WO2018230700A1 - Dialkoxy magnesium, method for producing dialkoxy magnesium, solid catalyst component for olefin polymerization, and method for producing olefin polymer - Google Patents

Abstract

A dialkoxy magnesium which is characterized in that: the arithmetic mean roughness (Ra) of particle surfaces is 0.5 or less; and the maximum height (Rz) of particle surfaces is 2.0 or less. The present invention is able to provide a dialkoxy magnesium which has a smooth surface.

Description

Dialkoxymagnesium, dialkoxymagnesium production method, solid catalyst component for olefin polymerization, and olefin polymer production method

The present invention relates to a novel dialkoxymagnesium suitable as a carrier material for a catalyst component for olefin polymerization and a method for producing the same.

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

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

In such circumstances, in the polymerization of olefins, as one of the requirements in the shape control of polyolefin polymer particles, the particle surface is required to be smooth. 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 dialkoxymagnesium serving as a carrier for the solid catalyst component. That is, in order to obtain a smooth surface polyolefin, a smooth surface dialkoxymagnesium is required.

As a method for producing dialkoxymagnesium, for example, Patent Document 1 discloses a method in which metal magnesium and ethanol are reacted under pressure without using a reaction accelerator.

Patent Document 2 discloses a method of reacting magnesium metal and absolute ethanol in the presence of iodine as a reaction accelerator.

Patent Documents 3 and 4 include a method in which metallic magnesium and alcohol are reacted in the presence of iodine as a reaction accelerator, and iodine as a reaction accelerator is added to the reaction system in a plurality of times. It is disclosed.

JP 2010-202667 A Japanese Patent Laid-Open No. 3-74341 JP 2013-95890 A International Publication No. 2013/058193

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

Therefore, an object of the present invention is to provide a dialkoxymagnesium having a smooth particle surface and a method for producing dialkoxymagnesium for obtaining such dialkoxymagnesium.

Under such circumstances, the present inventor has intensively studied, and as a result, by using a specific silicon halide compound as a reaction accelerator when reacting magnesium metal and alcohol, dialalkoxymagnesium having a smooth surface can be obtained. In addition, by using a specific metal halogen compound as a reaction accelerator for reacting metal magnesium with alcohol, it was found that dialkoxymagnesium with a smooth particle surface can be obtained, and the present invention was completed. I came to let you.

That is, the present invention (1) is characterized in that the arithmetic average roughness (Ra) of the particle surface is 0.5 or less and the maximum height (Rz) of the particle surface is 2.0 or less. Dialkoxymagnesium is provided.

Further, the present invention (2) is a method for producing dialkoxymagnesium, wherein metalmagnesium and alcohol are reacted in the presence of a reaction accelerator to obtain dialkoxymagnesium,
The reaction accelerator is represented by the following general formula (1):
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, a plurality of R ¹ may be the same or different from each other, and when there are a plurality of X, the plurality of X may be the same or different from each other.
A halogenated silicon compound represented by:
A method for producing dialkoxymagnesium characterized by the above is provided.

The present invention (3) provides the method for producing dialkoxymagnesium according to (2), wherein the reaction accelerator is tetrafluorosilane, tetrachlorosilane, tetrabromosilane or tetraiodosilane. It is.

Further, the present invention (4) provides the method for producing dialkoxymagnesium according to either (2) or (3), wherein the alcohol is ethanol.

The present invention (5) is a method for producing dialkoxymagnesium to obtain dialkoxymagnesium by reacting metal magnesium and alcohol in the presence of a reaction accelerator,
The reaction accelerator is a powdered metal halide compound having an average particle diameter (D ₅₀ ) of 500 μm or less and a specific surface area of 1 m ² / g or more;
A method for producing dialkoxymagnesium characterized by the above is provided.

In addition, the present invention (6) provides the method for producing dialkoxymagnesium according to (5), wherein the particle diameter (D ₉₀ ) at D90 of the metal halide is 2000 μm or less.

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

The present invention (8) provides the method for producing dialkoxymagnesium according to any one of (5) to (7), wherein the metal halide is magnesium dichloride.

The present invention (9) provides the method for producing dialkoxymagnesium according to any one of (5) to (8), wherein the alcohol is ethanol.

Further, the present invention (10) is an olefin obtained by contacting the dialkoxymagnesium (a), the titanium halogen compound (b) and the electron donating compound (c) of (1). A solid catalyst component for polymerization is provided.

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

In the present invention (12), (A) (10) or (11) the solid catalyst component for olefin polymerization, (B) an organoaluminum compound, and (C) an external electron donating compound are brought into contact with each other. The present invention provides a catalyst for olefin polymerization, characterized in that it is obtained.

In the invention (13), the organoaluminum compound (B) is represented by the following general formula (2):
R ² _p AlQ _3-p (2)
(Wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 <.R ² is a real number p ≦ 3 there are a plurality, each R ² may be the same or different from each other, and when a plurality of Qs are present, each Q may be the same or different.)
(12) A catalyst for olefin polymerization according to (12), which is an organoaluminum compound represented by the formula:

Also, in the present invention (14), the external electron donating compound (C) is represented by 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, carbon 6 to an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent of 15, if R ³ there are a plurality, the plurality of R ³ may be the same or different R ⁴ represents an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. an aromatic hydrocarbon group having 7-12 carbon atoms having, if R ⁴ there are a plurality, the plurality of R ⁴ may optionally be the same or different .q is an integer of 0 ≦ q ≦ 3. )
And an organic silicon compound represented by the general formula (4):
(R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)
(Wherein R ⁵ and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms) A cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, wherein R ⁵ and R ⁶ may be the same or different from each other, and may be bonded to each other to form a ring; R ⁵ R ⁶ N group When a plurality of R ⁵ R ⁶ N groups are present, the plurality of R ⁵ R ⁶ N groups may be the same or different from each other, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon number. 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 cycloalkyloxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6-20 carbon atoms Shows the aryloxy group, if R ⁷ there is a plurality, a plurality of R ⁷ is optionally be the same or different .s is an integer from 1 to 3.)
The catalyst for olefin polymerization according to any one of (12) and (13), which is at least one selected from the group consisting of aminosilane compounds represented by the formula:

The present invention (15) also provides a method for producing an olefin polymer, characterized by polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of (12) to (14). It is.

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

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

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

The surface smoothness (Ra) of the dialkoxymagnesium of the present invention is 0.5 or less, preferably 0.49 or less, particularly preferably 0.47 or less. When the surface smoothness (Ra) of dialkoxymagnesium is in the above range, the fluidity of the solid catalyst component for olefin polymerization produced from dialkoxymagnesium is improved, and the flow of the polymer obtained from this solid catalyst component is improved. Therefore, the adhesion in the polymerization process is reduced and the transportability is improved. In addition, in this invention, surface smoothness (Ra) is arithmetic mean roughness (Ra) of the dialkoxymagnesium particle surface measured with a shape analysis laser microscope according to JISＪB 0601: 2001.

The maximum surface height (Rz) of dialkoxymagnesium of the present invention is 2.0 or less, preferably 1.95 or less, particularly preferably 1.00 to 1.95. Since the maximum surface height (Rz) of dialkoxymagnesium is in the above range, when dialkoxymagnesium is used as a carrier raw material for a solid catalyst component for olefin polymerization, the fluidity of the resulting solid catalyst component is improved. The transfer and discharge from the container are facilitated, the time taken to transfer the solid catalyst component from the container is shortened, or the remaining amount in the container is reduced. Moreover, since the fluidity of the obtained solid catalyst component and the polymer obtained from this solid catalyst component is also improved, the adhesion in the polymerization process is reduced, and the transportability is improved. In the present invention, the maximum surface height (Rz) is the maximum height (Rz) of the dialkoxymagnesium particle surface measured by a shape analysis laser microscope according to JIS B 0601: 2001.

