JP6830562B1 - Manufacturing method of Mg-containing particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing Mg-containing particles having a narrow particle size distribution and a good particle shape while reducing the content of fine coarse powder particles such as fine powder particles and coarse powder particles and improving the yield of products. .. SOLUTION: A method for producing Mg-containing particles includes a housing, a rotating body rotating in the housing, a classification chamber located on the outer edge side of the rotating body, an inner surface of the housing, and a top of the rotating body. It is a method for producing Mg-containing particles, which obtains Mg-containing particles by performing classification treatment using a centrifugal airflow classifying device including a flow path formed by a surface and connecting an upstream end portion and the classification chamber. Therefore, the average flow velocity of the unclassified Mg-containing particles on the downstream side of the upstream end in the flow path is smaller than the average flow velocity of the unclassified Mg-containing particles flowing inside the flow path at the upstream end. A step of supplying the unclassified Mg-containing particles to the classification chamber and a step of classifying the unclassified Mg-containing particles in the classification chamber to obtain Mg-containing particles are provided, and the determination is performed by the following formula (1). The abrasion durability A (%) of the unclassified Mg-containing particles is 85 or less. A = (Z ÷ Y) × 100… (1) [Selection diagram] Fig. 1

Description

The present invention relates to a method for producing Mg-containing particles in which the content of fine coarse powder particles is reduced.

Conventionally, a solid catalyst component for olefin polymerization containing magnesium, titanium, an electron donating compound and a halogen as essential components as constituent components of a polymerization catalyst used in a polymerization reaction of olefins (when referred to as "solid catalyst component"). In particular, a solid catalyst component prepared by using an alkoxymagnesium compound typified by diethoxymagnesium as a magnesium raw material has high performance and is widely used industrially.

The olefin polymerization catalyst (sometimes referred to as "polymerization catalyst") prepared by using such a solid catalyst component is a fine powder particle or a coarse powder particle (collectively referred to as "polymerization catalyst") generated in the preparation step. (Sometimes referred to as "fine coarse powder component") is a problem when polymerizing olefins.

That is, the olefin polymer polymerized using the solid catalyst component for olefin polymerization containing the fine crude powder component contains the fine crude powder component, which causes product defects of the olefin polymer. Therefore, in order to reduce such a fine coarse powder olefin polymer, it is required to reduce the fine coarse powder component in the solid catalyst component.

Usually, in the preparation of the solid catalyst component, the solvent is removed by drying under reduced pressure or the like, and the powdery solid catalyst component after removing the solvent contains a fine coarse powder component. Therefore, a method of removing the fine coarse powder component from the solid catalyst component by sieving or classifying the solid catalyst component after removing the solvent has been studied (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 6-287225

However, in the method described in Patent Document 1, the solid catalyst component having a desired particle size is obtained because the particle strength is particularly small and the fragile solid catalyst component particles are significantly destroyed and the classification yield of the obtained solid catalyst component is lowered. It is hard to say that the yield (product yield) is sufficiently high. Further, if the yield of the solid catalyst component decreases, the manufacturing cost will increase accordingly.

Further, the surface condition of the obtained solid catalyst component particles is also deteriorated due to destruction or wear, and when such a solid catalyst component is subjected to polymerization of olefins, the solid catalyst components withstand expansion during polymerization. It may collapse without being able to. It also contributes to increasing the amount of fine powder polymer in the obtained olefin polymer.

On the other hand, in sieving, the structure of secondary particles formed by bonding particles to each other is maintained, and the particles are not sufficiently separated as primary particles, which is not suitable for producing an olefin polymer. ..

The present invention has been made in view of the above problems, and an object of the present invention is to reduce the content of fine coarse powder particles such as fine powder particles and coarse powder particles, and to improve the yield of the product. An object of the present invention is to provide a method for producing Mg-containing particles having a narrow particle size distribution and a good particle shape.

The above problem is solved by the following. That is, the method for producing Mg-containing particles of the present invention (1) is
A housing, a rotating body rotating in the housing, a classification chamber located on the outer edge side of the rotating body, an inner surface of the housing and a top surface of the rotating body, and an upstream end portion and the classification chamber. A method for producing Mg-containing particles, which obtains Mg-containing particles by performing a classification treatment using a centrifugal airflow classifying device including a flow path connecting the two.
The average flow velocity of the unclassified Mg-containing particles on the downstream side of the upstream end in the flow path is made smaller than the average flow velocity of the unclassified Mg-containing particles flowing inside the flow path at the upstream end. A step of supplying the unclassified Mg-containing particles to the classification chamber and a step of classifying the unclassified Mg-containing particles in the classification chamber to obtain Mg-containing particles are provided.
A method for producing Mg-containing particles having an abrasion durability A (%) of 85 or less of the unclassified Mg-containing particles determined by the following formula (1).
A = (Z ÷ Y) × 100… (1)
(In the formula, Y is the average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 0.4 bar using a laser diffraction type particle size distribution measuring device, and Z is the laser diffraction type particle size distribution measurement. The average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 1.0 bar using the device is shown.)

Further, the method for producing Mg-containing particles of the present invention (2) is the method for producing Mg-containing particles according to (1).
In the step of supplying the unclassified Mg-containing particles to the classification chamber, the average flow velocity of the unclassified Mg-containing particles at the inlet of the classification chamber is less than half of the average flow velocity of the unclassified Mg-containing particles at the upstream end. Is.

The method for producing Mg-containing particles according to the present invention (3) is the method for producing Mg-containing particles according to (1) or (2).
In the step of supplying the unclassified Mg-containing particles to the classification chamber, the average flow velocity of the unclassified Mg-containing particles at a substantially intermediate position of the radius of the top surface of the rotating body is the unclassified Mg-containing particles at the upstream end. It is 2/3 or less of the average flow velocity of the particles.

Further, the method for producing Mg-containing particles of the present invention (4) is the method for producing Mg-containing particles according to any one of (1) to (3).
The average flow velocity of the unclassified Mg-containing particles at the entrance of the classification chamber is 15 m / s or less.

The Mg-containing particle classifying device of the present invention (5) is provided below the charging port in a housing having a charging port, and classifies unclassified Mg-containing particles in a classification chamber located on the outer edge side of a rotating classification rotor. An Mg-containing particle classifier that obtains Mg-containing particles.
A flow path defined by the housing and the top surface of the classification rotor and connecting the inlet and the classification chamber, which reduces the flow velocity of the unclassified Mg-containing particles flowing inside. Be prepared.

Further, the Mg-containing particle classifier of the present invention (6) is the Mg-containing particle classifier according to (5), and the flow path determines the average flow velocity of the unclassified Mg-containing particles at the inlet of the classification chamber. The flow velocity of the unclassified Mg-containing particles at the upstream end is reduced to half or less.

Further, the Mg-containing particle classifier of the present invention (7) is the Mg-containing particle classifier according to (5) or (6), and the flow path is the unclassified Mg-containing particles at the entrance of the classification chamber. The flow velocity of the particle is reduced to 15 m / s or less.

Further, the Mg-containing particle classifier of the present invention (8) is the Mg-containing particle classifier according to any one of (5) to (7).
The housing is
A first portion provided on the housing at a position facing the top surface and separated from the top surface by a first predetermined distance,
A second predetermined distance, which is provided on the housing at a position facing the top surface and on the inlet side of the first portion and is larger than the first predetermined distance, is separated from the top surface. 2 parts and
Have.

Further, the Mg-containing particle classifier of the present invention (9) is the Mg-containing particle classifier according to (8).
The second portion was inclined so as to move away from the top surface as it approached the inlet.

Further, the Mg-containing particle classifier of the present invention (10) is the Mg-containing particle classifier according to any one of (5) to (9).
The top surface is formed in a substantially flat shape.

Further, the Mg-containing particle classifier of the present invention (11) is the Mg-containing particle classifier according to (10).
The substantially flat shape includes a cone-shaped cone portion at a position facing the inlet.

According to the present invention, a method for producing Mg-containing particles having a narrow particle size distribution and a good particle shape while reducing the content of fine coarse powder particles such as fine powder particles and coarse powder particles and improving the yield of the product can be obtained. Can be provided.

It is sectional drawing which shows typically the Mg-containing particle classifying apparatus of embodiment. FIG. 5 is a cross-sectional view showing a detailed structure of a flow path connecting an inlet of the Mg-containing particle classifier shown in FIG. 1 and a classifying chamber. It is sectional drawing which shows the input port, the classification chamber, and the flow path of the Mg-containing particle classifying apparatus shown in FIG. 1, and also shows the AA position and the BB position. It is sectional drawing which shows the flow path of the Mg-containing particle classifying apparatus shown in FIG. 1, and shows the CC position, the DD position, the EE position, and the FF position. It is sectional drawing which shows the detailed structure of the input port, the classification chamber, and the flow path of the classification apparatus of a reference embodiment. FIG. 5 is a cross-sectional view showing an input port, a classification chamber, and a flow path of the classification device of the reference embodiment shown in FIG. 5, and also shows AA position and BB position. It is sectional drawing which shows the flow path of the classifying apparatus of the reference embodiment shown in FIG. 1, and shows the CC position, the DD position, the EE position, and the FF position. FIG. 5 is a perspective view showing a plurality of dispersion blades and cone portions provided on the top surface of the classification rotor of the classification device of the reference embodiment shown in FIG.

<Manufacturing method of Mg-containing particles>
The method for producing Mg-containing particles according to the present invention includes a housing, a rotating body rotating in the housing, a classification chamber located on the outer edge side of the rotating body, an inner surface of the housing, and a top of the rotating body. A method for producing Mg-containing particles, which obtains Mg-containing particles by performing classification treatment using a centrifugal airflow classifying device including a flow path formed by a surface and connecting an upstream end portion and the classification chamber. hand,
The flow velocity of the unclassified Mg-containing particles flowing inside the flow path on the downstream side of the upstream end of the flow path is smaller than the flow velocity of the unclassified Mg-containing particles at the upstream end of the flow path. A step of supplying the unclassified Mg-containing particles to the classification chamber and a step of classifying the unclassified Mg-containing particles in the classification chamber to obtain Mg-containing particles are provided.
A method for producing Mg-containing particles having an abrasion durability A (%) of 85 or less of the unclassified Mg-containing particles determined by the following formula (1).
A = (Z ÷ Y) × 100… (1)
(In the formula, Y is the average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 0.4 bar using a laser diffraction type particle size distribution measuring device, and Z is the laser diffraction type particle size distribution measurement. The average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 1.0 bar using the device is shown.)

In the method for producing Mg-containing particles according to the present invention, unclassified Mg-containing particles are classified by using a centrifugal airflow classifier (described later) having a predetermined rotating body. That is, the unclassified Mg-containing particles are the processing targets to be classified. Here, the unclassified Mg-containing particles are fragile particles having a small particle strength (described later), which include particles whose agglutinated state is dissociated and particles which are still agglutinated. Then, in the method for producing Mg-containing particles according to the present invention, the particles obtained by classifying such unclassified Mg-containing particles are Mg-containing particles. Further, the target to be removed as "other particles" in the classification treatment is fine powder described later. In addition, in this specification, "other particles" does not mean particles which do not contain Mg (particles which do not contain Mg). Examples of the Mg-containing particles include granular magnesium compounds, granular solid catalyst components for olefin polymerization, and granular solid catalysts for olefin polymerization, which will be described later. The Mg-containing particles in the present invention may be porous in themselves, or may include agglomerates of particles having gaps (gap between agglomerated particles). Hereinafter, in the present invention, the Mg-containing particles include the magnesium compound described below and a solid catalyst component for olefin polymerization containing the magnesium compound as a main component (for example, titanium, halogen and one or more internal electrons donated together with the magnesium compound). It is a concept including a solid catalyst component for olefin polymerization including a compound). Further, in the concept of Mg-containing particles in the present invention, particles of the solid catalyst component for olefin polymerization, organoaluminum compounds and, if necessary, an external electron donating compound obtained by using the above-mentioned solid catalyst component for olefin polymerization are used. It may contain particles of the catalyst for olefin polymerization having.

The solid catalyst component for olefin polymerization contains a magnesium compound as a main component, and the upper limit of the magnesium compound in the Mg-containing particles is not particularly limited. The content ratio of the magnesium compound in the solid catalyst component for olefin polymerization is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and 75% by mass. The above is more preferable.

The magnesium compound is not particularly limited, and examples thereof include one or more selected from magnesium dihalogenate, magnesium chloride / alcohol / water adduct, and the like.

Examples of magnesium dihalogen include one or more selected from magnesium dichloride, magnesium dibromide, magnesium diiodide and the like, and magnesium dichloride is preferable.

The following general formula (i) is used as a magnesium chloride / alcohol / water adduct.
MgCl ₂・ mROH ・ nH ₂ O… (i)
[In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, m is a real number of 2 to 4, n is a real number of 0 to 0.7], and a magnesium compound / alcohol / water adduct is mentioned. it can.

In the method for producing Mg-containing particles according to the present invention, the magnesium compound constituting the Mg-containing particles may be prepared from alkoxymagnesium as a raw material, or a commercially available product may be purchased and used to obtain Mg-containing particles. May be used for the production of.

In the magnesium compound prepared from alkoxymagnesium as a raw material, the alkoxymagnesium particles easily adhere to each other during production, so that particles containing coarse powder particles are easily formed, but the particle strength is small and the particles are fragile. The method according to the above can be preferably applied to classify.

