JP2022051551A - Ion-exchangeable layered silicate particles, catalyst component for olefin polymerization, catalyst for olefin polymerization, method for producing catalyst for olefin polymerization and method for producing olefin polymer using the same - Google Patents

Abstract

To provide ion-exchangeable layered silicate particles having a novel pore structure that improve catalytic activity and polymer quality.SOLUTION: Ion-exchangeable layered silicate particles have the following characteristics (i) and (ii). Characteristic (i): In a pore distribution curve calculated by BJH method from a desorption isotherm measured by nitrogen adsorption/desorption method, the sum of pore volumes with diameters of 2 nm to 10 nm is 40% or more and 93% or less of the total mesopore volume. Characteristic (ii): a specific surface area is not less than 300 m2/g and not more than 700 m2/g.SELECTED DRAWING: None

Description

The present invention relates to ion-exchangeable layered silicate particles, a catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same.

Ion-exchangeable layered silicates, zirconium phosphate and clay minerals are widely used in adsorbents, catalysts, catalyst carriers and the like. There are various factors that affect the performance in these applications, but the pore volume, pore distribution, and specific surface area have a particularly large effect. For example, Patent Document 1 exemplifies a clay mineral having a specific pore distribution as an adsorbent.
Further, it is known to polymerize an olefin in the presence of a catalyst using clay or a clay mineral as a catalyst component for olefin polymerization to produce an olefin polymer (for example, Patent Document 2).

Further, a catalyst for olefin polymerization containing an ion-exchangeable layered compound subjected to acid treatment or salt treatment as a component is also known (for example, Patent Document 3).
Patent Document 4 discloses an ion-exchangeable layered silicate having a specific pore distribution as a catalyst carrier and a catalyst for olefin polymerization. However, the ion-exchangeable layered silicate having the specific pore distribution has a small specific surface area that greatly affects the performance as a catalyst or an adsorbent, and is not always sufficient.

On the other hand, as a method for controlling the pore distribution of a solid composed of ion-exchangeable layered silicate, for example, in Patent Document 5, the pore structure is controlled by amorphizing the SiO ₂ crystal component contained in the clay mineral. is doing. However, in this method, the SiO ₂ component having no catalytic activity is contained, and there is a concern that the catalytic activity may be lowered.

In Patent Document 6, after dry granulation of clay minerals in a state containing calcium carbonate, magnesium carbonate, calcium hydroxide and the like which are substantially insoluble salts in the slurry, the clay mineral is reacted with an acid to generate carbonic acid gas. By doing so, the pore structure of the activated clay particles is controlled. Patent Document 6 does not mention the particle size distribution of the insoluble salt, and it is said that the pore volume of 1 μm or more increases. However, the method of Patent Document 6 does not affect the volume of the mesopores of 10 to 50 nm.

In Patent Document 7, a fine particle solid compound such as zinc oxide or titania and an ion-exchangeable layered silicate are mixed in a liquid to dry granulate, and then at least a part of the fine particle solid compound is eluted with an acid. This discloses a method for controlling the pore structure. Since the average particle size of the fine particle solid compound used is 2.25 μm to 2.98 μm, it is presumed to be a technique for controlling the pore structure on the order of μm. Further, the ion-exchangeable layered silicate obtained by the technique of Patent Document 7 has a small specific surface area, which is important for the performance as a catalyst or a catalyst carrier.

Patent Document 8 discloses that an ion-exchangeable layered silicate having a specific composition is used to form a specific pore structure.
In Patent Document 9, improvement is achieved by eluting the aluminum component of the ion-exchangeable layered silicate granulated to a specific particle size and adjusting the particle strength to a specific particle strength.
By controlling the pore distribution of a solid made of ion-exchangeable layered silicate as described above, the catalytic activity, filterability, operability during polymer production, and product quality are improved. However, it cannot be said that it is sufficient yet, and further improvement is required.

International Publication No. 2010/032568 Japanese Unexamined Patent Publication No. 5-295022 Japanese Unexamined Patent Publication No. 7-228621 Japanese Unexamined Patent Publication No. 2002-088114 Japanese Unexamined Patent Publication No. 2013-08267 Japanese Unexamined Patent Publication No. 2000-344513 Japanese Patent Application Laid-Open No. 2003-2529223 Japanese Unexamined Patent Publication No. 2015-108138 Japanese Unexamined Patent Publication No. 2019-172958

In view of the situation of the prior art, the present invention comprises ion-exchangeable layered silicate particles having a novel pore structure that improves catalytic activity and quality of the polymer, and an olefin containing the ion-exchangeable layered silicate particles. It is an object of the present invention to provide a polymerization catalyst component, an olefin polymerization catalyst, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer using the same.

In the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption / desorption method, the present inventor has a specific range of the total pore volume having a diameter of 2 nm to 10 nm with respect to the total mesopore volume. We have found a novel ion-exchangeable layered silicate particles with. That is, ion-exchangeable layered silicate particles having a novel pore structure in which the total volume of pores having a diameter of more than 10 nm and not more than 50 nm is larger than that of the total mesopore volume and the specific surface area is large in a specific range. However, it has been found that the catalytic activity and the quality of the polymer are improved.

The ion-exchangeable layered silicate particles of the present invention are characterized by having the following properties (i) and (ii).
Property (i): In the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption and desorption method, the total pore volume with a diameter of 2 nm to 10 nm is 40% of the total mesopore volume. Above, it is 93% or less.
Characteristics (ii): The specific surface area is 300 m ² / g or more and 700 m ² / g or less.

Further, the ion-exchangeable layered silicate particles of the present invention preferably have the following characteristics (iii) from the viewpoint of operability when used as an adsorbent, a catalyst, or a catalyst carrier.
Characteristics (iii): The average particle size is 2 μm or more and 500 μm or less.

The catalyst component for olefin polymerization of the present invention is characterized by containing the ion-exchangeable layered silicate particles according to the present invention.

The catalyst for olefin polymerization of the present invention is characterized by containing the following components [A], [B], and [C].
Component [A]: Ion-exchangeable layered silicate particle component according to the present invention [B]: Transition metal compound component [C]: Organoaluminum compound

The method for producing a catalyst for olefin polymerization of the present invention is characterized by mixing the following components [A], component [B], and component [C].
Component [A]: Ion-exchangeable layered silicate particle component according to the present invention [B]: Transition metal compound component [C]: Organoaluminum compound

The method for producing an olefin polymer of the present invention is characterized in that olefin polymerization is carried out using the catalyst for olefin polymerization described above.

According to the present invention, an ion-exchangeable layered silicate particles having a novel pore structure that improves catalytic activity and polymer quality, and an olefin polymerization catalyst component containing the ion-exchangeable layered silicate particles, olefin polymerization. A catalyst for production, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same can be provided.

FIG. 1 shows the ratio of the total pore volume having a diameter of 2 nm to 10 nm to the total mesopore volume for the ion-exchangeable layered silicate particles described in Examples and Comparative Examples with respect to the BET specific surface area m ² / g. It is a plotted figure. FIG. 2 is a diagram in which the polymerization activity of the results of propylene homopolymerization using the olefin polymerization catalysts described in Examples and Comparative Examples is plotted against the MFR of the obtained polymer. FIG. 3 shows the number of fish eyes contained in the sheet for the results of the two-stage polymerization of propylene-ethylene using the olefin polymerization catalysts described in Examples and Comparative Examples, and the molecular weight ratio of the obtained polymer (second stage). It is a figure plotted with respect to the value obtained by dividing the molecular weight of a polymer by the molecular weight of a polymer of the first stage). FIG. 4 is a diagram plotting the results of crushing strength measurement of the ion-exchangeable layered silicate particles described in Examples and Comparative Examples.

1. 1. Ion-exchangeable layered silicate particles The ion-exchangeable layered silicate particles of the present invention are characterized by having the following properties (i) and (ii).
Property (i): In the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption and desorption method, the total pore volume with a diameter of 2 nm to 10 nm is 40% of the total mesopore volume. Above, it is 93% or less.
Characteristics (ii): The specific surface area is 300 m ² / g or more and 700 m ² / g or less.

The pore structure of a porous catalyst affects performance such as catalyst activity and strength, as well as economic efficiency, operability, and product quality.
In earnest research, the present inventor found that the total pore volume of 2 nm to 10 nm in diameter is the total mesopore volume in the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption / desorption method. We have found a novel ion-exchangeable silicate particles having the above-mentioned specific range. That is, ion-exchangeable layered silicate particles having a novel pore structure in which the total volume of pores having a diameter of more than 10 nm and not more than 50 nm is larger than that of the total mesopore volume and the specific surface area is large in a specific range. However, it has been found that the catalytic activity and the quality of the polymer are improved.
More specifically, the ion-exchangeable layered silicate particles of the present invention can be used as a catalyst component for olefin polymerization capable of producing an olefin polymer with high polymerization activity. Further, the ion-exchangeable layered silicate particles of the present invention can produce an olefin polymer having less fish eyes (poor dispersion of incompatible components, gels and catalyst residues) in the product, which deteriorates the appearance of the product, and is a catalyst for olefin polymerization. It can also be an ingredient. The present invention provides an ion-exchangeable layered silicate particles having a novel pore structure exhibiting such an effect, an olefin polymerization catalyst component containing the ion-exchangeable layered silicate particles, and an olefin polymerization catalyst. Can be done.

In the conventional ion-exchangeable layered silicate particles, there is a problem that when the proportion of mesopores having a large diameter increases, the specific surface area decreases, which causes a decrease in activity. This is because it was difficult to produce ion-exchangeable layered silicate particles having a high proportion of mesopores having a large diameter and a large specific surface area. On the other hand, in the ion-exchangeable layered silicate particles of the present invention, the total pore volume of more than 10 nm and 50 nm or less is larger than the conventional one with respect to the total mesopore volume, and the specific surface area is large in a specific range. It is considered that having appropriate pores increases the active points of the catalyst and improves the catalytic activity. Further, the ion-exchangeable layered silicate particles of the present invention also improve the diffusion of the monomer in the particles and reduce the variation in the activity of the active points, so that the active points generate an extremely high molecular weight polymer. It is considered that a uniform polymer can be easily produced, such as a decrease in the amount of particles, and an olefin polymer having less fish eyes in the product can be produced.

Hereinafter, the ion-exchangeable layered silicate particles of the present invention, the catalyst component for olefin polymerization, the catalyst for olefin polymerization, the method for producing a catalyst for olefin polymerization, and the method for producing an olefin polymer using the same will be described in detail for each item. explain.
In addition, in this specification, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
Further, the following characteristics of the ion-exchangeable layered silicate particles are characteristics as an aggregate of ion-exchangeable layered silicate particles, except for the crushing strength measured with a single particle.

1-1. Characteristics of ion-exchangeable layered silicate particles (1) Pore volume The ion-exchangeable layered silicate particles of the present invention are obtained from the desorption isotherm measured by the nitrogen adsorption / desorption method in the pore distribution curve calculated by the BJH method. The total pore volume (PV (2-10)) having a diameter of 2 nm to 10 nm is 40% or more and 93% or less with respect to the total mesopore volume (PV (2-50)) (characteristic (i)). ).
In the ion-exchangeable layered silicate particles of the present invention, the ratio of the total pore volume (PV (2-10)) having a diameter of 2 nm to 10 nm to the total mesopore volume (PV (2-50)) (PV (2-50)). For 10) / PV (2-50)), the lower limit is preferably 45% or more, more preferably 50% or more, further preferably 60% or more, still more preferably 65% or more, and the upper limit is preferably 92%. Below, it is more preferably 90% or less. Any combination of the upper limit value and the lower limit value can be adopted.
As the proportion of small-diameter pores increases, the specific surface area increases and the number of active points of the catalyst can be increased. However, if the proportion of pores having a small diameter is too large, the diffusion rate of the reaction substrate such as a monomer is lowered and the particle strength is excessively increased. As a result, in the case of an olefin polymerization catalyst that requires a carrier decay process during polymerization, the polymerization activity is lowered and fish eyes appear in the polymer product, which adversely affects the quality. On the other hand, increasing the proportion of pores with a large diameter is preferable for the diffusion of the reaction substrate. However, if the proportion of pores with a large diameter increases too much, the specific surface area becomes smaller, which causes a decrease in activity, or the particle strength decreases, which tends to generate fine powder, etc., which improves operability and product quality. It may have an adverse effect. For these reasons, it is considered that by keeping PV (2-10) / PV (2-50) in the optimum range, the catalyst or catalyst component has an excellent balance of catalytic activity, operability, and product quality.

Here, the mesopores represent pores having a diameter of 2 nm to 50 nm, as defined in IUPAC. Various methods are known for measuring the pore diameter and the pore volume. However, the pore diameter and pore volume in the present invention refer to those calculated by the BJH method from the data of the desorption isotherm measured by the gas adsorption / desorption method using nitrogen.
The measurement of pore volume by the gas suction / desorption method is described in, for example, JIS Z8831-2 and ISO15901-2, and measurement by a commercially available device is possible. In the present invention, nitrogen is used as a gas, and the data of the desorbed isotherm obtained by heating the sample at 200 ° C. under vacuum (1.3 Pa or less) under reduced pressure for 2 hours and then measuring at 77 K are used. The pore volume can also be calculated from the adsorption isotherm. However, in a porous material, the pore distribution calculated from the desorption isotherm data and the pore distribution calculated from the adsorption isotherm data often do not match. This is considered to be due to the fact that the thermodynamic equilibrium state is not reached within the actual measurement time, and the effects of cavitation and pore blocking. Assuming ink bottle type pores, the pore distribution obtained from the desorbed isotherm is said to be influenced by the pore diameter of the bottle neck.

