TW201906806A - Dialkoxymagnesium, a method for producing dialkoxymagnesium, solid catalyst component for olefin polymerization, and a method for producing olefin polymerization - Google Patents

Abstract

Dialkoxymagnesium is provided that has a particle surface on which the arithmetic mean roughness (Ra) is 0.5 or less and the maximum height (Rz) is 2.0 or less. The present invention provides dialkoxymagnesium having a smooth surface.

Description

 Method for producing dialkoxymagnesium, dialkoxymagnesium, solid catalyst component for olefin polymerization, and method for producing olefin polymer  

The present invention relates to a novel dialkoxy magnesium suitable for a carrier raw material for a catalyst component for olefin polymerization and a process for producing the same.

Conventionally, as a polymerization method of an olefin, a polymerization method of a large amount of olefins is proposed, which comprises a solid catalyst component obtained by bringing a dialkoxymagnesium, a titanium halogen compound, and an internal electron-donating compound into contact with each other, and an organic solvent. The olefins are polymerized or copolymerized in the presence of an olefin polymerization catalyst of an aluminum compound.

In the polymerization method of such an olefin, since the shape of the obtained polyolefin depends on the shape of the solid catalyst component used for the polymerization, it is important to control the form (particle structure) of the solid catalyst component. Researching widely.

In this case, in the polymerization of olefins, as one of the requirements for the shape control of the polyolefin polymer particles, the surface of the particles is required to be smooth. Further, in order to obtain a polyolefin having a smooth surface, a solid catalyst component having a smooth surface is required.

Here, the particle structure of the solid catalyst component depends on the particle structure of the dialkoxymagnesium which is a carrier of the solid catalyst component. That is, in order to obtain a polyolefin having a smooth surface, a surface smoothing of a dialkoxy magnesium is required.

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

Further, Patent Document 2 discloses a method of reacting metallic magnesium with anhydrous ethanol in the presence of iodine as a reaction accelerator.

Further, Patent Documents 3 and 4 disclose a method of adding iodine as a reaction accelerator to a reaction system in a method of reacting magnesium metal with an alcohol in the presence of iodine as a reaction accelerator. .

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-202667

[Patent Document 2] Japanese Patent Laid-Open No. 3-74341

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-95890

[Patent Document 4] International Publication No. 2013/058193

However, in the production method of Patent Document 1, only amorphous diethoxymagnesium can be obtained, and the surface smooth diethoxymagnesium cannot be obtained. Further, the manufacturing methods of Patent Documents 2, 3, and 4 also require further improvement in the smoothness of the particle surface.

Accordingly, it is an object of the present invention to provide a method for producing a dialkoxy magnesium which is smooth on the surface of a particle and a dialkoxymagnesium for obtaining such a dialkoxymagnesium.

In this practical case, the inventors have conducted diligent research and found that a smooth surface of dialkoxymagnesium can be obtained by using a specific ruthenium halide compound as a reaction accelerator for reacting magnesium metal with an alcohol. The present invention can be accomplished by using a specific metal halide as a reaction accelerator for reacting magnesium metal with an alcohol to obtain a dialkoxy magnesium or the like having a smooth surface.

That is, the present invention (1) provides a dialkoxymagnesium characterized in that the arithmetic mean roughness (Ra) of the surface of the particles is 0.5 or less, and the maximum height (Rz) of the surface of the particles is 2.0 or less.

Further, the present invention (2) provides a method for producing a dialkoxymagnesium which is obtained by reacting magnesium metal with an alcohol in the presence of a reaction accelerator to obtain a dialkoxymagnesium, characterized in that the reaction The accelerator is of the following formula (1): SiR ¹ _n X _(4-n) (1)

(In the formula (1), R ¹ is an alkyl group or an alkoxy group; X is a chlorine atom or a bromine atom; n is an integer of 0 to 3; when n is 2 or more, several R ¹ may be the same or each other Different; when there are several Xs, several Xs may be the same or different from each other)

The halogenated ruthenium compound is represented.

Further, the present invention (3) provides a process for producing a magnesium alkoxide of (2), characterized in that the reaction accelerator is tetrafluorodecane, tetrachlorodecane, tetrabromodecane or tetraiododecane.

Further, the invention (4) provides the method for producing a dialkoxymagnesium according to any one of (2) or (3), wherein the alcohol is ethanol.

Further, the present invention (5) provides a method for producing a dialkoxymagnesium, which is characterized in that the method is obtained by reacting magnesium metal with an alcohol in the presence of a reaction accelerator to obtain a dialkoxymagnesium. The reaction accelerator is a powdery metal halide having an average particle diameter (D ₅₀ ) of 500 μm or less and a specific surface area of 1 m ² /g or more.

Further, the invention (6) provides a method for producing a magnesium alkoxide according to (5), characterized in that the particle diameter (D ₉₀ ) of the metal halide D90 is 2000 μm or less.

Further, the present invention (7) provides the method for producing a dialkoxymagnesium according to any one of (5) or (6), characterized in that the particle size distribution index (SPAN) of the above metal halide: SPAN = (D) _{90 -} D ₁₀ ) / D ₅₀ is 7 or less.

Further, the present invention provides the process for producing a dialkoxy magnesium according to any one of (5) to (7), wherein the metal halide is magnesium dichloride.

Further, the present invention provides the process for producing a dialkoxy magnesium according to any one of (5) to (8), wherein the alcohol is ethanol.

Further, the present invention (10) provides a solid catalyst component for olefin polymerization, which is characterized in that it is a (1) dialkoxy magnesium (a), a titanium halogen compound (b), and an electron supply property. Compound (c) is obtained by contact.

Furthermore, the present invention (11) provides a solid catalyst component for olefin polymerization, which is obtained by the method for producing a dialkoxymagnesium according to any one of (2) to (9). The bis- alkoxy magnesium (a) is obtained by contacting with the titanium halogen compound (b) and the electron-donating compound (c).

Furthermore, the present invention (12) provides a catalyst for olefin polymerization, which is characterized in that (A) is a solid catalyst component for olefin polymerization according to any one of (10) or (11), B) An organoaluminum compound and (C) an external electron-donating compound are obtained by contacting each other.

Further, the present invention (13) provides the olefin polymerization catalyst according to (12), wherein the (B) organoaluminum compound is an organoaluminum compound represented by the following formula (2): R ² _P AlQ _3-P (2)

(wherein R ² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p≦3; in the case where there are a plurality of R ² , each R ² may be each other The same or different, in the case of a number of Q, each Q may be the same or different).

The catalyst for olefin polymerization according to any one of (12) or (13), wherein the (C) external electron-donating compound is selected from the following formula ( 3): R ³ _q Si(OR ⁴ ) _4-q (3)

(wherein R ³ represents 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, and a carbon number; when the aromatic hydrocarbon group of 6 to 15 or a substituent group having a carbon number of the aromatic hydrocarbon group of 6 to 15, in the case of the presence of a number of R ^3, a plurality of R ³ may be mutually the same or different; R ⁴ is a C 1 ~4 alkyl group, vinyl group, carbon number 3 to 12 alkenyl group, carbon number 3 to 6 cycloalkyl group, carbon number 6 to 12 aromatic hydrocarbon group or substituted carbon number 7 to 12 aromatic hydrocarbon group, in the presence of a number of R ⁴ of the case, a plurality of R ⁴ may be the same or different from each other; Q is an integer of 0 ≦ q ≦ 3's).

The organic ruthenium compound represented, and the general formula (4): (R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)

(wherein R ⁵ and R ⁶ represent 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, and a carbon number of 3 to 20; a cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, and R ⁵ and R ⁶ may be the same or different from each other, or may be bonded to each other to form a ring, in the case where a plurality of R ⁵ R ⁶ N groups are present. a plurality of R ⁵ R ⁶ N groups may be the same or different from each other; R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. , a vinyloxy group, an alkenyloxy group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 6 to 20 the aryloxy group, in the case when there are several of R ^7, R ⁷ may be a number of mutually identical or different; S is an integer of from 1 to 3).

One or more of the amino decane compounds represented.

Furthermore, the present invention (15) provides a method for producing an olefin polymer, which is characterized in that the olefin is used in the presence of a catalyst for olefin polymerization according to any one of (12) to (14). Aggregation.

According to the present invention, there can be provided a method for producing a dialkoxy magnesium having a smooth surface of a particle and a dialkoxymagnesium for obtaining such a dialkoxymagnesium.

1 is a scanning electron micrograph (SEM) of Example 1.

2 is a scanning electron micrograph (SEM) of Example 3.

3 is a scanning electron micrograph (SEM) of Comparative Example 3.

The dialkoxymagnesium of the present invention is characterized in that the arithmetic mean roughness (Ra) of the surface of the particles is 0.5 or less and the maximum height (Rz) of the surface of the particles is 2.0 or less.

The surface smoothness (Ra) of the dialkoxy magnesium of the present invention is 0.5 or less, preferably 0.49 or less, and particularly preferably 0.47 or less. When the surface smoothness (Ra) of the magnesium dialkoxide is in the above range, the fluidity of the solid catalyst component for olefin polymerization produced from the dialkoxymagnesium is improved, even obtained by the solid catalyst component. The fluidity of the polymer is also improved, so that the adhesion in the polymerization step is lowered and the transferability is improved. Further, in the present invention, the surface smoothness (Ra) means the arithmetic mean roughness (Ra) of the surface of the dialkoxy magnesium particles measured by a shape analysis laser microscope according to JIS B 0601:2001. .