In the method for producing Mg-containing particles according to the present invention, the Mg-containing particles are not particularly limited, but for example, olefin polymerization containing titanium, halogen and one or more internal electron donors together with a magnesium compound and the above-mentioned magnesium compound. Examples thereof include solid catalyst components for olefin polymerization, and among them, solid catalyst components for olefin polymerization are preferable. Further, the Mg-containing particles may contain the above-mentioned solid catalyst component for olefin polymerization, an organoaluminum compound and, if necessary, an olefin polymerization catalyst having an external electron donating compound.

In the method for producing Mg-containing particles according to the present invention, as the solid catalyst component for olefin polymerization containing titanium, halogen and one or more internal electron donors together with the above-mentioned magnesium compound, alkoxymagnesium, tetravalent titanium halogen compound and A contact reaction product of an internal electron donor compound can be mentioned.

Examples of the alkoxymagnesium include dialkoxymagnesium.

Specific examples of the dialkoxymagnesium include one or more selected from dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like. Is particularly preferable.

The dialkoxymagnesium may be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen, a halogen-containing metal compound, or the like.

In the method for producing Mg-containing particles according to the present invention, the dialkoxymagnesium is preferably spherical.

When a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be obtained, and the operability of handling the polymer powder produced during the polymerization operation is improved. This is improved, and it becomes easier to suppress the occurrence of clogging or the like caused by the fine powder contained in the produced polymer powder.

In the method for producing Mg-containing particles according to the present invention, the magnesium compound is preferably in the form of a solution or suspension at the time of reaction, and the reaction can be suitably proceeded by the state of solution or suspension. ..

In the method for producing Mg-containing particles according to the present invention, the tetravalent titanium halogen compound is not particularly limited, but the following general formula (I)
Ti (OR ¹ ) _r X _4-r ... (I)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom which may be the same or different from each other, and r is 0 or 1-3. of an integer, if the oR ¹ there are a plurality, it is preferable that at least one compound selected from titanium halides or alkoxy titanium halide groups also represented by different or may be) identical to one another.

Examples of the titanium halide include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.

Examples of the alkoxytitanium halide include methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, and di-n-butoxytitanium. Examples thereof include dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride and the like.

As the tetravalent titanium halogen compound, titanium tetrahalide is preferable, and titanium tetrachloride is more preferable.

These titanium compounds may be used alone or in combination of two or more.

In the method for producing Mg-containing particles according to the present invention, the internal electron donating compound is not particularly limited, but is monocarboxylic acid esters, dicarboxylic acid esters, monoethers, diethers, ethercarboxylic acid esters, and diols. It is preferably one or more selected from diesters and ether carbonates, and is preferably an aromatic polycarboxylic acid ester such as an aromatic dicarboxylic acid diester, an aliphatic polycarboxylic acid ester, an alicyclic polycarboxylic acid ester, or a diether. More preferably one or more selected from the class and ether carbonates.

In the method for producing Mg-containing particles according to the present invention, the aromatic dicarboxylic acid diester is referred to as the following general formula (II).
(R ² ) _j C ₆ H _4-j (COOR ³ ) (COOR ⁴ )… (II)
(In the formula, R ² represents an alkyl group or a halogen atom having 1 to 8 carbon atoms, and R3 and R4 are alkyl groups having 1 to 12 carbon atoms, which may be the same or different, and may be substituted. The number j of the group R ² is 0, 1 or 2, and when j is 2, each R ² may be the same or different.)
The compound represented by is mentioned.

In the aromatic dicarboxylic acid diester represented by the general formula (II), R ² is a halogen atom or an alkyl group having 1 to 8 carbon atoms.

When R ² is a halogen atom, examples of the halogen atom include one or more atoms selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When R ² is an alkyl group having 1 to 8 carbon atoms, the alkyl group having 1 to 8 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and t-. Select from butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group. There are more than one type.

The R ^2, a methyl group, a bromine atom, a fluorine atom is preferably a methyl group, further preferably a bromine atom.

In the aromatic dicarboxylic acid diester represented by the general formula (II), R ³ and R ⁴ are alkyl groups having 1 to 12 carbon atoms, and R ³ and R ⁴ may be the same as or different from each other. May be good.

Examples of the alkyl group having 1 to 12 carbon atoms include an ethyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, an isohexyl group and an isooctyl group, and examples thereof include an ethyl group, an n-propyl group and n. -Preferably a butyl group, an isobutyl group, or a neopentyl group.

In the aromatic dicarboxylic acid diester represented by the formula (II), the number j of the substituents ^{R 2} is 0, 1 or 2, when j is 2, each ^R 2 (2 one ^{R 2)} is a same May be different.

When j is 0, the compound represented by the general formula (II) is a phthalic acid diester, and when j is 1 or 2, the compound represented by the general formula (II) is a substituted phthalic acid diester.

When j is 1, in the aromatic dicarboxylic acid diester represented by the general formula (II), it is preferable that R ² is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the benzene ring.

When j is 2, in the aromatic dicarboxylic acid diester represented by the general formula (II), it is preferable that R ² is substituted with a hydrogen atom at the 4- and 5-position positions of the benzene ring.

Specific examples of the aromatic dicarboxylic acid diester represented by the general formula (II) include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, and diisobutyl phthalate. , Di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, di-n-hexyl phthalate, ditexyl phthalate, methyl ethyl phthalate, (ethyl) n-propyl phthalate, ethyl isopropyl phthalate, phthalate Phthalic acid diesters such as (ethyl) n-butyl, ethylisobutyl phthalate, (ethyl) n-pentyl phthalate, ethylisopentyl phthalate, ethylneopentyl phthalate, n-hexyl phthalate, 4-chlorophthalate Diethyl acid, di-n-propyl 4-chlorophthalate, diisopropyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-propyl 4-bromophthalate , Halogen-substituted phthalates such as diisopropyl 4-bromophthalate, di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate, 4-methylphthalic acid Examples thereof include alkyl-substituted phthalic acid diesters such as diisopropyl, di-n-butyl 4-methylphthalate and diisobutyl 4-methylphthalate.

When aliphatic polycarboxylic acid esters are used as the internal electron donating compound, examples of the aliphatic polycarboxylic acid esters include saturated aliphatic polycarboxylic acid esters and unsaturated aliphatic polycarboxylic acid esters. it can.

Examples of the saturated aliphatic polycarboxylic acid ester include malonic acid diesters, succinic acid diesters, fumaric acid diesters, adipic acid diesters, glutaric acid diesters and the like. More preferably, one or more selected from malonic acid diesters, alkyl-substituted malonic acid diesters, alkylene-substituted malonic acid diesters, and succinic acid diesters.

Examples of the unsaturated aliphatic polycarboxylic acid ester include maleic acid diesters, and one or more selected from maleic acid diesters and alkyl-substituted maleic acid diesters are more preferable.

When succinic acid diester is used as the internal electron donating compound, examples of the succinic acid diester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diethyl 2,3-diisopropyl succinate and the like, and diethyl succinate or 2 , 3-Diisopropl succinate diethyl is preferred.

When a maleic acid diester is used as the internal electron donating compound, the maleic acid diester is preferably diethyl maleate, di-n-butyl maleate, and diisobutyl maleate.

When an alkyl-substituted maleic acid diester is used as the internal electron-donating compound, the alkyl-substituted maleic acid diester is preferably dibutyl dimethyl maleate, dibutyl diethyl maleate and diethyl diisobutyl maleate.

When a malonic acid diester is used as the internal electron donating compound, the malonic acid diester is preferably dimethyl malonate, diethyl malonate or diisobutyl malonate.

Further, as the internal electron donating compound, a substituted malonic acid diester is suitable.

When a substituted malonic acid diester is used as the internal electron donating compound, the substituted malonic acid diester is preferably an alkyl-substituted malonic acid diester and a halogen-substituted malonic acid diester, and more preferably an alkyl-substituted malonic acid diester.

Examples of the alicyclic polycarboxylic acid ester include a saturated alicyclic polycarboxylic acid ester and an unsaturated alicyclic polycarboxylic acid ester. Specific examples thereof include a cycloalkane dicarboxylic acid diester and a cycloalkene dicarboxylic acid diester.

When a cycloalcandicarboxylic acid diester is used as the internal electron donating compound, the cycloalcandicarboxylic acid diester includes cyclopentane-1,2-dicarboxylic acid diester, cyclopentane-1,3-dicarboxylic acid diester, cyclohexane-1, 2-dicarboxylic acid diester, cyclohexane-1,3-dicarboxylic acid diester, cycloheptane-1,2-dicarboxylic acid diester, cycloheptane-1,2-dicarboxylic acid diester, cyclooctane-1,2-dicarboxylic acid diester, cyclo Octane-1,3-dicarboxylic acid diester, cyclononan-1,2-dicarboxylic acid diester, cyclononan-1,3-dicarboxylic acid diester, cyclodecane-1,2-dicarboxylic acid diester, cyclodecane-1,3-dicarboxylic acid diester, etc. Can be mentioned.

When diethers are used as the internal electron donating compound, the diethers are represented by the following general formula (III).
R ⁵ _k H _(3-k) CO- (CR ⁶ R ⁷ ) _p- O-CR ⁸ _q H _(3-q) … (III)
(In the general formula (III), R ⁵ and R ⁸ are halogen atoms or organic groups having 1 to 20 carbon atoms, and may be the same or different from each other, and R ⁶ and R ⁷ are hydrogen. Atoms, oxygen atoms, sulfur atoms, halogen atoms or organic groups having 1 to 20 carbon atoms, which may be the same or different from each other. Organic groups having 1 to 20 carbon atoms are oxygen atoms and fluorine atoms. , Chlorine atom, bromine atom, iodine atom, nitrogen atom, sulfur atom, phosphorus atom, and boron atom may contain at least one atom, and there are a plurality of organic groups having 1 to 20 carbon atoms. case, a plurality of organic groups may be bonded together to form a ring, k is an integer of 0 to 3, when k is an integer of 2 or more, the R ⁵ to plural present be identical to each other It may be different, p is an integer of 1 to 10, and when p is an integer of 2 or more, a plurality of R ⁶ and R ⁷ may be the same or different, and q is 0 to 3. of an integer, q is an integer of 2 or more, R ⁸ to plural groups may be the same or different from each other.)
A compound represented by is used.

In the compound represented by the general formula (III), when R ⁵ or R ⁸ is a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be mentioned, and a fluorine atom, a chlorine atom or a bromine atom is preferable. Is.

When R ⁵ or R ⁸ is an organic group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-propyl group, an n-butyl group, a t-butyl group, or a hexyl. Examples thereof include a group, an octyl group, a cyclopentyl group, a cyclohexyl group and a phenyl group, and a methyl group and an ethyl group are preferable.

When a plurality of organic groups having 1 to 20 carbon atoms are present in the compound represented by the general formula (III), the plurality of organic groups may be bonded to each other to form a ring. In this case, the plurality of organic groups constituting the ring, (1) (when k is 2 or more) ^{R 5} together, (2) (when q is 2 or more) ^{R 8} together, (3) R ^{6 to} each other (when p is 2 or more), (4) R ^{7 to} each other (when p is 2 or more), (5) R ⁵ and R ⁶ , (6) R ⁵ and R ⁷ , (7) R ^{The combinations of 5} and R ⁸ , (8) R ⁶ and R ⁷ , (9) R ⁶ and R ⁸ , and (10) R ⁷ and R ⁸ can be mentioned, of which (8) R ⁶ and R ⁷ Is preferable, and it is more preferable that R ⁶ and R ⁷ are bonded to each other to form a fluorene ring or the like.

Specific examples of the compound represented by the general formula (III) include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, and 2-isopropyl-2. One or more selected from −isopentyl-1,3-dimethoxypropane, 3,3-bis (methoxymethyl) -2,6-dimethylheptane, 9,9-bis (methoxymethyl) fluorene and the like can be mentioned. -Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 3,3-bis (methoxymethyl) -2,6-dimethylheptane, 9,9-bis (methoxymethyl) ) One or more selected from fluorene is preferable, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene. One or more selected from are more preferable.

In the compound represented by the general formula (III), k is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. If k is an integer of 2 or more, to the R ⁵ which there exist a plurality may be the same as each other or may be different.

In the compound represented by the general formula (III), p is an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably 1 to 6. When p is an integer of 2 or more, a plurality of R ⁶ and R ⁷ existing may be the same as each other or may be different from each other.

In the compound represented by the general formula (III), q is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. when q is an integer of 2 or more, it may be the R ⁸ where there exist a plurality identical to each other or may be different.

When ether carbonates are used as the internal electron donating compound, the ether carbonates are represented by the following general formula (IV).
R ^9- OC (= O) -OZ-OR ¹⁰ ... (IV)
In formula (IV), R ⁹ and R ¹⁰ are linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, vinyl groups, and linear alkenyl groups having 3 to 20 carbon atoms. Alternatively, a branched alkenyl group, a linear halogen-substituted alkyl group having 1 to 20 carbon atoms, a branched halogen-substituted alkyl group having 3 to 20 carbon atoms, a linear halogen-substituted alkenyl group having 2 to 20 carbon atoms, and 3 to 20 carbon atoms. Branched halogen-substituted alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms. , An aromatic hydrocarbon group having 6 to 24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and a nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms having a carbon atom at the bond end (provided that the bond is bonded). (Excluding those having a C = N group at the end), an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms having a carbon atom at the bond end (excluding those having a carbonyl group at the bond end), or a bond end Indicates a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms, which is a carbon atom (excluding those having a C = P group at the bond end), and R ⁹ and R ¹⁰ may be the same or different. Often, Z can be a compound represented by a carbon atom or a bonding group bonded via a carbon chain.).

As specific examples of the compound represented by the general formula (IV), (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethyl carbonate, and (2-ethoxyethyl) phenyl carbonate are particularly preferable.

