JP2018188382A - Method for producing dialkoxymagnesium, catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing dialkoxymagnesium that makes it possible to obtain dialkoxymagnesium having a smooth surface, a large average particle size, and a narrow particle size distribution.SOLUTION: The present invention provides a method for producing dialkoxymagnesium including preparing dialkoxymagnesium by the reaction between magnesium metal and alcohol in the presence of a reaction promoter, where the reaction promoter is a carboxylic acid monohalogen compound or dicarboxylic acid dihalogen compound represented by formula (1) (Ris a C1-20 a hydrocarbon group; Z is Cl or Br).SELECTED DRAWING: Figure 1

Description

  TECHNICAL FIELD The present invention relates to a method for producing dialkoxymagnesium, and more particularly to a method for producing dialkoxymagnesium suitable for a carrier raw material for a catalyst component for olefin polymerization. The present invention also provides an olefin polymerization catalyst component using dialkoxymagnesium obtained by the dialkoxymagnesium production method, an olefin polymerization catalyst using the catalyst component, and an olefin polymer production using the catalyst. Regarding the method.

  Conventionally, as an olefin polymerization method, there is an olefin polymerization catalyst comprising a solid catalyst component obtained by bringing dialkoxymagnesium, a titanium halongen compound and an internal electron donating compound into contact with each other, and an organoaluminum compound. A number of methods for polymerizing olefins in which olefins are polymerized or copolymerized have been proposed.

  In such olefin polymerization methods, the shape of the resulting polyolefin depends on the shape of the solid catalyst component used in the polymerization, so control of the morphology (particle structure) of the solid catalyst component is important, and many studies have been made. Has been made.

  Under such circumstances, in the polymerization of olefins, one of the requirements for shape control of polyolefin polymer particles is that the particle surface is smooth, the average particle size is large, and the particle size distribution is narrow. In order to obtain a polyolefin having a large average particle size, a narrow particle size distribution, and a smooth surface, a solid catalyst component having a large average particle size, a narrow particle size distribution, and a smooth surface is required.

  Here, the particle structure of the solid catalyst component depends on the particle structure of dialkoxymagnesium serving as a carrier for the solid catalyst component. In other words, in order to obtain a polyolefin having a smooth surface, a large average particle diameter and a narrow particle size distribution, dialkoxymagnesium having a smooth surface, a large average particle diameter and a narrow particle size distribution is required.

  As a method for producing dialkoxymagnesium, for example, Patent Document 1 discloses a method of reacting metal magnesium and ethanol under pressure without using a reaction accelerator.

  Patent Document 2 discloses a method in which metallic magnesium and absolute ethanol are reacted in the presence of iodine as a reaction accelerator.

  Patent Documents 3 and 4 disclose a method of adding iodine, which is a reaction accelerator, to a reaction system in a plurality of times in a method of reacting metal magnesium and alcohol in the presence of a reaction accelerator. ing.

JP 2010-202667 A JP-A-3-74341 JP2013-95890A International Publication No. 2013/058193

  However, since only the amorphous diethoxymagnesium can be obtained by the production method of Patent Document 1, it is not suitable as diethoxymagnesium as a raw material for producing the solid catalyst component.

  Moreover, in the manufacturing method of patent document 2, only a small diethoxymagnesium whose average particle diameter is about 20 micrometers is obtained.

  In addition, in the production methods of Patent Documents 3 and 4, although there are examples in which the average particle size exceeds 50 μm, from the viewpoint of improving fluidity and reducing the amount of fine powder generated, in the smoothness of the particle surface, Further improvement is required.

  Accordingly, an object of the present invention is to provide a method for producing dialkoxymagnesium in which dialkoxymagnesium having a smooth particle surface, a large average particle size and a narrow particle size distribution can be obtained.

  In such a situation, the present inventors have intensively studied, and as a result, by using a specific carboxylic acid halogen compound as a reaction accelerator when reacting magnesium metal and alcohol, the surface of the particles is smooth, The inventors have found that dialkoxymagnesium having a large particle size and a narrow particle size distribution can be obtained, and have completed the present invention.

That is, the present invention (1) is a method for producing dialkoxymagnesium to obtain dialkoxymagnesium by reacting metal magnesium and alcohol in the presence of a reaction accelerator,
The reaction accelerator is represented by the following general formula (1):

(In the formula, Z is Cl or Br. R ¹ is a hydrocarbon group having 1 to 20 carbon atoms.)
Or a carboxylic acid monohalogen compound represented by the following general formula (2):

(In the formula, R ² is a hydrocarbon group having 1 to 20 carbon atoms. Z is Cl or Br, and the two Zs may be the same or different from each other.)
A dicarboxylic acid dihalogen compound represented by:
A method for producing dialkoxymagnesium, wherein

  In the invention (2), the reaction accelerator is any one selected from an aliphatic carboxylic acid dihalogen compound, an aliphatic dicarboxylic acid dihalogen compound, an aromatic carboxylic acid monohalogen compound, and an aromatic dicarboxylic acid dihalogen compound. The method for producing dialkoxymagnesium as described in (1) above is provided.

  In addition, the present invention (3) provides the method for producing dialkoxymagnesium according to either (1) or (2), wherein the alcohol is ethanol.

  In addition, the present invention (4) includes dialkoxymagnesium (a) obtained by performing the method for producing dialkoxymagnesium according to any one of (1) to (3), a titanium halogen compound (b), and an electron donating compound. The solid catalyst component for olefin polymerization is provided, which is obtained by contacting (c).

In addition, the present invention (5) includes (A) (4) a solid catalyst component for olefin polymerization, (B) the following general formula (IV):
R ¹⁵ _p AlQ _3-p (IV)
^{(Wherein, R 15} represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 ^{<.R 15} is a real number p ≦ 3 there are a plurality, each R ¹⁵ may be the same as or different from each other, and when a plurality of Qs are present, each Q may be the same or different.)
And (C) an olefin polymerization catalyst characterized by comprising an external electron donating compound.