Further, the surface maximum height (Rz) of the dialkoxymagnesium of the present invention is 2.0 or less, preferably 1.95 or less, and particularly preferably 1.00 to 1.95. When the surface maximum height (Rz) of the dialkoxymagnesium is in the above range, when the dialkoxymagnesium is used as a carrier material for the solid catalyst component for olefin polymerization, the fluidity of the obtained solid catalyst component is improved. Therefore, it is easy to transfer or discharge from the container, and the time taken for the transfer of the solid catalyst component from the container is shortened, or the residual amount in the container is lowered. Further, the fluidity of the obtained solid catalyst component or even the polymer obtained from the solid catalyst component is also improved, so that the adhesion in the polymerization step is lowered and the transfer property is improved. Further, in the present invention, the maximum surface height (Rz) means the maximum height (Rz) of the surface of the dialkoxy magnesium particles measured by a shape analysis laser microscope in accordance with JIS B 0601:2001.

Since the dialkoxy magnesium of the present invention has the surface maximum height (Rz) and the maximum height (Rz) in the above range, it is a dialkoxy magnesium excellent in surface smoothness. Further, by using the dialkoxymagnesium of the present invention excellent in surface smoothness as a carrier material for the solid catalyst component for olefin polymerization, the content of the fine powder particles in the obtained solid catalyst component is lowered, and as a result, The polymer has a small amount of fine particles, and has a smooth surface and excellent fluidity. The mechanism for obtaining the above-described excellent effects by using a dialkoxy magnesium excellent in surface smoothness as a carrier raw material for a solid catalyst component for olefin polymerization is not clear, but the reason is considered as follows. It is known that, in general, the Ziegler-Natta catalyst is reflected in the so-called replication phenomenon, and the shape and properties of the raw material carrier are also reflected to the obtained catalyst, and will be reflected to the polymer obtained by using the catalyst. Shape or trait. Therefore, by using a raw material carrier (the dialkoxymagnesium of the present invention) having less particle surface attachment and excellent smoothness, the content of fine powder particles in the solid catalyst for olefin polymerization obtained can be reduced and obtained. A solid catalyst with a smooth surface. The polymer obtained by using the solid catalyst has a small amount of fine powder particles, and a polymer having a smooth surface and excellent fluidity can be produced.

The sphericity of the dialkoxymagnesium of the present invention is preferably 2 or less, and particularly preferably 1.5 or less. Further, in the present invention, the sphericity of the dialkoxymagnesium is measured by an image analysis device (manufactured by Mountech Co., Ltd., Mac-View), and an external quadrilateral is calculated for the particle image taken from several directions. When the length of one side becomes maximum, the long side (maximum length) of the quadrilateral and the diameter of the circle (Heywood diameter) of the area equal to the projected area of the particle when the length of the one side is the largest is obtained by the following formula Out.

Sphericality = {(maximum length) ÷ (Heywood Trail)} ³

The average particle diameter (D ₅₀ ) of the dialkoxymagnesium of the present invention is preferably 5 μm or more, more preferably 8 to 100 μm, still more preferably 10 to 80 μm. The average particle diameter (D ₅₀ ) of the magnesium dialkoxide is in the above range, and when the dialkoxymagnesium is used as a carrier material for the solid catalyst component for olefin polymerization, the solid catalyst component obtained is The content of the fine powder particles is lowered, and as a result, the fine powder particles of the obtained polymer are less.

Particle size distribution index (SPAN) of the dialkoxymagnesium of the present invention: SPAN = (D _{90 -} D ₁₀ ) / D ₅₀

It is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.0 or less. The particle size distribution index (SPAN) of the dialkoxymagnesium is in the above range, and when the dialkoxymagnesium is used as a carrier material for the solid catalyst component for olefin polymerization, the fine powder in the solid catalyst component obtained is obtained. The particle content is lowered, and as a result, the fine powder particles of the obtained polymer are reduced.

In the present invention, D ₁₀ , D ₅₀ and D ₉₀ are determined by measurement using a laser diffraction type particle size distribution measuring apparatus (MICROTRAC HRA Model No. 9320-X100, manufactured by Nikkiso Co., Ltd.). The particle size distribution (μm) corresponding to the cumulative volume fraction in the particle size distribution of 10%, 50%, and 90%, respectively.

The total density of the dialkoxymagnesium of the present invention is preferably from 0.1 to 0.6 g/ml, more preferably from 0.2 to 0.5 g/ml, still more preferably from 0.25 to 0.40 g/ml. When the total density of the magnesium dialkoxide is in the above range, the total density of the polymer obtained by polymerizing the solid catalyst component using magnesium dialkoxide as a carrier material becomes good.

The dialkoxy magnesium of the present invention is preferably an alcohol-free one, but it is acceptable if the content of the alcohol is 2% by mass or less.

In the case where the dialkoxymagnesium of the present invention is obtained by using a magnesium halide as a reaction accelerator, the halogen content in the dialkoxymagnesium of the present invention is 0.05 to 10.0% by mass, preferably 0.05 to 8.0 by mass. % is more preferably 0.1 to 5.0% by mass, particularly preferably 0.3 to 3.0% by mass. When the halogen content of the dialkoxymagnesium is in the above range, a good dialkoxymagnesium having a particle shape and a particle surface state can be obtained. Further, the metal halide used as a reaction accelerator in the present invention does not easily remain in the obtained dialkoxymagnesium or in the case of preparing a solid catalyst component using the dialkoxymagnesium. When the magnesium oxychloride is chlorinated, it is not eluted into the inert organic solvent as iodine which is generally used as a reaction accelerator. Further, when the metal halide used as the reaction accelerator in the present invention can be used as a carrier component of the solid catalyst component, it is not necessary to remove it from the interior of the magnesium dialkoxide particles.

The method for producing a dialkoxymagnesium according to the first aspect of the present invention is a method in which magnesium metal and an alcohol are reacted in the presence of a reaction accelerator to obtain a dialkoxymagnesium, characterized in that the reaction accelerator is as follows. General formula (1): SiR ¹ _n X _(4-n) (1)

(In the formula (1), R ¹ is an alkyl group or an alkoxy group; X is a chlorine atom or a bromine atom; n is an integer of 0 to 3; when n is 2 or more, R ¹ may be the same or different; When several Xs, several Xs can be the same or different from each other)

The halogenated ruthenium compound is represented.

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

The alcohol of the method for producing dialkoxymagnesium according to the first aspect of the present invention is not particularly limited, and for example, a lower alcohol having a carbon number of 1 to 6 such as methanol, ethanol, propanol, butanol or hexanol is preferable. Good for ethanol. The water content of the alcohol is not particularly limited, and the smaller the water content, the better, and more preferably an anhydrous alcohol or a dehydrated alcohol having a water content of 200 ppm or less.

In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the following general formula (1): SiR ¹ _n X _(4-n) (1) is used.

The represented ruthenium halide compound acts as a reaction accelerator to react the magnesium metal with the alcohol.

In the formula (1), R ¹ is an alkyl group or an alkoxy group, preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and particularly preferably an alkyl group having 1 to 2 carbon atoms or an alkoxy group. . X is a chlorine atom or a bromine atom, and X is preferably a chlorine atom. n is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0. Furthermore, when n is 2 or more, several R ^{1 's} may be the same or different from each other. Moreover, when there are several Xs, several Xs may be the same or different from each other.

The antimony halide compound represented by the formula (1) is preferably tetrafluorodecane, tetrachlorodecane, tetrabromodecane or tetraiododecane. By the reaction accelerator being tetrafluorodecane, tetrachlorodecane, tetrabromodecane or tetraiododecane, it is easy to obtain a dialkoxymagnesium having a large average particle diameter and a smooth surface.

In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the molar ratio of alcohol to metal magnesium (alcohol/magnesium metal) is preferably from 3 to 30, particularly preferably from 5 to 20. By the molar ratio of the alcohol to the metal magnesium in the above range, the obtained dialkoxymagnesium has a larger average particle diameter and a smoother surface.

In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the molar ratio of the ruthenium halide compound represented by the formula (1) to the metal magnesium (the ruthenium halide compound represented by the formula (1) / The metal magnesium) is preferably from 0.0001 to 0.1, particularly preferably from 0.003 to 0.03. By the molar ratio of the ruthenium halide compound represented by the general formula (1) to the metal magnesium in the above range, a dialkoxy magnesium having a large average particle diameter and a smooth surface and high purity can be obtained.

In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the metal magnesium and the alcohol are stirred while the metal magnesium is dispersed in the alcohol to carry out the reaction. Further, in the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the ruthenium halide compound represented by the formula (1) is previously mixed into an alcohol, and the compound represented by the formula (1) is contained. The alcohol of the ruthenium halide compound is mixed with the magnesium metal, or by adding the ruthenium halide compound represented by the general formula (1) to the suspension obtained by mixing the magnesium metal with the alcohol, or by using the ruthenium halide compound as a liquid In the case where it is not directly mixed with an alcohol, the ruthenium halide compound represented by the formula (1) is introduced into the reaction system to cause the metal magnesium and the alcohol to be ruthenium halide represented by the formula (1). The reaction is carried out in the presence of a compound. In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the introduction of the antimony halide compound represented by the formula (1) in the reaction system may be carried out once or may be carried out in several steps. In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, all of the antimony halide compounds represented by the formula (1) may be mixed with the metal magnesium and the alcohol, or the metal may be used. After the magnesium is mixed with the alcohol, the total amount of the antimony halide compound represented by the formula (1) may be added before the start of the reaction, or a part of the antimony halide compound represented by the formula (1) may be added to the magnesium metal and After the alcohol is present in combination and the reaction is started, the remaining ruthenium halide compound represented by the formula (1) is added to the reaction system in one portion or in portions during the course of continuing the reaction. Further, in the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the introduction of the magnesium metal and the alcohol into the reaction system may be carried out at once, or may be carried out in several steps. That is, in the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the reaction may be started first by using the total amount of the magnesium metal and the alcohol, or after the reaction is started using one of the magnesium metal and the alcohol, During the course of the reaction, the remaining magnesium metal and alcohol are added to the reaction system in one portion or in portions.