In the method for producing Mg-containing particles according to the present invention, when the solid catalyst component is a contact reaction product of a magnesium compound, a tetravalent titanium halogen compound and an internal electron donating compound, a magnesium compound, a tetravalent titanium halogen compound and The contact and reaction of the internal electron donating compound may be carried out in the presence of polysiloxane, which is a third component.

Polysiloxane is a polymer having a siloxane bond (-Si-O- bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 10000 cm). Stokes), more preferably 0.03 to ⁵ cm ² / s (3 to 500 cm Stokes), meaning a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

The chain polysiloxane includes hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane 1,3-divinyltetramethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, and 1 as disiloxane. , 3-Dibromotetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis (chloromethyl) tetramethyldisiloxane, and other polysiloxanes other than disiloxane include dimethylpolysiloxane and methylphenylpolysiloxane. As the partially hydride polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used, and as the cyclic polysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2, 4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethyl. Siloxane is exemplified. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.

In the method for producing Mg-containing particles according to the present invention, olefin polymerization in which Mg-containing particles containing a magnesium compound as a main component have an organoaluminum compound and, if necessary, an external electron donating compound, together with the above-mentioned solid catalyst component for olefin polymerization. In the case of a catalyst for use, the organoaluminum compound has the following general formula (V).
R ¹¹ sAlQ _3-s ... (V)
(In the formula, R ¹¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and s is a real number of 0 <p≤3.)
Examples thereof include organoaluminum compounds represented by.

In the organoaluminum compound represented by the general formula (V), R ¹¹ is an alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , Isobutyl group and the like.

In the organic aluminum compound represented by the general formula (V), Q represents a hydrogen atom or a halogen atom, and when Q is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned.

Specific examples of the organoaluminum compound represented by the general formula (V) include one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and triethylaluminum. , Triisobutylaluminum is suitable.

Further, examples of the external electron donating compound include organic compounds containing an oxygen atom or a nitrogen atom. Specific examples thereof include alcohols, phenols, ethers, esters, ketones, acid halides, and the like. Examples thereof include aldehydes, amines, amides, nitriles, isocyanates, organic silicon compounds, and organic silicon compounds having a Si—OC bond.

Among the external electron donating compounds, esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluic acid, ethyl p-toluic acid, methyl anisate, ethyl anisate and the like. , 1,3-Diethers, organic silicon compounds containing Si—OC bonds are preferred, and organic silicon compounds having Si—OC bonds are particularly preferred.

The content ratios of the solid catalyst component, the organoaluminum compound and the external electron donating compound constituting the catalyst for olefin polymerization are not particularly limited, but the organoaluminum compound per 1 mol of titanium atoms in the solid catalyst component. However, it is preferably 1 to 2000 mol, more preferably 50 to 1000 mol. Further, the amount of the external electron donating compound is preferably 0.001 to 10 mol, more preferably 0.002 to 2 mol, and 0.002 to 0.5 mol per 1 mol of the organoaluminum compound. It is more preferable to have.

In the method for producing Mg-containing particles according to the present invention, the unclassified Mg-containing particles and Mg-containing particles subjected to the dissociation treatment and the classification treatment have a particle size of 1 to 200 μm, and those having a particle size of 5 to 180 μm are suitable. It is more suitable that the particle size is 9 to 160 μm.

Further, in the method for producing Mg-containing particles according to the present invention, the unclassified Mg-containing particles and Mg-containing particles subjected to the dissociation treatment and the classification treatment are preferably those having an average particle size (D ₅₀ ) of _{5 to} 100 μm. Yes, those with a diameter of 7 to 80 μm are more suitable, and those with a diameter of 10 to 60 μm are more suitable.

In the present application documents, the particle size of the unclassified Mg-containing particles and the Mg-containing particles means a value measured by a laser light scattering diffraction method, and the average particle size (D ₅₀ ) of the unclassified Mg-containing particles is. It means a particle size of 50% in terms of volume-based integrated particle size measured by a laser light scattering diffraction method.

In the method for producing Mg-containing particles according to the present invention, the unclassified Mg-containing particles and Mg-containing particles are represented by the following formula (ii).
Particle size distribution index (SPAN) = (D _90- D ₁₀ ) / D ₅₀ ... (ii)
(D ₁₀ , D ₅₀ and D ₉₀ are volume-based integrated particle sizes measured using the above measuring machine, and mean 10% particle size, 50% particle size and 90% particle size, respectively. )
The particle size distribution index (SPAN) represented by is 0.5 to 5.0 is suitable, 0.5 to 4.0 is more suitable, and 0.5 to 3.0. Some are even more appropriate.

In the present specification, the average particle size (D ₅₀ ) and the particle size distribution mean those obtained by using a laser diffraction type particle size distribution measuring device (Mastersizer 3000 manufactured by Spectris Co., Ltd.).

The unclassified Mg-containing particles are represented by the following formula (1).
Abrasion durability A = (Z ÷ Y) × 100… (1)
(In the formula, Y is the average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 0.4 bar using a laser diffraction type particle size distribution measuring device, and Z is the laser diffraction type particle size distribution measurement. The average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 1.0 bar using the device is shown.)
The abrasion durability A (%) represented by is 85 or less, 60 to 85% is suitable, 65 to 80% is more suitable, and 70 to 75% is further suitable. Appropriate.

In the method for producing Mg-containing particles according to the present invention, unclassified Mg-containing particles which are fragile porous particles having low particle strength, that is, particles having an abrasion durability A of 90% or less, which are usually difficult to classify, are used. Even in the case of classification, it is possible to reduce the content of fine coarse powder particles such as fine powder particles and coarse powder particles, prevent particle destruction, and obtain classified particles having a narrow particle size distribution and a good particle shape. it can.

In the present specification, the abrasion durability A is a laser diffraction type particle size distribution measuring device (manufactured by Spectris Co., Ltd., Mastersizer 3000) and a dry dispersion unit for dry powder dispersion (manufactured by Spectris Co., Ltd., Aero). It means what was obtained using S).

<Manufacturing method of Mg-containing particles>
[Preparation process]
In the method for producing Mg-containing particles according to the present invention, a preparation step for preparing unclassified Mg-containing particles will be described. The composition of the unclassified Mg-containing particles having the magnesium compound as the main component obtained in the preparation step is as described above, and thus the description thereof will be omitted.

In the method for producing Mg-containing particles according to the present invention, it is appropriate that the magnesium compound constituting the unclassified Mg-containing particles is prepared using alkoxymagnesium as a raw material.

For example, a method for producing spherical dialkoxymagnesium is, for example, JP-A-58-4132, JP-A-62-51633, JP-A-3-74341, which are specifications of Japanese patent applications. , Japanese Patent Application Laid-Open No. 4-368391, Japanese Patent Application Laid-Open No. 8-73388, and the like.

In the method for producing Mg-containing particles according to the present invention, the obtained dialkoxymagnesium can be classified by the method shown in the classification step described later.

In the method for producing Mg-containing particles according to the present invention, the solid catalyst component for olefin polymerization containing titanium, halogen and one or more internal electron donors in addition to the above-mentioned magnesium compound includes alkoxymagnesium and a tetravalent titanium halogen compound. And the contact reaction product of the internal electron donor compound may be classified by the method shown in the classification step described later.

The treatment of contacting and reacting the magnesium compound, the tetravalent titanium halogen compound, and the internal electron donating compound (and polysiloxane in some cases) is preferably carried out in the presence of an inert organic solvent such as toluene or hexane.

The inert organic solvent is preferably a liquid at room temperature (20 ° C.) and a boiling point of 50 to 150 ° C., and is an aromatic hydrocarbon compound or an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. at room temperature. Saturated hydrocarbon compounds are more preferred.

The temperature at the time of the reaction is preferably 0 to 130 ° C., more preferably 40 to 130 ° C., even more preferably 30 to 120 ° C., and even more preferably 80 to 120 ° C. The reaction time is preferably 1 minute or longer, more preferably 10 minutes or longer, further preferably 30 minutes to 6 hours, further preferably 30 minutes to 5 hours, and even more preferably 1 to 4 hours.

When contacting and reacting a magnesium compound, a tetravalent titanium halogen compound and internal electron donating compounds, the amount of the tetravalent titanium halogen compound used per 1 mol of the magnesium compound is preferably 0.5 to 100 mol. , 1 to 50 mol, more preferably 1 to 10 mol.

The contact of each component is preferably carried out while stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where water and the like are removed.

After completion of the above reaction, the reaction product is washed by allowing the reaction solution to stand still and appropriately removing the supernatant liquid to make it wet (slurry), or further drying it by hot air drying or the like. Is preferable.

The above cleaning treatment is usually performed using a cleaning liquid.

Examples of the cleaning liquid include those similar to the above-mentioned inert organic solvent, and by using the above-mentioned cleaning liquid, by-products and impurities can be easily dissolved and removed from the reaction product.

By contacting and reacting each of the above components and then performing a washing treatment, impurities of unreacted raw material components and reaction by-products (alkoxytitanium halide, titanium tetrachloride-carboxylic acid complex, etc.) remaining in the reaction product can be removed. Can be removed.

The contact reaction product of each of the above components is usually in the form of a suspension, and the product in the form of a suspension is allowed to stand, and the supernatant liquid is removed to form a wet state (slurry), or the product is further dried with hot air or the like. A solid catalyst component can be obtained by drying.

In the above solid catalyst component, the content of magnesium atom is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, further preferably 15 to 40% by mass, and particularly preferably 15 to 25% by mass.

In the above solid catalyst component, the content of titanium atoms is preferably 0.5 to 8.0% by mass, more preferably 0.5 to 5.0% by mass, still more preferably 0.5 to 3.0% by mass. ..

In the solid catalyst component, the content of halogen atoms is preferably 20 to 88% by mass, more preferably 30 to 85% by mass, further preferably 40 to 80% by mass, still more preferably 45 to 75% by mass.

In the above solid catalyst component, the content ratio of the internal electron donating compound is preferably 1.5 to 30.0% by mass, more preferably 3.0 to 25.0% by mass, and 6.0 to 25.0% by mass. Is even more preferable.

In the present application documents, the content of magnesium atom in the solid catalyst component means a value measured by an EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

In the present application documents, the content of titanium atoms in the solid catalyst component means a value measured according to the method (oxidation-reduction titration) described in JIS 8311-1997 "Titanium quantification method in titanium ore". To do.

In the present application documents, the content of magnesium atom in the solid catalyst component means a value measured by an EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

In the present application documents, the content of halogen atoms in the solid catalyst component is determined by treating the solid catalyst component with a mixed solution of sulfuric acid and pure water to obtain an aqueous solution, then fractionating a predetermined amount and using a silver nitrate standard solution to obtain halogen atoms. It shall mean the value measured by the silver nitrate titration method.

In the present application documents, the content of the internal electron donating compound in the solid catalyst component is a known concentration in advance when measured under the following conditions using gas chromatography (manufactured by Shimadzu Corporation, GC-14B). It means the result obtained by using the calibration curve measured based on.

<Measurement conditions for gas chromatography>
Column: Packed column (φ2.6 × 2.1m, Silicone SE-30 10%, Chromosorb WAWDMCS 80/100, manufactured by GL Sciences Co., Ltd.)
Detector: FID (Flame Ionization Detector, hydrogen flame ionization detector)
Carrier gas: helium, flow rate 40 ml / min Measurement temperature: vaporization chamber 280 ° C, column 225 ° C, detector 280 ° C, or vaporization chamber 265 ° C, column 180 ° C, detector 265 ° C
In the method for producing Mg-containing particles according to the present invention, the obtained solid catalyst component for olefin polymerization can be classified by the method shown in the classification step described later.

In the method for producing Mg-containing particles according to the present invention, the unclassified Mg-containing particles containing a magnesium compound as a main component have the above-mentioned solid catalyst component for olefin polymerization, as well as an organoaluminum compound and, if necessary, an external electron donating compound. In the case of a catalyst for olefin polymerization, the catalyst for olefin polymerization is prepared by contacting (α) a solid catalyst component, (β) an organoaluminum compound and (γ) an external electron donating compound by a known method. Can be done.

The order in which each of the above components is brought into contact is arbitrary, but for example, the following contact order can be exemplified.
(I) (α) Solid catalyst component → (γ) External electron donating compound → (β) Organoaluminium compound (ii) (β) Organoaluminium compound → (γ) External electron donating compound → (α) Solid catalyst component (Iii) (γ) External electron donating compound → (α) Solid catalyst component → (β) Organoaluminium compound (iv) (γ) External electron donating compound → (β) Organoaluminium compound → (α) Solid catalyst component In the above contact examples (i) to (iv), the contact example (ii) is preferable.

In the above contact examples (i) to (iv), “→” means the contact order, for example, “(α) solid catalyst component for olefin polymerization → (β) organoaluminum compound → (γ) external electron. The “donating compound” means that a (β) organoaluminum compound is added to the (α) solid catalyst component and brought into contact with the compound, and then a (γ) external electron donating compound is added and brought into contact with the compound.

The catalyst for olefin polymerization may be formed by contacting a solid catalyst component, an organoaluminum compound and an external electron donating compound in the absence of olefins, or in the presence of olefins (polymerization system). It may be in contact (inside).

The contact between the solid catalyst component, the organoaluminum compound and the external electron donating compound is performed in an atmosphere of an inert gas such as argon or nitrogen, or in order to prevent deterioration of the solid catalyst component and the catalyst for olefin polymerization after preparation. It is preferable to carry out in a monomer atmosphere such as propylene.

Further, considering the ease of operation, it is also preferable to carry out the operation in the presence of a dispersion medium such as an inert solvent.