Considering the case where a porous substance is used as a catalyst or a catalyst component, it is presumed that the reaction substrate is also affected by this “neck portion”. Therefore, since the pore distribution obtained from the desorption isotherm is considered to indirectly represent the performance of the catalyst, the present invention uses the pore distribution obtained from the desorption isotherm as a reference.
As a method for calculating the pore distribution from the desorption isotherm data, specifically, the method described in Examples described later can be adopted.

Further, the ion-exchangeable layered silicate particles of the present invention have pores having a diameter of more than 10 nm and a diameter of 50 nm or less in the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption / desorption method. The total volume {(PV (2-50) -PV (2-10)} may be 0.020 mL / g or more, more preferably 0.030 mL / g or more, still more preferably 0.040 mL / g. The upper limit value may be 0.230 mL / g or less. Any combination of the upper limit value and the lower limit value can be adopted.

(2) Specific surface area The ion-exchangeable layered silicate particles of the present invention have a specific surface area of 300 m ² / g or more and 700 m ² / g or less (characteristic (ii)).
In the ion-exchangeable layered silicate particles of the present invention, the specific surface area has a lower limit of preferably 325 m ² / g or more, more preferably 340 m ² / g or more, still more preferably 355 m ² / g or more, and an upper limit. It is preferably 600 m ² / g or less, more preferably 500 m ² / g or less. Any combination of the upper limit value and the lower limit value can be adopted.
Generally, as the specific surface area increases, the amount of the active ingredient of the catalyst or the amount that can support the active ingredient increases, so that the activity increases. On the other hand, if the specific surface area is too large, the pore diameter may become small. This causes a decrease in the diffusion rate of the reaction substrate, which may lead to a decrease in activity as a catalyst and an adsorption performance as an adsorbent.
The specific surface area in the present invention refers to a value calculated by BET multipoint method analysis (Rouquarol conversion) from adsorption isotherm data measured using nitrogen gas in the gas adsorption method. A method for measuring the specific surface area by the gas adsorption method is described in, for example, JIS Z8830. Specifically, the measurement method described in Examples described later can be adopted.

(3) Particle size The particle size of the ion-exchangeable layered silicate particles of the present invention is not particularly limited. The average particle size is preferably 2 μm or more and 500 μm or less (characteristic (iii)).
In the ion-exchangeable layered silicate particles of the present invention, the lower limit value is more preferably 3 μm or more, further preferably 8 μm or more, particularly preferably 10 μm or more, and the upper limit value is preferably 200 μm or less, more preferably. Is 100 μm or less, more preferably 70 μm or less, still more preferably 60 μm or less, and particularly preferably 55 μm or less. Any combination of the upper limit value and the lower limit value can be adopted.
Generally, if the particle size is too small, it may cause a decrease in efficiency during solid-liquid separation such as filtration when used as an adsorbent or decolorizing agent, and when used as a catalyst carrier, it may adhere to the inside of the reactor or pipe. It may cause the filter to be blocked. On the other hand, if the particle size is too large, when it is used as an adsorbent or a decolorizing agent, or when it is used as a catalyst carrier, it may cause poor dispersion in liquid (slurry state) or during a gas phase reaction.
Here, the average particle diameter of the present invention refers to a volume-based median diameter obtained from a sphere-equivalent particle diameter distribution. As the method for measuring the average particle size of the ion-exchangeable layered silicate particles of the present invention, specifically, the measuring method described in Examples described later can be adopted.

(4) Crushing strength The crushing strength of the ion-exchangeable layered silicate particles in the present invention is not particularly limited. However, in view of its use as a catalyst carrier, it is preferable to keep the crushing strength in an appropriate range.
As a method for measuring the crushing strength of a single particle, JIS R 1639-5: 2007 can be measured by the method described in JIS R 1639-5: 2007, single particle crushing strength, etc., and specifically, the measurement described in Examples described later. It can be measured by the method.
The average crushing strength of the ion-exchangeable layered silicate particle aggregate of the present invention is preferably 3.0 MPa or more and 25.0 MPa or less, and the lower limit is more preferably 4.0 MPa or more, still more preferably 5.0 MPa or more. The upper limit is more preferably 20.0 MPa or less, still more preferably 15.0 MPa or less. Any combination of the upper limit value and the lower limit value can be adopted.
If the average crushing strength is too low, the particles may be destroyed in unfavorable situations such as when preparing a catalyst, and fine powder or the like may be generated. On the other hand, if the average crushing strength is too high, it may prevent the polymer from being smoothly formed on the catalyst particles when used as a carrier for an olefin polymerization catalyst.

Further, it is known that the strength of an inorganic brittle material such as the ion-exchangeable layered silicate particles of the present invention has a so-called dimensional effect. That is, the larger the size, the higher the probability of containing a large defect that is likely to cause destruction, and the smaller the size, the higher the strength. From this, the crushing strength S of the particles can be generally expressed by the following formula (1) (Chemical Engineering Papers, 1984, pp. 108 to 112).
S = (S ₀・ V ₀ ^{1 / m} ) ・ V ^{-1 / m}・ ・ ・ Equation (1)
(In the formula (1), S is the crushing strength (MPa) of the ion-exchangeable layered silicate particles, S ₀ is the crushing strength at the unit volume V ₀ , and V is the volume of the ion-exchangeable layered silicate particles (μm ³ ). ), M is the uniformity coefficient of Weibul)
The measured value of the crush strength S can be obtained by the above-mentioned measuring method. The volume V of the ion-exchangeable layered silicate particles can be calculated as a true sphere having a diameter d (unit: μm ³ ), where the average value (μm) of the major axis diameter and the minor axis diameter of the particles is the diameter d. m is defined as a number greater than 1.
As a method for obtaining (S ₀ · V ₀ ^{1 / m} ) and 1 / m, the least squares method is used from the relationship between the measured value of the crushing strength S and the value of the volume V of the ion-exchangeable layered silicate particles. Can be decided.

In the above equation (1), the larger the value of m, that is, the smaller the value of 1 / m, the more uniform the material, and the smaller the dependence of the crushing strength on the size (particle size). Therefore, the smaller 1 / m is, the more stable the property is shown as a catalyst carrier, and the wider the size (particle diameter) can be used, which is preferable.
In the above equation (1), the value of (S ₀ · V ₀ ^{1 / m} ) represents the strength per unit volume. When the size dependence of the crush strength is sufficiently small, the value is equivalent to the average value of the measured values S of the crush strength.
In the ion-exchangeable layered silicate particles of the present invention, the above (S0 ・ V ₀₀₁ ^{/ m} ) and ₁ / m are not particularly limited. 1 / m is preferably 0.035 or less, more preferably 0.020 or less, still more preferably 0.010 or less, and the smaller the value, the more preferably the lower limit is 0.000.
Further, the above (S0 ・ V ₀₀₁ ^{/ m} ) is preferably _3.0 or more and 25.0 or less, and the lower limit value is more preferably 4.0 or more, further preferably 5.0 or more, and the upper limit. The value is more preferably 20.0 or less, still more preferably 15.0 or less. Any combination of the upper limit value and the lower limit value can be adopted.
In the ion-exchangeable layered silicate particles of the present invention, the absolute value of the difference between the average crushing strength value, which is the average value of the measured crushing strength S, and the above ( _S0・ V ₀₀₁ ^{/ m} ) is preferable. Is 8 or less, more preferably 5 or less.

(5) Metal element ratio The ion-exchangeable layered silicate particles in the present invention have a structure in which a part of the octahedron sheet forming the ion-exchangeable layered silicate is deleted by weathering, acid treatment, salt treatment, or the like. Is preferable. Those having such a structure are known as acidic clay and activated clay, for example, when the ion-exchangeable layered silicate is montmorillonite or byderite type.
The ion-exchangeable layered silicate in the present invention is preferably montmorillonite or a byderite type layered silicate. The octahedral sheet of montmorillonite is composed of metal atoms such as aluminum and magnesium. It is preferable that these octahedral sheet constituents are eluted by 15% to 75% with respect to the content before the chemical treatment such as acid treatment. It is more preferably 15% to 70%, still more preferably 17% to 65%, and particularly preferably 20% to 60%.
When the main constituent metal element of the octahedral sheet is aluminum and the main constituent metal element of the tetrahedral sheet is silicon, the molar ratio of aluminum to silicon is preferably 0.05 to 0.40, more preferably 0.08. It is ~ 0.30, more preferably 0.10 to 0.25, and even more preferably 0.12 to 0.20.
If the amount of aluminum is too large with respect to silicon, the pore volume and specific surface area tend to be small. On the other hand, if aluminum is too low relative to silicon, the amount of active sites tends to decrease. Therefore, the activity as a catalyst or a catalyst carrier may be reduced, and the quality of the product may be adversely affected.
The molar ratio of iron to silicon is preferably 0 to 0.20, more preferably 0.0005 to 0.10, still more preferably 0.001 to 0.08, and even more preferably, from the viewpoint of ion exchangeability. Is 0.005 to 0.05.
The molar ratio of magnesium to silicon is preferably 0 to 0.30, more preferably 0.001 to 0.30, still more preferably 0.01 to 0.20, and even more preferably, from the viewpoint of ion exchangeability. Is 0.02 to 0.10.

1-2. Method for Producing Ion-Exchangeable Layered Silicate Particles The method for producing the ion-exchangeable layered silicate particles of the present invention is not particularly limited as long as ion-exchangeable layered silicate particles having the above-mentioned characteristics can be obtained. do not have.
From the viewpoint that the pore structure can be easily controlled and the characteristics of the ion-exchangeable layered silicate particles of the present invention can be easily obtained, the following steps 1, 2 and 3 are described as the method for producing the ion-exchangeable layered silicate particles of the present invention. It is preferable that the method for producing ion-exchangeable layered silicate particles is characterized by containing the particles.
Step 1: A step of preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and a soluble compound which is solid at 20 ° C. and has solubility in the liquid in the slurry. , 10% by mass to 150% by mass with respect to the solid component containing the ion-exchangeable layered silicate in the 20 ° C. step 2: The slurry prepared in the above step 1 is granulated to form the ion-exchangeable layer. Step 3: Obtaining the ion-exchangeable layered silicate composite particles containing the silicate and the soluble compound: Step of dissolving the soluble compound from the ion-exchangeable layered silicate composite particles obtained from the step 2.

When the ion-exchangeable layered silicate slurry is impregnated with a specific amount of a soluble compound and granulated, the primary particles of the silicate in the obtained composite particles are loosened by the soluble compound which has become solid by drying. Conceivable. After that, when the soluble compound is eluted from the composite particles into a solvent by chemical treatment or the like, as a result, appropriate voids are generated in the particles, and it is considered that the pore size of the silicate particles can be controlled. Since the controllable pore diameter is the size when the soluble compound is dissolved, the amount of the pore diameter smaller than that in the case of adding the conventional insoluble fine particle solid to control the pores can be controlled.

(1) Step 1
Step 1 is a step of preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and the soluble compound.

(1-1) Ion-exchangeable layered silicate The ion-exchangeable layered silicate particles of the present invention are made of an ion-exchangeable layered silicate.
The ion-exchangeable layered silicate in the present invention is a kind of silicate compound having a crystal structure in which planes composed of ionic bonds and the like are stacked in parallel with each other with a weak bonding force. The ion-exchangeable layered silicate in the present invention is not limited to a naturally produced one, and may be an artificial synthetic product.
As a specific example, for example, as described in "Clay Minerals" by Haruo Shiramizu, Asakura Shoten (1995), etc.
i) The 1: 1 layer is the main constituent layer of kaolinites such as decite, nalite, kaolinite, and naphthite, serpentine tribes such as chrysotile, lizardite, and antigolite, and serpentine-related minerals such as amesite and al lizardite. etc.
ii) 2: 1 layers are the main constituent layers: montmorillonite, biderite, nontronite, saponite, hectorite, smectite silicates such as stephensite, vermiculite silicates such as vermiculite, mica, illite, sericite, Examples include mica silicates such as vermiculite, attapargite, sepiolite, parigolskite, and chlorite group. These may form a mixed layer. Since many smectites are naturally produced as a mixture of clay minerals, they often contain impurities (including quartz, cristobalite, opal, carbonates, etc.), but they may be contained. Examples of such examples include bentonite, which is a clay containing montmorillonite as a main component, and acidic white clay. The ion-exchangeable layered silicate of the present invention is preferably a layered silicate having a 2: 1 type structure.
More preferably, it is a smectite group silicate, and even more preferably, it is montmorillonite.
These ion-exchangeable layered silicates may be used alone or in combination of two or more.

In the present invention, the composition analysis of the ion-exchangeable layered silicate and the ion-exchangeable layered silicate particles prepares a calibration curve according to JIS R2212 and quantifies it by fluorescent X-ray measurement. Specifically, as the method for measuring fluorescent X-rays, the method described in Examples described later can be adopted.

Further, it is more preferable to purify these natural products by elutriation or elutriation. By performing elutriation or wind elutriation, impurities such as quartz and feldspar having a large specific density can be removed, and silicates that do not swell can also be removed, so that a preferable ion-exchangeable layered silicate can be obtained. As the method of elutriation and eruption, a commonly used method can be used. It may be dried or pulverized before purification. Examples of the pulverization mode include dry pulverization and wet pulverization. Examples of the crusher include a jaw crusher, a gyre crusher, a roll crusher, an edge runner, a hammer mill, a ball mill, a bead mill, and a jet mill.

Further, for example, the ion exchange treatment may be performed in advance using a very small amount of sodium carbonate or the like.
Examples of such examples include those obtained by converting Ca-type bentonite into Na-type activated bentonite (Customs Central Analysis Bulletin No. 56, P85, Clay Science Vol. 21, No. 1 to 13 (1981). )) Review article). As a result, smectite is easily dispersed in the elutriation, and coarse quartz or the like can be quickly settled and separated due to the difference in particle size. Further, a known substance may be added as a dispersant, and examples thereof include sodium silicate and sodium pyrophosphate.