The reaction temperature of the method for producing a dialkoxymagnesium according to the first aspect of the present invention is not particularly limited as long as it is at most the boiling point of the raw material mixture, and is preferably 30 to 100 ° C, particularly preferably 50 to 90 ° C, and further, the reaction The time is preferably from 0.5 to 15 hours, particularly preferably from 1 to 10 hours, and the reaction environment is an inert gas atmosphere.

After the method for producing the dialkoxymagnesium of the first aspect of the present invention, the obtained dialkoxymagnesium is dried by heating, drying by air flow or drying under reduced pressure, or by using inertia. The hydrocarbon is washed and the alcohol is removed from the magnesium dialkoxide.

In the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the reaction accelerator is a ruthenium halide compound represented by the formula (1), and a smooth surface, a large average particle diameter, and a high purity are obtained. Magnesium dialkoxide.

Further, in the production of magnesium dialkoxide, in the case of reacting magnesium metal with an alcohol, when iodine is used as a reaction accelerator, iodine is mixed into the obtained dialkoxymagnesium even if it is washed. Etc., iodine cannot be completely removed from the dialkoxymagnesium, and iodine remains in the dialkoxymagnesium. Further, when a solid catalyst component is produced using magnesium dialkoxide remaining with iodine, residual iodine causes a decrease in performance of the solid catalyst component. On the other hand, in the method for producing a dialkoxymagnesium according to the first aspect of the present invention, there is no problem of residual iodine in the magnesium dialkoxide. Further, in the method for producing a dialkoxymagnesium according to the first aspect of the present invention, the amount of residual halogen in the dialkoxymagnesium of the antimony halide compound represented by the formula (1) used as a reaction accelerator is small. The amount of halogen remaining in the dialkoxymagnesium obtained by using iodine as a reaction accelerator.

The surface of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is relatively smooth. In the present invention, the surface smoothing of the dialkoxymagnesium is observed by a surface observation by a scanning electron microscope (SEM), and a dialkoxymagnesium obtained by a shape-analyzed laser microscope according to JIS B 0601:2001. The arithmetic mean roughness (Ra) of the particle surface and the maximum surface height (Rz) were confirmed.

The surface smoothness (Ra) of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is 0.5 or less, preferably 0.49 or less, and particularly preferably 0.47 or less. Further, the surface maximum height (Rz) of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is 2.0 or less, preferably 1.95 or less, and more preferably 1.00 to 1.95. Moreover, the sphericity of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is preferably 2 or less, and more preferably 1.5 or less. Further, the total density of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is preferably from 0.1 to 0.6 g/ml, more preferably from 0.2 to 0.5 g/ml. Good is 0.25~0.40g/ml.

The average particle diameter (D ₅₀ ) of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is 50 μm or more, preferably 55 μm or more, more preferably 55 to 100 μm. Good is 60~80μm. In the method for producing a dialkoxy magnesium according to the first aspect of the present invention, a dialkoxy magnesium having a smooth surface and a large average particle diameter can be obtained. The method for producing a dialkoxymagnesium according to the first aspect of the present invention has a particle size distribution index (SPAN) (SPAN = (D _{90 -} D ₁₀ ) / D ₅₀ ) of 2.0 or less, more preferably 1.5 or less.

The purity of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is 99% by mass or more, more preferably 99 to 100% by mass, even more preferably 99.1 to 99.9% by mass.

Further, in the present invention, the purity of the dialkoxymagnesium refers to the purity of the dialkoxymagnesium after removal of the solvent, and refers to the determination of the halogen content in the dialkoxymagnesium after removal of the solvent. The content of the reaction accelerator in the magnesium alkoxide and the value calculated by the following formula.

Magnesium dialkoxymagnesium purity (% by mass) = 100 - reaction accelerator content (% by mass)

The dialkoxy magnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is preferably an alcohol-free one, but the alcohol content is 5% by mass or less, preferably 2 mass. % or less, particularly preferably 1% by mass or less, is acceptable.

The dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention can be preferably used as a dialkoxymagnesium as a raw material for producing a solid catalyst component for olefin polymerization. The dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention is particularly preferably used as a solid for producing a polyolefin having a smooth surface, a large average particle diameter and a high purity. The raw material alkoxymagnesium of the catalyst component.

The method for producing the solid catalyst component for olefin polymerization using the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the first aspect of the present invention as a raw material is not particularly limited and may be appropriately selected.

The method for producing a dialkoxymagnesium according to the second aspect of the present invention is a method for obtaining a dialkoxymagnesium by reacting magnesium metal with an alcohol in the presence of a reaction accelerator, wherein the reaction accelerator is A powdery metal halide having an average particle diameter (D ₅₀ ) of 500 μm or less and a specific surface area of 1 m ² /g or more.

The shape of the metal magnesium of the method for producing a dialkoxy magnesium according to the second aspect of the present invention is not particularly limited, and examples thereof include a pellet, a ribbon, and a powder. Among these, as the metal magnesium, preferably in the form of a powder, the average particle diameter of the powdered metal magnesium is preferably from 10 to 1,000 μm, more preferably from 20 to 800 μm, still more preferably from 50 to 500 μm. The surface state of the metallic magnesium is not particularly limited, and it is preferred that a film such as magnesium oxide is not formed on the surface. The content of the fine powder component having an average particle diameter of less than 5 μm in the metallic magnesium is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and a coarse powder component having an average particle diameter of 500 μm or more. The content is preferably 10% by mass or less, more preferably 5% by mass or less.

The alcohol of the method for producing a dialkoxymagnesium according to the second aspect of the present invention is not particularly limited, and for example, a lower alcohol having a carbon number of 1 to 6 such as methanol, ethanol, propanol, butanol or hexanol is preferable. Good for ethanol. Further, the water content of the alcohol is not particularly limited, and the smaller the water content, the better, and more preferably an anhydrous alcohol or a dehydrated alcohol having a water content of 200 ppm or less.

Further, in the method for producing a dialkoxymagnesium according to the second aspect of the present invention, a metal halide is used as a reaction accelerator to carry out a reaction between magnesium metal and an alcohol. The metal halide of the method for producing a dialkoxy magnesium of the present invention is not particularly limited as long as it has a powder having an average particle diameter (D ₅₀ ) of 500 μm or less and a specific surface area of 1 m ² /g or more. Examples thereof include metal monohalogen compounds such as halogenated alkali metals and alkoxy magnesium halides, metal dihalogen compounds such as calcium dihalide, magnesium dihalide, iron dihalide, and nickel dihalide, aluminum trihalide, iron trihalide, and nickel trihalide. a metal trihalide compound such as vanadium trihalide, zirconium trihalide, antimony trihalide or chromium trihalide, and a metal tetrahalide compound such as vanadium tetrahalide, zirconium tetrahalide, antimony tetrahalide or chromium tetrahalide, among which metal II is preferred. A halogen compound, particularly preferably magnesium dichloride.

The metal halide of the second aspect of the present invention has a metal halide having an average particle diameter (D ₅₀ ) of 500 μm or less, preferably 300 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less. By having the average particle diameter (D ₅₀ ) of the metal halide in the above range, it is easy to obtain a dialkoxy magnesium which is smooth on the surface of the particles.

The lower limit of the average particle diameter (D ₅₀ ) of the metal halide of the method for producing a dialkoxymagnesium according to the second aspect of the present invention is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more. It is preferably 3 μm or more, and more preferably 5 μm or more. By having the average particle diameter (D ₅₀ ) of the metal halide in the above range, it is easy to obtain a dialkoxy magnesium which is smooth on the surface of the particles.

The specific surface area of the metal halides of the method of manufacturing the second aspect of the present invention dialkoxy magnesium is 1m ² / g or more, preferably of 5m ² / g or more, and particularly preferably 7m ² / g or more. By the specific surface area of the metal halide being in the above range, it is easy to obtain a dialkoxy magnesium which is smooth on the surface of the particles.

The upper limit of the specific surface area of the metal halide of the method for producing a dialkoxy magnesium according to the second aspect of the present invention is not particularly limited, but is preferably 100 m ² /g or less, more preferably 80 m ² /g or less. Good is 70m ² /g or less. By the specific surface area of the metal halide being in the above range, it is easy to obtain a dialkoxy magnesium which is smooth on the surface of the particles.

The metal halide of the method for producing a dialkoxymagnesium according to the second aspect of the present invention has a (D ₉₀ ) of 2000 μm or less, preferably 5 to 1000 μm, more preferably 10 to 500 μm, still more preferably 50 to 300 μm. By the D ₉₀ of the metal halide being in the above range, it is easy to obtain a dialkoxy magnesium which is smooth on the surface of the particles.

The metal halide of the second aspect of the present invention has a particle size distribution index (SPAN) of 10 or less, preferably 8.0 or less, more preferably 0.1 to 8.0, still more preferably 0.5 to 7.0. By the particle size distribution index (SPAN) of the metal halide being in the above range, it is easy to obtain a dialkoxy magnesium which is smooth on the surface of the particles.