The contact temperature at the time of contacting each of the above components is preferably −10 ° C. to 100 ° C., more preferably 0 ° C. to 90 ° C., and even more preferably 20 ° C. to 80 ° C. The contact time is preferably 1 minute to 10 hours, more preferably 10 minutes to 5 hours, and even more preferably 30 minutes to 2 hours.

By setting the contact temperature and contact time within the above ranges, it becomes easy to improve the polymerization activity of the olefin polymerization catalyst and the stereoregularity of the obtained polymer, and the mechanical properties of the resulting olefin polymer can be improved. It becomes easy to improve.

[Processing process]
Next, in the method for producing Mg-containing particles according to the present invention, a treatment step for treating unclassified Mg-containing particles will be described. In the treatment step, unclassified Mg-containing particles containing the disaggregated particles and the aggregated particles are treated to dissociate the aggregated Mg-containing particles, and further, the agglomeration is released. The unclassified Mg-containing particles are classified to obtain Mg-containing particles. That is, in the treatment step, the unclassified Mg-containing particles are dissociated and classified to obtain Mg-containing particles, and fine particles other than the Mg-containing particles are removed. In the treatment step, unclassified Mg-containing particles are classified using a centrifugal airflow classifier having a rotating body having a diameter of 200 to 1000 mm. The pretreatment step may be performed prior to the treatment step. By providing the pretreatment step, coarse powder particles such as linked particles and impurities such as iron powder can be removed from the unclassified Mg-containing particles by means such as sieving.

Here, the fine powder (particles other than fine powder particles and Mg-containing particles) in the present specification produces a "fine powder-like polymer (also referred to as fine powder polymer)" having a predetermined particle size when subjected to polymerization of olefins. It refers to particles that can be polymerized. If the amount of such fine powder polymer increases during the polymerization of olefins, it is not preferable because it hinders the continuation of a uniform polymerization reaction and causes process troubles such as blockage of piping during polymer transfer. In addition, it is desired to reduce the amount of fine powder polymer because it has an unfavorable effect on the molding process of the polymer, such as an increase in defective products. Therefore, in the method for producing Mg-containing particles according to the present invention, the unclassified Mg-containing particles are dissociated and classified in the above treatment step to remove fine particles other than the Mg-containing particles.

In the present specification, the fine powder (fine powder particles) to be removed by the classification treatment is calculated by the following formula (A) according to the average particle size (D ₅₀ ) and the polymerization activity of the target polymer. be able to.
Particle size of fine powder = (average particle size of polymer) / ( ³ √ (polymerization activity)) (A)
For example, in the case of a polymer having an average particle size (D ₅₀ ) of 75 (μm) and a polymerization activity of 40,000 to 65,000 (g-pp / g-cat), 75 ÷ (34.2 to 39. 6) = A solid catalyst (fine powder) of 1.9 to 2.9 (μm) can be a “fine powder polymer”. Therefore, the fine particles (fine powder particles) to be removed by the classification treatment in this case are particles of approximately less than 5 (μm).
In the present specification, the average particle size (D ₅₀ ) of the polymer formed by subjecting Mg-containing particles (products) to the polymerization of olefins is 100 to 5000 μm, and the polymerization activity of the polymer is 8, It is 000 to 150,000 (g-pp / g-cat). Therefore, the particle size of the fine powder (fine powder particles) to be removed by the classification treatment in the present specification is 0.1 to 100.0 μm.

Here, the rotating body means a disk-shaped classifying rotor provided in the centrifugal airflow classifying device.

The diameter of the disc-shaped classification rotor is 200 to 1000 mm, preferably 300 to 800 mm, and more preferably 300 to 700 mm.

In the method for producing Mg-containing particles according to the present invention, the diameter of the disk-shaped classifying rotor constituting the centrifugal airflow classifying device is within the above range, so that the unclassified Mg-containing particles are not destroyed. It is possible to suitably remove fine coarse powder particles such as fine powder particles and coarse powder particles, and easily achieve a rotation speed and an air volume capable of recovering Mg-containing particles having a narrow particle size distribution and a good particle shape.

In the method for producing Mg-containing particles according to the present invention, as the centrifugal airflow classifying device, the powder is dry-classified by a method of rotating a disk-shaped classifying rotor at high speed with a balance between the centrifugal force of rotation and the centripetal force of gas suction. The device is not particularly limited, but it is a forced vortex centrifugal classification that has a rotating body inside the device, exerts a centrifugal force on the particles by the rotational force, and exerts a counterforce on the particles by an inward airflow passing through the inside of the device. Semi-free vortex centrifugal type that does not have a rotating body inside the device or the device, creates a swirling airflow by providing guide blades, etc., and exerts a centrifugal force on the particles by the swirling movement, and exerts a counterforce on the particles by the swirling airflow itself. A classification device or the like is preferably used.

In the method for producing Mg-containing particles according to the present invention, the rotation speed at which unclassified Mg-containing particles are airflow-classified using a centrifugal airflow classifier having a disk-shaped classifying rotor is 3000 rpm (rotation / minute) or less. , 100-3000 rpm is more suitable, and 500-2500 rpm is more suitable.

In the method for producing Mg-containing particles according to the present invention, unclassified Mg-containing particles for airflow classification using a centrifugal airflow classifier having a disk-shaped classifying rotor are supplied to the centrifugal airflow classifier. The total air volume (total air volume) in the sum of the air volume to be generated and the air volume to send particles into the disk-shaped classification rotor is 1 to 50 m ³ / min, 5 to 40 m ³ / min, and 5 to ³⁰ m ³ / Minute is more appropriate.

In the method for producing Mg-containing particles according to the present invention, the air volume for sending particles into the disk-shaped classifying rotor when the unclassified Mg-containing particles are airflow-classified using a centrifugal airflow classifying device having a disk-shaped classifying rotor ( The circulating air volume) is 1 to 50 m ³ / min, 1 to 35 m ³ / min is appropriate, and 5 to 20 m ³ / min is more appropriate.

In the method for producing Mg-containing particles according to the present invention, the peripheral speed of the disk-shaped classifying rotor (rotating body) at the time of classifying is preferably 2 to 130 m / sec, more preferably 6 to 110 m / sec, and 9 to 90 m. The / sec range is even more preferred.

The peripheral speed of the disk-shaped classification rotor (rotating body) is calculated by the following formula (2) based on the diameter L (mm) of the classification rotor and the rotation speed S (rpm) of the classification rotor (rotating body). Means the value.

Peripheral speed (m / sec) of disk-shaped classifying rotor (rotating body) = L (mm) x π x S (rotation / minute) ÷ 1000 ÷ 60 ... (2)
In the method for producing Mg-containing particles according to the present invention, the classification time is preferably 20 to 900 minutes, more preferably 40 to 800 minutes, and even more preferably 60 to 600 minutes.

In the method for producing Mg-containing particles according to the present invention, the flow velocity of unclassified Mg-containing particles flowing inside the flow path defined by the housing and the top surface of the classification rotor (rotating body) and connecting the inlet and the classification chamber. A step of supplying the unclassified Mg-containing particles to the classification chamber is provided. As a result, the energy of impact when the Mg-containing particles collide with the inner surface of the housing or the like is reduced, and the yield of the product is improved. At that time, the amount of decrease in the flow velocity of the Mg-containing particles is preferably as follows.

That is, in the method for producing Mg-containing particles according to the present invention, in the step of supplying unclassified Mg-containing particles to the classification chamber, the average flow velocity of the unclassified Mg-containing particles in the vertical cross section at the entrance of the classification chamber is determined by the flow path. It is preferable that the average flow velocity of the unclassified Mg-containing particles at the upstream end is reduced to half or less.

Further, in the method for producing Mg-containing particles according to the present invention, in the step of supplying unclassified Mg-containing particles to the classification chamber, the average flow velocity of the unclassified Mg-containing particles in the vertical cross section at a position substantially intermediate to the radius of the classification rotor. Is preferably 2/3 or less of the average flow velocity of the unclassified Mg-containing particles at the upstream end of the flow path. Further, in the method for producing Mg-containing particles according to the present invention, the average flow velocity of the Mg-containing particles in the vertical cross section of the entrance of the classification chamber is preferably 15 m / s or less. In the present specification, the "substantially intermediate position" of the radius of the top surface of the classification rotor (rotating body) is the intermediate position of the radius of the top surface of the classification rotor and the radius of the top surface of the classification rotor from the intermediate position. A position including an arbitrary position within a length range corresponding to 10% of the length of the above. When the length of the radius of the classifying rotor (rotating body) is X, the distance Y from the center of the top surface of the classifying rotor (rotating body) to the substantially intermediate position can be expressed by, for example, the following formula.

In the method for producing Mg-containing particles according to the present invention, it is preferable to use a dry gas having a water content of 20 mass ppm or less as the classification medium when classifying by the air flow classifying device having the above-mentioned classifying rotor, and unclassified. When the Mg-containing particles are solid catalyst components for olefin polymerization, it is preferable to use an inert gas such as argon or nitrogen so that the active titanium component or the like supported on the magnesium compound particles is not deactivated.

In the method for producing Mg-containing particles according to the present invention, the supply amount of unclassified Mg-containing particles is preferably 1 to 60 kg / hour, more preferably 3 to 50 kg / hour, and even more preferably 5 to 40 kg / hour.

In the method for producing Mg-containing particles according to the present invention, the obtained Mg-containing particles (classified particles) preferably have a particle size distribution index (SPAN) defined by the above formula (ii) of 1 or less, preferably 0.9. It is more preferably less than or equal to, and even more preferably 0.8 or less.

According to the present invention, unclassified Mg-containing particles containing magnesium as a main component and having an average particle size D50 (μm) of 5 to 100 μm are subjected to a centrifugal air flow classifier having a rotating body having a diameter in a specific range. By classifying the airflow under predetermined conditions, fine coarse powder particles such as fine powder particles and coarse powder particles can be removed, and the aggregated state of coarse powder particles having low particle strength can be appropriately solved, and particles having a desired particle size. Since it is possible to increase the content ratio while suppressing the destruction of the particles, it is possible to easily obtain classified particles having a desired particle size and a narrow particle size distribution in a high yield.

<Method for producing olefin polymers>
Next, a method for producing an olefin polymer using the Mg-containing particles produced by the method for producing Mg-containing particles of the present invention will be described.

In the method for producing an olefin polymer, when the unclassified Mg-containing particles are a solid catalyst component for olefin polymerization or an olefin polymerization catalyst in the method for producing Mg-containing particles according to the present invention, the obtained classified particles are used. It is characterized by polymerizing olefins.

Specifically, in the Mg-containing particle production method according to the present invention, when the unclassified Mg-containing particles are solid catalyst components for olefin polymerization, the obtained solid catalyst component is used to form an olefin polymerization catalyst. In the presence of the olefin polymerization catalyst, and when the unclassified Mg-containing particles are the olefin polymerization catalyst in the Mg-containing particle production method according to the present invention, in the presence of the obtained olefin polymerization catalyst. , Polymerize olefins.

In the method for producing an olefin polymer, examples of the olefins 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, with propylene being more preferred.

When propylene is polymerized, copolymerization with other olefins may be carried out, and as copolymerization of propylene and a monomer of other olefins, propylene and a small amount of ethylene are used as a comonomer and polymerized in one step. Random copolymerization and homopolymerization of propylene in the first stage (first polymerization tank), and other than propylene and ethylene in the second stage (second polymerization tank) or higher multi-step (multi-stage polymerization tank). The so-called propylene-ethylene block copolymerization, in which the above-mentioned α-olefin is copolymerized, is typical, and block copolymerization of propylene and another α-olefin is preferable.

The block copolymer obtained by block copolymerization is a polymer containing segments in which two or more kinds of monomer compositions change continuously, and is a monomer type, a comonomer type, a comonomer composition, a comonomer content, a comonomer arrangement, and a conformational rule. It refers to a form in which two or more types of polymer chains (segments) having different primary structures such as sex 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), and specifically, ethylene, 1-butene, 1-pentene, 4-. Examples thereof include methyl-1-pentene and vinylcyclohexane, and one or more of these olefins can be used in combination. Ethylene or 1-butene is preferable as the olefins to be copolymerized, and ethylene is particularly preferable.

In the method for producing an olefin polymer, the polymerization of olefins can be carried out in the presence or absence of an organic solvent.

Further, the olefins to be polymerized can be used in either a gas state or a liquid state.

Polymerization of olefins is carried out, for example, in a reaction furnace such as an autoclave in the presence of a catalyst for olefin polymerization, in which olefins are introduced and heated and pressurized.

In the method for producing an olefin polymer, the polymerization temperature is usually 200 ° C. or lower, preferably 100 ° C. or lower, and from the viewpoint of improving activity and stereoregularity, 60 to 100 ° C. is more preferable, and 70 to 90 ° C. ℃ is more preferable, and 75 to 80 ° C is even more preferable. In the method for producing an olefin polymer of the present invention, the polymerization pressure is preferably 10 MPa or less, more preferably 5 MPa or less.

In the method for producing an olefin polymer, a polymer having excellent hydrogen activity, high stereoregularity and MFR is produced under high productivity even when homopolymerized at a relatively high temperature in the above polymerization temperature range. In addition, even when copolymerized at a high temperature, excellent hydrogen activity and copolymerization activity can be achieved, and a copolymer having excellent impact resistance can be produced.

Further, either a continuous polymerization method or a batch type polymerization method is possible. Further, the polymerization reaction may be carried out in one stage or in two or more stages.