The ion-exchangeable layered silicate used in the present invention is subjected to granulation and chemical treatment described later.
Further, in the present invention, if the silicate has an ion exchange property before the chemical treatment is applied, the physical and chemical properties are changed by the treatment, and the silicate having no ion exchange property and layer structure is also an ion. Treat as an exchangeable layered silicate.

The type of the interlayer cation of the ion-exchangeable layered silicate of the present invention (cation contained between the layers of the ion-exchangeable layered silicate) is not particularly limited. The interlayer cation is selected from the group consisting of alkali metals of Group 1 of the Periodic Table such as lithium and sodium, alkaline earth metals of Group 2 of the Periodic Table such as calcium and magnesium, aluminum, and silicon as main components. It may contain at least one of the above. Alternatively, the interlayer cation may contain a transition metal such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold. Such an ion-exchangeable layered silicate or a raw material required for an ion exchange treatment is preferable because it is relatively easily available as an industrial raw material.

(1-2) Raw Material Slurry In the method for producing ion-exchangeable layered silicate particles, the ion-exchangeable layered silicate, the solvent, and the solution which is solid at 20 ° C. and has solubility in the liquid in the slurry. A slurry containing a sex compound (hereinafter, may be referred to as a raw material slurry) is used as a raw material.

The shape of the ion-exchangeable layered silicate before granulation is not particularly limited, and may be a naturally produced shape or a shape at the time of artificial synthesis. Then, an ion-exchangeable layered silicate whose shape has been processed by operations such as pulverization, granulation, and classification may be used. Further, the slurry obtained by a purification operation such as elutriation may be used as it is. It may also contain impurities (including quartz, cristobalite, opal, carbonate and the like).
The concentration of the ion-exchangeable layered silicate in the slurry is not particularly limited. The concentration is preferably 0.5% by mass to 60% by mass, more preferably 0.7% by mass to 40% by mass, still more preferably 0.8% by mass to 20% by mass, and most preferably 1% by mass to 10%. It is mass%.

The particle size of the raw material ion-exchangeable layered silicate measured by dispersing the ion-exchangeable layered silicate used in the present invention in a solvent may be 2 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less. Is.
The particle size here means the equivalent circle diameter measured by the following method.
As a method for measuring the particle size of the ion-exchangeable layered silicate (raw material), specifically, the method described in Examples described later can be adopted.

There is no particular limitation on the type of solvent constituting the slurry. Examples of the solvent include water, or organic solvents such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene and xylene, and more preferably water. Further, these solvents may be used alone or in combination of two or more.

The soluble compound is an additive that is solid at 20 ° C. and has solubility in the liquid in the slurry at the temperature at the time of granulation, preferably 20 ° C. Here, having solubility means that the concentration is 0.3% by mass or more, preferably 0.5% by mass or more, and more preferably 0.8% by mass or more with respect to the liquid in the slurry. ..
The soluble compound alone is solid at 20 ° C., has solubility in the liquid in the raw material slurry, and is not particularly limited as long as it is dissolved by chemical treatment in step 3 described later. As the soluble compound, salts are preferable because the pores can be easily controlled.
The salts include cations selected from the group consisting of organic cations and inorganic cations including metal ions, and anions selected from the group consisting of organic anions and inorganic anions including halide ions. Examples are salts composed of. Examples of salts include cations containing at least one atom selected from Group 1 to 14 of the periodic table, halogen anions, inorganic blended acid anions, and organic blended acid anions. A preferred example is a compound composed of at least one anion selected from the group consisting of. The salts are more preferably inorganic salts which are compounds composed of at least one anion selected from an anion of an inorganic blended acid and an anion of a halogen, and more preferably an inorganic salt which is soluble in water. Is.

Examples of the cations constituting such an inorganic salt include alkali metal ions such as lithium ion, sodium ion and potassium ion, alkaline earth metal ions such as magnesium ion and calcium ion, aluminum ion, iron ion, strontium ion and cobalt. Examples thereof include ion, copper ion, nickel ion, zinc ion, ruthenium ion, rhodium ion, palladium ion, silver ion, iridium ion, platinum ion and ammonium ion. Anions include sulfate ion, nitrate ion, chloride ion, hydrobromide ion, hydroiodide ion, phosphate ion, pyrophosphate ion, perchlorate ion, molybdenate ion, hexafluorosilicate ion. , Inorganic acid ions such as carbonate ion, and organic acid ions such as acetate ion, citric acid ion, oxalate ion, formate ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion, toluenesulfonic acid ion, taurine ion, and Examples thereof include oxygen ion (oxide ion) and hydroxide ion.

The soluble compound is more preferably a group in which the cation is composed of lithium ion, sodium ion, magnesium ion, aluminum ion, and iron ion from the viewpoint that it is easy to elute appropriately and industrially waste liquid treatment is easy. At least one salt selected from. More preferably, the cation is at least one selected from the group consisting of lithium ion, sodium ion, magnesium ion, aluminum ion, and iron ion, and the anion is sulfate ion, nitrate ion, chloride ion, and phosphoric acid. Examples include at least one salt selected from the group consisting of ions. Even more preferably, the cation is at least one selected from the group consisting of lithium ion, sodium ion, and magnesium ion, and the anion is from the group consisting of sulfate ion, nitrate ion, chloride ion, and phosphate ion. Examples include at least one salt selected. Lithium sulfate is particularly preferable.

These soluble compounds may be used alone or in combination of two or more.
The soluble compound may be added so as to be contained in an amount of 10% by mass to 150% by mass with respect to the solid component containing the ion-exchangeable layered silicate in the 20 ° C. slurry. It is preferable because the characteristics of salt particles can be easily obtained.
That is, the amount of the soluble compound added is the sum of the ion-exchangeable layered silicate and the insoluble solid component (the ion-exchangeable layered silicate and the solid component different from the soluble compound) in the 20 ° C. slurry. It is preferably 10% by mass to 150% by mass. The amount of the soluble compound added may be appropriately selected in the above range so as to control the pore distribution. The lower limit value is more preferably 15% by mass or more, further preferably 20% by mass or more, still more preferably 25% by mass or more, and the upper limit value is more preferably 130% by mass or less, still more preferably 110% by mass or less. , More preferably 100% by mass or less. Any combination of the upper limit value and the lower limit value can be adopted.
If the upper limit exceeds 150% by mass, the strength of the granulated solid is lowered, and there is a possibility that fine powder or the like is likely to be generated. On the other hand, if it is less than 10% by mass, the characteristics of the ion-exchangeable layered silicate particles of the present invention may not be obtained.
It is preferable to add the soluble compound in the slurry so as to be contained in an amount of 10% by mass to 150% by mass with respect to the ion-exchangeable layered silicate from the viewpoint that a desired pore structure can be easily obtained. The lower limit value is more preferably 15% by mass or more, further preferably 20% by mass or more, still more preferably 25% by mass or more, and the upper limit value is more preferably 130% by mass or less, still more preferably 110% by mass or less. , More preferably 100% by mass or less. Any combination of the upper limit value and the lower limit value can be adopted.

On the other hand, in carbonate, the gas generated when it reacts with acid affects the pore structure. Therefore, the amount of the carbonate added as the soluble compound is preferably 0% by mass to 75% by mass, more preferably 0% by mass to 50% by mass, and further preferably 0% by mass to 30% by mass. When the amount of the soluble compound added is insufficient, it is preferable to supplement with another soluble compound.
When an ion-exchange layered silicate containing a carbonate as an impurity or an ion-exchange layered silicate having Na-type activation by treatment with sodium carbonate or the like is used, the total amount of the carbonate is described above. The content is preferably.

In calculating the amount of these additions, in the case of a salt containing an adduct that becomes a liquid by itself such as hydrated water, it is calculated as having no adduct such as anhydrate.

The soluble compound is a substance that is dissolved in a slurry containing a solvent and does not exist as a solid, but becomes a solid when the slurry is dried and does not contain a solvent. Soluble compounds are particularly preferably substances that have crystallinity in the granulated state.
A crystalline substance is a substance having some kind of structural order. That is, it is a substance whose diffraction pattern by X-rays and particle beams shows discrete diffraction spots. It is preferable to use a substance having crystallinity after drying or granulation as a soluble compound because the pore structure can be adjusted by controlling the size of the crystals. However, not all of the soluble compounds used need to be crystalline, and some of them may be crystalline.
The presence or absence of crystallinity can be confirmed by the presence or absence of a diffraction pattern by X-rays and particle beams, and generally can be confirmed by scattering or diffraction phenomena of X-rays.

A binder may be added for the purpose of improving the shape at the time of granulation. Examples of the binder include sugar, dextrose, corn syrup, gelatin, glue, carboxymethyl cellulose, polyvinyl alcohol, water glass, alcohols, glycol, starch, casein, latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, and the like. Examples thereof include silica gel, gum arabic, and sodium alginate.
Further, a viscosity adjusting agent may be added for the purpose of adjusting the pH, viscosity and the like of the slurry. It is known that the pH of an ion-exchangeable layered silicate slurry affects the viscosity of the slurry. In addition to the binders mentioned above for the purpose of adjusting these, acids such as sulfuric acid, nitric acid and hydrochloric acid, and bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide may be added.
Further, a known substance as a dispersant or a flocculant may be added. Examples of the dispersant include sodium silicate, sodium pyrophosphate, aluminum sulfate and the like.
If these binders, viscosity modifiers, dispersants, flocculants and the like satisfy the properties of the soluble compound, they are treated as soluble compounds and are treated as a soluble component with respect to the solid component containing the ion-exchangeable layered silicate in the 20 ° C. slurry. It is preferable to adjust the addition amount and the like.

The order in which the ion-exchangeable layered silicate, the soluble compound, and the solvent are mixed is not particularly limited. However, the mixing order may affect the physical properties such as the viscosity of the slurry, which may affect the drying and granulation steps and the physical properties of the ion-exchangeable layered silicate particles.
As the mixing order, the ion-exchangeable layered silicate and the soluble compound may be added to the solvent sequentially or simultaneously. The ion-exchangeable layered silicate and the soluble compound may be dispersed or dissolved in a solvent and then mixed. The most preferable method is to dissolve a soluble compound in a solvent and add a slurry in which an ion-exchangeable layered silicate is dispersed in the solvent to this solution. There is no limitation on the mixing order when a binder, a dispersant, a flocculant, or a viscosity modifier is added.

The temperature at the time of mixing is also not particularly limited, but a temperature below the boiling point of the solvent is preferable. When water is used, it is 0 ° C to 80 ° C, more preferably 10 ° C to 70 ° C, and more preferably 20 ° C to 60 ° C.
There are no particular restrictions on the mixing method. A known method can be used. Examples of the mixing method include stirring and a static mixer. Further, in order to further improve the dispersibility, a high-speed stirrer, a media mill, a high-pressure homogenizer, an ultrasonic disperser, a thin-film swirling high-speed stirrer and the like can be used. A plurality of the above methods may be combined. Stirring, high speed stirrers, bead mills and high pressure homogenizers are particularly preferred.

The slurry viscosity is preferably 5 Pa · s to 5,000 Pa · s, more preferably 8 Pa · s to 3,000 Pa · s. The viscosity here can be measured at 12 rpm and 20 ° C. using a LV-3 type spindle with a B type viscometer (DV-I Viscometer manufactured by BROOKFIELD).

(2) Step 2
Step 2 is a step of granulating the slurry prepared in the step 1 to obtain ion-exchangeable layered silicate composite particles containing the ion-exchangeable layered silicate and the soluble compound.
In step 2, the raw material slurry obtained in step 1 is used for granulation and, if necessary, solid-liquid separation such as drying, concentration, filtration, or decantation, whereby ion-exchangeable layered silicate composite particles are performed. To manufacture.
The granulation and the solvent may be separated separately or simultaneously. The method and order of granulation and separation from the solvent are not particularly limited. However, it is necessary to contain a soluble compound in the granulated particles. Preferred granulation methods include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized layer granulation method, jet layer granulation method, and the like. Examples include an emulsified granulation method, an in-liquid granulation method, and a compression molding granulation method. More preferably, a spray-drying granulation method, a spray-cooled granulation method, a fluidized bed granulation method, a jet layer granulation method, a liquid granulation method, an emulsified granulation method and the like can be mentioned, and spray-drying granulation method is particularly preferable. Examples include the method and the spray-cooled granulation method.

When performing spray granulation, there are no particular restrictions on the spray method. A rotary atomizer, a one-fluid nozzle, a two-fluid nozzle, an ultrasonic nozzle, or the like can be used. There are no particular restrictions on the drying medium. Examples of the drying medium include nitrogen, argon and air.
There is no limit to the temperature at which the drying medium for spray-drying granulation is supplied. The temperature varies depending on the dispersion medium, but for example, water is 70 ° C. to 300 ° C., preferably 80 ° C. to 280 ° C.

The particle size distribution of the ion-exchangeable layered silicate composite particles to be produced can also be adjusted by the production conditions such as the atomizer, the temperature of the drying medium, and the flow rate. Further, it may be adjusted by using a known classification technique such as a sieve or wind power classification.

The average particle size of the ion-exchangeable layered silicate composite particles is preferably 2 μm to 500 μm, more preferably 3 μm to 200 μm, still more preferably 8 μm to 100 μm, and most preferably 20 μm to 70 μm. The average particle diameter here is the volume-based median diameter obtained from the sphere-equivalent particle diameter distribution measured by the laser diffraction method, similar to the average particle diameter of the ion-exchangeable layered silicate particles of the present invention. Point to.