In the present invention (6), the external electron donating compound (C) is represented by the following general formula (V):
R ¹⁶ _q Si (OR ¹⁷ ) _4-q (V)
(In the formula, R ¹⁶ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, carbon an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent having 6 to 15, if R ¹⁶ there are a plurality, a plurality of R ¹⁶ may be the same or different from each other R ¹⁷ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. an aromatic hydrocarbon group having 7 to 12 carbon atoms having, if R ¹⁷ there are a plurality, the plurality of R ¹⁷ may be the same or different from each other .q is an integer of 0 ≦ q ≦ 3. )
And an organic silicon compound represented by the general formula (VI):
(R ¹⁸ R ¹⁹ N) _s SiR ²⁰ _4-s (VI)
(In the formula, R ¹⁸ and R ¹⁹ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms. A cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, R ¹⁸ and R ¹⁹ may be the same or different from each other, and may be bonded to each other to form a ring. R ¹⁸ R ¹⁹ N group When a plurality of R ¹⁸ R ¹⁹ N groups are present, the plurality of R ¹⁸ R ¹⁹ N groups may be the same as or different from each other, and R ²⁰ represents an alkyl group having 1 to ²⁰ carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon number. 1-20 alkoxy group, vinyloxy group, C3-C20 alkenyloxy group, C3-C20 cycloalkyl group, C3-C20 cycloalkyloxy group, C6-C20 aryl Group, an aryloxy group having 6 to 20 carbon atoms, if R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different .s is an integer from 1 to 3.)
(5) A catalyst for olefin polymerization according to (5), which is at least one selected from aminosilane compounds represented by the formula:

  Moreover, this invention (7) provides the manufacturing method of the olefin polymer characterized by superposing | polymerizing olefins in presence of the catalyst for olefin polymerization of either (5) or (6). is there.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of dialkoxymagnesium from which the particle surface is smooth, an average particle diameter is large, and the dialkoxymagnesium with a narrow particle size distribution can be obtained can be provided.

2 is a scanning electron micrograph (SEM) of Example 1. FIG. 2 is a scanning electron micrograph (SEM) of Comparative Example 1. 6 is a scanning electron micrograph (SEM) of Comparative Example 3. 6 is a scanning electron micrograph (SEM) of Comparative Example 4.

The method for producing dialkoxymagnesium according to the present invention is a method for producing dialkoxymagnesium, wherein metalmagnesium and alcohol are reacted in the presence of a reaction accelerator to obtain dialkoxymagnesium,
The reaction accelerator is represented by the following general formula (1):

(In the formula, Z is Cl or Br. R ¹ is a hydrocarbon group having 1 to 20 carbon atoms.)
Or a carboxylic acid monohalogen compound represented by the following general formula (2):

(In the formula, Z is Cl or Br, and may be the same or different. R ² is a hydrocarbon group having 1 to 20 carbon atoms.)
A dicarboxylic acid dihalogen compound represented by:
Is a method for producing dialkoxymagnesium.

  The shape of the metallic magnesium according to the method for producing dialkoxymagnesium of the present invention is not particularly limited, and examples thereof include granules, ribbons, and powders. Among these, the powdered metal magnesium is preferable as the metal magnesium, and the average particle diameter of the powdered metal magnesium is preferably 10 to 1000 μm, more preferably 20 to 800 μm, and particularly preferably 50 to 500 μm. Although the surface state of metallic magnesium is not particularly limited, it is preferably one in which a film such as magnesium oxide is not formed on the surface. The content of the fine powder component having an average particle size of less than 5 μm in the magnesium metal is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, and the average particle size is 500 μm or more. The content of the coarse powder component is preferably 10% by mass or less, more preferably 5% by mass or less.

  The alcohol according to the method for producing dialkoxymagnesium of the present invention is not particularly limited, and for example, a lower alcohol having 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol, hexanol and the like is preferable, and ethanol is particularly preferable. The water content of the alcohol is not particularly limited, but the lower the water content, the better, and the anhydrous alcohol or the dehydrated alcohol having a water content of 200 ppm or less is particularly preferable.

  In the method for producing dialkoxymagnesium of the present invention, the following general formula (1) is used with metal magnesium and alcohol as a reaction accelerator:

Or a carboxylic acid monohalogen compound represented by the following general formula (2):

It reacts using the dicarboxylic acid dihalogen compound represented by these.

In the general formula (1), ^{R 1} is a hydrocarbon group having 1 to 20 carbon atoms. Examples of R ¹ include a saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 20 carbon atoms, and more specifically, a linear alkyl group having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms. An alkyl group, a vinyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group, or an aromatic group; Chain alkyl group, branched alkyl group having 3 to 12 carbon atoms, vinyl group, straight chain alkenyl group having 3 to 12 carbon atoms, branched chain alkenyl group having 3 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, A C5-C10 cycloalkenyl group and a C6-C10 aromatic group are preferable, a C1-C8 linear alkyl group, a C3-C8 branched alkyl group, a vinyl group, carbon number 3-8 linear alkenyl groups, carbon A branched alkenyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, and an aromatic group having 6 to 10 carbon atoms are particularly preferable. Z is a chlorine atom or a bromine atom, and as Z, a chlorine atom is preferable.

  Examples of the carboxylic acid monohalogen compound represented by the general formula (1) include propionic acid chloride, caproic acid chloride, caprylic acid chloride, pelargonic acid chloride, capric acid chloride, lauric acid chloride, myristic acid chloride, and palmitic acid chloride. , Isopalmitic acid chloride, stearic acid bromide, isostearic acid bromide, oleic acid bromide, propionic acid bromide, caproic acid bromide, caprylic acid bromide, pelargonic acid bromide, capric acid bromide, lauric acid bromide, myristic acid bromide, palmitic acid bromide, Isopalmitic acid bromide, stearic acid bromide, isostearic acid bromide, oleic acid bromide, methacrylic acid chloride, Kosan chloride, phenylacetic acid chloride, trimethoxy benzoic acid chloride include trimellitic anhydride acid chloride and the like. Among these, propionic acid chloride, caproic acid chloride, caprylic acid chloride, and benzoic acid chloride are preferable in that the reactivity of metal magnesium and alcohol can be appropriately controlled.