The metal halide of the method for producing dialkoxymagnesium according to the second aspect of the present invention includes a metal dihalide compound and a metal monohalide compound. Examples of the metal dihalogen compound in the method for producing a dialkoxymagnesium according to the second aspect of the present invention include calcium dihydrate, calcium dichloride, calcium dibromide, calcium diiodide, and the like. Nickel dihalide and magnesium difluoride such as iron dichloride, iron difluoride, iron difluoride, nickel difluoride, nickel dichloride, nickel dibromide and nickel diiodide, such as iron, iron dichloride, iron dibromide or iron diiodide And a magnesium dihalide such as magnesium dichloride, magnesium dibromide or magnesium diiodide. Examples of the metal monohalogen compound include a methoxy magnesium halide, an ethoxy magnesium halide, a butoxy magnesium halide, and a phenoxy group. A magnesium halide alkoxide such as a magnesium halide. The magnesium halide which is a method for producing a dialkoxymagnesium according to the second aspect of the present invention is preferably a magnesium dichloride or a magnesium diiodide, and is preferably a magnesium azide or a magnesium diiodide. It is magnesium dichloride. The magnesium halide may be used alone or in combination of two or more. Further, the magnesium dihalide of the method for producing a dialkoxymagnesium according to the second aspect of the present invention may be an anhydride or a hydrate, which does not impair the reactivity of the magnesium metal with the alcohol, and further serves as a solid catalyst component. The carrier material is also preferably a dihalogenated magnesium halide in terms of a smaller water content.

In the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the molar ratio of the alcohol to the metal magnesium (alcohol/magnesium metal) is preferably from 3 to 30, particularly preferably from 5 to 20. By the molar ratio of the alcohol to the metal magnesium in the above range, the surface of the obtained dialkoxymagnesium is easily smoothed.

In the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the molar ratio of the metal halide to the metal magnesium (metal halide/magnesium metal) is preferably 0.0001 to 0.1, more preferably 0.0005 to 0.1. Especially preferred is 0.001~0.01. By the molar ratio of the metal halide to the metal magnesium in the above range, the obtained magnesium dialkoxide has a particle shape or a bulk density and a narrow particle size distribution.

In the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the reaction is carried out while stirring the metal magnesium and the alcohol while stirring the metal magnesium in the alcohol. Further, in the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the metal halide is mixed with the alcohol in advance, and the metal halide-containing alcohol is mixed with the metal magnesium or the metal is used. The halide is added to the suspension obtained by mixing the magnesium metal with the alcohol, and the metal halide is introduced into the reaction system to react the metal magnesium with the alcohol in the presence of the metal halide. In the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the introduction of the metal halide into the reaction system may be carried out at once, or may be carried out in several steps. That is, in the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the entire amount of the metal halide may be mixed with the metal magnesium and the alcohol, or after the magnesium metal and the alcohol are mixed. Before the reaction is started, the total amount of the metal halide is added, or a part of the metal halide may be present together with the metal magnesium and the alcohol to start the reaction, and the remaining metal halide may be once during the reaction. Ground or fractional addition to the reaction system. Further, in the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the introduction of the magnesium metal and the alcohol into the reaction system may be carried out at once, or may be carried out in several steps. That is, in the method for producing a dialkoxymagnesium according to the second aspect of the present invention, the reaction may be started first by using the total amount of the magnesium metal and the alcohol, or after the reaction is started using one of the magnesium metal and the alcohol. During the course of the reaction, the remaining magnesium metal and alcohol are added to the reaction system in one portion or in portions.

The reaction temperature of the method for producing a dialkoxymagnesium according to the second aspect of the present invention is not particularly limited as long as it is at most the boiling point of the raw material mixture, and is preferably 30 to 100 ° C, particularly preferably 50 to 90 ° C, and further, the reaction The time is preferably from 0.5 to 15 hours, particularly preferably from 1 to 10 hours, and the reaction environment is an inert gas atmosphere.

After the method for producing the dialkoxymagnesium of the second aspect of the present invention, the obtained dialkoxymagnesium is dried by heat drying, air flow drying, or reduced pressure drying, or by utilizing The inert hydrocarbon is washed and the alcohol is removed from the magnesium dialkoxide.

The surface of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is relatively smooth.

The surface smoothness (Ra) of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is 0.5 or less, preferably 0.49 or less, and particularly preferably 0.47 or less. Further, the surface maximum height (Rz) of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is 2.0 or less, preferably 1.95 or less, and more preferably 1.00 to 1.95. Moreover, the sphericity of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is preferably 2 or less, and more preferably 1.5 or less. Further, the total density of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is preferably from 0.1 to 0.6 g/ml, more preferably from 0.2 to 0.5 g/ml. Good is 0.25~0.40g/ml.

The average particle diameter (D ₅₀ ) of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is preferably 5 μm or more, more preferably 8 to 100 μm, and particularly preferably 10 °. 80μm. Further, the particle size distribution index of the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is preferably 2.0 or less, more preferably 1.5 or less, and still more preferably 1.0 or less.

The dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention can be preferably used as a dialkoxymagnesium as a raw material for producing a solid catalyst component for olefin polymerization. The dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention is particularly preferably an alkoxy group as a raw material for producing a solid catalyst component for producing a polyolefin having a smooth surface. magnesium.

The method for producing the solid catalyst component for olefin polymerization using the dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium according to the second aspect of the present invention as a raw material is not particularly limited, and can be appropriately selected.

Examples of the solid catalyst component for olefin polymerization and a method for producing the same include the following solid catalyst components for olefin polymerization and a method for producing the same.

The solid catalyst component for olefin polymerization of the present invention is characterized in that it is a dialkoxy group obtained by the method for producing a dialkoxymagnesium of the present invention and the method for producing a dialkoxymagnesium according to the first aspect of the present invention. Magnesium or the contact of the dialkoxymagnesium (a) obtained by the method for producing a dialkoxymagnesium of the second aspect of the present invention with the titanium halogen compound (b) and the electron-donating compound (c) .

The dialkoxymagnesium (a) of the solid catalyst component for olefin polymerization of the present invention is obtained by the method for producing a dialkoxymagnesium of the present invention or the method for producing a dialkoxymagnesium according to the first aspect of the present invention. A dialkoxymagnesium or a dialkoxymagnesium obtained by the method for producing a dialkoxymagnesium of the second aspect of the present invention. The details of the method for producing a dialkoxy magnesium of the present invention, the method for producing a dialkoxymagnesium according to the first aspect of the present invention, and the method for producing a dialkoxymagnesium according to the second aspect of the present invention are as described above.

The titanium halide compound (b) constituting the solid catalyst component for olefin polymerization of the present invention may be one or more selected from the known titanium halogen compounds, preferably a tetravalent titanium halogen compound, more preferably titanium tetrachloride.

The electron-donating compound (c) constituting the solid catalyst component for olefin polymerization of the present invention may be one or more selected from known electron-donating compounds, and preferably an organic compound having an oxygen atom or a nitrogen atom.

The electron-donating compound (c) is preferably one or more selected from the group consisting of succinate, maleate, cyclohexene carboxylate, ether carboxylate, dicarbonate, and ether carbonate.

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

In the solid catalyst component for olefin polymerization of the present invention, the content of the titanium atom is preferably from 0.5 to 8.0% by mass, more preferably from 1.0 to 6.0% by mass, still more preferably from 1.0 to 4.0% by mass.

In the solid catalyst component for olefin polymerization of the present invention, the content of the magnesium atom is preferably from 10 to 70% by mass, more preferably from 10 to 50% by mass, still more preferably from 15 to 40% by mass, further preferably It is 15 to 25% by 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, still more preferably 40 to 80% by mass, further preferably It is 45 to 75 mass%.

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

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

The method for producing the solid catalyst component for olefin polymerization of the present invention is such that the alkoxymagnesium (a), the titanium halide compound (b) and the electron-donating compound (c) are inert at a boiling point of 50 to 150 ° C. A method of contacting in the presence of an organic solvent (d).

The inert organic solvent (d) having a boiling point of 50 to 150 ° C may be one or more selected from the group consisting of toluene, xylene, ethylbenzene, heptane, octane, and decane. The inert organic solvent (d) having a boiling point of 50 to 150 ° C is generally an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound, and may be a deodorized as long as the reactivity or the solubility of the impurities during washing after the reaction is not lowered. An inert organic solvent other than a hydrocarbon and a saturated hydrocarbon.

Further, in the case of producing the solid catalyst component for olefin polymerization of the present invention, polysiloxane may be further added to the reaction system. As the polyoxyalkylene, it is suitably selected from the well-known polyoxyalkylene, preferably one or more selected from the group consisting of decamethylcyclopentaoxane and dimethylpolyoxyalkylene, and more preferably decamethyl Cyclopentaoxane.

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

Further, as described above, the solid catalyst component for olefin polymerization of the present invention is a dialkoxymagnesium (a) or a titanium halide compound (b) obtained by the method for producing a dialkoxymagnesium of the present invention. And the electron-supplying compound (c) is obtained by contacting and reacting.

According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization which has a smooth particle surface and can form a polymer having a low fine powder amount under a high polymerization activity.

The catalyst for olefin polymerization of the present invention is characterized in that (A) the solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound, and (C) an external electron-donating compound are contacted. .

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

The catalyst for olefin polymerization of the present invention contains (B) an organoaluminum compound.

The (B) organoaluminum compound is not particularly limited as long as it is used as a catalyst for olefin polymerization.

In the catalyst for olefin polymerization of the present invention, the (B) organoaluminum compound is preferably an organoaluminum compound represented by the following formula (2): R ² _P AlQ _3-P (2)

(wherein R ² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p≦3; in the case where there are a plurality of R ² , each R ² may be each other The same or different, in the case of a number of Q, each Q may be the same or different).