The ion-exchangeable layered silicate composite particles are particles containing an ion-exchangeable layered silicate and a soluble compound. In the ion-exchangeable layered silicate composite particles, the soluble compound is a solid, preferably a solid exhibiting crystallinity. The presence or absence of crystallinity can be confirmed by the presence or absence of a diffraction pattern by X-rays and particle beams, and generally can be confirmed by scattering or diffraction phenomena of X-rays.

(3) Step 3
Step 3 is a step of dissolving the soluble compound from the ion-exchangeable layered silicate composite particles obtained from the step 2.
By appropriately performing chemical treatment on the ion-exchangeable layered silicate composite particles, a part or all of the soluble compound is dissolved from the ion-exchangeable layered silicate composite particles, and the ion-exchangeable layered silicate is dissolved. Remove outside the particles.
As the chemical treatment, a treatment method capable of dissolving the soluble compound may be appropriately selected and used from the ion-exchangeable layered silicate composite particles. For example, acid treatment in contact with acids, base treatment in contact with bases, salt treatment in contact with salts, elution treatment (washing) with an appropriate solvent (for example, a mixed solvent of alcohol and water) in which the soluble compound is dissolved. , Other chemical treatments and the like. Each process may be performed a plurality of times. A plurality of processes may be combined.
Hereinafter, the ion-exchangeable layered silicate composite particles and the ion-exchangeable layered silicate particles that have undergone the step of dissolving the soluble compound may be collectively referred to as ion-exchangeable layered silicate (composite) particles. Ion-exchangeable layered silicate (composite) particles mean ion-exchangeable layered silicate composite particles or ion-exchangeable layered silicate particles.
Above all, from the viewpoint of improving the specific surface area that affects the strength, catalytic activity, adsorption performance, etc. of the particles, it is preferable to perform acid treatment in which the ion-exchangeable layered silicate composite particles are brought into contact with acids. It is more preferable to carry out an acid treatment in which the ion-exchangeable layered silicate composite particles are brought into contact with the acids, and then a base treatment in which the ion-exchangeable layered silicate particles are brought into contact with the bases or a salt treatment in which the ion-exchangeable layered silicate particles are brought into contact with the salts.

(3-1) Acid Treatment In the present invention, it is preferable to perform acid treatment in which ion-exchangeable layered silicate (composite) particles are brought into contact with acids.
The acid treatment dissolves soluble compounds and impurities, and exchanges cations existing between the layers of the ion-exchangeable layered silicate. Further, the acid treatment can change the characteristics of the pore structure by eluting some or all of the cations such as Al, Fe, and Mg constituting the crystal structure of the ion-exchangeable layered silicate, and the specific surface area can be changed. The surface area can be increased. This contributes to increasing the acid strength of the ion-exchangeable layered silicate particles and increasing the amount of acid points per unit mass.

The acid treatment preferably elutes the metal cations constituting the octahedral sheet by 15% to 75%, more preferably 15% to 70%, still more preferably 17%, based on the content before the acid treatment. Elute up to 65%, particularly preferably 20% to 60%. The ratio (%) of the metal cations to be eluted is expressed by the following formula, for example, when the metal cations are aluminum.
[Aluminum / silicon (molar ratio) before chemical treatment-aluminum / silicon (molar ratio) after chemical treatment] ÷ Aluminum / silicon (molar ratio) before chemical treatment x 100
When the elution rate is within the above range, the specific surface area is improved, and the adsorption performance and the catalytic activity are improved. Further, when used as an olefin polymerization catalyst component, fish eyes in the product tend to be reduced.

Examples of the acids used in the acid treatment include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propyrionic acid, fumaric acid, maleic acid and phthalic acid. Among them, inorganic acids are preferable, and hydrochloric acid, nitric acid, and sulfuric acid are preferable. Hydrochloric acid and sulfuric acid are more preferable, and sulfuric acid is particularly preferable.

The contact between the ion-exchangeable layered silicate (composite) particles and the acids is preferably performed under the slurry of the ion-exchangeable layered silicate (composite) particles from the viewpoint of efficient and uniform reaction.
The solvent for slurrying is not particularly limited. A solvent that does not cause a reaction during the acid treatment is preferable, and an organic solvent such as water or methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene is preferable. More preferably, it is water. Further, these solvents may be used alone or in combination of two or more.

There is no particular limitation on the acid concentration (mass percentage of acid to the total mass of the reaction system) during the acid treatment of the present invention. The acid concentration is preferably 3% by mass to 50% by mass, more preferably 4% by mass to 40% by mass, and further preferably 5% by mass to 20% by mass.
In addition, there is no limitation on the temperature during acid treatment. The temperature is preferably 30 ° C. to 102 ° C., more preferably 40 ° C. to 100 ° C., and even more preferably 50 ° C. to 95 ° C.
There is no particular limitation on the solid content concentration in the solvent during the acid treatment. The concentration is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, and further preferably 8% by mass to 20% by mass.
There is no limit to the acid treatment time. The time is preferably 5 minutes to 3000 minutes, more preferably 10 minutes to 1500 minutes, and even more preferably 30 minutes to 750 minutes.
The degree of elution of soluble compounds, impurities, cations and the like can be adjusted by appropriately selecting the type of acid, the concentration of the acid, the treatment temperature, the treatment time and the like.
It is also possible to perform the acid treatment in a plurality of times.

(3-2) Base Treatment In the present invention, a base treatment may be performed in which ion-exchangeable layered silicate (composite) particles are brought into contact with bases.
The ion-exchangeable layered silicate composite particles may be subjected to the above-mentioned acid treatment and then further subjected to a base treatment in which they are brought into contact with bases.
The base treatment dissolves soluble compounds and impurities, and exchanges cations existing between the layers of the ion-exchangeable layered silicate. In addition, the base treatment changes the characteristics of the pore structure by eluting some or all of the cations such as Al, Fe, Mg, and Si that constitute the crystal structure of the ion-exchangeable layered silicate. And can increase the specific surface area.

The bases used in the base treatment are substances that act as Bronsted bases. Bases are substances that have the property of generating water by reacting with protons (neutralization reaction). Preferred are hydroxides of metals selected from the group consisting of alkali metals, alkaline earth metals, and metals of Groups 3-14 of the Periodic Table. More preferably, it is a hydroxide of alkali metal, alkaline earth metal, Mn, Fe, Ni, Cu, Zn, Al, Sn and Pb. More preferably, it is a hydroxide of an alkali metal, an alkaline earth metal, Mg, Zn, and Al.
The bases are not limited to the following. Specific examples include LiOH, NaOH, KOH, CsOH, RbOH, Be (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Mn (OH) ₂ , Cu (OH) ₂ . , Cu (OH) ₃ , Zn (OH) ₂ , Al (OH) ₃ , Sn (OH) ₄ , Pb (OH) ₂ , Ni (OH) ₂ , Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , Rb ₂ CO ₃ , BeCO ₃ , MgCO ₃ , CaCO ₃ , MnCO ₃ , CuCO ₃ , Al ₂ (CO) ₃ , ZnCO ₃ , PbCO ₃ , LiHCO ₃ , NaHCO ₃ , RpHCO _{3 3} , Ca (HCO ₃ ) ₂ , Mg (HCO ₃ ) ₂ , and the like can be mentioned.
The bases may be used alone or in combination of two or more. There are no particular restrictions on how to use it.
The state of the bases upon contact with the ion-exchangeable layered silicate (composite) particles may be dissolved in a solvent or may remain solid. When it is dissolved in a solvent and brought into contact with it, the concentration is not limited, and the upper limit is preferably not more than the saturated concentration.

The base treatment is preferably performed under an ion-exchangeable layered silicate (composite) particle slurry from the viewpoint of efficient and uniform reaction.
Examples of the solvent for slurrying include water, an organic solvent such as alcohol, and the like. It is preferably ethanol, methanol, ethylene glycol, glycerin, or water, more preferably water. Further, these solvents may be used alone or in combination of two or more.

The amount of the base used also varies depending on the amount of acid contained in the ion-exchangeable layered silicate (composite) particle slurry before contact with the base and the purpose of the treatment thereof.
When an ion-exchangeable layered silicate (composite) particle slurry after acid treatment using water as a solvent is used, the amount of bases used is such that the pH becomes 8 or less during the base treatment step and the base treatment step is completed. It is preferable that the pH is 4.5 to 8 when the pH is adjusted.

Further, there is no limitation on the temperature at the time of base treatment. The temperature is preferably −20 ° C. to 120 ° C., more preferably 0 ° C. to 105 ° C., and even more preferably 10 ° C. to 80 ° C.
There is no particular limitation on the solid content concentration in the solvent during base treatment. The concentration is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, and further preferably 3% by mass to 20% by mass.
There is no limit to the time of base treatment. The time is preferably 1 minute to 600 minutes, more preferably 5 minutes to 300 minutes, and even more preferably 10 minutes to 120 minutes.
The degree of elution of soluble compounds, impurities, cations and the like can be adjusted by appropriately selecting the type of bases, the concentration of bases, the treatment temperature, the treatment time and the like.
It is also possible to perform the base treatment in a plurality of times.

(3-3) Other Chemical Treatments In the present invention, ion-exchangeable layered silicate (composite) particles may be subjected to other chemical treatments in addition to acid treatment and base treatment.
The ion-exchangeable layered silicate composite particles may be further subjected to other chemical treatments after the acid treatment or the base treatment.

Other chemical treatments include contact with treatment agents containing salts, oxidizing agents, reducing agents, or compounds that can intercalate between layers of ion-exchangeable layered silicate (composite) particles, and cleaning with a solvent. Can be mentioned.
Intercalation refers to the introduction of another substance between layers of a layered substance. The substance to be introduced is called a guest compound.
Further, in intercalation, salt treatment, acid treatment, or base treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area and the interlayer distance can be changed.
By utilizing the ion exchange property and substituting the exchangeable ions between the layers with another large bulky ion, it is possible to obtain a layered substance in a state where the layers are expanded. That is, bulky ions play a supporting role in supporting the layered structure, and are called pillars. Specific examples of the treatment agent are shown below.

The salts include cations selected from the group consisting of organic cations and inorganic cations including metal ions, and anions selected from the group consisting of organic anions and inorganic anions including halide ions. Examples are salts composed of. For example, at least one selected from the group consisting of cations containing at least one atom selected from Groups 1-14 of the Periodic Table and anions of halogen anions, inorganic blended acids and organic blended acids. Preferred examples include compounds composed of species anions. Particularly preferably, the anion is a compound composed of an inorganic Bronsted acid or a halogen.

Specific examples of such salts include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, Na ₂ SO ₄ , Na ₃ (PO ₄ ). , NaNO ₃ , Na (OOCCH ₃ ), KCl, KBr, K ₂ SO ₄ , K ₃ (PO ₄ ), KNO ₃ , K (OOCCH ₃ ), CaCl ₂ , CaSO ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrBr ₄ , ZrI ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ . ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), Hf (OOCCH ₃ ) ₄ , Hf (CO ₃ ) ₂ , Hf (NO ₃ ) ₄ , Hf (SO ₄ ) ₂ , HfOCl ₂ , HfF ₄ , HfCl ₄ , HfBr ₄ , HfI ₄ , CuCl ₂ , CuBr ₂ , Cu (NO ₃ ) ₂ , CuC ₂ O ₄ , Cu (ClO ₄ ) ₂ , CuSO ₄ , Cu (OOCCH ₃ ) ₂ , Zn (OOCH ₃ ) ₂ , Zn ( CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , nBr ₂ , ZnI ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , Sn (OOCCH ₃ ) ₄ , Sn (SO ₄ ) ₂ , SnF ₄ , SnCl ₄ , and the like, but are not limited thereto.

Examples of organic cations are trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5- Pentamethylanilinium, N, N-dimethyloctadecylammonium, octadodecylammonium, N, N-2,4,5-pentamethylanilinium, N, N-dimethyl-pn-butylanilinium, N, N- Ammonium compounds such as dimethyl-p-trimethylsilylanilinium, N, N-dimethyl-1-naphthylanilinium, N, N,2-trimethylanilinium, 2,6-dimethylanilinium, pyridinium, quinolinium, N-methylpi Nitrogen-containing aromatic compounds such as peridinium, 2,6-dimethylpyridinium, 2,2,6,6-tetramethylpiperidinium, and oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, and oxolanium. , Triphenylphosphonium, tri-o-tolylphosphonium, tri-p-tolylphosphonium, phosphonium compounds such as trimesitylphosphonium, and phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium are exemplified. It is not limited to these.
Examples of anions include, in addition to the anions exemplified above, anions composed of boron compounds and phosphorus compounds, such as hexafluoroborate, tetrafluoroborate, and tetraphenylborate, but are limited thereto. It is not something that will be done.
Further, these salts may be used alone or in combination of two or more.

The salts may be further used in combination with acids, bases, oxidizing agents, reducing agents, compounds intercalating between the layers of the ion-exchangeable layered silicate, and the like.
These combinations may be used in combination with respect to the treatment agent added at the start of treatment. Further, the treatment agents added in the middle of the treatment may be used in combination.

In the above-mentioned salt treatment, an appropriate solvent may be used, and the treatment agent may be dissolved therein and used as a treatment agent solution. Further, the treatment agent itself may be used as a solvent.
Examples of the solvent that can be used include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide and the like. Water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, more preferably water, alcohols, aliphatic hydrocarbons, ethers, particularly preferably water and alcohols.
The concentration of the treatment agent in the treatment agent solution is preferably about 0.1% by mass to 100% by mass, more preferably about 5% by mass to 50% by mass. If the concentration of the treatment agent is within this range, there is an advantage that the time required for the treatment is shortened and efficient production becomes possible.