In the general formula (2), ^{R 2} is a hydrocarbon group having 1 to 20 carbon atoms. R ² is a divalent linking group having 1 to 20 carbon atoms to which two acid halide groups (—C (═O) —X) are bonded, preferably two acid halides bonded to R ² A divalent linking group having 1 to 12 carbon atoms bonded by a carbon chain between the groups, and more preferably, the two acid halide groups bonded to R ² are composed of two carbon atoms. It is a C1-C12 bivalent bonding group. Specifically, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, a vinylene group, a linear alkenylene group having 3 to 12 carbon atoms or a branched alkenylene group, 3 to 3 carbon atoms, A cycloalkylene group having 12 carbon atoms, a cycloalkenylene group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. Incidentally, in the case where R ² is a cyclic group such as a cycloalkylene group, cycloalkenylene group or an aromatic hydrocarbon group, between 2 Tsunosan halide groups attached to R ² is composed of two carbon atoms The bonding group having a meaning means that two adjacent carbon chains in the carbon chain constituting the ring are carbon chains between two acid halide groups to which R ² is bonded. Z is a chlorine atom or a bromine atom, and a chlorine atom is preferable. Two Z's may be the same as or different from each other.

  Examples of the dicarboxylic acid dihalogen compound represented by the general formula (2) include malonic acid dichloride, malonic acid dibromide, diethylmalonic acid dichloride, diisobutylmalonic acid dichloride, terephthalic acid dichloride, phthalic acid dichloride, phthalic acid dibromide, o-toluic acid dichloride, m-toluic acid dichloride, 4,4′-biphenyldicarbonyl chloride) and the like. Among these, as the dicarboxylic acid dihalogen compound represented by the general formula (2), phthalic acid dichloride, o-toluic acid dichloride, and m-toluic acid dichloride can appropriately control the reactivity of metal magnesium and alcohol. ,preferable.

  In the method for producing dialkoxymagnesium of the present invention, the molar ratio of alcohol to metal magnesium (alcohol / metal magnesium) is preferably 2 to 100, particularly preferably 5 to 50. When the molar ratio of the alcohol to the metal magnesium is within the above range, dialkoxymagnesium having a good particle shape, a large average particle size and a narrow particle size distribution can be obtained with good yield.

  In the method for producing dialkoxymagnesium of the present invention, a reaction accelerator for metal magnesium (a carboxylic acid monohalogen compound represented by the general formula (1) or a dicarboxylic acid dihalogen compound represented by the general formula (2), The molar ratio (represented by the reaction accelerators according to the general formulas (1) to (2)) (reaction accelerators according to the general formulas (1) to (2) / metal magnesium) is preferably 0.0005 to 0.1. And particularly preferably in the range of 0.001 to 0.01. When the molar ratio of the reaction accelerator to metal magnesium is in the above range, the dialkoxymagnesium obtained has a good particle shape and bulk density and a narrow particle size distribution.

  In the dialkoxymagnesium production method of the present invention, the metal magnesium and the alcohol are reacted with stirring in a suspended state in which the metal magnesium is dispersed in the alcohol. And in the manufacturing method of dialkoxymagnesium of this invention, the reaction promoter which concerns on general formula (1)-(2) is mixed with alcohol previously, and reaction promotion which concerns on general formula (1)-(2) is carried out. The reaction accelerator according to the general formulas (1) to (2) is introduced into the reaction system by mixing the alcohol containing the agent and the metal magnesium, and the metal magnesium and the alcohol are converted into the general formula (1). The reaction is carried out in the presence of the reaction accelerator according to (2). In the method for producing dialkoxymagnesium of the present invention, the introduction of the reaction accelerator according to the general formulas (1) to (2) into the reaction system may be performed at once, or may be performed in multiple steps. Also good. That is, in the method for producing dialkoxymagnesium of the present invention, the whole amount of the reaction accelerator according to the general formulas (1) to (2) may be mixed together with the metal magnesium and the alcohol, or the metal magnesium and the alcohol After mixing, before starting the reaction, the total amount of the reaction accelerator according to the general formulas (1) to (2) may be added, or together with the metal magnesium and alcohol, the general formulas (1) to (1) After the reaction is started with a part of the reaction accelerator according to (2) being present, the reaction accelerators according to the general formulas (1) to (2) are added at once or a plurality of times while the reaction is continued. It may be added to the reaction system separately. In the method for producing dialkoxymagnesium of the present invention, the introduction of metal magnesium and alcohol into the reaction system may be performed at once, or may be performed in multiple steps. That is, in the dialkoxymagnesium production method of the present invention, the reaction may be started from the beginning using the whole amount of metal magnesium and alcohol, or after the reaction is started using a part of metal magnesium and alcohol. During the reaction, the remaining metal magnesium and alcohol may be added to the reaction system at one time or in several portions.

  The reaction temperature in the method for producing dialkoxymagnesium of the present invention is not particularly limited as long as it is not higher than the boiling point of the raw material mixture, preferably 30 to 100 ° C, particularly preferably 50 to 90 ° C, and the reaction time is Preferably it is in the range of 0.5 to 15 hours, particularly preferably 1 to 10 hours, and the reaction atmosphere is an inert gas atmosphere.

  After performing the dialkoxymagnesium production method of the present invention, the obtained dialkoxymagnesium is dried by a method such as heat drying, airflow drying or reduced pressure drying, or washed with an inert hydrocarbon compound. To remove alcohol from dialkoxymagnesium.

  In the method for producing dialkoxymagnesium of the present invention, since the reaction accelerator is a reaction accelerator according to the general formulas (1) to (2), the surface is smooth, the average particle size is large, and the particle size distribution is narrow. Dialkoxymagnesium is obtained.