The organoaluminum compound represented by the above formula (2) is not particularly limited, and R ² may be one or more selected from the group consisting of an ethyl group and an isobutyl group, and examples of Q include a hydrogen atom and a chlorine atom. More than or equal to one selected from the bromine atom, p is preferably 2, 2.5 or 3, and particularly preferably 3.

Specific examples of such an organoaluminum compound include trialkyl aluminum such as triethyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, and triisobutyl aluminum, diethyl aluminum chloride, and bromination. One or more selected from the group consisting of an alkyl aluminum halide such as diethyl aluminum and diethyl aluminum hydrogenate, and preferably an alkyl aluminum halide such as diethyl aluminum chloride or triethyl aluminum or tri-n-butyl aluminum. One or more selected from the group consisting of trialkyl aluminum such as triisobutyl aluminum, and more preferably one or more selected from the group consisting of triethyl aluminum and triisobutyl aluminum.

The catalyst for olefin polymerization of the present invention contains an external electron-donating compound (C). The external electron-donating compound (C) is not particularly limited as long as it is used as a catalyst for olefin polymerization. In the catalyst for olefin polymerization of the present invention, as the external electron-donating compound (C), it is preferred that the external electron-donating compound contains an oxygen atom or a nitrogen atom.

In the catalyst for olefin polymerization of the present invention, examples of the external electron-donating compound (C) include the following general formula (3): R ³ _q Si(OR ⁴ ) _4-q (3)

(wherein R ³ represents 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, and a carbon number; when the aromatic hydrocarbon group of 6 to 15 or a substituent group having a carbon number of the aromatic hydrocarbon group of 6 to 15, in the case of the presence of a number of R ^3, a plurality of R ³ may be mutually the same or different; R ⁴ is a C 1 ~4 alkyl group, vinyl group, carbon number 3 to 12 alkenyl group, carbon number 3 to 6 cycloalkyl group, carbon number 6 to 12 aromatic hydrocarbon group or substituted carbon number 7 to 12 aromatic hydrocarbon group, in the case when there are several R ^4, the plurality of R ⁴ may be the same or different from each other; Q is an integer of 0 ≦ q ≦ 3 of) the organic silicon compound represented by, and the general formula (4) :( R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)

(wherein R ⁵ and R ⁶ represent 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, and a carbon number of 3 to 20; a cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, and R ⁵ and R ⁶ may be the same or different from each other, or may be bonded to each other to form a ring, in the case where a plurality of R ⁵ R ⁶ N groups are present. a plurality of R ⁵ R ⁶ N groups may be the same or different from each other; R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. , a vinyloxy group, an alkenyloxy group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 6 to 20 when the aryloxy group, in the case of the presence of a plurality of R ^7, R ⁷ may be a number of mutually identical or different; S is an integer of from 1 to 3) a selected group of alkoxy silicon compound represented by the above.

Examples of the organic hydrazine compound represented by the above formula (3) or the amino decane compound represented by the formula (4) include a phenyl alkoxy decane, an alkyl alkoxy decane, and a phenylalkyl alkoxy group. Base decane, cycloalkyl alkoxy decane, alkyl (cycloalkyl) alkoxy decane, (alkylamino) alkoxy decane, alkyl (alkylamino) alkoxy decane, cycloalkyl (alkylamino)alkoxydecane, tetraalkoxydecane, tetrakis(alkylamino)decane, alkyltris(alkylamino)decane, dialkylbis(alkylamino)decane, three Alkyl (alkylamino) decane and the like.

Specific examples of the organic hydrazine compound represented by the above formula (3) or the amino decane compound represented by the formula (4) include n-propyltriethoxydecane and cyclopentyltriethoxy. Decane, phenyltrimethoxydecane, phenyltriethoxydecane, tert-butyltrimethoxydecane, diisopropyldimethoxydecane, isopropylisobutyldimethoxydecane, diiso Amyl dimethoxydecane, bis(2-ethylhexyl)dimethoxydecane, tert-butylmethyldimethoxydecane, tert-butylethyldimethoxydecane, dicyclopentyldimethyl Oxydecane, dicyclohexyldimethoxydecane, cyclopentylcyclopentyldimethoxydecane, cyclohexylmethyldimethoxydecane, tetraethoxydecane, tetrabutoxydecane, double (B Aminomethyl)methylethyl decane, bis(ethylamino)tributylmethyldecane, bis(ethylamino)dicyclohexyldecane, dicyclopentylbis(ethylamino)decane, bis ( Methylamino)(methylcyclopentylamino)methyldecane, diethylaminotriethoxydecane, bis(cyclohexylamino)dimethoxydecane, bis(perhydroisoquinolyl) Dimethyl More than one selected from the group consisting of decane, bis(perhydroquinolinyl)dimethoxydecane, ethyl(isoquinolyl)dimethoxydecane, and the like, preferably, n-propyltriethoxy Decane, phenyltrimethoxydecane, tert-butylmethyldimethoxydecane, tert-butylethyldimethoxydecane, diisopropyldimethoxydecane, isopropylisobutyldimethoxy Baseline, diisoamyldimethoxydecane, diphenyldimethoxydecane, dicyclopentyldimethoxydecane, cyclohexylmethyldimethoxydecane, tetramethoxydecane, tetraethyl Oxydecane, tert-butylmethylbis(ethylamino)decane, bis(ethylamino)dicyclohexyldecane, dicyclopentylbis(ethylamino)decane, bis(perhydroisoquinolyl) One or more selected from the group consisting of dimethoxy decane, diethylaminotriethoxy decane, and the like.

In the catalyst for olefin polymerization of the present invention, (A) the solid catalyst component for olefin polymerization of the present invention, (B) the organoaluminum compound represented by the formula (2), and (C) the external electron-donating compound. The content ratio is arbitrarily selected within the range in which the effects of the present invention are obtained, and is not particularly limited. The titanium atom per 1 mol of the solid catalyst component (A) for olefin polymerization is preferably (B). 2) The organoaluminum compound represented is 1 to 2000 moles, more preferably 50 to 1000 moles. Further, (B) the organoaluminum compound represented by the formula (2) is preferably (C) an external electron-donating compound of from 0.002 to 10 mol, more preferably from 0.01 to 2 mol, per 1 mol. It is 0.01~0.5 m.

The method for producing the catalyst for olefin polymerization of the present invention is not particularly limited, and (A) the solid catalyst component for olefin polymerization of the present invention and (B) the formula (2) can be used by a known method. A method of producing an olefin polymerization catalyst by contacting an organoaluminum compound and (C) an external electron-donating compound.

The order in which the above components are brought into contact is arbitrary, and for example, 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 the formula (2)

(ii) (B) organoaluminum compound represented by the formula (2) → (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 of the present invention → (B) organoaluminum compound represented by the formula (2)

(iv) (C) External electron-donating compound → (B) organoaluminum compound represented by the formula (2) → (A) solid catalyst component for olefin polymerization of the present invention

Among the above contact examples (i) to (iv), the contact example (ii) is preferred.

Further, in the above contact examples (i) to (iv), "→" means a contact order, for example, "(A) solid catalyst component for olefin polymerization of the present invention → (B) Formula (2) The organoaluminum compound to be represented by the (C) external electron-donating compound means that (A) the organoaluminum compound represented by the formula (2) is added to the solid catalyst component for olefin polymerization of the present invention. After the contact, (C) an external electron-donating compound is added to make contact.

The catalyst for olefin polymerization of the present invention may be (A) the solid catalyst component for olefin polymerization of the present invention, (B) the organoaluminum compound represented by the formula (2), and (C) the external electron-donating compound. The contact may be carried out in the absence of olefins, or in the presence of an olefin (in a polymerization system).

According to the present invention, a catalyst for olefin polymerization having a smooth surface can be provided.

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

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

In the method for producing an olefin polymer of the present invention, examples of the olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like. One or more selected ones are preferably ethylene, propylene or 1-butene, more preferably propylene.

In the case of polymerizing propylene, copolymerization with other olefins may be carried out, and block copolymerization of propylene with other α-olefins is preferred. The so-called block copolymer obtained by block copolymerization is a polymer comprising two or more groups in which the monomer composition continuously changes, and means that two or more monomer species are linked to one molecule chain, and the copolymerization sheet is used. The morphology of the polymer chain (segment) in which the polymer has a different structure, such as the species, the comonomer composition, the comonomer content, the comonomer arrangement, and the stereoregularity. The olefin to be copolymerized is preferably an α-olefin having 2 to 20 carbon atoms (other than propylene having a carbon number of 3), and specific examples thereof include ethylene, 1-butene, 1-pentene, and 4- Methyl-1-pentene, vinylcyclohexane, etc., and these olefins may be used in combination of at least one type. In particular, ethylene and 1-butene can be preferably used.

In the method for producing an olefin polymer of the present invention, the polymerization of the olefin may be carried out in the presence of an organic solvent or in the absence of an organic solvent. Further, in the method for producing an olefin polymer of the present invention, an olefin to be polymerized may be used in any of a gas and a liquid.

In the polymerization of an olefin, for example, an olefin may be introduced in the presence of a catalyst for olefin polymerization of the present invention in a reaction furnace such as an autoclave, and olefin polymerization may be carried out under heating and under pressure.

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 improvement in activity or stereoregularity. It is preferably 70 to 90 °C. In the method for producing an olefin polymer of the present invention, the polymerization pressure is preferably 10 MPa or less, more preferably 5 MPa or less. Further, either the continuous polymerization method or the batch polymerization method can be used. Further, the polymerization reaction can be carried out in one stage or in two stages or more.