Further, as a chemical treatment, it is preferable to perform cleaning with a solvent. The washing involves dissolving soluble compounds and impurities, and exchanging the cations existing between the layers of the ion-exchangeable layered silicate. Further, the washing can remove the acids, bases, salts and solvents remaining during the treatment with the above-mentioned acids, bases and salts.

Examples of the solvent used for washing include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide and the like. These may be used by mixing two or more kinds. Water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters and ethers are preferable, water, alcohols, aliphatic hydrocarbons and ethers are more preferable, and water and alcohol are more preferable. Classes and mixed solvents thereof, particularly preferably water.
In addition, there is no limitation on the temperature at the time of washing. The temperature is preferably 0 ° C to 100 ° C, more preferably 50 ° C to 95 ° C, still more preferably 10 ° C to 60 ° C.
There is no particular limitation on the solid content concentration in the solvent during washing. The concentration is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and further preferably 8% by mass to 30% by mass.
There is no limit to the cleaning time. The time is preferably 1 minute to 3000 minutes, more preferably 3 minutes to 1500 minutes, still more preferably 5 minutes to 750 minutes.

The method of solid-liquid separation for separating the solvent and the ion-exchangeable layered silicate (composite) particles is also not particularly limited. Examples thereof include sedimentation separation, filtration separation, centrifugal sedimentation separation using centrifugal force, and centrifugal filtration. These may be performed a plurality of times, or a plurality of methods may be combined.
The cleaning rate is preferably 1/5 to 1/10000, and more preferably 1/10 to 1/1000. Here, the cleaning rate represents the residual ratio of the solvent at the start of cleaning. For example, when washing is performed by contacting 100 L of a solvent with ion-exchangeable layered silicate (composite) particles and then removing 90 L of the solvent, the washing rate is (100-90) / 100 = 1/10. ..
Further, the supernatant, which indicates the amount of remaining ions, is washed until the electrical conductivity is preferably 1000 mS / cm or less, more preferably 100 mS / cm or less, further preferably 10 mS / cm or less, and most preferably 1 mS / cm or less. Can be done.

(4) Other Steps After the chemical treatment including Step 3, it is preferable to dry the obtained ion-exchangeable layered silicate particles.
The drying method is not particularly limited, and drying can be carried out by various methods. Drying is preferably performed so as not to cause structural destruction of the ion-exchangeable layered silicate particles.
The drying temperature is generally 100 ° C. to 800 ° C., preferably 120 ° C. to 600 ° C., and particularly preferably 150 ° C. to 300 ° C.
The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours.
The atmosphere during drying is preferably dry air, dry nitrogen, dry argon, or under reduced pressure.

Since the characteristics of these ion-exchangeable layered silicate particles change depending on the drying temperature even if the structure is not destroyed, it is preferable to change the drying temperature according to the application.
When used as a component of an olefin polymerization catalyst, the water content after removal is 3% by mass or less when the water content after dehydration for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by mass. , Preferably 1% by mass or less.

1-3. Applications of Ion-Exchangeable Layered Silicate Particles The ion-exchangeable layered silicate particles of the present invention have the specific pore distribution and specific surface area. Therefore, the ion-exchangeable layered silicate particles of the present invention are widely used as carriers for olefin polymerization catalysts, catalysts for organic chemical reactions, dehydration, decolorization, purification of petroleum and oils and fats, drying materials, adsorbents, bleaching agents and the like. Be done.

2. 2. Olefin Polymerization Catalyst Component The olefin polymerization catalyst component of the present invention is characterized by containing the ion-exchangeable layered silicate particles of the present invention.
In one embodiment of the present invention, the ion-exchangeable layered silicate particles of the present invention can be used as a catalyst component for olefin polymerization or copolymerization. The ion-exchangeable layered silicate particles of the present invention function as a catalyst carrier, a co-catalyst, and the like.
The pore structure of the ion-exchangeable layered silicate particles affects the performance such as the activity and strength of the catalyst. Not only that, the pore structure further affects economic efficiency, operability, and product quality.
In the ion-exchangeable layered silicate particles of the present invention, the total pore volume having a diameter of 2 nm to 10 nm is the total meso in the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption / desorption method. It has the specific range with respect to the pore volume. That is, the ion of the present invention has a novel pore structure in which the total volume of pores having a diameter of more than 10 nm and 50 nm or less is larger than that of the total mesopore volume and the specific surface area is large in a specific range. Exchangeable layered silicate particles improve catalytic activity and polymer quality.
More specifically, when the ion-exchangeable layered silicate particles of the present invention are used as a catalyst component for olefin polymerization, an olefin polymer can be produced with high polymerization activity. Further, when the ion-exchangeable layered silicate particles of the present invention are used as a catalyst component for olefin polymerization, it is possible to produce an olefin polymer having less fish eyes in the product, which deteriorates the appearance of the product.

The method of using the catalyst component for olefin polymerization of the present invention is not particularly limited. For example, the methods described in JP-A-2002-053611A, JP-A-2009-280443, and the like can be mentioned.
Above all, it is preferable to use it like a catalyst for olefin polymerization described later from the viewpoint that improved catalyst performance can be easily obtained.

3. 3. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is characterized by containing the following components [A], component [B], and component [C].
Component [A]: Ion-exchangeable layered silicate particle component of the present invention [B]: Transition metal compound component of Group 4 of the periodic table [C]: Organoaluminum compound

3-1. Each component of the catalyst for olefin polymerization <Component [A]>
The component [A] is the ion-exchangeable layered silicate particles of the present invention. The ion-exchangeable layered silicate particles of the present invention may be the same as described above, and thus the description thereof is omitted here.

<Ingredient [B]>
The preferred transition metal compound of Group 4 of the periodic table of the component [B] used in the present invention is a metallocene compound having at least one conjugated five-membered ring ligand. Preferred transition metal compounds are compounds represented by the following general formulas (1) to (4).

［上記一般式（１）～（４）中、ＡおよびＡ’は、置換基を有してもよい共役五員環配位子（同一化合物内においてＡおよびＡ’は同一でも異なっていてもよい）を示し、
Ｑは、二つの共役五員環配位子を任意の位置で架橋する結合性基を示し、Ｚは、窒素原子、酸素原子、ケイ素原子、リン原子またはイオウ原子を含む配位子、水素原子、ハロゲン原子、又は炭化水素基を示し、Ｚ’は、窒素原子、酸素原子、ケイ素原子、リン原子またはイオウ原子を含む配位子、又は炭化水素基を示す。
Ｑ’は、共役五員環配位子の任意の位置とＺを架橋する結合性基を示し、Ｍは、周期表第４族から選ばれる金属原子を示し、ＸおよびＹは、水素原子、ハロゲン原子、炭化水素基、アルコキシ基、アミノ基、リン含有炭化水素基または珪素含有炭化水素基（同一化合物内においてＸ及びＹは、同一でも異なっていてもよい。）を示す。］

[In the above general formulas (1) to (4), A and A'may have a substituent, and the conjugated five-membered ring ligand (A and A'in the same compound may be the same or different. Good),
Q indicates a binding group that bridges two conjugated five-membered ring ligands at arbitrary positions, and Z indicates a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, and a hydrogen atom. , Halogen atom, or hydrocarbon group, and Z'represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, or a hydrocarbon group.
Q'represents a binding group that bridges Z with any position of the conjugated five-membered ring ligand, M represents a metal atom selected from Group 4 of the Periodic Table, and X and Y represent hydrogen atoms. Indicates a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group (X and Y may be the same or different in the same compound). ]

Conjugated five-membered ring ligands for A and A'include, for example, substituents derived from cyclopentadiene, indene, tetrahydroindene, fluorene, azulene, tetrahydroazulene. These may be unsubstituted or substituted. Of these, particularly preferred are substituted or unsubstituted indenyl or azurenyl groups.

As the substituent on the conjugated five-membered ring ligand, in addition to the above-mentioned hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, the number of carbon atoms is 1 substituted with a halogen such as fluorine, chlorine or bromine. ~ 30 Hydrocarbon groups, halogen atomic groups such as fluorine, chlorine, bromine, and alkoxy groups having 1 to 12 carbon atoms, for example, silicon-containing hydrocarbons represented by −Si (R ¹ ) (R ² ) (R ³ ). Groups include phosphorus-containing hydrocarbon groups represented by —P (R ¹ ) (R ² ), or boron-containing hydrocarbon groups represented by —B (R ¹ ) (R ² ). When there are a plurality of these substituents, the respective substituents may be the same or different.
The above-mentioned R ¹ , R ² , and R ³ may be the same or different, and represent an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.
Further, the substituent on the conjugated five-membered ring ligand may have at least one Group 15 to 16 element (that is, a hetero element). As such a substituent, a monocyclic or polycyclic group containing at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom in a 5-membered or 6-membered ring is preferable. Cyclic substituents can be mentioned. Further preferably, it is a substituent derived from a heteroaromatic compound which may be substituted, and particularly preferably, a frill group which may be substituted and a thienyl group which may be substituted may be mentioned. In the case of a compound having a cross-linking group represented by the general formula (2) or (4), these substituents are not particularly limited, but are at the α-position (bond to the cross-linking group) on the conjugated five-membered ring ligand. It is preferable that the site is used as a reference).

Q is a binding group that bridges between two conjugated five-membered ring ligands at an arbitrary position, and Q'is a bond that bridges an arbitrary position of the conjugated five-membered ring ligand and the group indicated by Z. Represents a sex group.
Specific examples of Q and Q'include the following groups.
(A) alkylene groups such as methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group (b) Dimethyltylylene group, diethylsilylene group, dipropylsilylene group, diphenylcilylene group, Syrylene groups such as methyl ethyl sylylene group, methyl phenyl sylylene group, methyl-t-butyl sylylene group, disyrylene group, tetramethyl disylylene group, silacyclobutylene group (c) Includes germanium, phosphorus, nitrogen, boron or aluminum. Hydro groupes

More specifically, (CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) P, (C ₆ H ₅ ) P, (C ₄ H ₉ ) N, (C ₆ H ₅ ). ) N, (C ₄ H ₉ ) B, (C ₆ H ₅ ) B, (C ₆ H ₅ ) Al, (C ₆ H ₅ O) Al and the like. Preferred are alkylene groups or silylene groups.

Further, M is a metal atom, and particularly represents a transition metal atom selected from Group 4 of the periodic table. Examples of M are titanium, zirconium, hafnium and the like. In particular, zirconium and hafnium are preferable.
Further, Z represents a nitrogen atom, an oxygen atom, a silicon atom, a ligand containing a phosphorus atom or a sulfur atom, a hydrogen atom, a halogen atom or a hydrocarbon group, and Z'is a nitrogen atom, an oxygen atom, a silicon atom, Indicates a ligand containing a phosphorus atom or a sulfur atom, or a hydrocarbon group.
Preferred specific examples of Z and Z'are an oxygen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a sulfur-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms. , A silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, preferably 1 to 40 carbon atoms, preferably carbon atoms. Examples thereof include phosphorus-containing hydrocarbon groups having 1 to 18 carbon atoms and carbon dioxide groups having 1 to 20 carbon atoms. As a preferable specific example of Z, a hydrogen atom, a chlorine atom and a bromine atom are further added.

X and Y are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 10 carbon atoms, and an amino group, respectively. A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a diphenylphosphino group, or 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms, such as a trimethylsilyl group and a bis (trimethylsilyl) methyl group. Twelve silicon-containing hydrocarbon groups.
X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an amino group having 1 to 12 carbon atoms are particularly preferable.

Examples of the compound represented by the general formula (1) include, for example.
(1) Bis (methylcyclopentadienyl) zirconium dichloride,
(2) Bis (n-butylcyclopentadienyl) zirconium dichloride,
(3) Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
(4) Bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(5) Bis (1-methyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(6) Bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride,
(7) Bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride,
(8) Bis (indenyl) zirconium dichloride,
(9) Bis (tetrahydroindenyl) zirconium dichloride,
(10) Bis (2-methyl-tetrahydroindenyl) zirconium dichloride,
And so on.