The dialkoxymagnesium of the present invention is dialkoxymagnesium having excellent surface smoothness because the maximum surface height (Rz) and the maximum height (Rz) are in the above range. Then, by using the dialkoxymagnesium of the present invention, which is excellent in surface smoothness, as a carrier raw material for the solid catalyst component for olefin polymerization, the content of fine particles in the resulting solid catalyst component is reduced, and the resulting heavy weight is obtained. The coalescence has few fine powder particles, has a smooth surface, and excellent fluidity. The use of dialkoxymagnesium having excellent surface smoothness as a carrier raw material for the solid catalyst component for olefin polymerization is not clear, but the following reasons are conceivable. In general, the Ziegler-Natta catalyst is reflected by the so-called replica phenomenon in the catalyst in which the shape and properties of the raw material carrier are obtained, and also in the shape and properties of the polymer obtained using the catalyst. It has been. Therefore, by using the raw material carrier (dialkoxymagnesium of the present invention) having few deposits and excellent smoothness on the particle surface, the content of fine particles in the solid catalyst for olefin polymerization obtained is reduced, and the surface A smooth solid catalyst is obtained. The polymer obtained by using the solid catalyst has few fine powder particles, and can produce a polymer having a smooth surface and excellent fluidity.

The sphericity of the dialkoxymagnesium of the present invention is preferably 2 or less, particularly preferably 1.5 or less. In the present invention, the sphericity of dialkoxymagnesium is measured by an image analyzer (Mac-View, manufactured by Mountec Co., Ltd.), a circumscribed rectangle is calculated for particle images taken from a plurality of directions, and the length of one side is calculated. From the long side (maximum length) of the circumscribed rectangle when the maximum is reached and the diameter (Heywood diameter) of a circle having the same area as the particle projection area when the length of the one side is the maximum, the following formula is used. It is done.
Sphericality = {(maximum length) ÷ (Heywood diameter)} 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, particularly preferably 10 to 80 μm. Since the average particle diameter (D ₅₀ ) of dialkoxymagnesium is in the above range, when dialkoxymagnesium is used as a carrier raw material for the solid catalyst component for olefin polymerization, the content of fine particles in the obtained solid catalyst component is Reduced, resulting in fewer polymer fines.
Particle size distribution index (SPAN) of dialkoxymagnesium of the present invention:
SPAN = (D ₉₀ -D ₁₀ ) / D ₅₀
Is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.0 or less. Due to the particle size distribution index (SPAN) of dialkoxymagnesium being in the above range, when dialkoxymagnesium is used as a carrier material for solid catalyst components for olefin polymerization, the content of fine particles in the resulting solid catalyst component is reduced. Resulting in fewer polymer fines particles.
In the present invention, D ₁₀ , D ₅₀ , and D ₉₀ are integrated volume fractions in the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring device (MICROTRAC HRA Model No. 9320-X100, manufactured by Nikkiso Co., Ltd.). Indicates particle diameters (μm) corresponding to 10%, 50%, and 90%, respectively.

The bulk specific gravity of the dialkoxymagnesium of the present invention is preferably 0.1 to 0.6 g / ml, more preferably 0.2 to 0.5 g / ml, particularly preferably 0.25 to 0.40 g / ml. . When the bulk specific gravity of dialkoxymagnesium is in the above range, the bulk specific gravity of the polymer obtained when polymerizing a solid catalyst component using dialkoxymagnesium as a carrier raw material becomes good.

The dialkoxymagnesium of the present invention preferably contains no alcohol, but is acceptable if the alcohol content is 2% by mass or less.

When the dialkoxymagnesium of the present invention is obtained using magnesium halide as a reaction accelerator, the halogen content in the dialkoxymagnesium of the present invention is 0.05 to 10.0% by mass, The amount is preferably 0.05 to 8.0% by mass, more preferably 0.1 to 5.0% by mass, and particularly preferably 0.3 to 3.0% by mass. When the halogen content of dialkoxymagnesium is in the above range, dialkoxymagnesium having a good particle shape and particle surface condition can be obtained. Furthermore, the metal halogen compound used as a reaction accelerator in the present invention hardly remains in the resulting dialkoxymagnesium, or when the dialkoxymagnesium is prepared from the dialkoxymagnesium, When chlorinated, it does not elute into an inert organic solvent unlike the iodine generally used as a reaction accelerator. Furthermore, when the metal halogen compound used as the reaction accelerator in the present invention can be used as it is as the carrier component of the solid catalyst component, it is not necessary to remove it from the dialkoxymagnesium particles.

The method for producing dialkoxymagnesium according to the first aspect of the present invention is a method for producing dialkoxymagnesium in which metalmagnesium and alcohol are reacted in the presence of a reaction accelerator to obtain dialkoxymagnesium,
The reaction accelerator is represented by the following general formula (1):
SiR ¹ _n X _(4-n) (1)
(In 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 is R. ¹ may be the same or different, and when there are a plurality of X, the plurality of X may be the same or different.
A halogenated silicon compound represented by:
Is a method for producing dialkoxymagnesium.

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

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

In the method for producing dialkoxymagnesium according to the first aspect of the present invention, the following general formula (1) is used with metal magnesium and alcohol as a reaction accelerator:
SiR ¹ _n X _(4-n) (1)
It is made to react using the silicon halide compound represented by these.

In general formula (1), R ¹ is an alkyl group or an alkoxy group, preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, particularly preferably an alkyl group or an alkoxy group having 1 to 2 carbon atoms. It is a group. X is a chlorine atom or a bromine atom, and as X, a chlorine atom is preferable. n is an integer of 0 to 3, preferably an integer of 0 to 2, and particularly preferably 0. When n is 2 or more, the plurality of R ¹ may be the same as or different from each other. When there are a plurality of Xs, the plurality of Xs may be the same as or different from each other.

The silicon halide compound represented by the general formula (1) is preferably tetrafluorosilane, tetrachlorosilane, tetrabromosilane, or tetraiodosilane. When the reaction accelerator is tetrafluorosilane, tetrachlorosilane, tetrabromosilane, or tetraiodosilane, dialkoxymagnesium having a large average particle diameter and a smooth surface is easily obtained.

In the method for producing dialkoxymagnesium according to the first aspect of the present invention, the molar ratio of alcohol to metal magnesium (alcohol / metal magnesium) is preferably 3 to 30, particularly preferably 5 to 20. When the molar ratio of alcohol to metal magnesium is in the above range, the resulting dialkoxymagnesium has a large average particle size and a smooth surface.

In the method for producing dialkoxymagnesium of the first aspect of the present invention, the molar ratio of the silicon halide compound represented by the general formula (1) to the metal magnesium (the silicon halide compound represented by the general formula (1) / The metal magnesium) is preferably from 0.0001 to 0.1, particularly preferably from 0.003 to 0.03. When the molar ratio of the silicon halide compound represented by the general formula (1) to the metal magnesium is in the above range, the average particle size is large, the surface is smooth, and high-purity dialkoxymagnesium is obtained.