In the method for producing an olefin polymer, the block copolymerization reaction between propylene and other α-olefins is usually carried out in the presence of the olefin polymerization catalyst according to the present invention, either propylene alone or in a small amount with propylene in the previous stage. This can be carried out by contacting α-olefin (ethylene or the like) and then contacting propylene and α-olefin (ethylene or the like) in the subsequent stage. The polymerization reaction in the first stage may be repeated a plurality of times, or the polymerization reaction in the second stage may be repeated a plurality of times by a multi-step reaction.

Specifically, the block copolymerization reaction between propylene and other α-olefins is polymerized so that the proportion of the polypropylene portion (in the finally obtained copolymer) is 20 to 90% by weight in the previous stage. Polymerization is carried out by adjusting the temperature and time, and then propylene and ethylene or other α-olefins are introduced in the subsequent stage, and rubber such as ethylene-propylene rubber (EPR) (occupying the final copolymer) is introduced. Polymerize so that the proportion is 10 to 80% by weight.

The polymerization temperature in both the first stage and the second stage is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, further preferably 75 to 80 ° C., and the polymerization pressure is preferably 10 MPa or less, more preferably 5 MPa or less.

In the above-mentioned copolymerization reaction, either a continuous polymerization method or a batch type polymerization method can be adopted, and the polymerization reaction may be carried out in one stage or in two or more stages.

Further, the polymerization time (residence time in the reaction furnace) is preferably 1 minute to 5 hours at each polymerization step of each polymerization step of the first stage or the second stage, or even during continuous polymerization.

Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a vapor phase polymerization method using substantially no solvent. , Bulk polymerization method or gas phase polymerization method is preferable, and the reaction in the latter stage is generally preferably a gas phase polymerization reaction for the purpose of suppressing elution of EPR from PP particles.

In the method for producing an olefin polymer, when polymerizing olefins (hereinafter, appropriately referred to as main polymerization), some or all of the constituent components of the olefin polymerization catalyst are added to the olefins to be polymerized. Preliminary polymerization (hereinafter, appropriately referred to as prepolymerization) may be carried out by contacting them.

When performing the prepolymerization, the constituent components of the catalyst for olefin polymerization and the contact order of the olefins are arbitrary, but the organic aluminum compound is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere. Then, it is preferable to contact the solid catalyst component with one or more olefins such as propylene. Alternatively, the organoaluminum compound is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, then an external electron donating compound is contacted if necessary, and then a solid catalyst component is contacted. It is preferable to contact one or more olefins such as propylene.

At the time of prepolymerization, the same olefins or monomers such as styrene can be used as in the main polymerization, and the prepolymerization conditions are the same as the above polymerization conditions.

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

According to the method for producing an olefin polymer, it is appropriate that the particle size distribution index (SPAN) defined by the above formula (ii) of the obtained olefin polymer is 1 or less, and 0.9 or less. It is more appropriate to be, and it is more appropriate to be 0.8 or less.

By using the Mg-containing particles obtained by the method for producing Mg-containing particles of the present invention, the content of fine powder particles and coarse powder particles in the polymer particles is reduced, and an olefin polymer having a narrow particle size distribution is produced. A method can be provided.

[Embodiment of Mg-containing particle classifier]
Hereinafter, the Mg-containing particle classifying device 11 of the embodiment will be described with reference to FIGS. 1 to 4. The Mg-containing particle classifier 11 is an example of a centrifugal airflow classifier.

As shown in FIG. 1, the Mg-containing particle classifying device 11 supports a housing 12 that covers the whole, a classification rotor 13 and a balance rotor 14 provided in the housing 12, and a classification rotor 13 and a balance rotor 14. A rotating shaft 15 for rotating the rotating shaft 15, a motor (not shown) for rotationally driving the rotating shaft 15, and a flow path 17 whose outer edge is defined by the inner surface 19 of the housing 12 and the top surface 16 of the classification rotor 13. Be prepared.

In the present specification, the housing 12 refers to a casing having a substantially cylindrical overall shape. The housing 12 is formed in the shape of a container constituting the outer shell of the Mg-containing particle classifying device 11, and surrounds a part of the classifying rotor 13, the balance rotor 14, and the rotating shaft 15. The casing 12 is provided at a cylindrical tubular portion 30, a charging port 18 provided at the tip of the tubular portion 30 and capable of charging unclassified Mg-containing particles 20, and a classification process provided at the upper part of the peripheral side portion. Air provided on the peripheral side at a position between the outlet 21 of the Mg-containing particles 24, which will be the later product, the spiral casing 22 provided at the lower part of the peripheral side, and the outlet 21 and the spiral casing 22. It is provided with an introduction port 23. Unclassified Mg-containing particles 20 are charged into the Mg-containing particle classifying device 11 together with air into the charging port 18. The tip of the input port 18 is formed in a flange shape and is connected to an unclassified Mg-containing particle supply device (not shown) that supplies the unclassified Mg-containing particles 20. The spiral casing 22 is connected to a collecting device and a fan, and can remove fine powder 24a together with air.

The rotating shaft 15 is provided at the center of the housing 12. The rotating shaft 15 is rotatably supported by a bearing 25, and a pulley 26 is attached to the lower end. The rotary shaft 15 is rotationally driven by a motor via the pulley 26. The classification rotor 13 and the balance rotor 14 are provided so as to be rotatable (rotatable) in a horizontal plane.

The classification rotor 13 is an example of a rotating body that rotates in a horizontal plane. The classification rotor 13 includes a top surface 16, a first cavity 27 provided inside and communicating with the lower part of the center, and a plurality of classification blades provided at equal intervals in the vicinity of the outer edge of the first cavity 27. 28, a plurality of classification chambers 31 provided in a space portion between the classification blades 28, and a plurality of openings 32 provided on the top surface 16 and formed at positions corresponding to substantially the center in the radial direction of the classification blades 28. , A plurality of auxiliary blades 33 provided at equal intervals on the lower surface facing the classification blade 28. The diameters of the classification rotor 13 and the balance rotor 14 are, for example, 200 to 1000 mm, preferably 300 to 800 mm, and more preferably 300 to 700 mm. Each of the plurality of classification blades 28 includes, for example, an inner classification blade 28A and an outer classification blade 28B.

The top surface 16 is formed in a substantially flat shape. The top surface 16 has a flat portion 16A and a truncated cone-shaped cone portion 16B provided at the center of the flat portion 16A. Inside the cone portion 16B, a pin for preventing the classification rotor 13 and the balance rotor 14 from falling off from the rotating shaft 15 is housed.

Each of the plurality of classification blades 28 extends radially in the radial direction of the classification rotor 13. Each of the plurality of openings 32 is formed so as to form a substantially annular shape along the outer edge of the top surface 16, and powder can be dropped toward the classification chamber 31.

The auxiliary blade 33 gives air a flow in the rotation direction when the classification rotor 13 rotates, and can introduce air into the classification chamber 31 in a swirled state.

The Mg-containing particle classifying device 11 has a space 34 between the outer edge portion of the classifying rotor 13 and the housing 12. The outlet 21 is formed so as to communicate with the vacant space 34.

The balance rotor 14 has a shape that is vertically symmetrical with the classification rotor 13 with respect to the horizontal plane, and has substantially the same weight as the classification rotor 13. The balance rotor 14 has a second cavity portion 35 communicating from the outer edge portion to the upper part of the center portion in substantially the same manner as the classification rotor 13, and a plurality of blades 36 provided in the vicinity of the opening in the second cavity portion 35. Have. The second cavity portion 35 is integrally fixed to the classification rotor 13 and the rotating shaft 15 so as to communicate with the first cavity portion 27 of the classification rotor 13 above the central portion. A spiral casing 22 is arranged near the outlet of the second cavity 35 of the balance rotor 14 so as to surround the outlet.

As shown in FIG. 2, the flow path 17 is formed as a part of the path connecting the input port 18 and the classification chamber 31. The flow path 17 is a concept including an inner surface 19 of the housing 12 forming the outer edge thereof, a top surface 16 of the classification rotor 13, and a hollow portion located between them and through which a fluid flows. As shown in FIGS. 3 and 4, the flow path 17 is located on the upstream side thereof, and is provided between the lower inner surface of the tubular portion 30 forming the input port 18 and the upper end portion of the cone portion 16B. The upstream end portion 17A and the entrance 31A of the classification chamber provided on the downstream side thereof and located at the boundary with the classification chamber 31 are included. That is, the flow path 17 connects the upstream end portion 17A and the classification chamber 30. The upstream end portion 17A corresponds to the upstream end portion of the flow path 17 in the flow direction of the unclassified Mg-containing particles 20, and corresponds to the inlet of the flow path 17. The cross-sectional area of the flow path 17 of the present embodiment is larger than that of the flow path 17 of the classification device 41 of the reference embodiment described later. In the present embodiment, the inner surface 19 of the housing 12 is arranged at a position separated from the top surface 16 of the classification rotor 13 as compared with the classification device 41 of the reference embodiment.

The flow path 17 is formed in a space defined by the inner surface 19 of the housing 12 and the top surface 16 of the classification rotor 13, and is formed in a substantially disk shape extending outward around the input port 18. The housing 12 is inserted into the first portion 12A provided on the housing 12 at a position facing the flat portion 16A of the top surface 16 and at a position facing the flat portion 16A of the top surface 16 and more than the first portion 12A. It has a second portion 12B provided on the housing 12 on the mouth 18 side (inside) and a third portion 12C provided on the housing 12 at a position facing the cone portion 16B on the top surface 16. The first portion 12A is separated from the top surface 16 (flat portion 16A) by a first predetermined distance. The first predetermined distance is, for example, shown in dimension d in FIG. 2, for example, 6 to 15 mm, and more preferably 8 to 12 mm.

The second portion 12B is separated from the top surface 16 (flat portion 16A) by a second predetermined distance or more, which is larger than the first predetermined distance. The second predetermined distance is shown, for example, by dimension c in FIG. The second portion 12B is formed so as to satisfy the relationship of dimension c> dimension d. The second predetermined distance is, for example, 11 to 16 mm, more preferably 12 to 15 mm.

The second portion 12B is slanted so as to move away from the top surface 16 as it approaches the center of the classification rotor 13 (as it approaches the inlet 18). The distance between the portion of the second portion 12B that is farthest from the top surface 16 and the top surface 16 (flat portion 16A) is shown by dimension b in FIG. 2, for example, 17 to 22 mm, and 18 to 18 to It is more preferably 21 mm.

The third portion 12C is formed so as to chamfer the corner portion so as not to generate an edge in the flow path 17 at a position facing the cone portion 16B. The third portion 12C is formed substantially in parallel along the side surface of the cone portion 16B. The distance between the third portion 12C and the side surface of the cone portion 16B is shown in dimension a in FIG. 2, for example, 14 to 19 mm, more preferably 15 to 18 mm.

The flow path 17 is formed so as to have a relatively large cross-sectional area at a portion corresponding to the third portion 12C and the second portion 12B as described above. Therefore, according to the continuity equation of fluid dynamics, the average flow velocity of the unclassified Mg-containing particles 20 flowing inside the flow path 17 at the upstream end 17A is on the downstream side of the upstream end 17A in the flow path 17. The average flow velocity of the unclassified Mg-containing particles 20 can be reduced.

More specifically, the flow path 17 can reduce the average flow velocity of the unclassified Mg-containing particles 20 at the inlet 31A of the classification chamber 31 to less than half the average flow velocity of the unclassified Mg-containing particles 20 at the upstream end 17A. Further, the flow path is the average flow velocity of the unclassified Mg-containing particles 20 at a substantially intermediate position of the radius of the classification rotor 13 (the top surface 16 of the classification rotor 13), and the average flow velocity of the unclassified Mg-containing particles 20 at the upstream end 17A. It can be reduced to 2/3 or less of. Therefore, the flow path 17 of the Mg-containing particle classifying device 11 of the present embodiment can significantly reduce the flow velocity of the unclassified Mg-containing particles 20 in the first half portion (second portion 12B and third portion 12C). Further, the flow path 17 can set the average flow velocity of the unclassified Mg-containing particles 20 at the inlet 31A of the classification chamber 31 to, for example, 15 m / s or less.
Further, the Mg-containing particle classifier 11 can remove fine powder particles (particles other than Mg-containing particles) having a particle size of less than 5 μm contained in the unclassified Mg-containing particles 20. The particle size (cut point) of the particles to be removed as fine particles during classification is within the range of 5 μm or more and the average particle size (D ₅₀ ) or less of the unclassified Mg-containing particles 20, and the dimensions of the classification rotor 13 and the classification rotor 13. The rotation speed, the dimensions of the flow path 17, the size of the fan connected to the spiral casing 22, and other conditions can be appropriately adjusted by setting within the above ranges. As a result, the Mg-containing particle classifier 11 can reliably remove the fine particles to be removed (for example, fine particles having a particle size of less than 5 μm). The particle size of the fine powder particles can be calculated by the above formula (A) and can be appropriately set in the range of 0.1 to 100.0 μm.

Subsequently, with reference to FIGS. 1 to 4, the operation of the Mg-containing particle classifier 11 of the present embodiment and the method for producing Mg-containing particles will be described.

The classification rotor 13 and the balance rotor 14 are rotated at a predetermined speed by driving the motor. The rotation speed of the classification rotor 13 is as described in the above classification step.

A fan connected to the spiral casing 22 creates a negative pressure inside the housing 12. As a result, air is sucked from the air introduction port 23 as shown by an arrow, and the air introduced by this suction is converted into a flow in the rotation direction of the classification rotor 13 by the auxiliary blade 33. In the vacant space 34, the air swirling along the rotation direction of the classification rotor 13 forms an air flow flowing toward the inside of the classification chamber 31. The air that has entered the classification chamber 31 moves along the classification blades 28, passes through the first cavity 27 of the classification rotor 13 and the second cavity 35 of the balance rotor 14, as shown by the arrows, and passes through the spiral casing 22. It is sucked to the outside of the housing 12 via. At the same time, the negative pressure inside the housing 12 forms an air flow from the inlet 18 through the flow path 17 to the classification chamber 31.