Examples of the compound represented by the general formula (2) include, for example.
(1) Dimethylsilylenebis {1- (2-methyl-4-isopropyl-4H-azurenyl)} zirconium dichloride,
(2) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(3) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azurenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azurenyl}] zirconium dichloride,
(5) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(6) Diphenylcilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(8) Ethylene bis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(9) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(10) Dimethylsilylenebis {1- [2-methyl-4- (2', 6'-dimethyl-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(11) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(12) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azurenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(13) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azurenyl)} zirconium dichloride,
(14) Dimethylsilylenebis {1- (2-ethyl-4-indrill-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(17) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(18) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(19) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(20) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,

(21) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(22) Ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(23) Ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(24) Isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(25) Ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(26) Isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(27) Dimethylgelmilenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(28) Dimethylgelmilenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(29) Phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(30) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(31) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(32) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(33) Dimethylsilylenebis [2- (2- (5-methyl) frill) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(34) Dimethylsilylenebis [2- (2- (5-trimethylsilyl) frill) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(35) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(36) Dimethylsilylene [2- (2- (5-methyl) frill) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(37) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(38) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(39) Dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride,
(40) Silacyclobutylenebis [2- (2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,

(41) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(42) Silacyclobutylenebis [2- (4,5-dimethyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(43) Silacyclobutylenebis [2- (5-t-butyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(44) Silacyclobutylenebis [2- (5-phenyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(45) Silacyclobutylenebis [2- (2-thienyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(46) Silacyclobutylenebis [2- (5-methyl-2-thienyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(47) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -5-methyl-1-indenyl] zirconium dichloride,
(48) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -5-methyl-1-indenyl] zirconium dichloride,
(49) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-methylphenyl) -5-methyl-1-indenyl] zirconium dichloride,
(50) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -5-methyl-1-indenyl] zirconium dichloride,
(51) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (3,5-dimethylphenyl) -5-methyl-1-indenyl] zirconium dichloride,
(52) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (3,5-dit-butylphenyl) -5-methyl-1-indenyl] zirconium dichloride,
(53) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (1-naphthyl) -5-methyl-1-indenyl] zirconium dichloride,
(54) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (2-naphthyl) -5-methyl-1-indenyl] zirconium dichloride,
(55) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-biphenylyl) -5-methyl-1-indenyl] zirconium dichloride,
(56) Silacyclobutylenebis [2- (2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,
(57) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,
(58) Silacyclobutylenebis [2- (4,5-dimethyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,
(59) Silacyclobutylenebis [2- (5-t-butyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,
(60) Silacyclobutylenebis [2- (5-phenyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,

(61) Silacyclobutylenebis [2- (2-thienyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,
(62) Silacyclobutylenebis [2- (5-methyl-2-thienyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride,
(63) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(64) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(65) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-methylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(66) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(67) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(68) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (3,5-dit-butylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(69) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (1-naphthyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(70) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (2-naphthyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(71) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-biphenylyl) -5,6-dimethyl-1-indenyl] zirconium dichloride,
(72) Silacyclobutylenebis [2- (2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(73) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride,
(74) Silacyclobutylenebis [2- (4,5-dimethyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(75) Silacyclobutylenebis [2- (5-t-butyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(76) Silacyclobutylenebis [2- (5-phenyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride,
(77) Silacyclobutylenebis [2- (2-thienyl) -4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride,
(78) Silacyclobutylenebis [2- (5-methyl-2-thienyl) -4-phenyl-1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(79) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(80) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,

(81) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(82) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium Zirconium,
(83) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium Zirconium,
(84) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (3,5-dit-butylphenyl) -1,5,6,7-tetrahydro-s-indasen-1- Il] Zirconium dichloride,
(85) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (1-naphthyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(86) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (2-naphthyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(87) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-biphenylyl) -1,5,6,7-tetrahydro-s-indacene-1-yl] zirconium dichloride,
(88) Silacyclobutylenebis [2- (2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacene-1-yl] zirconium Zirconium,
(89) Silacyclobutylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indasen-1 -Il] Zirconium dichloride,
(90) Silacyclobutylene [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] [2,5-dimethyl-4-phenyl-1-indenyl] zirconium dichloride,
(91) Silacyclobutylene [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] [2- (2-furyl) -4-phenyl-5-methyl-1- Indenyl] Zirconium dichloride,
(92) Silacyclobutylene [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] [2- (5-t-butyl-2-furyl) -4-phenyl- 5-Methyl-1-indenyl] zirconium dichloride,
(93) Silacyclobutylene [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] [2- (5-methyl-2-furyl) -4-phenyl-1- Indenyl] Zirconium dichloride,
(94) Silacyclobutylene [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] [2- (5-methyl-2-furyl) -4-phenyl-5, 6-Dimethyl-1-indenyl] zirconium dichloride,
(95) Silacyclobutylene [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] [2- (5-methyl-2-furyl) -4-phenyl-1, 5,6,7-Tetrahydro-s-Indacene-1-yl] Zirconium dichloride,
(96) Silacyclopentylenebis [2- (2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(97) Silacyclopentylenebis [2- (5-methyl-2-furyl) -4-phenyl-5-methyl-1-indenyl] zirconium dichloride,
(98) Silacyclopentylenebis [2- (2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride,
(99) Silacyclopentylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride, etc. may be mentioned. ..

Examples of the compound represented by the general formula (3) include, for example.
(1) (Tetramethylcyclopentadienyl) Titanium (bist-butylamide) dichloride,
(2) (Tetramethylcyclopentadienyl) Titanium (bisisopropylamide) dichloride,
(3) (Tetramethylcyclopentadienyl) Titanium (biscyclododecylamide) dichloride,
(4) (Tetramethylcyclopentadienyl) Titanium {bis (trimethylsilyl) amide)} dichloride,
(5) (2-Methyl-4-phenyl-4H-azurenyl) titanium {bis (trimethylsilyl) amide} dichloride,
(6) (2-Methylindenyl) titanium (bist-butylamide) dichloride,
(7) (Fluorenyl) Titanium (Bist-Buyramide) Dichloride,
(8) (3,6-diisopropylfluorenyl) titanium (bist-butylamide) dichloride,
(9) (Tetramethylcyclopentadienyl) titanium (phenoxide) dichloride, (10) (tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride,
And so on.

Examples of the compound represented by the general formula (4) include, for example.
(1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamide) titanium dichloride,
(2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(3) Dimethylsilanediyl (2-methylindenyl) (t-butylamide) titanium dichloride,
(4) Dimethylsilanediyl (fluorenyl) (t-butylamide) titanium dichloride, etc. may be mentioned.

The dichloride of these exemplary compounds is similarly exemplified by compounds in which dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide and the like are replaced. Further, a compound in which zirconium in the exemplified compound is replaced with hafnium or titanium and titanium is replaced with hafnium or zirconium is also exemplified.

As the transition metal compound used in the present invention, the compound represented by the general formula (2) is preferable.
The metallocene compound may be used alone or in combination of two or more.

When two or more kinds are used in combination, two or more kinds can be selected from the compound group included in any one of the above general formulas (1) to (4). Further, one or more selected from the compound group included in one general formula and one or two or more selected from the compound group included in the other general formula can be selected.

<Ingredient [C]>
As the component [C], an organoaluminum compound represented by the general formula (AlR _n X _3-n ) _m is used. In the formula, R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, an alkoxy group or an amino group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2. The organoaluminum compound can be used alone or in combination of two or more.

Specific examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormalaloctylaluminum, trinormalaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like.
Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferable.
More preferably, it is trialkylaluminum in which R has 1 to 8 carbon atoms.

3-2. Preparation of Catalyst for Olefin Polymerization and Prepolymerization The method for producing a catalyst for olefin polymerization of the present invention is characterized by mixing the following components [A], component [B], and component [C].
In the catalyst for olefin polymerization of the present invention, the component [B] is brought into contact with the component [A] and the component [C] to form a catalyst.
The contact method is not particularly limited, but the contacts can be made in the following order.
Further, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with an olefin or the time of polymerization of an olefin. A solvent may be used for sufficient contact in these contacts.
1) Contact component [B] and component [A] 2) Add component [C] after contacting component [B] and component [A] 3) Contact component [B] and component [C] 4) The component [A] and the component [C] are brought into contact with each other and then the component [B] is added. In addition, the three components may be brought into contact with each other at the same time.

The preferred contact method is to bring the component [A] of the above 4) into contact with the component [C], remove the unreacted component [C] by washing or the like, and then add the minimum necessary component [C] again. This is a method of contacting with [A] and then with component [B].

The molar ratio of Al of component [C] to the transition metal of component [B] is in the range of 0.1 to 1,000, preferably 1 to 100, and more preferably 4 to 50.

The contact temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 80 ° C, and particularly preferably 20 ° C to 60 ° C.

As the solvent, an organic solvent is preferable. Saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene, and the olefins described below are more preferred. These may be used alone or in combination of two or more.
The concentration of the component [B] in the solvent is also not limited, but is preferably 3 mmol / L to 50 mmol / L, more preferably 4 mmol / L to 40 mmol / L, and further preferably 6 mmol / L to 30 mmol / L.
The amount of the component [B] used is more preferably in the range of 0.001 mmol to 10 mmol, preferably 0.001 mmol to 1 mmol per 1 g of the component [A].

The catalyst for olefin polymerization of the present invention may be subjected to a prepolymerization treatment consisting of contacting olefins and polymerizing in a small amount.
The olefin used is not particularly limited. Ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc. can be used, especially ethylene. , Or propylene is preferably used.
Any method can be used as the method for supplying the olefin. For example, a supply method for maintaining the olefin in the reaction vessel at a constant speed or a constant pressure state, a combination thereof, and a method of making a stepwise change can be mentioned.

The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours.
The amount of prepolymerized polymer is preferably 0.01 to 100, more preferably 0.1 to 50, with respect to one part of the component [A].
The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 70 ° C, particularly preferably 20 ° C to 60 ° C, and even more preferably 30 ° C to 50 ° C.
At the time of prepolymerization, it can be carried out in a liquid such as an organic solvent, and this is preferable.
The concentration of the solid catalyst at the time of prepolymerization is not particularly limited, but is preferably 10 g / L to 300 g / L, more preferably 20 g / L to 200 g / L, and particularly preferably 25 g / L to 150 g / L.

The catalyst may be dried after contact with each component.
There are no particular restrictions on the drying method. Examples thereof include vacuum drying, heat drying, and drying by circulating a dry gas. These methods may be used alone or in combination of two or more.
The catalyst may be agitated, vibrated, flowed or allowed to stand in the drying step.

Further, it is also possible to allow a polymer such as polyethylene, polypropylene or polystyrene or an inorganic oxide solid such as silica or titania to coexist at the time of or after the contact of each of the above components. Further, alkoxysilanes, aminosilanes, ethers, phthalates, carboxylic acid esters and the like known as donors in various surfactants, antistatic agents and olefin polymerization catalysts can also be added.

4. Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention is characterized in that olefin polymerization is carried out using the catalyst for olefin polymerization of the present invention.
The method for producing an olefin (co) polymer is to homopolymerize or copolymerize an α-olefin having 2 to 20 carbon atoms in the presence of the olefin polymerization catalyst of the present invention. That is, in this production method, one kind of α-olefin is polymerized, or two or more kinds of α-olefins are copolymerized. In addition, in this specification, a (co) polymer means at least one of a homopolymer and a copolymer.

In the case of copolymerization, the amount ratio of each monomer in the reaction system does not have to be constant over time, and each monomer can be supplied at a constant mixing ratio. It is also possible to change the mixing ratio of the supplied monomers over time. Further, any of the monomers may be added in portions in consideration of the copolymerization reaction ratio.

The α-olefin that can be polymerized is preferably 2 to 20 carbon atoms, and specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-. Examples thereof include 1,7-octadiene, cyclopentene, norbornene, etilidennorbornene and the like. It is preferably an α-olefin having 2 to 8 carbon atoms, and more preferably ethylene or propylene.

In the case of copolymerization, as the type of comonomer used, one type or two or more types of α-olefins other than those listed as the main component can be selected and used from those listed as the α-olefins. The main component of the preferred comonomer is propylene.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer are in efficient contact with each other. Specifically, the slurry method using an inert solvent, the method using a monomer such as propylene as a solvent without substantially using the inert solvent, the solution polymerization method, or the method using substantially no liquid solvent, each monomer is used. A gas phase method that keeps the gas in a gaseous state can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.

In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the polymerization solvent.
The polymerization temperature is usually 0 ° C to 150 ° C.

Further, hydrogen can be used as the molecular weight adjusting agent. Further, in order to adjust the reaction amount, a compound having an action of inactivating a catalyst such as oxygen or alcohol may be supplied. Known additives such as oxygen, alcohol, alkoxysilane, and surfactant may be added for the purpose of improving operability and the like.
The appropriate polymerization pressure is 0 kg / cm ² to 2000 kg / cm ² G (≈0 MPaG to 196.14 MPaG), preferably 0 kg / cm ² to 60 kg / cm ² G (≈0 MPaG to 5.88 MPaG).

The olefin (co) polymer obtained by the method for producing an olefin (co) polymer is not particularly limited. For example, ethylene homopolymers, propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, propylene / ethylene-α-olefin copolymers and the like are preferably used.

The olefin polymer obtained by the production method of the present invention has few fish eyes that deteriorate the appearance of the product.
The smaller the number of fish eyes, the better the olefin polymer obtained by the production method of the present invention. The number of fish eyes may be 0/900 mm ² to 100/900 mm ² , preferably 0/900 mm ² to 70/900 mm ² .
Mixtures of incompatible polymers are so-called impact copolymers, block copolymers. This is obtained by multistage polymerization or kneading of polymers. Fisheye in this mixture may be caused by poor dispersion caused by the compatibility (composition), mixing ratio, and molecular weight difference (viscosity difference) of the polymer. Generally, when the compatibility is low, or when the difference in molecular weight and viscosity of each component is large, the fish eye tends to increase.
Since the measurement method of each of the above characteristics will be described later, the description here is omitted.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not restricted by these Examples as long as it does not deviate from the gist thereof. The measurement method in this embodiment is as follows.

(Various physical property measurement methods)
[Composition analysis of ion-exchangeable layered silicate and ion-exchangeable layered silicate particles]
A calibration curve was prepared according to JIS R2212, and the compositions of the ion-exchangeable layered silicate and the ion-exchangeable layered silicate particles were quantified by fluorescent X-ray measurement.
As the apparatus, ZSX Primus IV manufactured by Rigaku Co., Ltd. was used.
After baking the sample at 1050 ° C. for 1 hour, 0.4 g is separated and mixed with 4 g of a flux (Li ₂ B ₄ O ₇ ) and 15 μL of a 50% LiBr aqueous solution (release agent) to prepare a glass bead. Prepared in.

[Calculation method of Al elution rate (ΔAl amount)]
Al elution rate (%) = {[(aluminum / silicon (molar ratio) before chemical treatment)-(aluminum / silicon (molar ratio) after chemical treatment)] ÷ (aluminum / silicon (molar ratio) before chemical treatment ))} × 100.