In the method for producing an olefin polymer of the present invention, part or all of the constituent components of the catalyst for olefin polymerization of the present invention may be obtained by polymerizing an olefin (hereinafter, referred to as "formal polymerization" as the case may be). The prepolymerization (hereinafter, referred to as prepolymerization) is carried out by contacting with an olefin to be polymerized.

In the prepolymerization, the contact order of the constituent components of the olefin polymerization catalyst of the present invention and the olefin is arbitrary, but it is preferably first charged in a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere. The organoaluminum compound is then contacted with the solid catalyst component for olefin polymerization of the present invention, and then contacted with one or more olefins such as propylene. Or preferably, the organoaluminum compound is first charged in a prepolymerized system set in an inert gas atmosphere or an olefin gas atmosphere, and then contacted with an external electron-donating compound to further contact with the solid olefin polymerization polymer of the present invention. The medium component is contacted, and thereafter, it is contacted with one or more olefins such as propylene. In the prepolymerization, an olefin or a monomer such as styrene which is the same as the main polymerization can be used, and the prepolymerization conditions are also the same as those described above.

By performing the above prepolymerization, the catalytic activity is improved, and the stereoregularity and particle properties of the obtained polymer are easily improved.

According to the present invention, it is possible to provide a process for producing an olefin polymer which can produce a polymer having a smooth surface under a high polymerization activity. Further, in the present invention, since a solid catalyst component for olefin polymerization having a smooth surface is used, the amount of fine powder in the polymer obtained by polymerization is also reduced.

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

The invention is further illustrated by the following examples, but is not intended to limit the invention.

 [Examples]    (Example 1)    <Manufacture of diethoxy magnesium>  

Metallic magnesium powder (average particle size: 169 μm) 1.6 g, absolute ethanol 29 g, and tetrachloroethylene were placed in a four-necked flask equipped with a cumulative gas meter, a dropping funnel, a stirrer, and a reflux condenser and filled with nitrogen. 0.34 g (2 mmol) of hydrazine was heated to the reflux temperature of ethanol by an oil bath and maintained at reflux. Then, a mixture of 6.4 g of metallic magnesium powder and 84 g of ethanol was added thereto every 10 minutes in 4 portions.

After the entire amount was added, the mixture was further heated under reflux for 2 hours to complete the reaction. Then, the reaction liquid was dried by a rotary evaporator to obtain 100 g of powdered diethoxymagnesium.

The analysis of the obtained diethoxymagnesium showed that the halogen content was 0.3% by mass (0.4% by mass in terms of the content of ruthenium tetrachloride). Further, the surface of the obtained diethoxymagnesium was observed by a scanning electron microscope (SEM). As a result, it was confirmed that the surface of the diethoxymagnesium obtained in Example 1 was smoother than Comparative Examples 1 to 4. The results of the analysis and evaluation are shown in Table 1, and the SEM photograph of the obtained diethoxymagnesium is shown in Fig. 1.

<Average particle size (D ₅₀ ) and SPAN analysis>

Using a laser diffraction type particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., MICROTRAC HRA 9320-X100), disperse the magnesium dialkoxide in absolute ethanol, perform two automatic measurements, and measure the particle size distribution. A particle size (D ₁₀ ) having an accumulated volume fraction of 10%, a particle diameter (D ₅₀ ) of 50% of the cumulative volume fraction, and a particle diameter (D ₉₀ ) of 90% of the cumulative volume fraction, and the average value is taken as D _{10 .} , D ₅₀ , D ₉₀ . Further, the value of D ₅₀ obtained was taken as an average particle diameter, and SPAN was calculated from the following formula based on the values of D ₁₀ , D ₅₀ and D _{90 obtained} .

SPAN=(D ₉₀ -D ₁₀ )/D ₅₀

 <Dialkyloxymagnesium purity>  

The purity (% by mass) of the obtained dialkoxymagnesium was measured by an automatic titration apparatus (manufactured by Mitsubishi Chemical Analytech Co., Ltd., model GT-200), and the halogen in the dialkoxymagnesium after removal of the solvent The content (% by mass) of each of the compounds used as the reaction accelerator in the magnesium dialkoxide was determined by the following formula.

Magnesium dialkoxymagnesium purity (% by mass) = 100 - reaction accelerator content (% by mass)

 <Measurement of surface smoothness (Ra) and maximum surface height (Rz)>  

Using a shape-resolving laser microscope (Smartproof 5, manufactured by Carl Zeiss), for each of 100 samples of dialkoxymagnesium particles, the arithmetic mean roughness (Ra) and maximum height (Rz) of the particle surface according to JIS B 0601:2001 The measurement was performed and the average value was determined.

 (Example 2)  

The production and evaluation of diethoxymagnesium were carried out in the same manner as in Example 1 except that 0.34 g (2 mmol) of ruthenium tetrachloride was changed to 0.68 g (4 mmol). Further, the halogen content of the obtained diethoxymagnesium was 0.5% by mass (0.6% by mass in terms of cerium tetrachloride content), and the surface thereof was smoother than Comparative Examples 1 to 4. The analysis results of the obtained diethoxymagnesium are shown in Table 1.

 (Example 3)  

Diethoxymagnesium was carried out in the same manner as in Example 1 except that 0.51 g (4 mmol) of Si(CH ₃ ) ₂ Cl _{2 was used} instead of 0.34 g (2 mmol) of hafnium tetrachloride. Manufacturing and evaluation. Further, the halogen content of the obtained diethoxymagnesium was 0.4% by mass (0.7% by mass in terms of Si(CH ₃ ) ₂ Cl ₂ content), and the surface thereof was smoother than Comparative Examples 1 to 4.

The analysis results of the obtained diethoxymagnesium are shown in Table 1, and the obtained SEM photograph is shown in Fig. 2.

 (Example 4)  

Diethoxymagnesium was used in the same manner as in Example 1 except that 0.86 g (8 mmol) of Si(CH ₃ ) ₃ Cl was used instead of 0.34 g (2 mmol) of hafnium tetrachloride. Manufacturing and evaluation. In addition, the halogen content of the obtained diethoxy magnesium was 0.2% by mass (0.7% by mass in terms of Si(CH ₃ ) ₃ Cl content), and the surface thereof was smoother than Comparative Examples 1 to 4.

The analysis results of the obtained diethoxymagnesium are shown in Table 1.

 (Example 5)  

The same procedure as in Example 1 was carried out except that 0.56 g (4 mmol) of Si(CH ₃ )(C ₂ H ₅ )Cl _{2 was used} instead of 0.34 g (2 mmol) of hafnium tetrachloride. Production and evaluation of diethoxymagnesium. Further, the halogen content of the obtained diethoxymagnesium was 0.4% by mass (0.8% by mass in terms of Si(CH ₃ )(C ₂ H ₅ )Cl ₂ content), and the surface thereof was compared with Comparative Example 1~ 4 smooth.

The analysis results of the obtained diethoxymagnesium are shown in Table 1.

 (Comparative Example 1)  

The production and evaluation of diethoxymagnesium were carried out in the same manner as in Example 1 except that 1.0 g (4 mmol) of iodine was used instead of 0.34 g (2 mmol) of antimony tetrachloride. Further, the obtained diethoxymagnesium had a halogen content of 1.8% by mass, and the surface thereof was not smooth.

The analysis results of the obtained diethoxymagnesium are shown in Table 1.

 (Comparative Example 2)  

It is set to be magnesium chloride (manufactured by Wako Pure Chemical Industries, purity 97% or more, blocky, not screened) 0.38 g (4 mmol) instead of antimony tetrachloride 0.34 g (2 mmol), in addition to The production and evaluation of diethoxymagnesium were carried out in the same manner as in Example 1. Further, the obtained diethoxymagnesium had a halogen content of 0.5% by mass (0.6% by mass in terms of magnesium chloride content), and the surface thereof was not smooth.

The analysis results of the obtained diethoxymagnesium are shown in Table 1.

 (Comparative Example 3)  

The production and evaluation of diethoxymagnesium were carried out in the same manner as in Example 1 except that 0.37 g (2 mmol) of titanium tetrachloride was used instead of 0.34 g (2 mmol) of antimony tetrachloride. . Further, the obtained diethoxymagnesium had a halogen content of 1.1% by mass (1.5% by mass in terms of titanium tetrachloride content), and the surface thereof was not smooth.

The analysis results of the obtained diethoxymagnesium are shown in Table 1, and the obtained SEM photograph is shown in Fig. 3.

 (Comparative Example 4)  

1.6 g of metallic magnesium powder, 29 g of absolute ethanol and 0.23 g of titanium tetrachloride (1.2 mmol) were substituted for 1.6 g of metallic magnesium powder, 29 g of absolute ethanol and 0.34 g of ruthenium tetrachloride (2 mmol). Further, a mixture of 6.4 g of metallic magnesium powder, 84 g of ethanol, and 0.53 g of titanium tetrachloride (2.8 mmol) was added in four or more portions instead of a mixture of 6.4 g of metal magnesium powder and 84 g of ethanol in four portions. Production and evaluation of diethoxymagnesium were carried out in the same manner as in Example 1. Further, the halogen content of the obtained diethoxymagnesium was 1.3% by mass (1.7% by mass in terms of the content of titanium tetrachloride), and the surface thereof was not smooth.

The analysis results of the obtained diethoxymagnesium are shown in Table 1.

According to the examples 1 to 5, the reaction of the metal magnesium with the alcohol is preferably carried out by using the antimony halide compound represented by the above formula (1) which is more reactive than the halogen atom as a reaction accelerator. Since it is introduced into the reaction system, the reaction between the magnesium metal and the alcohol proceeds smoothly, so that a large-diameter dialkoxymagnesium having a smooth surface, high purity, and an average particle diameter of 55 μm or more is obtained.