In this state, the unclassified Mg-containing particles 20 can be classified (manufactured) by charging the unclassified Mg-containing particles 20 from the charging port 18. That is, the unclassified Mg-containing particles 20 thrown in together with the air from the charging port 18 ride on the air flow and are dispersed substantially uniformly in the radial direction centered on the axis of the classifying rotor 13 while passing through the flow path. , The primary dispersion of the unclassified Mg-containing particles 20 is performed. In the step of supplying the unclassified Mg-containing particles 20 to the classification chamber 31 in this way, the average flow velocity of the unclassified Mg-containing particles 20 at the inlet 31A of the classification chamber 31 is the average of the unclassified Mg-containing particles 20 at the upstream end 17A. It is reduced to less than half the flow velocity. Further, in the step of supplying the unclassified Mg-containing particles 20 to the classification chamber 31, the average flow velocity of the unclassified Mg-containing particles 20 at a substantially intermediate position of the radius of the classification rotor 13 is the unclassified Mg-containing particles at the upstream end 17A. It is reduced to less than 2/3 of the flow velocity of 20. The average flow velocity of the unclassified Mg-containing particles 20 at the inlet 31A of the classification chamber 31 is 15 m / s or less. The unclassified Mg-containing particles 20 protruding outward from the outer edge of the top surface 16 are radiated in the tangential direction of the outer edge of the classifying rotor 13 as the classifying rotor 13 rotates, and are secondarily dispersed.

In many cases, the unclassified Mg-containing particles 20 charged into the charging port 18 form secondary particles in which the primary particles are bonded to each other to form agglomerates. In the primary dispersion and the secondary dispersion, the secondary particles of the unclassified Mg-containing particles 20 are appropriately loosened by colliding with the top surface 16 of the classification rotor 13 and the inner surface 19 of the housing 12, and the shape of the primary particles is formed. It is crushed to. At that time, in the flow path 17, since the flow velocity of the unclassified Mg-containing particles 20 when being supplied to the classification chamber 31 is sufficiently lowered, the unclassified Mg-containing particles 20 before being supplied to the classification chamber 31 Is prevented from colliding with the inner surface 19 of the housing 12, the top surface 16 of the classification rotor, and the like and being broken.

The unclassified Mg-containing particles 20 crushed into the form of primary particles are supplied to the classification chamber 31 through the opening 32. Here, the unclassified Mg-containing particles 20 receive the centrifugal force due to the rotation of the classifying rotor 13 and the drag force due to the air flowing in the radial direction. Of the unclassified Mg-containing particles 20, the Mg-containing particles 24 (product) after the classification treatment in which the relationship of centrifugal force> drag is established are blown into the empty space around the outside of the classification rotor 13, and the Mg-containing particles are classified from the outlet 21. It is taken out of the device 11. Further, the fine powder 24a having a small particle size for which the relationship of centrifugal force <drag force is established passes through the first cavity portion 27 of the classification rotor 13 and the second cavity portion 35 of the balance rotor 14 while riding on the air flow in the radial direction. It is sent to the spiral casing 22. The fine powder 24a is collected and removed by a collecting device connected to the spiral casing 22.

According to this embodiment, the following can be said. The Mg-containing particle classifying device 11 is provided below the charging port 18 in the housing 12 having the charging port 18, and classifies the unclassified Mg-containing particles 20 in the classification chamber 31 located on the outer edge side of the rotating classification rotor 13. This is an Mg-containing particle classifier for obtaining Mg-containing particles 24a, which is a flow path 17 defined by a housing 12 and a top surface 16 of a classifying rotor 13 and connecting an inlet 18 and a classifying chamber 31. A flow path 17 for reducing the flow velocity of the unclassified Mg-containing particles 20 flowing inside is provided.

The method for producing Mg-containing particles is to connect the upstream end 17A formed by the inner surface of the housing 12 and the top surface 16 of the rotating body rotating in the housing 12 and the classification chamber 31 located on the outer edge side of the rotating body. The average flow velocity of the unclassified Mg-containing particles 20 on the downstream side of the upstream end 17A in the flow path 17 is smaller than the average flow velocity of the unclassified Mg-containing particles 20 flowing inside the flow path 17 at the upstream end 17A. The step of supplying the unclassified Mg-containing particles 20 to the classification chamber 31 and the step of classifying the unclassified Mg-containing particles 20 into the classification chamber 31 to obtain the Mg-containing particles 24a are provided by the following formula (1). The required abrasion durability A (%) of the unclassified Mg-containing particles 20 is 85 or less.
A = (Z ÷ Y) × 100… (1)
(In the formula, Y is the average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 0.4 bar using a laser diffraction type particle size distribution measuring device, and Z is the laser diffraction type particle size distribution measurement. The average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 1.0 bar using the device is shown.)

According to these configurations, the flow velocity of the unclassified Mg-containing particles 20 can be sufficiently reduced in the flow path 17, so that the unclassified Mg-containing particles 20 are placed on the inner surface 19 or the like of the housing 12 before being supplied to the classification chamber 31. Even in the case of a collision, the energy at the time of a collision can be reduced. As a result, the secondary particles of the unclassified Mg-containing particles 20 can be appropriately crushed so as to become primary particles, and the unclassified Mg-containing particles 20 can be prevented from being further finely broken from the desired primary particle shape. .. As a result, the yield of the Mg-containing particles 24 after the classification treatment can be improved. Further, according to the above configuration, even when the so-called fragile unclassified Mg-containing particles 20 are used, it is possible to prevent the unclassified Mg-containing particles 20 from being damaged and improve the yield of the Mg-containing particles 24 after the classification treatment.

In this case, in the step of supplying the unclassified Mg-containing particles 20 to the flow path 17 of the Mg-containing particle classifying device 11 and the classification chamber 31 in the method for producing Mg-containing particles, the unclassified Mg-containing particles 20 at the inlet 31A of the classification chamber 31 The average flow velocity of the unclassified Mg-containing particles 20 at the upstream end 17A is reduced to less than half of the average flow velocity of the unclassified Mg-containing particles 20. According to this configuration, the energy when colliding with the inner surface 19 or the like of the housing 12 can be reduced, and the Mg-containing particles 24 can be prevented from being further finely broken from the desired primary particle shape. As a result, the yield of the Mg-containing particles 24 after the classification treatment can be improved.

In the step of supplying the unclassified Mg-containing particles 20 to the classification chamber 31, the average flow velocity of the unclassified Mg-containing particles 20 at a substantially intermediate position of the radius of the top surface 16 of the classification rotor 13 is the unclassified Mg-containing particles 20 at the upstream end 17A. It is 2/3 or less of the average flow velocity of the particles 20. According to this configuration, the flow velocity of the unclassified Mg-containing particles 20 flowing through the flow path 17 in the first half of the flow path 17 can be significantly reduced. As a result, even if the unclassified Mg-containing particles 20 collide with the inner surface 19 of the housing in the latter half of the flow path 17, the energy at the time of collision can be significantly reduced. Therefore, for example, the yield of the Mg-containing particles 24 after the classification treatment can be further improved as compared with a structure in which the flow velocity of the unclassified Mg-containing particles 20 is reduced in the latter half of the flow path 17.

In this case, the step of supplying the unclassified Mg-containing particles 20 to the flow path 17 of the Mg-containing particle classifying device 11 and the classification chamber 31 in the method for producing Mg-containing particles is the unclassified Mg-containing particles 20 at the inlet 31A of the classification chamber 31. The average flow velocity of the particles is reduced to 15 m / s or less. According to this configuration, by suppressing the flow velocity of the unclassified Mg-containing particles 20 immediately before being supplied to the classification chamber 31, the unclassified Mg-containing particles 20 may collide with the inner surface 19 of the housing 12. The energy at the time of collision can be reduced. As a result, the yield of the classified Mg-containing particles 24 produced by the Mg-containing particle classifying device 11 can be significantly improved.

The housing 12 is provided in the housing 12 at a position facing the top surface 16 and is separated from the top surface 16 by a first predetermined distance, and a first portion 12A and a position facing the top surface 16 and the first portion 12A. It has a second portion 12B which is provided in the housing 12 on the side of the insertion port 18 and is separated from the top surface 16 by a second predetermined distance or more larger than the first predetermined distance.

According to this configuration, by increasing the cross-sectional area of the flow path 17 at the position corresponding to the second portion 12B near the input port 18, the unclassified Mg contained in the flow path 17 passing through the flow path 17 on the upstream side of the flow path 27. The flow velocity of the particles 20 can be greatly reduced. As a result, even if the unclassified Mg-containing particles 20 collide with the inner surface 19 of the housing 12 on the downstream side of the flow path 17, the energy at the time of collision can be reduced. Therefore, the yield of the classified Mg-containing particles 24 produced by the Mg-containing particle classifying device 11 can be remarkably improved.

The second portion 12B is slanted so as to move away from the top surface 16 as it approaches the inlet 18. According to this configuration, the cross-sectional area of the flow path 17 can be gradually increased as it approaches the inlet 18 side. As a result, the flow velocity of the unclassified Mg-containing particles 20 can be positively reduced on the side close to the input port 18. Therefore, even if the unclassified Mg-containing particles 20 collide with the inner surface 19 of the housing 12 on the downstream side of the flow path 17, the energy at the time of collision can be reduced. According to this configuration, apparently, the cross-sectional area of the flow path 17 seems to decrease as the distance from the input port 18 increases, but in reality, the flow path 17 radiates around the input port 18. Since it is widened, the cross-sectional area of the flow path 17 does not actually decrease significantly as the distance from the inlet 18 increases.

In this case, the top surface 16 is formed into a substantially flat shape. In the conventional classification device, a dispersion blade is provided on the top surface 16 of the classification rotor 13, and particles are dispersed by the dispersion blade. As a result, the dispersion and crushing of the particles could be made more efficient, but the air ejection action of the dispersion blades promoted the acceleration of the particles toward the outer edge of the top surface 16. The inventors have found that the acceleration of the particles by the dispersion blades increases the energy when the unclassified Mg-containing particles 20 collide with the inner surface 19 of the housing 12 and the top surface 16 of the classification rotor 13, and as a result, the unclassified particles 20 are unclassified. It has been found as a problem that the Mg-containing particles 20 are damaged and the yield of the Mg-containing particles 24 after classification is deteriorated. According to the above configuration, the top surface 16 of the classification rotor 13 is not provided with protrusions such as dispersion blades. Therefore, the flow velocity of the unclassified Mg-containing particles 20 can be suppressed as compared with the case where the dispersion blades are provided. As a result, the energy when the unclassified Mg-containing particles 20 collide with the inner surface 19 or the like of the housing can be reduced, and the yield of the Mg-containing particles 24 after the classification treatment can be improved.

In this case, the substantially flat shape includes a cone-shaped cone portion 16B at a position facing the inlet 18. According to this configuration, a large cross-sectional area of the flow path 17 can be secured in the vicinity of the inlet 18 of the flow path 17. As a result, the flow velocity of the unclassified Mg-containing particles 20 can be positively reduced on the side close to the inlet 18, thereby improving the yield of the Mg-containing particles 24 after the classification treatment.

The above-described embodiment can be implemented with various replacements and modifications. In addition, it is naturally possible to realize the invention by appropriately combining the above embodiments.
(Reference embodiment)

The classification device 41 of the reference embodiment will be described with reference to FIGS. 5 to 8. In the following description, the differences from the Mg-containing particle classifying device 11 of the above embodiment will be mainly described.

The classification device 41 of the reference embodiment includes a housing 12 that covers the entire housing, a classification rotor 13 and a balance rotor 14 provided in the housing 12, and a rotating shaft 15 that supports and rotates the classification rotor 13 and the balance rotor 14. A motor (not shown) for rotationally driving the rotary shaft 15 and a flow path 17 defined by the housing 12 and the top surface 16 of the classification rotor 13 are provided.

As shown in FIGS. 5 to 8, the classification rotor 13 has a plurality of dispersion blades 42 on the top surface 16. The plurality of dispersion blades 42 stand upward from the flat portion 16A of the top surface 16 and extend along the radial direction of the classification rotor 13. The plurality of dispersion blades 42 are separated from each other. The cone portion 16B of the top surface 16 is formed in a conical shape. The inlet 18 provided in the housing 12 is provided with a constricted portion 43 so that the cross-sectional area of the flow path 17 inside the inlet 18 becomes smaller in the middle.

The operation of the classification device 41 of the reference embodiment will be described. Similar to the Mg-containing particle classifying device 11 of the above-described embodiment, the classifying device 41 of the reference embodiment is the air from the inlet 18 to the classifying chamber 31 through the flow path 17 due to the negative pressure generated inside the housing 12. A stream is formed. When the unclassified Mg-containing particles 20 are charged from the charging port 18, the unclassified Mg-containing particles 20 are supplied to the classification chamber 31 by riding on this air flow. At that time, the unclassified Mg-containing particles 20 pass through the flow path 17 through the gap 44A between the dispersion blades 42, or pass through the gap 44B between the dispersion blade 42 and the inner surface 19 of the housing 12. And pass through the flow path 17. By passing through such a relatively narrow space, the flow velocity of the unclassified Mg-containing particles 20 is maintained at a high flow rate. In particular, the flow velocity of the particles passing through the gap 44A between the dispersion blades 42 is significantly increased by the air feeding action (fan action) of the dispersion blades 42.