In the method for producing dialkoxymagnesium according to the first aspect of the present invention, these reactions are carried out in a suspended state in which metallic magnesium is dispersed in alcohol while stirring metallic magnesium and alcohol. And in the manufacturing method of dialkoxymagnesium of the 1st form of this invention, the silicon halide compound represented by General formula (1) is previously mixed with alcohol, and is represented by General formula (1). A silicon halide compound represented by the general formula (1) in a suspension obtained by mixing an alcohol containing a silicon halide compound with metal magnesium or by mixing metal magnesium and alcohol. Or when the silicon halide compound is liquid, it is added as it is without mixing with the alcohol, thereby introducing the silicon halide compound represented by the general formula (1) into the reaction system, Metal magnesium and alcohol are reacted in the presence of a silicon halide compound represented by the general formula (1). In the method for producing dialkoxymagnesium according to the first aspect of the present invention, the introduction of the silicon halide compound represented by the general formula (1) into the reaction system may be performed at once, or multiple times. It may be done separately. That is, in the method for producing dialkoxymagnesium according to the first aspect of the present invention, the whole amount of the silicon halide compound represented by the general formula (1) may be mixed with the metal magnesium and the alcohol, or the metal After mixing the magnesium and the alcohol, before starting the reaction, the total amount of the silicon halide compound represented by the general formula (1) may be added, or together with the metal magnesium and the alcohol, the general formula ( After starting the reaction in the presence of a part of the silicon halide compound represented by 1), the remaining silicon halide compound represented by the general formula (1) is added all at once or while the reaction is continued. It may be added to the reaction system in batches. Moreover, in the manufacturing method of dialkoxymagnesium of the 1st form of this invention, introduction | transduction of metallic magnesium and alcohol to a reaction system may be performed at once, or may be performed in multiple times. That is, in the method for producing dialkoxymagnesium according to the first aspect of the present invention, the reaction may be started from the beginning using the whole amount of metal magnesium and alcohol, or using part of metal magnesium and alcohol. After the reaction is started, the remaining metal magnesium and alcohol may be added to the reaction system at one time or divided into a plurality of times while the reaction is continued.

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

After performing the method for producing dialkoxymagnesium of the first aspect of the present invention, the obtained dialkoxymagnesium is dried by a method such as heat drying, airflow drying or vacuum drying, or an inert hydrocarbon. The alcohol is removed from dialkoxymagnesium by washing with a compound.

In the method for producing dialkoxymagnesium according to the first aspect of the present invention, the reaction accelerator is a silicon halide compound represented by the general formula (1), so that the surface is smooth and the average particle size is large. Moreover, high-purity dialkoxymagnesium is obtained.

Further, in the production of dialkoxymagnesium, when iodine is used as a reaction accelerator during the reaction between metal magnesium and alcohol, iodine is mixed in the resulting dialkoxymagnesium, and washing is performed. Iodine cannot be completely removed from dialkoxymagnesium, and iodine remains in dialkoxymagnesium. And if a solid catalyst component is manufactured using dialkoxymagnesium in which iodine remains, the residual iodine causes a decrease in performance of the solid catalyst component. On the other hand, in the method for producing dialkoxymagnesium according to the first aspect of the present invention, there is no problem of residual iodine in dialkoxymagnesium. In the method for producing dialkoxymagnesium according to the first aspect of the present invention, the amount of residual halogen in dialkoxymagnesium derived from the silicon halide compound represented by the general formula (1) used as a reaction accelerator is: The residual amount of halogen in dialkoxymagnesium obtained using iodine as a reaction accelerator is small.

The surface of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the first aspect of the present invention is smooth. In the present invention, the surface of dialkoxymagnesium is smooth because the surface of dialkoxymagnesium particles is measured by surface observation using a scanning electron microscope (SEM) and by a shape analysis laser microscope according to JIS B 0601: 2001. This is confirmed by the arithmetic average roughness (Ra) and the maximum surface height (Rz).

The surface smoothness (Ra) of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the first aspect of the present invention is 0.5 or less, preferably 0.49 or less, particularly preferably 0.47 or less. is there. The maximum surface height (Rz) of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the first aspect of the present invention is 2.0 or less, preferably 1.95 or less, particularly preferably 1. 00 to 1.95. Further, the sphericity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the first aspect of the present invention is preferably 2 or less, particularly preferably 1.5 or less. The bulk specific gravity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the first aspect of the present invention is preferably 0.1 to 0.6 g / ml, more preferably 0.2 to 0.5 g. / Ml, particularly preferably 0.25 to 0.40 g / ml.

The average particle diameter (D ₅₀ ) of dialkoxymagnesium obtained by carrying out the method for producing 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, particularly preferably. Is 60 to 80 μm. In the method for producing dialkoxymagnesium according to the first aspect of the present invention, dialkoxymagnesium having a smooth surface and a large average particle diameter is obtained. The particle size distribution index (SPAN) (SPAN = (D ₉₀ -D ₁₀ ) / D ₅₀ ) of the method for producing dialkoxymagnesium according to the first aspect of the present invention is 2.0 or less, more preferably 1.5 or less. is there.

The purity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the first aspect of the present invention is 99% by mass or more, more preferably 99 to 100% by mass, particularly preferably 99.1 to 99.99. 9% by mass.
In the present invention, the purity of dialkoxymagnesium is the purity of dialkoxymagnesium after removal of the solvent. From the halogen content in dialkoxymagnesium after removal of the solvent, It is a value calculated by the following formula after obtaining the reaction accelerator content.
Dialkoxymagnesium purity (mass%) = 100-reaction accelerator content (mass%)

The dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the first aspect of the present invention preferably contains no alcohol, but the alcohol content is 5% by mass or less, preferably 2% by mass or less. And particularly preferably 1% by mass or less.

The dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the first aspect of the present invention is suitably used as dialkoxymagnesium as a raw material for producing a solid catalyst component for olefin polymerization. In particular, the dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the first aspect of the present invention produces a solid catalyst component for producing polyolefins having a smooth surface, a large average particle diameter, and high purity. Suitable as a raw material alkoxymagnesium.

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

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

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

The alcohol according to the method for producing dialkoxymagnesium of the second aspect of the present invention is not particularly limited, and is preferably a lower alcohol having 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol, hexanol, etc. Is particularly preferred. The water content of the alcohol is not particularly limited, but it is preferably as the water content is small, and anhydrous alcohol or dehydrated alcohol having a water content of 200 ppm or less is particularly preferable.

And in the manufacturing method of dialkoxy magnesium of the 2nd form of this invention, metal magnesium and alcohol are made to react using a metal halogen compound as a reaction accelerator. The metal halide compound according to the method for producing dialkoxymagnesium of the present invention is particularly a powdery compound having an average particle size (D ₅₀ ) of 500 μm or less and a specific surface area of 1 m ² / g or more. Without limitation, metal monohalogen compounds such as alkali metal halides and alkoxymagnesium halides, metal dihalogen compounds such as calcium dihalide, magnesium dihalide, iron dihalide and nickel dihalide, aluminum trihalide, iron trihalide, Metal trihalogen compounds such as nickel trihalide, vanadium trihalide, zirconium trihalide, hafnium trihalide, chromium trihalide and vanadium tetrahalide, zirconium tetrahalide, hafnium tetrahalide, tetrahalogenated Mentioned metal tetrahalogen compounds such as chromium. Among these metal dihalide compounds are preferred, magnesium chloride is particularly preferable.