On the other hand, since iodine is a halogen atom, the reactivity is strong, and the titanium tetrachloride which is an inorganic halogen compound has extremely strong reactivity with the alcohol as a raw material, and therefore the effect as a promoter cannot be stably obtained. Magnesium chloride is difficult to sufficiently obtain reactivity as a reaction accelerator, and any compound can hinder the growth of magnesium dialkoxide particles when used as a reaction accelerator, and only a dialkoxy group having a smaller average particle diameter can be obtained. In the case of the magnesium particles, even if particles having a large average particle diameter can be formed, the surface of the particles is not smooth, or the halogen content is high, and the purity is low. Therefore, it is understood that when the antimony halide compound of the present invention is used as a reaction accelerator. A dialkoxy magnesium particle having a smooth surface and a large average particle diameter and high purity.

 (Example 6)    <Manufacture of diethoxy magnesium>  

Metallic magnesium powder (average average particle diameter: 169 μm) 1.6 g, absolute ethanol 29 g, and anhydrous were placed in a four-necked flask equipped with a cumulative gas meter, a dropping funnel, a stirrer, and a reflux condenser and filled with nitrogen. Magnesium dichloride (purity 99.9%, average particle size (D ₅₀ ) 96.7 μm, particle size distribution index (SPAN) 2.7, specific surface area 7.9 m ^{2 /} g) 0.38 g (4 mmol), after which it was heated to an oil bath The reflux temperature of ethanol is maintained at reflux. Then, a mixture of 6.4 g of metallic magnesium powder and 84 g of ethanol was added thereto every 10 minutes in 4 portions.

After the entire amount was added, the mixture was further heated under reflux for 2 hours to complete the reaction. Then, the reaction liquid was dried by a rotary evaporator to obtain 100 g of powdered diethoxymagnesium.

Then, the surface smoothness (Ra), the surface maximum height (Rz), the average particle diameter (D ₅₀ ), the particle size distribution index (SPAN), and the halogen content (% by mass) were measured for the obtained diethoxymagnesium. Further, the surface of the particles was observed by a scanning electron microscope (SEM) on the obtained diethoxymagnesium. As a result, the surface of the diethoxy magnesium particles obtained in Example 6 was smoother than Comparative Examples 5 to 8. The evaluation results are shown in Table 2.

 (Example 7)  

As anhydrous magnesium chloride, a purity of 99.8%, an average particle diameter (D ₅₀ ) of 30.1 μm, a particle size distribution index (SPAN) of 6.3, and a specific surface area of 60.8 m ² /g of 0.38 g (4 mmol) were used. The production and analysis of diethoxymagnesium was carried out in the same manner as in Example 6.

The analysis results of the obtained diethoxymagnesium are shown in Table 2.

 (Comparative Example 5)  

As anhydrous magnesium chloride, scaly anhydrous magnesium chloride (manufactured by Wako Pure Chemical Industries, purity 97% or more, screen mesh 500 μm or more and 1180 μm or less, specific surface area 0.6 m ^{2 /} g) 0.38 g (4 mmol) was used. Except for this, the production and analysis of diethoxymagnesium were carried out in the same manner as in Example 6.

The analysis results of the obtained diethoxymagnesium are shown in Table 2.

 (Comparative Example 6)  

The production and analysis of diethoxymagnesium were carried out in the same manner as in Example 6 except that 0.9 g (3.5 mmol) of iodine was used instead of 0.38 g (4 mmol) of anhydrous magnesium chloride.

The analysis results of the obtained diethoxymagnesium are shown in Table 2.

 (Comparative Example 7)  

The production and analysis of diethoxymagnesium were carried out in the same manner as in Example 6 except that 1.1 g (4.3 mmol) of iodine was used instead of 0.33 g (4 mmol) of anhydrous magnesium chloride.

The analysis results of the obtained diethoxymagnesium are shown in Table 2.

In the case where a magnesium halide (metal halide) having a specific shape is used as a reaction accelerator in the reaction of magnesium metal and an alcohol, since the reactivity is smoother than that of the halogen atom itself, the reaction of the magnesium metal with the alcohol proceeds smoothly. Therefore, the growth of the particles (granulation) is not hindered, and the dialkoxy magnesium particles having a smooth surface and a small amount of fine powder components are easily formed.

On the other hand, since iodine is a halogen atom, the reactivity is strong, and the titanium tetrachloride which is an inorganic halogen compound has extremely strong reactivity with the alcohol as a raw material, so that it is difficult to obtain an effect as a promoter in a stable state. Any compound hinders the growth of the dialkoxymagnesium particles, and it is difficult to form a large particle size dialkoxymagnesium. Further, even if a large particle is formed, the particle size distribution is wide or the particle surface is not smooth. Therefore, it is impossible to obtain a dialkoxymagnesium particle having a smooth surface and a small fine powder component when a magnesium halide (metal halide) having a specific shape is used for the accelerator.

Further, magnesium chloride having an average particle diameter and a specific surface area deviated from a specific range is too high or insufficient in reactivity as a promoter, so that a magnesium halide (metal halide) having a specific range cannot be obtained in a good yield. A dialkoxide magnesium particle that is smooth on the surface of the accelerator.

 (Example 8)    <Preparation of solid catalyst component for olefin polymerization>  

A round bottom flask which was sufficiently substituted with nitrogen and equipped with a stirrer having a capacity of 500 ml was charged with 30 ml of titanium tetrachloride and 20 ml of toluene to form a mixed solution. Then, a suspension formed by using 10 g of diethoxymagnesium, 50 ml of toluene and 3.3 ml (12.5 mmol) of di-n-butyl phthalate obtained in the above Example 1 was added to the solution maintained at 10 ° C. Warm in the above mixed solution.

Thereafter, the liquid temperature was raised from 10 ° C to 90 ° C, and the reaction was carried out at 90 ° C for 2 hours while stirring.

After completion of the reaction, the obtained solid product was washed four times with 100 ml of toluene at 90 ° C, and 30 ml of titanium tetrachloride and 70 ml of toluene were newly added, and the temperature was raised to 110 ° C, and the mixture was stirred for 2 hours to cause a reaction. After completion of the reaction, the mixture was washed 10 times with 100 ml of n-heptane at 40 ° C to obtain a solid catalyst component (A-1) for olefin polymerization.

Further, the solid catalyst component (A-1) contained 14.2% by mass of a phthalic acid diester as an internal electron-donating compound. Further, the titanium content in the solid catalyst component was measured and found to be 2.2% by weight.

 <Formation of olefin polymerization catalyst and propylene polymerization>  

The autoclave with 2.0 liter of internal volume completely replaced by nitrogen was charged with triethylaluminum 1.32 mmol, cyclohexylmethyldimethoxydecane 0.13 mmol and the above solid catalyst component (A- 1) 0.0026 mmol in terms of titanium atom to form a catalyst for olefin polymerization.

Then, 4 liters of hydrogen and 1.4 liters of liquefied propylene were placed in an autoclave, and prepolymerization was carried out at 20 ° C for 5 minutes. Thereafter, the temperature was raised to 70 ° C, and polymerization was carried out at 70 ° C for 1 hour, thereby obtaining propylene. Polymer. The polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer are shown in Table 3.

 <Average particle size, particle size distribution index, and amount of fine powder having a particle diameter of less than 75 μm>  

The average particle diameter of the obtained polymer, the particle size distribution index, and the amount of fine powder having a particle diameter of less than 75 μm were measured by the following image analysis type particle size distribution measuring apparatus (Camsizer, manufactured by Horiba, Ltd.). The volumetric basis cumulative particle size distribution of the polymer is automatically measured under conditions.

 (measurement conditions)  

Funnel position: 6mm

Coverage area of the camera: the base camera is less than 3%, and the zoom camera is less than 10%

Target coverage area: 0.5%

Feeder width: 40mm

Feeder control volume: 57,40 seconds

Determination of initial amount: 47

Maximum control: 80

Control benchmark: 20

Image rate: 50% (1:2)

Particle size definition: the minimum value of Martin's diameter obtained by measuring n times per particle

SPHT (spherical) fitting: 1

Upper limit of type: Set to logarithmic scale, select 50 points in the range of 32μm~4000μm

 (Comparative Example 8)  

The solid catalyst component for olefin polymerization was subjected to the same procedure as in Example 8 except that 10 g of diethoxymagnesium obtained in the above Comparative Example 1 was used instead of 10 g of diethoxymagnesium obtained in the above Example 1. Preparation, formation of an olefin polymerization catalyst, and propylene polymerization, and physical property evaluation of the obtained polymer. The polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer are shown in Table 3.

In Example 8 which was obtained as the raw material of the solid catalyst component for olefin polymerization which was obtained as the raw material of the solid catalyst component for olefin polymerization obtained in Example 1, which had a smooth surface, a large average particle diameter and a high purity, was obtained, an average particle diameter (D) was obtained. ₅₀ ) Polypropylene particles which are larger, have a narrow particle size distribution, and have less fine powder polymer.

On the other hand, in Comparative Example 8 which was obtained as a raw material of a solid catalyst component for olefin polymerization, which was obtained by the use of Comparative Example 1 and having a rough surface, a small average particle diameter and a low purity, was used as a raw material for a solid catalyst component for olefin polymerization. The polypropylene particles have a smaller average particle diameter (D ₅₀ ), a wider particle size distribution, and a larger proportion of the fine powder polymer.