  In the method for producing dialkoxymagnesium of the present invention, the reaction accelerator according to the general formulas (1) to (2) used as the reaction accelerator is a carboxylic acid monohalogen compound represented by the general formula (1) after the reaction. Or dicarboxylic acid diester corresponding to the dicarboxylic acid dihalogen compound represented by the general formula (2), and remains in dialkoxymagnesium. Here, the carboxylic acid ester corresponding to the carboxylic acid monohalogen compound represented by the general formula (1) or the dicarboxylic acid diester corresponding to the dicarboxylic acid dihalogen compound represented by the general formula (2) is used for olefin polymerization. The Ziegler-Natta catalyst functions as an internal electron donor that plays an important role in improving olefin polymerization performance, particularly stereospecificity. Therefore, in the method for producing dialkoxymagnesium of the present invention, the carboxylic acid ester corresponding to the carboxylic acid monohalogen compound represented by the general formula (1) derived from the reaction accelerator, or represented by the general formula (2) Whether the dicarboxylic acid diester corresponding to the dicarboxylic acid dihalogen compound remains in the product dialkoxymagnesium, does not adversely affect the Ziegler-Natta catalyst for olefin polymerization obtained using the dialkoxymagnesium, Alternatively, dialkoxymagnesium that can improve the catalyst performance can be obtained.

  On the other hand, in the production of dialkoxymagnesium, when iodine is used as a reaction accelerator for the reaction between metal magnesium and alcohol, iodine is mixed in the resulting dialkoxymagnesium, and washing is performed. Iodine remains in dialkoxymagnesium because iodine cannot be completely removed from dialkoxymagnesium. And if a solid catalyst component is manufactured using dialkoxymagnesium in which iodine remains, the residual iodine causes a decrease in performance of the solid catalyst component.

  In addition, in the production of dialkoxymagnesium, when iodine is used as a reaction accelerator for the reaction between metal magnesium and alcohol, if iodine as a reaction accelerator is introduced into the reaction system at once, the average particle size is Since a large dialkoxymagnesium cannot be obtained, it is necessary to add iodine in two or more portions. On the other hand, in the method for producing dialkoxymagnesium of the present invention, dialkoxymagnesium having a large average particle diameter is obtained even if the reaction accelerators according to the general formulas (1) to (2) are introduced into the reaction system at once. Or, compared to the case of using iodine as a reaction accelerator, dialkoxymagnesium having a large average particle diameter can be obtained even if the number of divided additions is small.

  The sphericity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention is preferably 2 or less, particularly preferably 1.5 or less. In the present invention, the sphericity of dialkoxymagnesium is measured by an image analysis apparatus (Mac-View, manufactured by Mountec Co., Ltd.).

The average particle diameter (D ₅₀ ) of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention is 5 μm or more, preferably 8 to 100 μm, particularly preferably 10 to 80 μm. The particle size distribution index of dialkoxy magnesium obtained performed a method of manufacturing a dialkoxy magnesium present invention _{(SPAN) (SPAN = (D} 90 -D 10) / D 50) is 2.0 or less, preferably 1.5 or less Particularly preferably, it is 1.0 or less. In the present invention, D ₁₀ , D ₅₀ , and D ₉₀ are integrated volume fractions in the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring device (MICROTRAC HRA Model No. 9320-X100, manufactured by Nikkiso Co., Ltd.). Indicates particle diameters (μm) corresponding to 10%, 50%, and 90%, respectively.

  The dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention does not contain iodine derived from the reaction accelerator.

  The bulk specific gravity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention is preferably 0.1 to 0.6 g / ml, more preferably 0.2 to 0.5 g / ml, particularly preferably 0. .25 to 0.40 g / ml.

  The dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention preferably contains no alcohol, but is acceptable if the alcohol content is 2% by mass or less.

  Dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention is suitably used as dialkoxymagnesium as a raw material for producing a solid catalyst component for olefin polymerization. In particular, dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the present invention is used for producing a solid catalyst component for producing polyolefins having a smooth particle surface, a large average particle size and a narrow particle size distribution. Suitable as raw material alkoxymagnesium.

  The solid catalyst component for olefin polymerization using the dialkoxymagnesium obtained as a raw material by the dialkoxymagnesium production method of the present invention, and the olefins polymerization catalyst as dialkoxymagnesium, the dialkoxymagnesium production method of the present invention There is no particular limitation except that dialkoxymagnesium obtained by the above is used, and it is appropriately selected.

  Examples of the solid catalyst component for olefin polymerization include the following solid catalyst components for olefin polymerization.

  The solid catalyst component for olefin polymerization of the present invention comprises dialkoxymagnesium (a) obtained by performing the dialkoxymagnesium production method of the present invention, a titanium halogen compound (b), an electron donating compound (c), It is a solid catalyst component for olefin polymerization, characterized in that it is obtained by contacting with.

  The details of the method for producing dialkoxymagnesium (a) according to the solid catalyst component for olefin polymerization of the present invention are as described above.

  As the titanium halogen compound (b) constituting the solid catalyst component for olefin polymerization of the present invention, one or more selected from known materials may be mentioned, a tetravalent titanium halogen compound is preferable, and titanium tetrachloride is more preferable.

  Examples of the electron donating compound (c) constituting the solid catalyst component for olefin polymerization of the present invention include one or more selected from known materials, and an organic compound having an oxygen atom or a nitrogen atom is preferable.

  The electron donating compound (c) is preferably at least one selected from succinic acid esters, maleic acid esters, cyclohexene carboxylic acid esters, ether carboxylic acid esters, dicarbonates, and ether carbonates.

  In the solid catalyst component for olefin polymerization of the present invention, the content of titanium atom, magnesium atom, halogen atom and electron donating compound is not particularly defined.

  In the solid catalyst component for olefin polymerization of the present invention, the content of titanium atoms is preferably 0.5 to 8.0% by mass, more preferably 1.0 to 6.0% by mass, More preferably, it is 1.0-4.0 mass%.

  In the solid catalyst component for olefin polymerization of the present invention, the magnesium atom content is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, and 15 to 40% by mass. Is more preferable, and it is still more preferable that it is 15-25 mass%.

  In the solid catalyst component for olefin polymerization of the present invention, the halogen atom content is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 40 to 80% by mass. Is more preferable, and it is still more preferable that it is 45-75 mass%.

  In the solid catalyst component for olefin polymerization of the present invention, the total content of the electron donating compound (c) is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass. Preferably, it is 2-20 mass%, and it is still more preferable.

  In the solid catalyst component for olefin polymerization of the present invention, in order to exert its overall performance in a balanced manner, the titanium content is 1-4% by mass, the magnesium content is 15-25% by mass, and the halogen atom content is It is desirable that the content of the electron donating compound (c) is 45 to 75% by mass and 2 to 20% by mass.