The average particle diameter (D ₅₀ ) of the metal halide compound according to the method for producing dialkoxymagnesium of the second aspect of the present invention is 500 μm or less, preferably 300 μm or less, more preferably 150 μm or less, and particularly preferably 100 μm or less. . When the average particle diameter (D ₅₀ ) of the metal halogen compound is in the above range, dialkoxy magnesium having a smooth particle surface can be easily obtained.

The lower limit of the average particle diameter (D ₅₀ ) of the metal halide compound according to the method for producing dialkoxymagnesium of the second aspect of the present invention is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more, More preferably, it is 3 micrometers or more, Most preferably, it is 5 micrometers or more. When the average particle diameter (D ₅₀ ) of the metal halogen compound is in the above range, dialkoxy magnesium having a smooth particle surface can be easily obtained.

The specific surface area of the metal halide compound according to the method for producing dialkoxymagnesium of the second aspect of the present invention is 1 m ² / g or more, preferably 5 m ² / g or more, particularly preferably 7 m ² / g or more. . When the specific surface area of the metal halide is in the above range, dialkoxymagnesium having a smooth particle surface can be easily obtained.

The upper limit of the specific surface area of the metal halide compound according to the method for producing dialkoxymagnesium of 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, particularly Preferably it is 70 m < ² > / g or less. When the specific surface area of the metal halide is in the above range, dialkoxymagnesium having a smooth particle surface can be easily obtained.

The (D ₉₀ ) of the metal halide compound according to the method for producing dialkoxymagnesium of the second aspect of the present invention is 2000 μm or less, preferably 5 to 1000 μm, more preferably 10 to 500 μm, and particularly preferably 50 to 300 μm. is there. By D ₉₀ of the metal halide compound is in the above range, it is easy particle surface obtained dialkoxy magnesium smooth.

The particle size distribution index (SPAN) of the metal halide according to the method for producing dialkoxymagnesium of the second aspect of the present invention is 10 or less, preferably 8.0 or less, more preferably 0.1 to 8.0, Particularly preferred is 0.5 to 7.0. When the particle size distribution index (SPAN) of the metal halide is in the above range, dialkoxymagnesium having a smooth particle surface can be easily obtained.

Examples of the metal halide compound according to the method for producing dialkoxymagnesium according to the second aspect of the present invention include metal dihalogen compounds and metal monohalogen compounds. Examples of the metal dihalogen compound according to the method for producing dialkoxymagnesium according to the second aspect of the present invention include calcium difluoride, calcium dichloride, calcium dibromide, calcium diiodide dihalides, and iron difluoride. Iron dichloride, iron dibromide, iron diiodide dihalides, nickel difluoride, nickel dichloride, nickel dibromide, nickel diiodide nickel dihalides and magnesium difluoride, Examples include magnesium dihalides such as magnesium chloride, magnesium dibromide, and magnesium diiodide. Examples of metal monohalogen compounds include magnesium halide alkoxides such as methoxymagnesium halide, ethoxymagnesium halide, butoxymagnesium halide, and phenoxymagnesium halide. It is below. The magnesium halide according to the method for producing dialkoxymagnesium according to the second aspect of the present invention is preferably magnesium dichloride or magnesium diiodide in that dialoxymagnesium having a smooth particle surface is easily obtained. Magnesium chloride is particularly preferred. The magnesium halide may be a single type or a combination of two or more types. Further, the magnesium dihalide according to the method for producing dialkoxymagnesium of the second aspect of the present invention may be anhydrous or hydrated, but the reactivity of metal magnesium and alcohol is not impaired, Further, when used as a carrier raw material for a solid catalyst component, a magnesium dihalide anhydride is preferred because the water content is preferably as low as possible.

In the method for producing dialkoxymagnesium according to the second aspect of the present invention, the molar ratio of alcohol to metal magnesium (alcohol / metal magnesium) is preferably 3 to 30, particularly preferably 5 to 20. When the molar ratio of alcohol to metal magnesium is in the above range, the surface of dialkoxymagnesium obtained is likely to be smooth.

In the method for producing dialkoxymagnesium according to the second aspect of the present invention, the molar ratio of the metal halogen compound to metal magnesium (metal halide compound / metal magnesium) is preferably 0.0001 to 0.1, more preferably 0.00. 0005 to 0.1, particularly preferably 0.001 to 0.01. When the molar ratio of the metal halogen compound to the metal magnesium is in the above range, the dialkoxymagnesium obtained has a good particle shape and bulk density and a narrow particle size distribution.

In the method for producing dialkoxymagnesium according to the second aspect of the present invention, these reactions are performed in a suspended state in which metallic magnesium is dispersed in alcohol while stirring metallic magnesium and alcohol. And in the method for producing dialkoxymagnesium of the second aspect of the present invention, the metal halogen compound is mixed in advance with the alcohol, and the alcohol containing the metal halogen compound and the metal magnesium are mixed, or The metal halide is introduced into the reaction system by adding the metal halide to the suspension obtained by mixing the metal magnesium and the alcohol, and the metal magnesium and the alcohol are added in the presence of the metal halide. , React. In the method for producing dialkoxymagnesium according to the second aspect of the present invention, the introduction of the metal halide compound into the reaction system may be performed at once, or may be performed in multiple steps. That is, in the method for producing dialkoxymagnesium according to the second aspect of the present invention, the total amount of the metal halide compound may be mixed with the metal magnesium and the alcohol, or the metal magnesium and the alcohol may be mixed and then reacted. Before starting the reaction, the entire amount of the metal halide compound may be added, or after starting the reaction in the presence of a part of the metal halide compound together with the metal magnesium and the alcohol, These metal halide compounds may be added to the reaction system at one time or divided into a plurality of times. Moreover, in the method for producing dialkoxymagnesium according to the second aspect of the present invention, the introduction of metal magnesium and alcohol into the reaction system may be performed at once, or may be performed in multiple steps. That is, in the method for producing dialkoxymagnesium according to the second aspect of the present invention, the reaction may be started from the beginning using the whole amount of metal magnesium and alcohol, or using part of metal magnesium and alcohol. After the reaction is started, the remaining metal magnesium and alcohol may be added to the reaction system at one time or divided into a plurality of times while the reaction is continued.

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

After performing the method for producing dialkoxymagnesium of the second aspect of the present invention, the obtained dialkoxymagnesium is dried by a method such as heat drying, airflow drying or reduced pressure drying, or an inert hydrocarbon. The alcohol is removed from dialkoxymagnesium by washing with a compound.

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

The surface smoothness (Ra) of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the second aspect of the present invention is 0.5 or less, preferably 0.49 or less, particularly preferably 0.47 or less. is there. The maximum surface height (Rz) of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the second aspect of the present invention is 2.0 or less, preferably 1.95 or less, particularly preferably 1. 00 to 1.95. Further, the sphericity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the second aspect of the present invention is preferably 2 or less, particularly preferably 1.5 or less. The bulk specific gravity of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the second aspect of the present invention is preferably 0.1 to 0.6 g / ml, more preferably 0.2 to 0.5 g. / Ml, particularly preferably 0.25 to 0.40 g / ml.

The average particle diameter (D ₅₀ ) of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the second aspect of the present invention is preferably 5 μm or more, more preferably 8 to 100 μm, particularly preferably 10 to 80 μm. is there. The particle size distribution index of dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the second aspect of the present invention is preferably 2.0 or less, more preferably 1.5 or less, particularly preferably 1.0. It is as follows.

The dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the second aspect of the present invention is suitably used as dialkoxymagnesium as a raw material for producing a solid catalyst component for olefin polymerization. In particular, dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium according to the second aspect of the present invention is suitable as a raw material alkoxymagnesium for producing a solid catalyst component for polyolefin production having a smooth particle surface. .

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

Examples of the solid catalyst component for olefin polymerization and the production method thereof include the following solid catalyst component for olefin polymerization and the production method thereof.

The solid catalyst component for olefin polymerization of the present invention is dialkoxymagnesium of the present invention, dialkoxymagnesium obtained by carrying out the method for producing dialkoxymagnesium of the first aspect of the present invention, or the second aspect of the present invention. The dialkoxymagnesium (a) obtained by carrying out the method for producing dialkoxymagnesium, the titanium halogen compound (b), and the electron-donating compound (c) obtained in contact with each other, It is a solid catalyst component for olefin polymerization.

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

Examples of the titanium halogen compound (b) constituting the solid catalyst component for olefin polymerization of the present invention include one or more selected from known materials, preferably a tetravalent titanium halogen compound, and more preferably titanium tetrachloride.

As the electron-donating compound (c) constituting the solid catalyst component for olefin polymerization of the present invention, one or more selected from known substances can be mentioned, and an organic compound having an oxygen atom or a nitrogen atom is preferable.

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

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

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

In the solid catalyst component for olefin polymerization of the present invention, the magnesium atom content is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, and 15 to 40% by mass. Is more preferably 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, and 40 to 80% by mass. Is more preferable, and more preferably 45 to 75% by mass.

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

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

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

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

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

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

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

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

The olefin polymerization catalyst according to the present invention is obtained by contacting (A) the solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound and (C) an external electron donating compound. This is a catalyst for olefin polymerization.

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

The olefin polymerization catalyst of the present invention contains (B) an organoaluminum compound. (B) The organoaluminum compound is not particularly limited as long as it is used for an olefin polymerization catalyst.

In the olefin polymerization catalyst of the present invention, as the (B) organoaluminum compound, the following general formula (2):
R ² _p AlQ _3-p (2)
(Wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 <.R ² is a real number p ≦ 3 there are a plurality, each R ² may be the same or different from each other, and when a plurality of Q are present, each Q may be the same or different.

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

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

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

In the olefin polymerization catalyst of the present invention, the external electron donating compound (C) is represented by the following general formula (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, carbon 6 to an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent of 15, if R ³ there are a plurality, the plurality of R ³ may be the same or different R ⁴ represents an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. an aromatic hydrocarbon group having 7-12 carbon atoms having, if R ⁴ there are a plurality, the plurality of R ⁴ may optionally be the same or different .q is an integer of 0 ≦ q ≦ 3. And an organic silicon compound represented by formula (4):
(R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)
(Wherein R ⁵ and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms) A cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, wherein R ⁵ and R ⁶ may be the same or different from each other, and may be bonded to each other to form a ring; R ⁵ R ⁶ N group When a plurality of R ⁵ R ⁶ N groups are present, the plurality of R ⁵ R ⁶ N groups may be the same as or different from each other, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, 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 cycloalkyloxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6-20 carbon atoms Shows the aryloxy group, R ⁷ may be more than one present, is selected from a plurality of R ⁷ are the same good .s be different or the integer from 1 to 3 from each other.) Aminosilane compound represented by the One or more.

Examples of the organosilicon compound represented by the general formula (3) or the aminosilane compound represented by the general formula (4) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and alkyl (cycloalkyl). Alkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkyl Amino) silane, trialkyl (alkylamino) silane and the like.

Specific examples of the organosilicon compound represented by the general formula (3) or the aminosilane compound represented by the general formula (4) include n-propyltriethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di Cyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetrabutoxy Silane, bis (ethylamino) methylethylsilane, bis (ethylamino) t-butylmethylsilane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane One or more selected from diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and the like. Among them, n-propyltriethoxysilane, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, isopropyl Ruisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexyl One or more selected from silane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, diethylaminotriethoxysilane and the like are preferable.

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

The production method of the olefin polymerization catalyst of the present invention is not particularly limited, and (A) the solid catalyst component for olefin polymerization of the present invention, (B) the organoaluminum compound represented by the general formula (2) and (C ) A method of producing an olefin polymerization catalyst by bringing an external electron donating compound into contact with each other by a known method.
The order in which the above components are brought into contact is arbitrary, but the following contact order can be exemplified.
(I) (A) Solid catalyst component for polymerization of olefins of the present invention → (C) External electron donating compound → (B) Organoaluminum compound represented by general formula (2) (ii) (B) General formula ( 2) organoaluminum compound represented by (C) external electron donating compound (A) solid catalyst component for olefin polymerization of the present invention (iii) (C) external electron donating compound (A) of the present invention Solid catalyst component for olefin polymerization → (B) Organoaluminum compound represented by general formula (2) (iv) (C) External electron donating compound → (B) Organoaluminum compound represented by general formula (2) → (A) Solid catalyst component for olefin polymerization of the present invention Of the above contact examples (i) to (iv), contact example (ii) is preferred.
In the above contact examples (i) to (iv), “→” means the contact order. For example, “(A) solid catalyst component for olefin polymerization of the present invention → (B) in the general formula (2)” The organoaluminum compound represented by formula (2) is added to (A) the solid catalyst component for polymerizing olefins according to the present invention. (C) means that an external electron donating compound is added and contacted.

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

According to the present invention, it is possible to provide an olefin polymerization catalyst having a smooth surface.

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

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

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

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

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

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

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

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

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

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

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the olefin polymer which can manufacture a polymer with a smooth surface under high polymerization activity can be provided. In the present invention, since the 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 according to the present invention is particularly applied to a polyolefin production process by a gas phase method.

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

(Example 1)
<Manufacture of diethoxymagnesium>
Equipped with an integrating gas meter, dropping funnel, stirrer and reflux condenser, in a 1 L four-necked flask filled with nitrogen gas, 1.6 g of metal magnesium powder (average particle size 169 μm), absolute ethanol 29 g and 0.34 g (2 mmol) of silicon tetrachloride were charged and heated to the reflux temperature of ethanol in an oil bath to maintain the reflux state. Next, a mixture of 6.4 g of metal magnesium powder and 84 g of ethanol was added to the inside in four portions every 10 minutes.
After the total amount was added, the mixture was further heated under reflux for 2 hours to complete the reaction. Subsequently, the reaction liquid was dried with a rotary evaporator to obtain 100 g of powdery diethoxymagnesium.
When the obtained diethoxymagnesium was analyzed, the halogen content was 0.3% by mass (0.4% by mass in terms of silicon tetrachloride content). Further, as a result of observing the surface of the obtained diethoxymagnesium with a scanning electron microscope (SEM), the surface of the diethoxymagnesium obtained in Example 1 is smoother than those in Comparative Examples 1 to 4. confirmed. The results of the analytical evaluation are shown in Table 1, and the SEM photograph of the obtained diethoxymagnesium is shown in FIG.