In the classification device 41 of the reference embodiment, the flow velocity of the unclassified Mg-containing particles 20 when entering the classification chamber 31 is extremely high, and as a result, the inner surface 19 of the housing 12 and the top of the classification rotor 13 before entering the classification chamber 31. It collides with the surface 16 and the dispersion blade 42, and the unclassified Mg-containing particles 20 are damaged by the impact at the time of the collision. Therefore, in the classification device 41 of the reference embodiment, the yield of the Mg-containing particles 24 after the classification treatment deteriorates. Further, in the classification device 41 of the reference embodiment, when the fragile unclassified Mg-containing particles 20 are used, the problem of deterioration of the yield becomes more apparent.

(Example A1)
Example A1 of the Mg-containing particle classifier 11 described in the above embodiment will be described. In Example A1, the flow velocity of the unclassified Mg-containing particles passing through the flow path 17 of the Mg-containing particle classifying device 11 described in the above embodiment was analyzed using fluid analysis software. AnSYS SCDM was used to create the CAD shape, and ANSYS Fluent was used to analyze the flow velocity. The actual analysis work was outsourced to a third-party organization (Cybernet Systems Co., Ltd.) unrelated to the applicant in order to ensure objectivity.

In the analysis model of the Mg-containing particle classifier of Example A1, the dimensions of each part of the flow path 17 are as shown in FIG. 2 with dimensions a = 17.3 mm, dimensions b = 19 mm, dimensions c = 13.97 mm, and dimensions d = 11 mm. I set it. Further, the diameter of the classification rotor 13 was set to 380 mm. The amount of unclassified Mg-containing particles charged to the charging port 18 was 5.611 × 10 ^-3 kg / s, and the air flow rate of the charging port 18 was 0.190049 kg / s. The rotation speed of the classification rotor 13 was set to 1350 rpm. The pressure (outlet pressure) of the classification chamber 31 was set to 0.0 Pa (simulating the opening to the atmosphere with a gauge pressure). The working fluid was nitrogen, which is a fluid in consideration of compressibility. The density of the unclassified Mg-containing particles was 2060 kg / m ³ , and the particle size of the unclassified Mg-containing particles was 4.13 × ^10-5 m. The coefficient of restitution of the unclassified Mg-containing particles with respect to the housing 12 and the classifying rotor 13 was set to 0.1.

As a result of the analysis, the flow velocities of the unclassified Mg-containing particles in each part were as follows. The average flow velocity of the unclassified Mg-containing particles at the position of the AA line shown in FIG. 3 is 26.342 m / s, and the average flow velocity of the unclassified Mg-containing particles at the position of the BB line is 34.184 m / s. It was s. The average flow velocity of the unclassified Mg-containing particles at the position of the CC line shown in FIG. 4 is 30.713 m / s, and the average flow velocity of the unclassified Mg-containing particles at the position of the DD line is 20.939 m / s. The average flow velocity of the unclassified Mg-containing particles at the position of the EE line is 20.434 m / s, and the average flow velocity of the unclassified Mg-containing particles at the position of the FF line is 12.677 m / s. It was s. The results are shown in Table 1. The unit is m / s.

Therefore, in Example A1, the average flow velocity of the unclassified Mg-containing particles gradually decreases as the input port 18 passes through the flow path 17 to the classification chamber 31. In particular, the average flow velocity of the unclassified Mg-containing particles at the inlet 31A (position of the FF line) of the classification chamber 31 is half the average flow velocity of the unclassified Mg-containing particles at the upstream end 17A (position of the BB line). It can be understood that it is reduced as follows. Further, the average flow velocity of the unclassified Mg-containing particles at the inlet 31A (position of the FF line) of the classification chamber 31 is suppressed to 15 m / s or less.

Further, the average flow velocity of the unclassified Mg-containing particles at a substantially intermediate position (position of the EE line) of the radius of the classifying rotor 13 is the average flow velocity of the unclassified Mg-containing particles at the upstream end 17A (position of the BB line). It is reduced to less than 2/3 of the average flow velocity. Therefore, in the Mg-containing particle classifying device 11 of Example A1, it can be understood that the average flow velocity of the unclassified Mg-containing particles is significantly reduced on the upstream side of the flow path 17.

(Comparative Example A1)
In Comparative Example A1, the flow velocity of the unclassified Mg-containing particles passing through the flow path 17 of the classification device 41 described in the above reference embodiment was analyzed by using fluid analysis software. AnSYS SCDM was used to create the CAD shape, and ANSYS Fluent was used to analyze the flow velocity. The actual analysis work was outsourced to a third-party organization (Cybernet Systems Co., Ltd.) unrelated to the applicant in order to ensure objectivity.

In the analysis model of the classification device 41 of Comparative Example A1, the dimensions of each part of the flow path 17 were set to imitate the actual machine shown in FIGS. 5 to 8. That is, the dimensions a = 11 mm, the dimension b = 5.97 mm, the dimension c = 1 mm, and the dimension d = 3.25 mm shown in FIG. 5 were set. The input port 18 has a constricted portion 43 having an inner diameter smaller than that of the maximum diameter portion, the inner diameter of the constricted portion 43 is 50 mm, and the inner diameter of the maximum diameter portion of the input port 18 is 90 mm. The width of the gap between the dispersion blades was set to 6 mm.

Further, the diameter of the classification rotor 13 was set to 380 mm. The amount of unclassified Mg-containing particles charged to the charging port 18 was 5.611 × 10 ^-3 kg / s, and the air flow rate of the charging port 18 was 0.190049 kg / s. The rotation speed of the classification rotor 13 was set to 1350 rpm. The classification chamber pressure (outlet pressure) was set to 0.0 Pa (simulating the opening to the atmosphere with a gauge pressure). The working fluid was nitrogen, which is a fluid in consideration of compressibility. The density of the unclassified Mg-containing particles was 2060 kg / m ³ , and the particle size of the unclassified Mg-containing particles was 4.13 × ^10-5 m. The coefficient of restitution of the unclassified Mg-containing particles with respect to the housing 12 and the classifying rotor 13 was set to 0.1.

As a result of the analysis, the flow velocities of the unclassified Mg-containing particles in each part were as follows. The average flow velocity of the unclassified Mg-containing particles at the position of the AA line shown in FIG. 6 is 63.563 m / s, and the average flow velocity of the unclassified Mg-containing particles at the position of the BB line is 56.237 m / s. It was s. The average flow velocity of the unclassified Mg-containing particles at the position of the CC line shown in FIG. 7 is 41.187 m / s, and the average flow velocity of the unclassified Mg-containing particles at the position of the DD line is 71.931 m / s. The average flow velocity of the unclassified Mg-containing particles at the position of the EE line is 120.161 m / s, and the average flow velocity of the unclassified Mg-containing particles at the position of the FF line is 43.439 m / s. It was s. The results are shown in Table 1.

Further, at the positions of the DD line and the EE line, the average flow velocity is at the position between the dispersion blades 42 (gap 44A) and the position between the dispersion blades 42 and the housing 12 (gap 44B). Was different. The average flow velocity between the dispersed blades 42 at the position of the DD line is 76.262 m / s, and the average of the positions between the dispersed blades 42 and the housing 12 at the position of the DD line is 76.262 m / s. The flow velocity was 43.419 m / s. The average flow velocity at the position between the dispersion blades 42 at the position of the EE line is 136.431 m / s, and the average of the positions between the dispersion blade 42 and the housing 12 at the position of the EE line. The flow velocity was 101.533 m / s. The results are shown in Table 2. The unit is m / s.

Therefore, in Comparative Example A1, the flow velocity of the unclassified Mg-containing particles is already higher than that in Example A1 at the position near the constricted portion 43 (the position of the AA line).

In Comparative Example A1, the unclassified Mg-containing particles are accelerated in the section from the position of the CC line to the position of the DD line by the air feeding action of the dispersion blade 42, and the unclassified Mg-containing particles are accelerated from the position of the DD line to the EE. Unclassified Mg-containing particles are further accelerated in the section up to the position of the line. Therefore, in Comparative Example A1, the flow velocity of the unclassified Mg-containing particles at the position outside the dispersion blade 42 was accelerated to about twice the flow velocity of the unclassified Mg-containing particles at the position near the input port 18. Understood.

Further, from the results in Table 2, the position between the dispersion blades 42 (gap 44A) is more due to the air feeding action of the dispersion blades 42 than the position between the dispersion blades 42 and the housing 12 (gap 44B). It is understood that the flow velocity of the unclassified Mg-containing particles is greatly increased.

(Manufacturing Example 1)
<Preparation of solid catalyst components>
According to the method for preparing a solid catalyst component described in Japanese Patent No. 6515038 (Example 1), about 60 kg of a powdery solid catalyst component (unclassified product) N1 was obtained.

Specifically, a flask equipped with a stirrer and having an internal volume of 500 mL replaced with nitrogen gas is filled with 10 g (87.4 mmol) of diethoxymagnesium, 55 mL of toluene, 30 mL of titanium tetrachloride, and (2-ethoxyethyl) ethyl carbonate. (A) 9 mmol (1.46 g) and 1.2 mmol (0.26 g) of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (B) were added, and the mixture was reacted at a temperature of 100 ° C. for 90 minutes. After completion of the reaction, the reaction product was washed 4 times with 75 mL of toluene at 100 ° C. Next, 100 mL of a new toluene solution of 10% by volume of titanium tetrachloride was added, the temperature was raised to 100 ° C., and the mixture was stirred for 15 minutes for reaction. After the reaction, the product was washed once with toluene at 100 ° C. After performing this operation two more times, the mixture was washed 6 times with 75 mL of n-heptane at 40 ° C., and the residual solvent was removed by drying under reduced pressure to obtain a solid catalyst component (unclassified product) N1.

The particle size distribution of the obtained solid catalyst component (unclassified product) N1 was measured. The results are shown in Table 3. The abrasion durability of this solid catalyst component (unclassified product, unclassified Mg-containing particles) N1 was measured and found to be 73%.

<Calculation method of abrasion durability of solid catalyst component>
Using a laser diffraction type particle size distribution measuring device (manufactured by Spectris Co., Ltd., Mastersizer 3000) equipped with a dry powder dispersion unit (manufactured by Spectris Co., Ltd., Aero S), the particle size distribution of the obtained solid catalyst component was measured. , measured automatically respectively feeding air pressure 0.4 bar and 1.0 bar, wear durability a (%) by the following equation from the obtained _{D 50} value (1) was calculated.

Abrasion durability A (%) = (Z ÷ Y) × 100… (1)
(In the formula, Y is the average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 0.4 bar using a laser diffraction type particle size distribution measuring device, and Z is the laser diffraction type particle size distribution measurement. The average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 1.0 bar using the device is shown.)

<Calculation method of particle size distribution and average particle size of solid catalyst components>
Using a laser light scattering diffraction type particle size analyzer (MT-3300EX: manufactured by Nikkiso Co., Ltd.), the powder of the solid catalyst component was put into an n-heptane solvent to which tridecyl aluminum was added in advance, and the solid catalyst component was 0. The particle size is added so that it is included in the optimum dispersion concentration range indicated by the device in the range of .05 g to 0.20 g, the volume-based integrated particle size is obtained by automatic measurement, and the particle size distribution index (SPAN) is calculated by the following formula (ii). did. The average particle size was used the value of D _50. The results are shown in Table 3.

Particle size distribution index (SPAN) = (D _90- D ₁₀ ) / D ₅₀ ... (ii)
(D ₁₀ , D ₅₀ and D ₉₀ mean a particle size of 10%, a particle size of 50% and a particle size of 90%, respectively, in terms of volume-based integrated particle size when measured using the above measuring machine.)
The particle size of each particle is automatically calculated by assuming a peripheral major axis, that is, a circle having the same peripheral length as the peripheral length of the projected image of each particle, and obtaining the diameter.

(Manufacturing Example 2)
<Preparation of solid catalyst components>
According to the method for preparing a solid catalyst component described in Japanese Patent No. 6345561 (Example 11), about 60 kg of a powdery solid catalyst component N2 (unclassified product) was obtained.

Specifically, a stirring device is provided, and 70 mL of titanium tetrachloride and 70 mL of toluene are charged into a round-bottom flask having an internal volume of 500 mL replaced with nitrogen gas to form a mixed solution, and the liquid temperature is maintained at -10 ° C. did. Next, a round-bottom flask equipped with a stirrer and having an internal volume of 200 mL replaced with nitrogen gas was charged with 20 g of diethoxymagnesium (average particle size 54 μm), 70 mL of toluene, and 0.25 mL of ethanol (relative to 100 parts by mass of diethoxymagnesium). 1.0 part by mass) was charged to form a suspension, and 26.3 mmol (7.0 mL) of di-n-butyl phthalate was further added. After adding the entire amount of this suspension to the mixed solution previously kept at a liquid temperature of −10 ° C., the temperature inside the flask is raised from −10 ° C. to 110 ° C. and stirred at 110 ° C. for 3 hours. It reacted while. After completion of the reaction, the obtained solid product was washed 4 times with 167 mL of toluene at 100 ° C. Then, 123 mL of toluene at room temperature and 20 mL of titanium tetrachloride were newly added, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the supernatant was removed, and then 125 mL of n-heptane at 40 ° C. was used for 8 The solid catalyst component (unclassified product) N2 was obtained by washing once.

The particle size distribution of the obtained solid catalyst component (unclassified product) N2 was measured. The abrasion durability of this solid catalyst component N2 (unclassified product, unclassified Mg-containing particles) was measured and found to be 72%. The results are shown in Table 3.