[Particle size of ion-exchangeable layered silicate (raw material)]
The equivalent circle diameter measured by the following method was defined as the particle diameter.
The procedure was performed according to the method described in SCANNNING VOL.26, 131-134 (2004). The surface of highly decomposed graphite was treated with polydiallyldimethylammonium chloride to prepare a substrate. An aqueous slurry of ion-exchangeable layered silicate, adjusted to 0.001 wt% and irradiated with ultrasonic waves for 30 minutes to be sufficiently dispersed, was applied to this substrate. Then, the sample was prepared by adsorbing water with a filter paper and blowing air. A secondary electron image of the ion-exchangeable silicate on this substrate was taken by SEM. After shooting, it was binarized by image processing to determine the area of each particle. After photographing until the number of particles became 10,000 or more, the diameter at which the area integration value with respect to the equivalent circle diameter was 50% was defined as the particle diameter.
The SEM imaging conditions are as follows.
Equipment used SU8020 field emission scanning electron microscope manufactured by Hitachi High-Technologies Corporation Measurement conditions DataSize: 1280x960
Acceleration voltage: 800 Volt
workingdistance: 3mm
Device magnification: 10K

[Pore distribution measurement and specific surface area measurement]
The adsorption and desorption isotherms of the ion-exchangeable layered silicate particles were measured by the nitrogen adsorption method.
The BET multipoint method analysis (Rouquarol conversion) was carried out using the obtained adsorption isotherm to determine the specific surface area of the ion-exchangeable layered silicate particles.
In addition, the pore distribution was calculated by BJH (Barrett, Joiner, Hallender, J. Am. Chem. Soc. 1951, P373) method analysis using the desorption isotherm. The c value was not constant, and the calculation was performed for each measured value. The thickness t (Å) of the adsorption layer was determined by the formula of de Boer.
t (Å) = [13.99 / (log (P ₀ / P) + 0.034)] ^1/2
The specific measurement conditions are as follows.
Device: Antonio-Paar gas adsorption amount measuring device Autosorb-iQ3
Measurement method: Nitrogen gas adsorption method Pretreatment conditions: Heat the sample under vacuum (1.3 Pa or less) at 200 ° C under reduced pressure for 2 hours Sample amount: Approximately 0.2 g
Gas liquefaction temperature: 77K

[Measurement of average particle size]
For the average particle size, a laser diffraction / scattering type particle size distribution measuring device LA-960 manufactured by Horiba Seisakusho was used, and the dispersion solvent was ethanol, the refractive index real number term 1.490, the imaginary number term 0.000, and the dispersion solvent refractive index real number term. It was measured after performing ultrasonic dispersion under the condition of 1.360. The average particle size refers to the volume-based median diameter.

[X-ray diffraction (XRD)]
X-ray diffraction measurement was carried out in the atmosphere under the following conditions.・ Equipment: Rigaku X-ray Diffractometer Smartlab ・ X-ray source: Cu-Kα ray (using Kβ absorber), tube voltage 40 kV, tube current 30 mA ・ Optical system: centralized method ・ divergence slit 2/3 degree, scattering slit 2/3 degree, light receiving slit 0.300 mm ・ Scan mode: 2θ / θ scan ・ 2θ scan range: 1.0000 degrees to 70.000 degrees ・ Angle step width: 0.0200 degrees ・ Scan speed: 4.00 degrees / Minutes / Detector: Scattering counter / Sample holder: 0.2 mm deep glass holder

[Crush strength]
Using the crushing tester "MCT-210" manufactured by Shimadzu Corporation, referring to JIS R 1639-5: 2007, the temperature is 23 ° C, the humidity is 35%, and the load speed is 1.9 mN / sec. Twenty particles selected so as not to cause a bias were measured, and the crushing strength of the particles was calculated according to the following formula.
S = 2.48 ・ P / (π ・ d ² )
(S: crush strength (MPa), P: test pressure at the time of fracture (N), d: diameter = average value of major axis diameter and minor axis diameter of particles (μm))
In addition, d was measured using an optical microscope.
The average value of the crushing strength of the obtained 20 particles was taken as the average crushing strength.
Further, for the obtained 20 particles, the following formula (the volume was calculated as a true sphere having the diameter d. The unit is μm ³ ) was calculated by the following formula (minimum square method). The coefficient 1 / m of ₁ ) and S0 ・ V ₀₀₁ ^{/ m} were calculated.
S = (S ₀・ V ₀ ^{1 / m} ) ・ V ^{-1 / m}・ ・ ・ Equation (1)
(In the formula (1), S is the crushing strength (MPa) of the ion-exchangeable layered silicate particles, S ₀ is the crushing strength at the unit volume V ₀ , and V is the volume of the ion-exchangeable layered silicate particles (μm ³ ). ), M is the uniformity coefficient of Weibul)

[MFR (Melt Mass Flow Rate)]
Using a melt indexer manufactured by Takara Co., Ltd., the test conditions of JIS K7210 "Plastic-Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics": 230 ° C, 2.16 kg load compliant And measured.

[Measurement of fisheye number]
Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), tris (2,4-di-tert-butylphenyl) phosphite, and calcium stearate are added to 20 g of the polymer. 10 mg each was added, and kneading (200 ° C., 50 rpm, 2 min) was performed using an Xplore polymer (manufactured by DSM), and then pressed to a thickness of 0.2 mm (190 ° C., 10 MPa) to obtain a sheet.
The sheet was captured as a 1200 dpi, 8-bit-grayscale image with a Canon Canon 9000F Mark2, and the image was binarized. For this binarized image, the number of fish eyes in a 30 mm × 30 mm area (square range: 900 mm ² ) was measured at three points, and the average value of the three points was adopted as the number of fish eyes (unit: piece / 900 mm). ² ). Points of 3 pixels or less were regarded as noise and were excluded from the measurement.

[Analysis method of polymer containing ethylene / propylene copolymer]
It was determined by a method of combining the cross fractionation method and the FT-IR method described in Japanese Patent Application Laid-Open No. 2015-193605.

(Synthesis Example 1)
Silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -5,6-dimethyl-1-indenyl] The synthesis of zirconium dichloride is described in JP-A-2015-193605. It was synthesized in the same manner as in Example 7 of the publication.

[Example a1: Production of ion-exchangeable layered silicate particles]
(A1-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used. The particle size of the ion-exchangeable layered silicate was 0.287 μm.
30.0 g of lithium sulfate monohydrate and 500 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer type: M type rotary disc ・ Atomizer rotation speed: 28000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The slurry supply time was 202 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 255 g. The coarse material was removed by passing this through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 229 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite), the peak derived from the lithium sulfate monohydrate crystal was observed.

(A1-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 88 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 70 g of the ion-exchangeable layered silicate composite particles of (a1-1) described above was added. Then, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 500 mL of distilled water. The obtained slurry was suction-filtered to obtain 151.3 g of the remaining solid content.

(A1-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
The solid content obtained from the above (a1-2) and 234.7 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., and 105.1 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto. Then, stirring was continued for 90 minutes to react.
The slurry pH after 90 minutes was 5.8.
The reaction slurry was poured into 450 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 38.6 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a2: Production of ion-exchangeable layered silicate particles]
(A2-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used.
To a 5 L beaker, 50.0 g of lithium sulfate monohydrate and 500 g of distilled water were added and stirred to prepare a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 28000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 150 ℃
The slurry supply time was 195 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 304 g. The coarse material was removed by passing this through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 255 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite), the peak derived from the lithium sulfate monohydrate crystal was observed.

(A2-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 88 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 70 g of the above-mentioned ion-exchangeable layered silicate composite particles (a2-1) was added. Then, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed with 400 mL of distilled water.

(A2-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
123.7 g of the solid content obtained in (a2-2) above and 262.3 g of distilled water were added to a 1 L flask and stirred. The temperature of this slurry was raised to 40 ° C., and 9.7 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto. Then, stirring was continued for 90 minutes to react.
The slurry pH after 90 minutes was 5.81.
The reaction slurry was poured into 450 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 300 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 34.6 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a3: Production of ion-exchangeable layered silicate particles]
(A3-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used.
30.6 g of lithium sulfate monohydrate and 240 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,100 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 4657 g, and the supply time was 371 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 214 g. Among them, the granulated material obtained in the lower part of the main body was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 94.5 g of ion-exchangeable layered silicate composite particles.

(A3-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
225 g of distilled water was put into a 500 mL flask equipped with a stirring blade and a reflux device, and 57 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 45 g of the above-mentioned ion-exchangeable layered silicate composite particles (a3-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 500 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed twice with 500 mL of distilled water.

(A3-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
66.6 g of the solid content of (a3-2) and 181.4 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 4.7 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.57.
The reaction slurry was poured into 450 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 300 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 23.8 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a4: Production of ion-exchangeable layered silicate particles]
(A4-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used.
58.0 g of lithium sulfate monohydrate and 440 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 4857 g, and the supply time was 392 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 258 g. Among them, the granulated material obtained in the lower part of the main body was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 166.3 g of ion-exchangeable layered silicate composite particles.

(A4-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 88 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 70 g of the above-mentioned ion-exchangeable layered silicate composite particles (a4-2) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed with 400 mL of distilled water.

(A4-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
46.2 g of the solid content of (a4-2) and 236.0 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 10.1 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.63.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 33.0 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a5: Production of ion-exchangeable layered silicate particles]
(A5-1) Production of Ion-Exchangeable Layered Silicate Composite Particles Ion-exchangeable layered silicate composite particles were prepared in the same manner as in Example a4.
(A5-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 69 g of 96% sulfuric acid was added dropwise.
It was heated in an oil bath until the internal temperature reached 95 ° C. After adding 70 g of the ion-exchangeable layered silicate composite particles of (a5-1) at 95 ° C., the reaction was carried out for 480 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed with 400 mL of distilled water.

(A5-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
146.2 g of the solid content of (a5-2) and 229.2 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 8.9 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.48.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 31.6 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a6: Production of ion-exchangeable layered silicate particles]
(A6-1) Production of Ion-Exchangeable Layered Silicate Composite Particles A purified product of Mizusawa Industrial Chemicals' clay minerals from Nakajo, Niigata Prefecture, purified by elutriation and centrifugation as ion-exchangeable layered silicates. Water slurry (main component is smectite group montmorillonite having a 2: 1 type layer structure, solid content 4.0 wt%) was used. The particle size of the ion-exchangeable silicate was 0.314 μm.
47.0 g of lithium sulfate monohydrate and 360 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,000 g of the above water slurry (4.0 wt%) was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 4422 g, and the supply time of the slurry was 333 minutes. The granulated product obtained in the lower part of the main body weighed 164 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 113.1 g of ion-exchangeable layered silicate composite particles.

(A6-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 88 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 100 g of the above-mentioned ion-exchangeable layered silicate composite particles (a6-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.

(A6-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
110.7 g of the solid content of (a6-2) and 265.5 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 7.5 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.52.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 33.7 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a7: Production of ion-exchangeable layered silicate particles]
(A7-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, 3 wt% sodium carbonate is kneaded with a clay mineral manufactured by Mizusawa Industrial Chemicals Co., Ltd. from Nakajo, Niigata Prefecture, and then elutriated. , A water slurry of a purified product purified by centrifugation (main component is smectite group montmorillonite having a 2: 1 type layer structure, solid content 3.8 wt%) was used. The particle size of the ion-exchangeable silicate was 0.184 μm.
55.0 g of lithium sulfate monohydrate and 333 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,500 g of the above water slurry (3.8 wt%) was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 5769 g, and the supply time of the slurry was 317 minutes. The granulated product obtained in the lower part of the main body weighed 176 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 122.6 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite), the peak derived from the lithium sulfate monohydrate crystal was observed.

(A7-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 88 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 100 g of the above-mentioned ion-exchangeable layered silicate composite particles (a7-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.

(A7-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
123.4 g of the solid content (a7-2) and 252.8 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 6.8 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
After 90 minutes, the slurry pH was 5.49.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The portion passed through the sieve was dried at 200 ° C. under reduced pressure for 2 hours to obtain 30.9 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a8: Production of ion-exchangeable layered silicate particles]
(A8-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, 3 wt% sodium carbonate is kneaded with a clay mineral manufactured by Mizusawa Industrial Chemicals Co., Ltd. from Nakajo, Niigata Prefecture, and then elutriated. , A water slurry of a purified product purified by centrifugation (main component is smectite group montmorillonite having a 2: 1 type layer structure, solid content 3.8 wt%) was used.
75.0 g of lithium sulfate monohydrate and 333 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,500 g of the above water slurry (3.8 wt%) was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 5703 g, and the supply time of the slurry was 320 minutes. The amount of granulated product obtained in the lower part of the main body was 200 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 115.5 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite), the peak derived from the lithium sulfate monohydrate crystal was observed.

(A8-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 93 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 70 g of the above-mentioned ion-exchangeable layered silicate composite particles (a8-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.

(A8-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
113.2 g of the solid content (a8-2) and 263.0 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 6.6 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.51.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 23.2 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a9: Production of ion-exchangeable layered silicate particles]
(A9-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, 3 wt% sodium carbonate is kneaded with a clay mineral manufactured by Mizusawa Industrial Chemicals Co., Ltd. from Nakajo, Niigata Prefecture, and then elutriated. , A water slurry of a purified product purified by centrifugation (main component is smectite group montmorillonite having a 2: 1 type layer structure, solid content 3.8 wt%) was used.
37.0 g of lithium sulfate monohydrate and 225 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,500 g of the above water slurry (3.8 wt%) was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 5422 g, and the supply time of the slurry was 350 minutes. The amount of granulated product obtained in the lower part of the main body was 163 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 110.2 g of ion-exchangeable layered silicate composite particles.

(A9-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 80 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 65 g of the above-mentioned ion-exchangeable layered silicate composite particles (a9-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.