  As a method for producing the solid catalyst component for olefin polymerization of the present invention, an alkoxymagnesium (a), a titanium halogen compound (b), and an electron donating compound (c) are mixed with an inert organic solvent having a boiling point of 50 to 150 ° C. The method of making it contact in presence of (d) is mentioned.

  Examples of the inert organic solvent (d) having a boiling point of 50 to 150 ° C. include one or more selected from toluene, xylene, ethylbenzene, heptane, octane, decane and the like. As the inert organic solvent (d) having a boiling point of 50 to 150 ° C., an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound are generally used, but the solubility of impurities does not decrease during the cleaning after the reaction or the reaction. If present, inert organic solvents other than aromatic hydrocarbons and saturated hydrocarbons may be used.

  Moreover, when manufacturing the solid catalyst component for olefin polymerization of this invention, you may add polysiloxane to a reaction system further. As the polysiloxane, conventionally known ones are appropriately selected, but at least one selected from decamethylcyclopentasiloxane and dimethylpolysiloxane is preferable, and decamethylcyclopentasiloxane is more preferable.

  The details of the method for preparing the solid catalyst component for olefin polymerization according to the present invention are the same as those for preparing a conventionally known solid catalyst component for olefin polymerization.

  As described above, the solid catalyst component for olefin polymerization of the present invention comprises dialkoxymagnesium (a), titanium halogen compound (b), and electrons obtained by performing the dialkoxymagnesium production method of the present invention. It is obtained by contacting and reacting with the donor compound (c).

  According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization that can form a polymer having a smooth particle surface, a large average particle size, and a narrow particle size distribution under high polymerization activity.

The olefin polymerization catalyst according to the present invention comprises (A) a solid catalyst component for olefin polymerization according to the present invention, (B) the following general formula (IV):
R ¹⁵ _p AlQ _3-p (IV)
^{(Wherein, R 15} represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 ^{<.R 15} is a real number p ≦ 3 there are a plurality, each R ¹⁵ may be the same as or different from each other, and when a plurality of Qs are present, each Q may be the same or different.)
And (C) an external electron donating compound. An olefin polymerization catalyst characterized by comprising:

  (A) The solid catalyst component for olefin polymerization of the present invention relating to the olefin polymerization catalyst according to the present invention is as described above.

The catalyst for olefin polymerization of the present invention comprises (B) the following general formula (IV):
R ¹⁵ _p AlQ _3-p (IV)
^{(Wherein, R 15} represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 ^{<.R 15} is a real number p ≦ 3 there are a plurality, each R ¹⁵ may be the same as or different from each other, and when a plurality of Qs are present, each Q may be the same or different.)
The organoaluminum compound represented by these is included.

Examples of the organoaluminum compounds represented by the general formula (IV), is not particularly limited, as R ¹⁵ is one or more selected from ethyl and isobutyl. Examples of the Q, hydrogen atom, a chlorine atom and One or more selected from bromine atoms can be mentioned, and p is preferably 2, 2.5 or 3, particularly preferably 3.

  Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum and triisobutylaluminum, alkylaluminum halide such as diethylaluminum chloride and diethylaluminum bromide, diethyl One or more selected from aluminum hydride and the like can be mentioned, and among them, one or more selected from halogenated alkylaluminum such as diethylaluminum chloride or trialkylaluminum such as triethylaluminum, tri-n-butylaluminum and triisobutylaluminum is preferable. More preferably one or more selected from triethylaluminum and triisobutylaluminum

  In the catalyst for olefin polymerization of the present invention, the external electron donating compound (C) is preferably a known external electron donating compound containing an oxygen atom or a nitrogen atom.

In the olefin polymerization catalyst of the present invention, the external electron donating compound (C) is represented by the following general formula (V):
R ¹⁶ _q Si (OR ¹⁷ ) _4-q (V)
(In the formula, R ¹⁶ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, carbon an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent having 6 to 15, if R ¹⁶ there are a plurality, a plurality of R ¹⁶ may be the same or different from each other R ¹⁷ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. an aromatic hydrocarbon group having 7 to 12 carbon atoms having, if R ¹⁷ there are a plurality, the plurality of R ¹⁷ may be the same or different from each other .q is an integer of 0 ≦ q ≦ 3. )
An organosilicon compound represented by the general formula (VI):
(R ¹⁸ R ¹⁹ N) _s SiR ²⁰ _4-s (VI)
(In the formula, R ¹⁸ and R ¹⁹ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms. A cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, R ¹⁸ and R ¹⁹ may be the same or different from each other, and may be bonded to each other to form a ring. R ¹⁸ R ¹⁹ N group When a plurality of R ¹⁸ R ¹⁹ N groups are present, the plurality of R ¹⁸ R ¹⁹ N groups may be the same as or different from each other, and R ²⁰ represents an alkyl group having 1 to ²⁰ carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon number. 1-20 alkoxy group, vinyloxy group, C3-C20 alkenyloxy group, C3-C20 cycloalkyl group, C3-C20 cycloalkyloxy group, C6-C20 aryl Group, an aryloxy group having 6 to 20 carbon atoms, if R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different .s is an integer from 1 to 3.)
1 type or more selected from the aminosilane compound represented by these.

  Examples of the organosilicon compound represented by the general formula (V) or the aminosilane compound represented by the general formula (VI) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and alkyl (cycloalkyl). Alkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkyl Amino) silane, trialkyl (alkylamino) silane and the like.

  Specific examples of the organosilicon compound represented by the general formula (V) or the aminosilane compound represented by the general formula (VI) include n-propyltriethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, and phenyl. Triethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di Cyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetrabutoxy Silane, bis (ethylamino) methylethylsilane, bis (ethylamino) t-butylmethylsilane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane One or more selected from diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and the like. Among them, n-propyltriethoxysilane, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, isopropyl Ruisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexyl One or more selected from silane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, diethylaminotriethoxysilane and the like are preferable.