<Average particle diameter _{(D 50)} and SPAN Analysis>
Using a laser diffraction particle size distribution analyzer (MICROTRAC HRA 9320-X100 manufactured by Nikkiso Co., Ltd.), dialkoxymagnesium is dispersed in absolute ethanol, automatic measurement is performed twice, particle size distribution is measured, and integral volume integral The particle diameter (D ₁₀ ) with a rate of 10%, the particle diameter (D ₅₀ ) with a cumulative volume fraction of 50%, and the particle diameter (D ₉₀ ) with a cumulative volume fraction of 90% were determined, and the average values were calculated as D ₁₀ , D _50, it was a _{D 90.} Then, the value of _{D 50} obtained as the average particle size, also from the obtained value of _{D 10, D 50} and _{D 90,} were calculated SPAN from the following equation.
SPAN = (D ₉₀ -D ₁₀ ) / D ₅₀

<Dialkoxymagnesium purity>
The purity (mass%) of the dialkoxymagnesium obtained was measured with an automatic titrator (automatic titrator, model GT-200, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The halogen in dialkoxymagnesium after removing the solvent. From the content (% by mass), the content (% by mass) in the dialkoxymagnesium of the compound used as the reaction accelerator was determined and calculated by the following formula.
Dialkoxymagnesium purity (mass%) = 100-reaction accelerator content (mass%)

<Measurement of surface smoothness (Ra) and surface maximum height (Rz)>
Using a shape analysis laser microscope (Smartproof 5, manufactured by Carl Zeiss), 100 dialkoxymagnesium particles per sample according to JIS B 0601: 2001, the arithmetic average roughness (Ra) and the maximum height of the particle surface (Rz) was measured and the average value was determined.

(Example 2)
Diethoxymagnesium was produced and evaluated in the same manner as in Example 1 except that 0.34 g (2 mmol) of silicon tetrachloride was changed to 0.68 g (4 mmol). The halogen content of the obtained diethoxymagnesium is 0.5% by mass (0.6% by mass in terms of silicon tetrachloride content), and its surface is smoother than that of Comparative Examples 1 to 4. there were. The analysis results of the obtained diethoxymagnesium are shown in Table 1.

(Example 3)
The production and evaluation of diethoxymagnesium were conducted 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 silicon tetrachloride. went. The halogen content of the obtained diethoxymagnesium is 0.4% by mass (0.7% by mass in terms of Si (CH ₃ ) ₂ Cl ₂ content), and the surface thereof is Comparative Examples 1 to 4. It was smoother than
The analysis result of the obtained diethoxymagnesium is shown in Table 1, and the obtained SEM photograph is shown in FIG.

Example 4
Diethoxymagnesium was produced and evaluated 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 silicon tetrachloride. . The halogen content of the obtained diethoxymagnesium is 0.2% by mass (0.7% by mass in terms of Si (CH ₃ ) ₃ Cl content), and the surface thereof is the same as in Comparative Examples 1 to 4. In comparison, it was smooth.
The analysis results of the obtained diethoxymagnesium are shown in Table 1.

(Example 5)
In the same manner as in Example 1, except that 0.54 g (4 mmol) of Si (CH ₃ ) (C ₂ H ₅ ) Cl ₂ was used instead of 0.34 g (2 mmol) of silicon tetrachloride, diethoxymagnesium was used. Was manufactured and evaluated. The halogen content of the obtained diethoxymagnesium is 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 is Compared with Comparative Examples 1 to 4, it was smooth.
The analysis results of the obtained diethoxymagnesium are shown in Table 1.

(Comparative Example 1)
Diethoxymagnesium was produced and evaluated 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 silicon tetrachloride. In addition, the halogen content of the obtained diethoxymagnesium was 1.8 mass%, and the surface was not smooth.
The analysis results of the obtained diethoxymagnesium are shown in Table 1.

(Comparative Example 2)
Instead of 0.34 g (2 mmol) of silicon tetrachloride, 0.38 g (4 mmol) of magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd., purity 97% or more, not bulked or sieved) is used. In the same manner as in Example 1, production and evaluation of diethoxymagnesium were performed. The halogen content of the obtained diethoxymagnesium was 0.5% by mass (0.6% by mass when converted to magnesium chloride content), and the surface was not smooth.
The analysis results of the obtained diethoxymagnesium are shown in Table 1.

(Comparative Example 3)
Diethoxymagnesium was produced and evaluated in the same manner as in Example 1 except that 0.34 g (2 mmol) of silicon tetrachloride was used and 0.37 g (2 mmol) of titanium tetrachloride was used. In addition, the halogen content of the obtained diethoxymagnesium was 1.1% by mass (1.5% by mass in terms of titanium tetrachloride content), and the surface was not smooth.
The analysis result of the obtained diethoxymagnesium is shown in Table 1, and the obtained SEM photograph is shown in FIG.

(Comparative Example 4)
Instead of charging 1.6 g of metallic magnesium powder, 29 g of anhydrous ethanol and 0.34 g (2 mmol) of silicon tetrachloride, 1.6 g of metallic magnesium powder, 29 g of anhydrous ethanol and 0.23 g of titanium tetrachloride (1. 2 mmol), and instead of adding a mixture of 6.4 g of metal magnesium powder and 84 g of ethanol in four portions, 6.4 g of metal magnesium powder, 84 g of ethanol and 0.53 g of titanium tetrachloride are added. Diethoxymagnesium was produced and evaluated in the same manner as in Example 1 except that the mixture (2.8 mmol) was added in four portions. In addition, the halogen content of the obtained diethoxymagnesium was 1.3% by mass (1.7% by mass in terms of titanium tetrachloride content), and the surface was not smooth.
The analysis results of the obtained diethoxymagnesium are shown in Table 1.

From Examples 1 to 5, in the reaction of magnesium metal and alcohol, the reaction is promoted by using the silicon halide compound represented by the general formula (1), which has a milder reactivity than the halogen atom, as a reaction accelerator. Even when all of the agent is introduced into the reaction system at once, the reaction between the magnesium metal and the alcohol proceeds gently, so the surface is smooth, the purity is high, and the large particle diameter dialkoxy having an average particle diameter of 55 μm or more Magnesium is obtained.
On the other hand, since iodine is a halogen group atom, it is highly reactive, and titanium tetrachloride, which is an inorganic halogen compound, is extremely reactive with alcohol as a raw material, so the effect as an accelerator can be stably obtained. In the case of bulk magnesium chloride, it is difficult to obtain sufficient reactivity as a reaction accelerator. Therefore, when any compound is used as a reaction accelerator, the growth of dialkoxymagnesium particles is hindered and the average particle size is reduced. It is difficult to obtain dialkoxymagnesium particles having a small diameter, and even if particles having a large average particle diameter can be formed, the particle surface is not smooth, and the halogen content is high and the purity is low. A high-purity dial having a smooth surface, a large average particle diameter, and a high purity, such as when the inventive silicon halide compound is used as a reaction accelerator Alkoxy magnesium particles seen can not be obtained.

(Example 6)
<Manufacture of diethoxymagnesium>
Equipped with integrating gas meter, dropping funnel, stirrer and reflux condenser, in a 2 L four-necked flask filled with nitrogen gas, 1.6 g of metallic magnesium powder (average average particle size 169 μm), anhydrous 29 g of ethanol and anhydrous 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) ) Was heated to the reflux temperature of ethanol in an oil bath, and the reflux state was maintained. Next, a mixture of 6.4 g of metal magnesium powder and 84 g of ethanol was added to the inside in four portions every 10 minutes.
After the total amount was added, the mixture was further heated under reflux for 2 hours to complete the reaction. Subsequently, the reaction liquid was dried with a rotary evaporator to obtain 100 g of powdery diethoxymagnesium.
Subsequently, surface smoothness (Ra), surface maximum height (Rz), average particle diameter (D ₅₀ ), particle size distribution index (SPAN), and halogen content (mass%) were measured for the obtained diethoxymagnesium. Moreover, the particle | grain surface of the obtained diethoxymagnesium was observed with the scanning electron microscope (SEM). As a result, the surfaces of the diethoxymagnesium particles obtained in Example 6 were smoother than those in Comparative Examples 5 to 8. The evaluation results are shown in Table 2.

