of solid catalyst component A three-necked flask having an internal volume of 0.5 liter and equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane and diethoxymagnesium (metal magnesium) were used. , Ethanol and iodine, iodine / Mg: 0.01
9g atomic ratio, reaction temperature: manufactured by reacting at 78 ° C,
16 g of D ₅₀ : 70 μm) was added. The mixture was heated to 40 ° C., 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) was added, and the mixture was stirred for 4 hours.
3.4 ml of n-butyl was added. The temperature of this solution was raised to 65 ° C., 47 ml of titanium tetrachloride was subsequently added dropwise, and the mixture was stirred at an internal temperature of 125 ° C. for 1 hour to perform a contact operation. After that, stirring is stopped and the solid is allowed to settle,
The supernatant liquid was extracted. 100 ml of dehydrated octane was added, the temperature was raised to 125 ° C. with stirring, the temperature was maintained for 1 minute, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. After that, 77 ml of titanium tetrachloride was added, and the internal temperature was 125 ° C.
After stirring for 1 hour to perform a contact operation, stirring was stopped to settle the solid, and the supernatant was extracted, and then the above washing with dehydrated octane at 125 ° C. was repeated 7 times. Furthermore, once again, 77 ml of titanium tetrachloride was added, and the internal temperature was 125.
The contact operation was performed at 2 ° C. with stirring for 2 hours. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Further, 100 ml of dehydrated octane was added and the mixture was stirred at room temperature. The stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in (1) above was used to obtain the propylene polymer obtained. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 1 (1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter equipped with a stirrer with nitrogen gas, 80 ml of dehydrated octane and diethoxymagnesium (metal magnesium) were replaced. , Ethanol and iodine, iodine / Mg: 0.01
9g atomic ratio, reaction temperature: manufactured by reacting at 78 ° C,
16 g of D ₅₀ : 70 μm) was added. The mixture was heated to 40 ° C., 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) was added, and the mixture was stirred for 4 hours.
3.4 ml of n-butyl was added. The temperature of this solution was raised to 65 ° C., 47 ml of titanium tetrachloride was subsequently added dropwise, and the mixture was stirred at an internal temperature of 125 ° C. for 1 hour to perform a contact operation. After that, stirring is stopped and the solid is allowed to settle,
The supernatant liquid was extracted. Further, 100 ml of dehydrated octane was added and the mixture was stirred at room temperature. The stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in the above (1) was used to obtain a propylene polymer obtained. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 2 (1) Preparation of Solid Catalyst Component A solid catalyst component was prepared and evaluated in the same manner as in Example 5 except that the treatment step with silicon tetrachloride was omitted in Example 5 (1). . The results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in the above (1) was used to obtain the propylene polymer obtained. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 3 (1) Preparation of solid catalyst component In the same manner as in Example 5 except that 0.8 ml of silicon tetrachloride (halogen / alkoxy group: 0.10) was used in Example 5 (1). Then, a solid catalyst component was prepared and evaluated. The results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in (1) above was used to obtain the propylene polymer obtained. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 4 (1) Preparation of solid catalyst component A three-necked flask having an internal volume of 0.5 liter and equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane and diethoxymagnesium (metal magnesium) were used. , Ethanol and iodine, iodine / Mg: 0.01
9g atomic ratio, reaction temperature: manufactured by reacting at 78 ° C,
16 g of D ₅₀ : 70 μm) was added. After heating to 50 ° C. and adding 4.8 ml of silicon tetrachloride (halogen / alkoxy group: 0.60) and stirring for 20 minutes, 2.5 ml of diethyl phthalate was added. Add this solution to 7
The temperature was raised to 0 ° C., 47 ml of titanium tetrachloride was subsequently added dropwise, and the internal temperature was 110 ° C. The mixture was stirred for 2 hours for contact operation. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. 100 ml of dehydrated octane was added, the temperature was raised to 90 ° C. with stirring, the temperature was maintained for 1 minute, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Then, 77 ml of titanium tetrachloride was added, and a contact operation was carried out by stirring at an internal temperature of 110 ° C. for 2 hours, stirring was stopped to precipitate a solid, and a supernatant was taken out. Then, 100 ml of dehydrated octane was added and stirred at room temperature, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. Table 1 shows the evaluation results
Shown in.

(2) Propylene Polymerization Propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in (1) above was used in Example 2 (2) to obtain a propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 5 (1) Preparation of solid catalyst component In Comparative Example 2 (1), diethoxymagnesium having an average particle size (D ₅₀ ) of 540 μm synthesized at a reaction temperature of 78 ° C. was used in a ball mill without using iodine. A solid catalyst component was prepared and evaluated in the same manner as in Comparative Example 2 except that the carrier pulverized for 24 hours was used. The results are shown in Table 1.