  In the olefin polymerization catalyst of the present invention, (A) a solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound represented by the general formula (IV) and (C) an external electron donating compound The ratio is arbitrarily selected within the range in which the effects of the present invention can be obtained, and is not particularly limited. However, per mole of titanium atom in the solid catalyst component for olefin polymerization (A), The organoaluminum compound represented by IV) is preferably 1 to 2000 mol, and more preferably 50 to 1000 mol. Moreover, it is preferable that the (C) external electron donating compound is 0.002 to 10 mol per mol of the organoaluminum compound represented by (B) the general formula (IV), and 0.01 to 2 mol. More preferably, it is more preferably 0.01 to 0.5 mol.

The production method of the olefin polymerization catalyst of the present invention is not particularly limited, and (A) the solid catalyst component for olefin polymerization of the present invention, (B) the organoaluminum compound represented by the general formula (IV) and (C ) A method of producing an olefin polymerization catalyst by bringing an external electron donating compound into contact with each other by a known method.
The order in which the above components are brought into contact is arbitrary, but the following contact order can be exemplified.
(I) (A) Solid catalyst component for olefin polymerization of the present invention → (C) External electron donating compound → (B) Organoaluminum compound represented by general formula (IV) (ii) (B) General formula ( IV) Organoaluminum compound represented by (C) External electron donating compound → (A) Solid catalyst component for olefin polymerization of the present invention (iii) (C) External electron donating compound → (A) Solid catalyst component for olefin polymerization → (B) Organoaluminum compound represented by general formula (IV) (iv) (C) External electron donating compound → (B) Organoaluminum compound represented by general formula (IV) → (A) Solid catalyst component for olefin polymerization of the present invention Among the above contact examples (i) to (iv), the contact example (ii) is preferable.
In the above contact examples (i) to (iv), “→” means the contact order. For example, “(A) Solid catalyst component for olefin polymerization of the present invention → (B) in the general formula (IV)” The organoaluminum compound represented by formula (IV) is added to (A) the solid catalyst component for polymerizing olefins according to the present invention. (C) means that an external electron donating compound is added and contacted.

  The catalyst for olefin polymerization of the present invention comprises (A) a solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound represented by the general formula (IV) and (C) an external electron donating compound. It may be contacted in the absence of olefins, or may be contacted in the presence of olefins (in the polymerization system).

  According to the present invention, it is possible to provide an olefin polymerization catalyst having a smooth surface, a large average particle size, and a narrow particle size distribution.

  The method for producing an olefin polymer of the present invention is characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention.

  In the method for producing an olefin polymer of the present invention, the polymerization of olefins may be homopolymerization or copolymerization.

  In the method for producing an olefin polymer of the present invention, examples of the olefin include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like. Propylene or 1-butene is preferred, and propylene is more preferred.

  When polymerizing propylene, it may be copolymerized with other olefins, and is preferably block copolymerization of propylene and other α-olefins. A block copolymer obtained by block copolymerization is a polymer containing a segment in which two or more types of monomer compositions continuously change, and includes monomer type, comonomer type, comonomer composition, comonomer content, comonomer arrangement, and stereoregulation. It refers to a form in which two or more types of polymer chains (segments) having different primary structures of polymers are connected in one molecular chain. The olefin to be copolymerized is preferably an α-olefin having 2 to 20 carbon atoms (excluding propylene having 3 carbon atoms), and specifically, ethylene, 1-butene, 1-pentene, 4- Examples thereof include methyl-1-pentene and vinylcyclohexane. These olefins may be used in combination of one or more. In particular, ethylene and 1-butene are preferably used.

  In the method for producing an olefin polymer of the present invention, olefins can be polymerized in the presence or absence of an organic solvent. Moreover, in the manufacturing method of the olefin polymer of this invention, olefins used as superposition | polymerization object can be used in any state of gas and liquid.

  The polymerization of olefins. For example, in a reactor such as an autoclave, the olefins are introduced in the presence of the olefin polymerization catalyst of the present invention, and the olefins are polymerized under heating and pressure. be able to.

  In the method for producing an olefin polymer of the present invention, the polymerization temperature is usually 200 ° C. or lower, preferably 100 ° C. or lower, and more preferably 60 to 100 ° C. from the viewpoint of improving activity and stereoregularity. 70-90 degreeC is further more preferable. In the method for producing an olefin polymer of the present invention, the polymerization pressure is preferably 10 MPa or less, and more preferably 5 MPa or less. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  In the method for producing an olefin polymer of the present invention, when the olefin is polymerized (hereinafter, referred to as “main polymerization” as appropriate), the constituent components of the olefin polymerization catalyst of the present invention with respect to the olefin to be polymerized. Preliminary polymerization (hereinafter referred to as “preliminary polymerization” as appropriate) may be carried out by bringing a part or all of these into contact with each other.

  In the prepolymerization, the constituent components of the olefin polymerization catalyst of the present invention and the contact order of the olefins are arbitrary, but the organoaluminum compound is first put in the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere. After charging and then contacting the solid catalyst component for olefin polymerization of the present invention, one or more olefins such as propylene are preferably contacted. Alternatively, an organoaluminum compound is first charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, then contacted with an external electron donating compound, and further contacted with the solid catalyst component for olefin polymerization according to the present invention. Then, it is preferable to contact one or more olefins such as propylene. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used, and the prepolymerization conditions are the same as the above polymerization conditions.

  By performing the prepolymerization, the catalytic activity is improved, and the stereoregularity and particle properties of the resulting polymer can be further improved.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the olefin polymer which can manufacture the polymer with a smooth surface, a large average particle diameter, and a narrow particle size distribution under high polymerization activity can be provided.

  The method for producing an olefin polymer according to the present invention is particularly applied to a polyolefin production process by a gas phase method.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

(Example 1)
<Manufacture of diethoxymagnesium>
Metal magnesium powder (average particle diameter (D ₅₀ ): 118 μm, particles in a 2 L four-necked flask equipped with an integrating gas meter, dropping funnel, stirrer and reflux condenser and filled with nitrogen gas inside Diameter distribution index (SPAN): 1.36) 5 g, absolute ethanol 100 g and phthalic acid dichloride 0.8 g (4 mmol) were charged, and then heated to the reflux temperature of ethanol to maintain the reflux state. Next, a mixture of 2.5 g of metal magnesium powder and 25 g of ethanol was added in five portions.
After addition of the entire amount, heating under reflux was further continued for 2 hours to complete the reaction, and then the reaction solution was dried with a rotary evaporator to obtain 35 g of powdery diethoxymagnesium.
Next, the diethoxy magnesium thus obtained was measured average particle diameter _{(D 50)} and particle size distribution index of the (SPAN). Moreover, the particle | grain surface of the obtained diethoxymagnesium was observed with the scanning electron microscope (SEM). As a result, the surface of the diethoxymagnesium particles obtained in Example 1 was smoother than Comparative Examples 1 to 4. The evaluation results are shown in Table 1, and the SEM photograph is shown in FIG.