(Example 7)
As anhydrous magnesium chloride, 0.38 g (4 mmol) having a purity of 99.8%, an average particle size (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 Except for the use, production and analysis of diethoxymagnesium were performed in the same manner as in Example 6.
Table 2 shows the analysis results of the obtained diethoxymagnesium.

(Comparative Example 5)
As anhydrous magnesium chloride, 0.38 g of scale-like magnesium chloride anhydride (manufactured by Wako Pure Chemical Industries, purity 97% or more, sieved product having a sieve opening of 500 μm or more and 1180 μm or less, specific surface area 0.6 m ² / g) The production and analysis of diethoxymagnesium were carried out in the same manner as in Example 6 except that 4 mmol) was used.
Table 2 shows the analysis results of the obtained diethoxymagnesium.

(Comparative Example 6)
Diethoxymagnesium was produced and analyzed 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.
Table 2 shows the analysis results of the obtained diethoxymagnesium.

(Comparative Example 7)
Diethoxymagnesium was prepared and analyzed in the same manner as in Example 6 except that 1.1 g (4.3 mmol) of iodine was used instead of 0.38 g (4 mmol) of anhydrous magnesium chloride.
Table 2 shows the analysis results of the obtained diethoxymagnesium.

In the reaction between magnesium metal and alcohol, when a specific form of magnesium halide (metal halide compound) is used as a reaction accelerator, the reactivity is milder than the halogen group atom itself, and the reaction between metal magnesium and alcohol is milder. Since it progresses, the growth (granulation) of the particles is not hindered, and it is easy to form dialkoxymagnesium particles with a smooth surface and few fine powder components.

On the other hand, iodine is a halogen group atom, so it is highly reactive. In addition, titanium tetrachloride, an inorganic halogen compound, is extremely reactive with the raw material alcohol, so it can be obtained in a stable state as an accelerator. Each compound hinders the growth of dialkoxymagnesium particles, making it difficult to form large-diameter dialkoxymagnesium, and even if large particles can be formed, the particle size distribution is wide and the particle surface is Since it is not smooth, dialkoxymagnesium particles having a smooth surface and a small amount of fine powder components as in the case where magnesium halide (metal halide compound) having a specific shape is used as an accelerator cannot be obtained.

In addition, magnesium dichloride whose average particle diameter and specific surface area are out of a specific range is too high or insufficient in reactivity as an accelerator, so a magnesium halide (metal halide compound) in a specific range. ) Cannot be obtained with a good yield, as in the case of using an accelerator as a promoter.

(Example 8)
<Preparation of solid catalyst component for olefin polymerization>
A 500 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 30 ml of titanium tetrachloride and 20 ml of toluene to form a mixed solution. The suspension formed using 10 g of diethoxymagnesium obtained in Example 1 above, 50 ml of toluene and 3.3 ml (12.5 mmol) of di-n-butyl phthalate was then brought to a liquid temperature of 10 ° C. It was added into the retained mixed solution.
Thereafter, the liquid temperature was raised from 10 ° C. to 90 ° C., and the mixture was reacted at 90 ° C. for 2 hours while stirring.
After completion of the reaction, the obtained solid product was washed 4 times with 100 ml of 90 ° C. toluene, newly added 30 ml of titanium tetrachloride and 70 ml of toluene, heated to 110 ° C., and reacted with stirring for 2 hours. After completion of the reaction, the solid was washed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A-1) for olefin polymerization.
The solid catalyst component (A-1) contained 14.2% by mass of phthalic acid diester as an internal electron donating compound. 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>
In an autoclave with a stirrer with an internal volume of 2.0 liters, completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and the above solid catalyst component (A-1) in terms of titanium atoms 0.0026 mmol was charged to form an olefin polymerization catalyst.
Next, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene are charged into an autoclave, preliminarily polymerized at 20 ° C. for 5 minutes, then heated to 70 ° C., and subjected to a polymerization reaction at 70 ° C. for 1 hour. Thus, a propylene polymer was obtained. Table 3 shows the polymerization activity per gram of the solid catalyst component and the physical properties of the obtained polymer.
<Average particle size of polymer, particle size distribution index, and amount of fine powder having particle size of less than 75 μm>
For the average particle size, particle size distribution index, and the amount of fine powder having a particle size of less than 75 μm, a digital image analysis type particle size distribution measuring device (Camsizer, manufactured by Horiba, Ltd.) was used. The volume-based integrated particle size distribution of the polymer was automatically measured.
(Measurement condition)
Funnel position: 6mm
Camera cover area: Basic camera less than 3%, Zoom camera less than 10% Target cover area: 0.5%
Feeder width: 40mm
Feeder control level: 57, 40 seconds Measurement start level: 47
Maximum control level: 80
Control criteria: 20
Image rate: 50% (1: 2)
Particle size definition: Minimum value of Martin diameter measured n times per particle SPHT (sphericity) fitting: 1
Upper limit of class: Logarithmic scale, select 50 points in the range of 32μm to 4000μm

(Comparative Example 8)
Preparation of olefin polymerization solid catalyst component and olefin polymerization in the same manner as in Example 8, except that 10 g of diethoxymagnesium obtained in Comparative Example 1 was used instead of 10 g of diethoxymagnesium obtained in Example 1 above. Catalyst formation and propylene polymerization were carried out, and physical properties of the obtained polymer were evaluated. Table 3 shows the polymerization activity per gram of the solid catalyst component and the physical properties of the obtained polymer.

In Example 8, which was obtained in Example 1 and used a dialkoxymagnesium having a smooth surface, a large average particle diameter, and high purity as a raw material of the solid catalyst component for olefin polymerization, the average particle diameter (D ₅₀ ) was Polypropylene particles having a large particle size distribution and a small amount of fine powder polymer were obtained.
On the other hand, in Comparative Example 8, which was obtained in Comparative Example 1 and used dialkoxymagnesium having a rough surface, a small average particle diameter, and low purity as a raw material for the solid catalyst component for olefin polymerization, The average particle size (D ₅₀ ) was small, the particle size distribution was wide, and the proportion of fine powder polymer was large.