(2) Propylene Polymerization In Example 2 (2), propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component prepared in (1) above was used to obtain the propylene polymer obtained. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 6 (1) Preparation of solid catalyst component Same as Example 4 except that 2.4 ml of silicon tetrachloride (halogen / alkoxy group: 0.30) was used in Example 4 (1). Then, a solid catalyst component was prepared and evaluated. The results are shown in Table 1.

(2) Propylene Polymerization Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (1) above was used in Example 1 (2) to obtain propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

[0117]

[Table 1]

As can be seen from Table 1, it was confirmed that the propylene polymers of the examples had high polymerization activity and were excellent in stereoregularity and powder form.

[0119]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization and a method for producing an olefin polymer, which can obtain an olefin polymer having a high polymerization activity and an excellent powder form.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a method for producing an olefin polymerization catalyst and an olefin polymer of the present invention.

Continued front page    F-term (reference) 4J128 AA02 AA03 AB01 AB02 AB03                       AC04 AC05 AC06 BA00A                       BA01B BB00A BB01B BC07A                       BC15B BC25B CA05A CA06A                       CA08A CA14A CA15A CA16A                       CB22A CB22C CB35A CB36A                       CB42A CB42C DB02A EA01                       EB01 EB02 EB04 EB05 EB07                       EB08 EB09 EB10 EB13 EB14                       EC01 EC02 GA04 GA09 GA14                       GA24 GB01 GB02

Claims (15)

[Claims] 1. The following compounds (a) to (c-1) or the following compounds (a) to (d) are reacted at a temperature of 120 ° C. or higher and 150 ° C. or lower, washed with an inert solvent, and further 1 More than once, halogen-containing titanium compound (a) 120 ° C or more 1
A solid catalyst component for olefin polymerization obtained by reacting at a temperature of 50 ° C. or lower and washing with an inert solvent. (A) Halogen-containing titanium compound (b) Alkoxy group-containing magnesium compound (c-1) Halogen-containing silicon compound (d) in which the molar ratio of halogen to alkoxy group in the alkoxy group-containing magnesium compound (b) is 0.50 or more. ) Electron-donating compound 2. The solid catalyst component for olefin polymerization according to claim 1, wherein the temperature of washing with the inert solvent after the first reaction is 100 ° C. or higher and 150 ° C. or lower. 3. The solid catalyst component for olefin polymerization according to claim 1, wherein the molar ratio (RO / Ti) of the residual amount of alkoxy groups (RO) to the amount of titanium supported (Ti) is 0.30 or less. 4. The molar ratio of the residual amount of alkoxy group (RO) to the amount of supported titanium (Ti), which is obtained by reacting the following compounds (a) to (c) or the following compounds (a) to (d): Solid catalyst component for olefin polymerization having a RO / Ti) of 0.30 or less. (A) Halogen-containing titanium compound (b) Alkoxy group-containing magnesium compound (c) Halogen-containing silicon compound (d) Electron-donating compound 5. The compound (c) is the compound (b).
The molar ratio of halogen to the alkoxy group in is 0.50
The solid catalyst component for olefin polymerization according to claim 4, which is the above halogen-containing silicon compound. 6. The compound (b) is obtained by reacting metal magnesium, alcohol, and a halogen and / or a halogen-containing compound containing 0.0001 gram atom or more of a halogen atom with respect to 1 mol of the metal magnesium. The solid catalyst component for olefin polymerization according to claim 1, which is a compound. 7. The solid catalyst component for olefin polymerization according to claim 6, wherein the reaction temperature of the metal magnesium, the alcohol, and the halogen and / or the halogen-containing compound is 30 to 60 ° C. 8. The solid catalyst component for olefin polymerization according to claim 1, wherein the compound (b) has an average particle diameter (D ₅₀ ) of 50 μm or less. 9. The solid catalyst component for olefin polymerization according to claim 1, wherein the compound (b) is dialkoxymagnesium. 10. The solid catalyst component for olefin polymerization according to claim 1, wherein the compounds (c) and (c-1) are silicon tetrachloride. 11. The molar ratio (RO / Ti) is 0.20.
It is the following, The solid catalyst component for olefin polymerization as described in any one of Claims 3-10. 12. The residual amount (RO) of the alkoxy group is 0.13.
The solid catalyst component for olefin polymerization according to any one of claims 1 to 11, which has a mmol / g or less. 13. The solid catalyst component for olefin polymerization according to claim 1, wherein the amount of titanium supported is 1.5% by weight or more. 14. A catalyst for olefin polymerization containing the following components [A], [B] or the following components [A], [B], [C]. [A] Solid catalyst component for olefin polymerization [B] Organoaluminum compound [C] Electron donating compound according to any one of claims 1 to 13. 15. A method for producing an olefin polymer, in which an olefin is polymerized using the olefin polymerization catalyst according to claim 14.