<Average particle diameter _{(D 50)} and SPAN Analysis>
Using a laser diffraction particle size distribution analyzer (MICROTRAC HRA Model No. 9320-X100, manufactured by Nikkiso Co., Ltd.), dialkoxymagnesium is dispersed in absolute ethanol, automatic measurement is performed twice, and the particle size distribution is measured and integrated. A particle diameter (D ₁₀ ) with a volume fraction of 10%, a particle diameter (D ₅₀ ) with an integrated volume fraction of 50%, and a particle diameter (D ₉₀ ) with an integrated volume fraction of 90% were determined, and the average value was calculated as D ₁₀ , D ₅₀ and D ₉₀ . Then, the obtained D ₅₀ value is used as an average particle diameter, and the SPAN is calculated from the obtained D ₁₀ , D ₅₀ and D ₉₀ values using the formula SPAN = (D ₉₀ −D ₁₀ ) / D _50. did.

(Example 2)
<Preparation of dialkoxymagnesium>
Diethoxymagnesium was produced and analyzed in the same manner as in Example 1 except that the amount of phthalic dichloride added was changed from 0.8 g (4 mmol) to 0.4 g (2 mmol).
In addition, the surface of the obtained diethoxymagnesium particles was smooth as compared with Comparative Example 1, Comparative Example 3, and Comparative Example 4. The analysis results are shown in Table 1.

(Comparative Example 1)
Production and analysis of diethoxymagnesium were carried out in the same manner as in Example 1 except that 0.5 g (4 mmol) of iodine was used instead of 0.8 g (4 mmol) of phthalic dichloride.
The analysis results of the obtained diethoxymagnesium are shown in Table 1. Moreover, the SEM photograph of the obtained diethoxymagnesium is shown in FIG.

(Comparative Example 2)
Diethoxymagnesium was produced and analyzed in the same manner as in Example 1 except that 0.38 g (4 mmol) of magnesium chloride was used instead of 0.8 g (4 mmol) of phthalic acid dichloride.
The analysis results of the obtained diethoxymagnesium are shown in Table 1.

(Comparative Example 3)
Diethoxymagnesium was produced and analyzed in the same manner as in Example 1 except that 0.86 g (4 mmol) of phthalic acid dichloride was used instead of 0.76 g (4 mmol) of titanium tetrachloride.
The analysis results of the obtained diethoxymagnesium are shown in Table 1. Moreover, the SEM photograph of the obtained diethoxymagnesium is shown in FIG.

(Comparative Example 4)
Instead of charging 5 g of metal magnesium powder, 100 g of anhydrous ethanol and 0.8 g (4 mmol) of phthalic acid dichloride, 5 g of metal magnesium powder, 100 g of anhydrous ethanol and 0.38 g (2 mmol) of titanium tetrachloride are charged. Instead of adding a mixture of 5 g of metal magnesium powder and 50 g of ethanol in 5 portions, a mixture of 2.5 g of metal magnesium powder, 25 g of absolute ethanol and 0.38 g (2 mmol) of titanium tetrachloride was added. Diethoxymagnesium was produced and evaluated in the same manner as in Example 1 except that it was added in 5 portions.
The evaluation results of the obtained diethoxymagnesium are shown in Table 1, and the SEM photograph is shown in FIG.

In the reaction between metal magnesium and alcohol, when the carboxylic acid halogen compound according to the present invention is used as a reaction accelerator, the reactivity is milder than that of the halogen atom, and the reaction between metal magnesium and alcohol proceeds gently. The growth (granulation) of particles is not hindered, and it is easy to form large-diameter dialkoxymagnesium particles having a smooth surface and an average particle size of 60 μm or more.
On the other hand, iodine is a halogen group atom, so it is highly reactive. In addition, titanium tetrachloride, an inorganic halogen compound, is extremely reactive with the raw material alcohol, so it can be obtained in a stable state as an accelerator. Magnesium chloride is difficult to obtain sufficient reactivity as an accelerator, so that any compound hinders the growth of dialkoxymagnesium particles, making it difficult to form large-diameter dialkoxymagnesium. Even if large particles can be formed, because the particle size distribution is wide or the particle surface is not smooth, such as when the carboxylic acid halogen compound according to the present invention is used as an accelerator, the surface is smooth, Moreover, dialkoxy magnesium particles having a large average particle diameter cannot be obtained.