Example 9
<Preparation of solid catalyst component for olefin polymerization>
A 500 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 30 ml of titanium tetrachloride and 20 ml of toluene to form a mixed solution. The suspension formed using 10 g of diethoxymagnesium obtained in Example 6 above, 50 ml of toluene and 3.6 ml (15.5 mmol) of di-n-propyl phthalate was then brought to a liquid temperature of 10 ° C. It was added into the retained mixed solution.
Thereafter, the liquid temperature was raised from 10 ° C. to 90 ° C., and the mixture was reacted at 90 ° C. for 2 hours while stirring.
After completion of the reaction, the obtained solid product was washed 4 times with 100 ml of 90 ° C. toluene, newly added 30 ml of titanium tetrachloride and 70 ml of toluene, heated to 110 ° C., and reacted with stirring for 2 hours. After completion of the reaction, the solid was washed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A-2) for olefin polymerization.
This solid catalyst component (A-2) contained 12.6% by mass of phthalic acid diester as an internal electron donating compound. Moreover, it was 2.93 weight% when the titanium content rate in this solid catalyst component was measured.
<Formation of olefin polymerization catalyst and propylene polymerization>
In an autoclave equipped with a stirrer with an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and the above solid catalyst component (A-2) are converted into titanium atoms. 0.0026 mmol was charged to form an olefin polymerization catalyst.
Next, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene are charged into an autoclave, preliminarily polymerized at 20 ° C. for 5 minutes, then heated to 70 ° C., and subjected to a polymerization reaction at 70 ° C. for 1 hour. Thus, a propylene polymer was obtained. Table 4 shows the polymerization activity per gram of the solid catalyst component and the physical properties of the obtained polymer.
<Average particle size of polymer, particle size distribution index, and amount of fine powder having particle size of less than 75 μm>
For the average particle size, particle size distribution index, and the amount of fine powder having a particle size of less than 75 μm, a digital image analysis type particle size distribution measuring device (Camsizer, manufactured by Horiba, Ltd.) was used. The volume-based integrated particle size distribution of the polymer was automatically measured.
(Measurement condition)
Funnel position: 6mm
Camera cover area: Basic camera less than 3%, Zoom camera less than 10% Target cover area: 0.5%
Feeder width: 40mm
Feeder control level: 57, 40 seconds Measurement start level: 47
Maximum control level: 80
Control criteria: 20
Image rate: 50% (1: 2)
Particle size definition: Minimum value of Martin diameter measured n times per particle SPHT (sphericity) fitting: 1
Upper limit of class: Logarithmic scale, select 50 points in the range of 32μm to 4000μm

(Comparative Example 9)
The solid catalyst component for olefin polymerization (A-3) was prepared in the same manner as in Example 9 except that 10 g of diethoxymagnesium obtained in Comparative Example 5 was used instead of 10 g of diethoxymagnesium obtained in Example 6 above. After the preparation, formation of an olefin polymerization catalyst and propylene polymerization were performed, and physical properties of the obtained polymer were evaluated.
This solid catalyst component (A-3) contained 13.3% by weight of phthalic acid diester as an internal electron donating compound.
The titanium content in the solid catalyst component was measured and found to be 2.83% by weight. Table 2 shows the polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer.

(Comparative Example 10)
The solid catalyst component for olefin polymerization (A-4) was prepared in the same manner as in Example 9 except that 10 g of diethoxymagnesium obtained in Comparative Example 7 was used instead of 10 g of diethoxymagnesium obtained in Example 6 above. After the preparation, formation of an olefin polymerization catalyst and propylene polymerization were performed, and physical properties of the obtained polymer were evaluated.
The solid catalyst component (A-4) contained phthalic acid diester as an internal electron donating compound.
Moreover, it was 3.08 weight% when the titanium content rate in this solid catalyst component was measured. Table 4 shows the polymerization activity per gram of the solid catalyst component and the physical properties of the obtained polymer.

In Example 9 using dialkoxymagnesium obtained in Example 6 with a smooth surface and a narrow particle size distribution, polypropylene particles with a narrow particle size distribution index and few fines were obtained in high yield. .
On the other hand, in Comparative Examples 9 and 10 using dialkoxymagnesium obtained in Comparative Examples 5 and 7 having a rough surface and a wide particle size distribution index, the obtained polypropylene has a wide particle size distribution index and the proportion of fine particles There were many.

Claims (15)

Dialkoxymagnesium having an arithmetic average roughness (Ra) of the particle surface of 0.5 or less and a maximum height (Rz) of the particle surface of 2.0 or less. A process for producing dialkoxymagnesium, wherein metalmagnesium and alcohol are reacted in the presence of a reaction accelerator to obtain dialkoxymagnesium,
The reaction accelerator is represented by the following general formula (1):
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, a plurality of R ¹ may be the same or different from each other, and when there are a plurality of X, the plurality of X may be the same or different from each other.
A halogenated silicon compound represented by:
A method for producing dialkoxymagnesium, wherein The method for producing dialkoxymagnesium according to claim 2, wherein the reaction accelerator is tetrafluorosilane, tetrachlorosilane, tetrabromosilane or tetraiodosilane. * The method for producing dialkoxymagnesium according to any one of claims 2 and 3, wherein the alcohol is ethanol. It is a method for producing dialkoxymagnesium to obtain dialkoxymagnesium by reacting metal magnesium and alcohol in the presence of a reaction accelerator,
The reaction accelerator is a powdered metal halide compound having an average particle diameter (D ₅₀ ) of 500 μm or less and a specific surface area of 1 m ² / g or more;
A method for producing dialkoxymagnesium, wherein 6. The method for producing dialkoxymagnesium according to claim 5, wherein a particle diameter (D ₉₀ ) at D90 of the metal halide compound is 2000 μm or less. Particle size distribution index (SPAN) of the metal halide:
SPAN = (D ₉₀ -D ₁₀ ) / D ₅₀
The method for producing dialkoxymagnesium according to any one of claims 5 and 6, characterized in that is 7 or less. The method for producing dialkoxymagnesium according to any one of claims 5 to 7, wherein the metal halide is magnesium dichloride. The method for producing dialkoxymagnesium 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 dialkoxymagnesium (a), titanium halogen compound (b) and electron donating compound (c) according to claim 1. A dialkoxymagnesium (a) obtained by carrying out the method for producing dialkoxymagnesium according to any one of claims 2 to 9, a titanium halogen compound (b) and an electron donating compound (c) are brought into contact with each other. A solid catalyst component for olefin polymerization, which is obtained. (A) The solid catalyst component for olefin polymerization according to any one of claims 10 or 11, (B) an organoaluminum compound, and (C) an external electron donating compound obtained by contacting each other. A catalyst for olefin polymerization. The (B) organoaluminum compound has the following general formula (2):
R ² _p AlQ _3-p (2)
(Wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 <.R ² is a real number p ≦ 3 there are a plurality, each R ² may be the same or different from each other, and when a plurality of Qs are present, each Q may be the same or different.)
The olefin polymerization catalyst according to claim 12, which is an organoaluminum compound represented by the formula: The (C) external electron donating compound is represented by 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, carbon 6 to an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent of 15, if R ³ there are a plurality, the plurality of R ³ may be the same or different R ⁴ represents an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. an aromatic hydrocarbon group having 7-12 carbon atoms having, if R ⁴ there are a plurality, the plurality of R ⁴ may optionally be the same or different .q is an integer of 0 ≦ q ≦ 3. )
And an organic silicon compound represented by the general formula (4):
(R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)
(Wherein R ⁵ and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms) A cycloalkenyl group or an aryl group having 6 to 20 carbon atoms, wherein R ⁵ and R ⁶ may be the same or different from each other, and may be bonded to each other to form a ring; R ⁵ R ⁶ N group When a plurality of R ⁵ R ⁶ N groups are present, the plurality of R ⁵ R ⁶ N groups may be the same or different from each other, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon number. 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 cycloalkyloxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6-20 carbon atoms Shows the aryloxy group, if R ⁷ there is a plurality, a plurality of R ⁷ is optionally be the same or different .s is an integer from 1 to 3.)
14. The olefin polymerization catalyst according to claim 12, which is at least one selected from the group consisting of aminosilane compounds represented by the formula: 15. A process for producing an olefin polymer, comprising polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 12 to 14.

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