 (Example 9)    <Preparation of solid catalyst component for olefin polymerization>  

A round bottom flask having a capacity of 500 ml of a stirrer which was sufficiently substituted with nitrogen was charged with 30 ml of titanium tetrachloride and 20 ml of toluene to form a mixed solution. Then, a suspension formed by using 10 g of diethoxymagnesium, 50 ml of toluene and 3.6 ml (15.5 mmol) of di-n-propyl phthalate obtained in the above Example 6 was added to the solution maintained at 10 ° C. Warm in the above mixed solution.

Thereafter, the liquid temperature was raised from 10 ° C to 90 ° C, and the reaction was carried out at 90 ° C for 2 hours while stirring.

After completion of the reaction, the obtained solid product was washed four times with 100 ml of toluene at 90 ° C, and 30 ml of titanium tetrachloride and 70 ml of toluene were newly added, and the temperature was raised to 110 ° C, and the mixture was stirred for 2 hours to cause a reaction. After completion of the reaction, the mixture was washed 10 times with 100 ml of n-heptane at 40 ° C to obtain a solid catalyst component (A-2) for olefin polymerization.

Further, the solid catalyst component (A-2) contained 12.6% by mass of a phthalic acid diester as an internal electron-donating compound. Further, the titanium content in the solid catalyst component was measured and found to be 2.93 wt%.

 <Formation of olefin polymerization catalyst and propylene polymerization>  

The autoclave with 2.0 liter of internal volume completely replaced by nitrogen was charged with triethylaluminum 1.32 mmol, cyclohexylmethyldimethoxydecane 0.13 mmol and the above solid catalyst component (A- 2) 0.0026 mmol in terms of titanium atom to form a catalyst for olefin polymerization.

Then, 4 liters of hydrogen and 1.4 liters of liquefied propylene were placed in an autoclave, and prepolymerization was carried out at 20 ° C for 5 minutes. Thereafter, the temperature was raised to 70 ° C, and polymerization was carried out at 70 ° C for 1 hour, thereby obtaining propylene. Polymer. The polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer are shown in Table 4.

 <Average particle size, particle size distribution index, and amount of fine powder having a particle diameter of less than 75 μm>  

The average particle diameter of the obtained polymer, the particle size distribution index, and the amount of fine powder having a particle diameter of less than 75 μm were measured by the following image analysis type particle size distribution measuring apparatus (Camsizer, manufactured by Horiba, Ltd.). The volumetric basis cumulative particle size distribution of the polymer is automatically measured under conditions.

 (measurement conditions)  

Funnel position: 6mm

Coverage area of the camera: the base camera is less than 3%, and the zoom camera is less than 10%

Target coverage area: 0.5%

Feeder width: 40mm

Feeder control volume: 57,40 seconds

Determination of initial amount: 47

Maximum control: 80

Control benchmark: 20

Image rate: 50% (1:2)

Particle size definition: the minimum diameter of the Martin diameter obtained by measuring n times per particle

SPHT (spherical) fitting: 1

Upper limit of type: Set to logarithmic scale, select 50 points in the range of 32μm~4000μm

 (Comparative Example 9)  

A solid catalyst component for olefin polymerization (A-) was prepared in the same manner as in Example 9 except that 10 g of diethoxymagnesium obtained in the above Comparative Example 5 was used instead of 10 g of diethoxymagnesium obtained in the above Example 6. 3) Thereafter, formation of an olefin polymerization catalyst and polymerization of propylene were carried out, and physical properties of the obtained polymer were evaluated.

Further, 13.3% by weight of phthalic acid diester was contained in the solid catalyst component (A-3) as an internal electron-donating compound.

Further, the titanium content in the solid catalyst component was measured and found to be 2.83 wt%. The polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer are shown in Table 2.

 (Comparative Example 10)  

A solid catalyst component for olefin polymerization was prepared in the same manner as in Example 9 except that 10 g of diethoxymagnesium obtained in the above Comparative Example 7 was used instead of 10 g of diethoxymagnesium obtained in the above Example 6. A-4) Thereafter, formation of an olefin polymerization catalyst and polymerization of propylene were carried out, and physical properties of the obtained polymer were evaluated.

Further, a phthalic acid diester is contained in the solid catalyst component (A-4) as an internal electron supply compound.

Further, the titanium content in the solid catalyst component was measured and found to be 3.08% by weight. The polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer are shown in Table 4.

In Example 9 of the dialkoxymagnesium obtained in Example 6 having a smooth surface and a narrow particle size distribution, polypropylene particles having a narrow particle size distribution index and a small amount of fine powder were obtained in a higher yield.

On the other hand, in Comparative Examples 9 and 10 using the dialkoxymagnesium obtained in Comparative Examples 5 and 7 having a rough surface and a broad particle size distribution index, the obtained polypropylene had a wide particle size distribution index and fine powder particles. There are also a large proportion.

Claims (15)

 A dialkoxymagnesium characterized in that the arithmetic mean roughness (Ra) of the surface of the particles is 0.5 or less, and the maximum height (Rz) of the surface of the particles is 2.0 or less.   A method for producing a dialkoxymagnesium which is obtained by reacting magnesium metal with an alcohol in the presence of a reaction accelerator to obtain a dialkoxymagnesium, characterized in that the reaction accelerator is of the following formula (1) The ruthenium halide compound represented by: SiR ¹ _n X _(4-n) (1) (in the formula (1), R ¹ is an alkyl group or an alkoxy group; X is a chlorine atom or a bromine atom; n is 0 to 3 An integer; when n is 2 or more, a plurality of R ¹ may be the same or different from each other; when there are several Xs, several Xs may be the same or different from each other).  The method for producing a magnesium alkoxide according to claim 2, wherein the reaction accelerator is tetrafluorodecane, tetrachlorodecane, tetrabromodecane or tetraiododecane.    A method for producing alkoxymagnesium according to claim 2 or 3, wherein the alcohol is ethanol.   A method for producing a dialkoxymagnesium obtained by reacting magnesium metal with an alcohol in the presence of a reaction accelerator to obtain a dialkoxymagnesium, wherein the reaction accelerator has an average particle diameter ( D ₅₀ ) is a powdery metal halide having a particle diameter of 500 μm or less and a specific surface area of 1 m ² /g or more. The method for producing a magnesium alkoxide according to claim 5, wherein the particle diameter (D ₉₀ ) of the metal halide D90 is 2000 μm or less. A method for producing alkoxymagnesium according to claim 5 or 6, wherein the metal halide has a particle size distribution index (SPAN): SPAN = (D _{90 -} D ₁₀ ) / D ₅₀ of 7 or less.  The method for producing a magnesium dialkoxide according to any one of claims 5 to 7, wherein the metal halide is magnesium dichloride.    The method for producing a magnesium dialkoxide according to any one of claims 5 to 8, wherein the alcohol is ethanol.    A solid catalyst component for olefin polymerization, which is obtained by contacting the alkoxy magnesium (a) of claim 1 and the titanium halogen compound (b) and the electron-donating compound (c).    A solid catalyst component for olefin polymerization, characterized in that it is a dialkoxymagnesium (a) obtained by the method for producing a dialkoxymagnesium according to any one of claims 2 to 9, and a titanium halide. The compound (b) and the electron-donating compound (c) are obtained by contact.    A catalyst for olefin polymerization, characterized in that (A) the solid catalyst component for olefin polymerization of claim 10 or 11, (B) an organoaluminum compound, and (C) an external electron supply compound Contact the winner.   The olefin polymerization catalyst according to claim 12, wherein the (B) organoaluminum compound is an organoaluminum compound represented by the following formula (2): R ² _P AlQ _3-P (2) (wherein R ² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 < p ≦ 3; in the case where there are several R ² , each R ² may be the same or different from each other. When there are several Qs, each Q may be the same or different). The catalyst for olefin polymerization according to claim 12 or 13, wherein the (C) external electron-donating compound is selected from the group consisting of the following formula (3): R ³ _q Si(OR ⁴ ) _4-q (3) (wherein R ³ represents 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, and a carbon number; when the aromatic hydrocarbon group of 6 to 15 or a substituent group having a carbon number of the aromatic hydrocarbon group of 6 to 15, in the case of the presence of a number of R ^3, a plurality of R ³ may be mutually the same or different; R ⁴ is a C 1 ~4 alkyl group, vinyl group, carbon number 3 to 12 alkenyl group, carbon number 3 to 6 cycloalkyl group, carbon number 6 to 12 aromatic hydrocarbon group or substituted carbon number 7 to 12 aromatic hydrocarbon group, in the case when there are several R ^4, the plurality of R ⁴ may be the same or different from each other; Q is an integer of 0 ≦ q ≦ 3 of) the organic silicon compound represented by, and the general formula (4) :( R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4) (wherein R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, and a carbon number a cycloalkyl group of 3 to 20, a cycloalkenyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁵ and R ⁶ may be the same or different from each other, or may be bonded to each other to form a ring. ,to When a number of case ⁵ R group of the R ⁶ N, a plurality of R ⁵ R ⁶ N groups may be the same or different from each other; R ⁷ represents an alkyl group having 1 to 20 carbon atoms, the vinyl carbon atoms of 3 to 12 Alkenyl group, alkoxy group having 1 to 20 carbon atoms, ethyleneoxy group, alkenyloxy group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkoxy group having 3 to 20 carbon atoms, carbon number an aryl group of 6 to 20 carbon atoms aryloxy of 6 to 20, in the case when there are several of R ^7, R ⁷ may be a number of mutually identical or different; S is an integer of from 1 to 3) represented by the One or more of the aminodecane compounds.  A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of a catalyst for olefin polymerization according to any one of claims 12 to 14.