Example 3
<Preparation of solid catalyst component for olefin polymerization>
A 500 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 30 ml of titanium tetrachloride and 20 ml of toluene to form a mixed solution. Subsequently, the mixed solution in which the suspension formed using 10 g of diethoxymagnesium obtained in Example 1 above, 50 ml of toluene and 3.8 ml (15 mmol) of diethyl benzylidenemalonate was maintained at a liquid temperature of 10 ° C. Added in.
Thereafter, the liquid temperature was raised from 10 ° C. to 90 ° C., and the mixture was reacted at 90 ° C. for 2 hours while stirring.
After completion of the reaction, the obtained solid product was washed 4 times with 100 ml of 90 ° C. toluene, newly added 30 ml of titanium tetrachloride and 70 ml of toluene, heated to 110 ° C., and reacted with stirring for 2 hours. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A-1) for olefin polymerization.
The solid catalyst component (A-1) contains 1.2% by mass of phthalic diester derived from phthalic dichloride in addition to 10.4% by mass of benzylidenemalonic acid diester as an internal electron donating compound. It was. The titanium content in the solid catalyst component was measured and found to be 2.93% by mass.
<Formation of olefin polymerization catalyst and propylene polymerization>
In an autoclave with a stirrer with an internal volume of 2.0 liters that is completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and the above solid catalyst component (A-1) are converted into titanium atoms. 0.0026 mmol was charged to form an olefin polymerization catalyst.
Next, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene are charged into an autoclave, preliminarily polymerized at 20 ° C. for 5 minutes, then heated to 70 ° C., and subjected to a polymerization reaction at 70 ° C. for 1 hour. Thus, a propylene polymer was obtained. Table 2 shows the polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer.
<Average particle size of polymer, particle size distribution index, and amount of fine powder having particle size of less than 75 μm>
For the average particle size, particle size distribution index, and the amount of fine powder having a particle size of less than 75 μm, a digital image analysis type particle size distribution measuring device (Camsizer, manufactured by Horiba, Ltd.) was used. The volume-based integrated particle size distribution of the polymer was automatically measured.
(Measurement condition)
Funnel position: 6mm
Camera cover area: Basic camera less than 3%, Zoom camera less than 10% Target cover area: 0.5%
Feeder width: 40mm
Feeder control level: 57, 40 seconds Measurement start level: 47
Maximum control level: 80
Control criteria: 20
Image rate: 50% (1: 2)
Particle size definition: Minimum value of Martin diameter measured n times per particle SPHT (sphericity) fitting: 1
Upper limit of class: Logarithmic scale, select 50 points in the range of 32μm to 4000μm

(Comparative Example 5)
A solid catalyst component for olefin polymerization (A-2) was prepared in the same manner as in Example 3 except that 10 g of diethoxymagnesium obtained in Comparative Example 1 was used instead of 10 g of diethoxymagnesium obtained in Example 1 above. Thereafter, formation of an olefin polymerization catalyst and propylene polymerization were performed, and physical properties of the obtained polymer were evaluated.
The solid catalyst component (A-2) contained 10.4% by weight of benzylidene malonic acid diester as an internal electron donating compound, and the phthalic acid diester content was 0% by mass.
Moreover, it was 3.05 weight% when the titanium content rate in this solid catalyst component was measured. Table 2 shows the polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer.

In Example 3 using dialkoxymagnesium obtained in Example 1 with a smooth surface, a large average particle size, and a narrow particle size distribution, the average particle size (D ₅₀ ) is large, the particle size distribution is narrow, And the polypropylene particle with few fine powders was obtained.
On the other hand, in Comparative Example 5 using dialkoxymagnesium obtained in Comparative Example 1 having a rough surface, a small average particle size, and a wide particle size distribution, the average particle size (D ₅₀ ) of the obtained polypropylene was small, The particle size distribution was wide and there were many fine powders.

Claims (7)

A process for producing dialkoxymagnesium, wherein metalmagnesium and alcohol are reacted in the presence of a reaction accelerator to obtain dialkoxymagnesium,
The reaction accelerator is represented by the following general formula (1):
(In the formula, Z is Cl or Br. R ¹ is a hydrocarbon group having 1 to 20 carbon atoms.)
Or a carboxylic acid monohalogen compound represented by the following general formula (2):
(In the formula, Z is Cl or Br, and may be the same or different. R ² is a hydrocarbon group having 1 to 20 carbon atoms.)
A dicarboxylic acid dihalogen compound represented by:
A method for producing dialkoxymagnesium, wherein   The reaction accelerator is any one or more selected from aliphatic carboxylic acid monohalogen compounds, aliphatic dicarboxylic acid dihalogen compounds, aromatic carboxylic acid monohalogen compounds, and aromatic dicarboxylic acid dihalogen compounds. The method for producing dialkoxymagnesium according to claim 1.   The method for producing dialkoxymagnesium according to claim 1, wherein the alcohol is ethanol.   A dialkoxymagnesium (a) obtained by carrying out the method for producing dialkoxymagnesium according to any one of claims 1 to 3, a titanium halogen compound (b), and an electron donating compound (c) are brought into contact with each other. A solid catalyst component for olefin polymerization, which is obtained. (A) Solid catalyst component for olefin polymerization according to claim 4, (B) the following general formula (IV):
R ¹⁵ _p AlQ _3-p (IV)
^{(Wherein, R 15} represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 ^{<.R 15} is a real number p ≦ 3 there are a plurality, each R ¹⁵ may be the same as or different from each other, and when a plurality of Qs are present, each Q may be the same or different.)
A catalyst for olefin polymerization, comprising: an organoaluminum compound represented by formula (C): and (C) an external electron donating compound. The (C) external electron donating compound is represented by the following general formula (V):
R ¹⁶ _q Si (OR ¹⁷ ) _4-q (V)
(In the formula, R ¹⁶ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, carbon an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent having 6 to 15, if R ¹⁶ there are a plurality, a plurality of R ¹⁶ may be the same or different from each other R ¹⁷ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. an aromatic hydrocarbon group having 7 to 12 carbon atoms having, if R ¹⁷ there are a plurality, the plurality of R ¹⁷ may be the same or different from each other .q is an integer of 0 ≦ q ≦ 3. )
And an organic silicon compound represented by the general formula (VI):
(R ¹⁸ R ¹⁹ N) _s SiR ²⁰ _4-s (VI)
(In the formula, R ¹⁸ and R ¹⁹ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms. A cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, R ¹⁸ and R ¹⁹ may be the same or different from each other, and may be bonded to each other to form a ring. R ¹⁸ R ¹⁹ N group When a plurality of R ¹⁸ R ¹⁹ N groups are present, the plurality of R ¹⁸ R ¹⁹ N groups may be the same as or different from each other, and R ²⁰ represents an alkyl group having 1 to ²⁰ carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon number. 1-20 alkoxy group, vinyloxy group, C3-C20 alkenyloxy group, C3-C20 cycloalkyl group, C3-C20 cycloalkyloxy group, C6-C20 aryl Group, an aryloxy group having 6 to 20 carbon atoms, if R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different .s is an integer from 1 to 3.)
The olefin polymerization catalyst according to claim 5, wherein the catalyst is one or more selected from the group consisting of aminosilane compounds represented by the formula: A method for producing an olefin polymer, comprising polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 5 and 6.