(Manufacturing Example 3)
<Preparation of solid catalyst components>
According to the method for preparing a solid catalyst component described in Japanese Patent No. 3258226 (Example 1), about 60 kg of a powdery solid catalyst component (unclassified product) N3 was obtained.

Specifically, a mixed solution was formed by charging 30 mL of titanium tetrachloride and 20 mL of toluene into a round-bottom flask having an internal volume of 500 mL, which was equipped with a stirrer and was replaced with nitrogen gas. Next, 10 g of diethoxymagnesium having an average particle size of 32 μm and a fine powder content of 5 μm or less, a particle size distribution index (SPAN) [(D ₉₀ − D ₁₀ ) / D ₅₀ ] 1.05, 50 mL of toluene and di-phthalate A suspension formed with 3.6 mL of n-butyl was added to the mixed solution maintained at a liquid temperature of 10 ° C. Then, the liquid temperature was raised from 10 ° C. to 90 ° C. over 80 minutes, and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 100 mL of toluene at 90 ° C., 30 mL of titanium tetrachloride and 70 mL of toluene were newly added, the temperature was raised to 112 ° C., and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the mixture was washed 10 times with 100 mL of n-heptane at 40 ° C. to obtain a solid catalyst component (unclassified product) N3.

The particle size distribution of the obtained solid catalyst component (unclassified product) N3 was measured. The abrasion durability of this solid catalyst component (unclassified product) N3 was measured and found to be 91%. The results are shown in Table 3.

(Manufacturing Example 4)
<Preparation of solid catalyst components>
10 g of diethoxymagnesium (average particle size 32 μm, fine powder content of 5 μm or less, particle size distribution index (SPAN) [(D ₉₀ − D ₁₀ ) / D ₅₀ ] 1.05), and other diethoxymagnesium (average) Particle size (D ₅₀ ) 37.5-43.5 μm, particle size 10.5 μm or less, fine powder content 8.0% or less, particle size distribution index (SPAN) [(D _90- D ₁₀ ) / D ₅₀ ] 1.0 Approximately 60 kg of powdery solid catalyst component (unclassified product) N4 was obtained in accordance with the method for preparing a solid catalyst component described in Patent No. 3258226 (Example 1), except that the amount was changed to 10 g. The particle size distribution of the obtained solid catalyst component (unclassified product) N4 was measured. The abrasion durability of this solid catalyst component (unclassified product) N4 was measured and found to be 87%. The results are shown in Table 3.

(Examples B1 and B2)
<Classification of solid catalyst components>
The unclassified solid catalyst component N1 obtained in Production Example 1 was charged into an air flow classifier (TC-40III manufactured by Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor having a diameter of 400 mm, and the classifying rotor was charged. Airflow classification treatment is performed for 1,360 minutes under the conditions of rotation speed 1,290 rpm, total air volume 10 m ³ / min, circulating air volume 6 m ³ / min, and solid catalyst component supply amount 27.9 kg / h to remove fine coarse powder components. The solid catalyst component (classified product, Mg-containing particles) C1 was obtained. The TC-40III is the catalyst particle classifying device 11 described in the above embodiment. The product yield of this solid catalyst component (classified product) C1 was 90.4% by mass, and the surface shape of the particles was also good. The results are shown in Table 4.

<Particle size distribution of solid catalyst components (classified products)>
The particle size distribution of the obtained solid catalyst component (classified product) C1 was measured in the same manner as in the above solid catalyst component (unclassified product) N1. The results are shown in Table 4. Table 5 shows the correspondence before and after the classification process and the classification conditions of each example.

<Preparation of polymerization catalyst>
Triethylaluminum 0.092 mmol, cyclohexylmethyldimethoxysilane 0.092 mmol and the solid catalyst component (classified product) obtained above were placed in an autoclave equipped with a stirrer and having an internal volume of 2.0 liters replaced with nitrogen gas. , Mg-containing particles) C1 was charged at 0.0018 mmol in terms of titanium atoms to prepare a catalyst for olefin polymerization.

<Propene polymerization>
1.6 liters of hydrogen gas and 1.0 liter of liquefied propylene were charged into an autoclave with a stirrer containing a catalyst for olefin polymerization prepared above, and prepolymerization was performed at 20 ° C. for 5 minutes, and then up to 70 ° C. A propylene homopolymer (PP) was produced by raising the temperature and carrying out a polymerization reaction at 70 ° C. for 1 hour.

<Polymer fine powder amount, coarse powder amount, average particle size, particle size distribution index (SPAN)>
Using a digital image analysis type particle size distribution measuring device (Camsizer, manufactured by Horiba Seisakusho Co., Ltd.), the volume-based integrated particle size distribution of the obtained polymer was automatically measured under the following measurement conditions, and fine powder with a particle size of less than 75 μm was measured. The amount (% by mass), the amount of coarse powder exceeding 1700 μm (mass%), and the particle size (average particle size D ₅₀ ) at a volume-based integrated particle size of 50% are measured, and the particle size distribution index (SPAN) is calculated by the above formula (ii). ). The results are shown in Table 6.

(Measurement condition)
Funnel position: 6mm
Camera coverage area: Basic camera less than 3%, Zoom camera less than 10% Target coverage area: 0.5%
Feeder width: 40 mm
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 for each particle SPHT (spherical) fitting: 1
Class upper limit: Logarithmic scale, select 50 points in the range of 32 to 4000 μm

(Comparative Example B1)
The unclassified solid catalyst component N1 obtained in Production Example 1 was subjected to airflow classification treatment. In the classification of solid catalyst components, an airflow classifier (TC-40III, manufactured by Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor with a diameter of 400 mm and an airflow classifier (Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor with a diameter of 400 mm Example B1 except that the classification time was changed from 1,360 minutes to 480 minutes and the solid catalyst component supply amount was changed from 27.9 kg / h to 26.6 kg / h in TC-40) manufactured by Co., Ltd. In the same manner as above, a solid catalyst component (classified product) C11, a polymerization catalyst and an olefin polymer were obtained, and their characteristics were evaluated. The TC-40 is the classification device 41 described in the above reference embodiment. The product yield of the obtained solid catalyst component (classified product) C11 was 75.9% by mass. The results are shown in Tables 4 and 6.

(Example B2)
The solid catalyst component (unclassified product) N2 obtained in Production Example 2 is charged into an air flow classifier (TC-40III manufactured by Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor having a diameter of 400 mm, and the rotation speed is increased. Airflow classification treatment was performed for 1,160 minutes under the conditions of 1,270 rpm, total air volume 12 m ³ / min, circulating air volume 8 m ³ / min, and solid catalyst component supply amount 18.0 kg / h to remove fine coarse powder components. A solid catalyst component (classified product, Mg-containing particles) C2 was obtained. The product yield of this solid catalyst component (classified product) C2 was 88.1% by mass, and the surface shape of the particles was also good. Further, using the obtained solid catalyst component (classified product, Mg-containing particles) C2, a polymerization catalyst and an olefin polymer were obtained in the same manner as in Example 1, and each characteristic was evaluated. The results are shown in Tables 4 and 6.

(Comparative Example B2)
The unclassified solid catalyst component N2 obtained in Production Example 2 was subjected to airflow classification treatment. In the classification of solid catalyst components, an airflow classifier (TC-40III, manufactured by Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor with a diameter of 400 mm and an airflow classifier (Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor with a diameter of 400 mm The solid catalyst component (classified product) is the same as in Example B2 except that the supply amount of the solid catalyst component is changed from 18.0 kg / h to 18.1 kg / h to TC-40, manufactured by Co., Ltd. ) C21, a catalyst for polymerization and an olefin polymer were obtained, and each characteristic was evaluated. The product yield of the obtained solid catalyst component (classified product) C21 was 81.8% by mass. The results are shown in Tables 4 and 6.

(Reference example B1)
The solid catalyst component (unclassified product) N3 obtained in Production Example 3 is charged into an air flow classifier (TC-40 manufactured by Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor having a diameter of 400 mm, and the rotation speed is increased. A solid catalyst in which airflow classification treatment was performed for 680 minutes under the conditions of 1,495 rpm, total air volume of 11 m ³ / min, circulating air volume of 7 m ³ / min, and solid catalyst component supply amount of 65.8 kg / h to remove fine coarse powder components. Ingredient (classified product) C3 was obtained. The product yield of this solid catalyst component (classified product) C3 was 91.4% by mass, and the surface shape of the particles was also good. Further, using the obtained solid catalyst component (classified product) C3, a polymerization catalyst and an olefin polymer were obtained in the same manner as in Example B1, and each characteristic was evaluated. The results are shown in Tables 4 and 6.

(Reference example B2)
The solid catalyst component (unclassified product) N4 obtained in Production Example 4 is charged into an airflow classifier (TC-40 manufactured by Nisshin Engineering Co., Ltd.) having a disk-shaped classifying rotor having a diameter of 400 mm, and the rotation speed is increased. A solid catalyst in which airflow classification treatment was performed for 280 minutes under the conditions of 1,850 rpm, total air volume 14 m ³ / min, circulating air volume 10 m ³ / min, and solid catalyst component supply amount 54.3 kg / h to remove fine coarse powder components. Ingredient (classified product) C4 was obtained. The product yield of this solid catalyst component (classified product) C4 was 87.9% by mass, and the surface shape of the particles was also good. Further, using the obtained solid catalyst component (classified product) C4, a polymerization catalyst and an olefin polymer were obtained in the same manner as in Example 1, and each characteristic was evaluated. The results are shown in Tables 4 and 6.

From Tables 3, 4, and 6, in Examples B1 and B2, the inner surface of the housing and the inner surface of the housing were reduced by reducing the flow velocity of the unclassified Mg-containing particles flowing through the flow path 17 in the Mg-containing particle classifying device 11. It can be understood that the energy given to the unclassified Mg-containing particles when the unclassified Mg-containing particles collide with the top surface of the classifying rotor is reduced, and the unclassified Mg-containing particles are prevented from being damaged. As a result, it can be understood that the Mg-containing particles after classification can significantly improve the product yield while maintaining the same particle size distribution as before, and further, the particle shape after classification is also good.

On the other hand, from Tables 3, 4 and 6, in Comparative Example B1 and Comparative Example B2, since the conventional classification device 41 increases the flow velocity of the unclassified Mg-containing particles flowing through the flow path 17, the inner surface of the housing When the unclassified Mg-containing particles collide with the top surface of the classifying rotor, the energy given to the unclassified Mg-containing particles increases, and the unclassified Mg-containing particles are damaged. Therefore, it is understood that the product yield of the classified Mg-containing particles is significantly reduced when the particle size distribution similar to that of the conventional one is maintained.

Therefore, the present invention can reduce the content of fine coarse powder particles such as fine powder particles and coarse powder particles, can appropriately dissociate (crush) the particles while preventing particle destruction, and have a particle size distribution. It is possible to provide an Mg-containing particle classifier having a narrow particle shape and a good particle shape, and a method for producing Mg-containing particles.

According to the present invention, among the solid catalyst components used for the polymerization of olefins, the content of fine coarse powder particles such as fine powder particles and coarse powder particles is reduced, particularly when the solid catalyst component having low particle strength and being fragile is classified. At the same time, it is very useful because a solid catalyst component having a narrow particle size distribution and a good particle shape can be obtained by preventing particle destruction. Further, the present invention includes not only solid catalyst components but also porous particles having low particle strength and fragility, such as metal oxide particles and metal chloride particles which are also carriers of solid catalyst components, and carriers of the solid catalyst components. It is a very useful technique because it can be applied to alkoxide metal particles as a raw material.

11 Mg-containing particle classifier 12 Housing 12A 1st part 12B 2nd part 12C 3rd part 13 Classifying rotor 16 Top surface 16A Flat part 16B Cone part 17 Flow path 18 Input 19 Inner surface 24 Mg-containing particles 24a Particles (fine powder)
31 Classroom

Claims (3)

A housing, a rotating body rotating in the housing, a classification chamber located on the outer edge side of the rotating body, an inner surface of the housing and a top surface of the rotating body, and an upstream end portion and the classification chamber. A method for producing Mg-containing particles, which obtains Mg-containing particles by performing a classification treatment using a centrifugal airflow classifying device including a flow path connecting the two.
The average flow velocity of the unclassified Mg-containing particles on the downstream side of the upstream end in the flow path is made smaller than the average flow velocity of the unclassified Mg-containing particles flowing inside the flow path at the upstream end. A step of supplying the unclassified Mg-containing particles to the classification chamber and a step of classifying the unclassified Mg-containing particles in the classification chamber to obtain Mg-containing particles are provided.
The average flow velocity of the unclassified Mg-containing particles at the entrance of the classification chamber is 15 m / s or less.
A method for producing Mg-containing particles having an abrasion durability A (%) of 85 or less of the unclassified Mg-containing particles determined by the following formula (1).
A = (Z ÷ Y) × 100… (1)
(In the formula, Y is the average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 0.4 bar using a laser diffraction type particle size distribution measuring device, and Z is the laser diffraction type particle size distribution measurement. The average particle size D ₅₀ (μm) automatically measured dry at a blowing pressure of 1.0 bar using the device is shown.) In the step of supplying the unclassified Mg-containing particles to the classification chamber, the average flow velocity of the unclassified Mg-containing particles at the inlet of the classification chamber is less than half of the average flow velocity of the unclassified Mg-containing particles at the upstream end. The method for producing Mg-containing particles according to claim 1. In the step of supplying the unclassified Mg-containing particles to the classification chamber, the average flow velocity of the unclassified Mg-containing particles at a substantially intermediate position of the radius of the top surface of the rotating body is the unclassified Mg-containing particles at the upstream end. The method for producing Mg-containing particles according to claim 1 or 2, wherein the average flow velocity of the particles is 2/3 or less.

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