(A9-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
97.5 g of the solid content (a9-2) and 279.3 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 8.1 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.44.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 28.9 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a10: Production of ion-exchangeable layered silicate particles]
(A10-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, 3 wt% sodium carbonate is kneaded with a clay mineral manufactured by Mizusawa Industrial Chemicals Co., Ltd. from Nakajo, Niigata Prefecture, and then elutriated. , A water slurry of a purified product purified by centrifugation (main component is smectite group montmorillonite having a 2: 1 type layer structure, solid content 3.8 wt%) was used.
25.5 g of lithium sulfate monohydrate and 155 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,500 g of the above water slurry (3.8 wt%) was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The amount of slurry supplied was 5239 g, and the supply time of the slurry was 340 minutes. The amount of granulated product obtained in the lower part of the main body was 153 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 81.8 g of ion-exchangeable layered silicate composite particles.

(A10-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 75 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 60 g of the above-mentioned ion-exchangeable layered silicate composite particles (a10-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.

(A10-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
136.6 g of the solid content (a10-2) and 240.8 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 7.1 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.68.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 29.5 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a11: Production of ion-exchangeable layered silicate particles]
(A11-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (4.5 wt%) was used.
94.0 g of lithium sulfate and 800 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 1,800 g of a water slurry (4.5 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 10 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 8000 rpm
・ Cyclone differential pressure: 1.10 kPa
・ Dry air inlet temperature: 110 ℃
The slurry supply time was 307 minutes. The amount of granulated product obtained in the lower part of the main body was 214 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 93.7 g of ion-exchangeable layered silicate composite particles.

(A11-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
200 g of distilled water was put into a 500 mL flask equipped with a stirring blade and a reflux device, and 70 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 70 g of the above-mentioned ion-exchangeable layered silicate composite particles (a11-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.

(A11-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2)
138.3 g of the solid content of (a11-2) and 146.7 g of distilled water were added to a 500 mL flask and stirred. The temperature of this slurry was raised to 40 ° C., 5.8 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.91.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 450 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 23.1 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a12: Production of ion-exchangeable layered silicate particles]
(A12-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used.
30.0 g of lithium sulfate monohydrate and 500 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 28000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The slurry supply time was 202 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 255 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 229 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite), the peak derived from the lithium sulfate monohydrate crystal was observed.

(A12-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
350 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 88 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 70 g of the above-mentioned ion-exchangeable layered silicate composite particles (a12-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 500 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 500 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 39.0 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a13: Production of ion-exchangeable layered silicate particles]
(A13-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used.
77.0 g of magnesium sulfate heptahydrate and 420 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 28000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The slurry supply time was 221 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 298 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 250.3 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite), the peak derived from magnesium sulfate hexahydrate crystals was observed.

(A13-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
500 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 126 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 100 g of the above-mentioned ion-exchangeable layered silicate composite particles (a13-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered to remove 109 g of the remaining solid content, which is half of the solid content, and the remaining solid content was washed 3 times with 400 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 24.4 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

[Example a14: Production of ion-exchangeable layered silicate particles]
(A14-1) Production of Ion-Exchangeable Layered Silicate Composite Particles As an ion-exchangeable layered silicate, water of "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure). A slurry (5.0 wt%) was used.
38.0 g of sodium sulfate and 460 g of distilled water were added to a 5 L beaker and stirred to prepare a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added with stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high speed stirrer. The above operation was performed twice. Using the obtained two batches of slurry, a spray-drying granulation apparatus (Okawara Kakoki Co., Ltd. "L-8") was used to perform spray-drying granulation under the following conditions.
・ Atomizer format: M type rotary disc
・ Atomizer rotation speed: 28000 rpm
・ Cyclone differential pressure: 1.05 kPa
・ Dry air inlet temperature: 110 ℃
The slurry supply time was 192 minutes. The amount of granulated matter obtained in the lower part of the cyclone and the lower part of the main body was 292 g. The granulated product was passed through a sieve having an opening of 75 μm to remove the coarse material. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 247.1 g of ion-exchangeable layered silicate composite particles.
When the analysis was performed by XRD, a peak derived from sodium sulfate crystals was observed in addition to the peak derived from the ion-exchangeable layered silicate (montmorillonite).

(A14-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1)
500 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 126 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95, 100 g of the above-mentioned ion-exchangeable layered silicate composite particles (a14-1) was added. After that, the reaction was carried out for 240 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The obtained slurry was suction-filtered to remove 102.9 g of the remaining solid content, which is half of the solid content, and the remaining solid content was washed 3 times with 400 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 24.2 g of ion-exchangeable layered silicate particles. Table 1 shows the results of various analyzes.

ｍ．ｒ．はモル比を表す。

m. r. Represents the molar ratio.

[Comparative Example a1: Production of Comparative Ion Exchangeable Layered Silicate Particles]
(A1-i)
As the ion-exchangeable layered silicate, "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component was smectite group montmorillonite having a 2: 1 type layer structure. The granulated product (median diameter 33.0 μm) was ion-exchanged. Prepared as layered silicate particles.
(A1-ii) Chemical treatment of ion-exchangeable layered silicate particles (1)
585 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 75 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 90 g of the above-mentioned ion-exchangeable layered silicate particles were added. After that, the reaction was carried out for 505 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 900 mL of distilled water. The obtained slurry was suction filtered and the remaining solid content was washed with 450 mL of distilled water.
(A1-iii) Chemical treatment of ion-exchangeable layered silicate particles (2)
268.6 g of the solid content of (a1-ii) and 357.6 g of distilled water were added to a 1 L flask and stirred. The temperature of this slurry was raised to 40 ° C., 22.1 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.50.
The reaction slurry was poured into 900 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 900 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 59.9 g of ion-exchangeable layered silicate particles. Table 2 shows the results of various analyzes.

[Comparative Example a2: Production of Comparative Ion Exchangeable Layered Silicate Particles]
(A2-i)
As an ion-exchangeable layered silicate, a water slurry of a refined product of Mizusawa Industrial Chemicals' clay mineral from Nakajo, Niigata Prefecture, purified by elutriation and centrifugation (main component is a 2: 1 type layer structure). Smectite tribe montmorillonite) was used. The granulated product (median diameter 33.3 μm) was prepared as ion-exchangeable layered silicate particles.
(A2-ii) Chemical treatment of ion-exchangeable layered silicate particles (1)
585 g of distilled water was put into a 1 L flask equipped with a stirring blade and a reflux device, and 76 g of 96% sulfuric acid was added dropwise. This aqueous sulfuric acid solution was heated in an oil bath until the internal temperature reached 95 ° C. At 95 ° C., 90 g of the above-mentioned ion-exchangeable layered silicate particles were added. After that, the reaction was carried out for 360 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 900 mL of distilled water. The obtained slurry was suction-filtered, and the remaining solid content was washed 3 times with 450 mL of distilled water.
(A2-iii) Chemical treatment of ion-exchangeable layered silicate particles (2)
270.9 g of the solid content of (a2-ii) and 355.1 g of distilled water were added to a 1 L flask and stirred. The temperature of this slurry was raised to 40 ° C., 20.6 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto, and then stirring was continued for 90 minutes for reaction.
The slurry pH after 90 minutes was 5.51.
The reaction slurry was poured into 800 mL of distilled water and then suction filtered. The recovered solid was washed 3 times with 900 mL of distilled water. After washing, the solid content was dried at 110 ° C. overnight, and coarse substances were removed through a sieve having an opening of 75 μm. The sieved portion was dried at 200 ° C. under reduced pressure for 2 hours to obtain 68.8 g of ion-exchangeable layered silicate particles. Table 2 shows the results of various analyzes.

[Comparative Example a3: Production of Comparative Ion Exchangeable Layered Silicate Particles]
Comparative ion-exchangeable layered silicate particles were produced in the same manner as in Example 3 of JP-A-2019-172955. Table 2 shows the results of various analyzes.

[Comparative Example a4: Production of Comparative Ion Exchangeable Layered Silicate Particles]
As the ion-exchangeable layered silicate, "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure) was used, and Example 5 of Japanese Patent Application Laid-Open No. 2015-108138 was used. Chemical treatment was carried out according to the above to obtain ion-exchangeable layered silicate particles. Table 2 shows the results of various analyzes.

[Comparative Example a5: Production of Comparative Ion Exchangeable Layered Silicate Particles]
As the ion-exchangeable layered silicate, "Benclay KK" manufactured by Mizusawa Industrial Chemicals Co., Ltd. (main component is smectite group montmorillonite having a 2: 1 type layer structure) was used, and Example 4 of Japanese Patent Application Laid-Open No. 2015-108138 was used. Chemical treatment was carried out according to the above to obtain ion-exchangeable layered silicate particles. Table 2 shows the results of various analyzes.

[Comparative Example a6: Production of Comparative Ion Exchangeable Layered Silicate Particles]
JP-A-2002-088114 Comparative ion-exchangeable layered silicate particles were produced in the same manner as in Comparative Example 3. Table 2 shows the results of various analyzes.

表中、ｍ．ｒ．はモル比を表し、「－」は未測定を表す。

In the table, m. r. Represents the molar ratio, and "-" represents unmeasured.

[Example b1: Production of catalyst for olefin polymerization]
10.0 g of ion-exchangeable layered silicate particles obtained in Example a1 and 66 mL of heptane were added to a flask having an internal volume of 1000 mL and stirred. 34 mL (24.5 mmol-Al) of a heptane solution of triisobutylaluminum (TiBA) was added thereto, and the mixture was stirred at room temperature for 1 hour.
Then, the obtained slurry was washed with heptane to a residual liquid ratio of 1/100, and finally the slurry amount was adjusted to 50 mL. 31 mL (12.2 mmol) of a heptane solution of trinormal octyl aluminum was added thereto to prepare an ion-exchangeable layered silicate particle slurry.
In another flask (volume 200 mL), (r) -silacyclobutylenebis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -5,6-dimethyl-1- Indenyl] A solution was prepared by mixing 287 μmol of zirconium dichloride and 30 mL of toluene. The mixed solution was added to the ion-exchangeable layered silicate particle slurry and stirred at 40 ° C. for 60 minutes.
After the above reaction, heptane was added to adjust the total volume to 300 mL, and the slurry was transferred to a stirring autoclave having an internal volume of 1 L, which had been sufficiently substituted with nitrogen.
The temperature of the slurry was set to 40 ° C., and propylene was supplied at a rate of 10 g / hour for 2 hours.
After stopping the supply of propylene, the reaction was carried out until the pressure reached 0.025 MPaG.
Then, the residual monomer was purged and the prepolymerization catalyst slurry was recovered from the autoclave.
The recovered prepolymerization catalyst slurry was allowed to stand, and the supernatant liquid was withdrawn. 8.5 mL (6 mmol) of a heptane solution of triisobutylaluminum was added at room temperature. Then, the prepolymerization catalyst slurry was dried under reduced pressure to obtain a catalyst for olefin polymerization.
The prepolymerization ratio (catalyst yield ÷ (ion-exchangeable layered silicate particles + metallocene complex amount) -1) was 2.43 g / g-catalyst.

[Example b2: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a2 were used.
The prepolymerization ratio was 2.37 g / g-catalyst.

[Example b3: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a3 were used.
The prepolymerization ratio was 2.31 g / g-catalyst.

[Example b4: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a4 were used.
The prepolymerization ratio was 2.31 g / g-catalyst.

[Example b5: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a5 were used.
The prepolymerization ratio was 2.37 g / g-catalyst.

[Example b6: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a6 were used.
The prepolymerization ratio was 2.39 g / g-catalyst.

[Example b7: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a7 were used.
The prepolymerization ratio was 2.40 g / g-catalyst.

[Example b8: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a8 were used.
The prepolymerization ratio was 2.40 g / g-catalyst.

[Example b9: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a9 were used.
The prepolymerization ratio was 2.33 g / g-catalyst.

[Example b10: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a10 were used.
The prepolymerization ratio was 2.36 g / g-catalyst.

[Example b11: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Example a11 were used.
The prepolymerization ratio was 2.31 g / g-catalyst.

[Comparative Example b1: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Comparative Example b1 were used.
The prepolymerization ratio was 2.36 g / g-catalyst.

[Comparative Example b2: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Comparative Example b2 were used. However, since the rate of pressure decrease after the propylene supply was stopped was small, the reaction was stopped at a pressure of 0.075 MPaG for 150 minutes after the propylene supply was stopped.
The prepolymerization ratio was 2.06 g / g-catalyst.

[Comparative Example b3: Production of catalyst for olefin polymerization]
A catalyst for olefin polymerization was produced in the same manner as in Example b1 except that the ion-exchangeable layered silicate particles obtained in Comparative Example b3 were used.
The prepolymerization ratio was 2.36 g / g-catalyst.

[Example P1: Propylene homopolymerization]
The inside of the stirring autoclave having an internal volume of 3 L was sufficiently replaced with propylene. Then, 5.6 mL (4.04 mmol) of a heptane solution of triisobutylaluminum (TiBA) was added. Next, 352 mL of hydrogen and 750 mL of liquid propylene were introduced, and the temperature was raised to 65 ° C.
The catalyst for olefin polymerization obtained in Example b1 was slurried into heptane. Using this slurry as a solid catalyst (the sum of the amount of ion-exchangeable layered silicate particles and the amount of metallocene complex) 11.1 mg was press-fitted to initiate polymerization.
After polymerization at 65 ° C. for 1 hour, 5 mL of ethanol was added to stop the polymerization reaction.
After purging the remaining propylene, the polymer was recovered and dried at 90 ° C. for 1 hour.
The results are shown in Table 3.

[Examples P2-P26: propylene homopolymerization]
Polymerization was carried out in the same manner as in Example P1 except that the type of catalyst for olefin polymerization, the amount of catalyst and the amount of hydrogenation were set as the conditions shown in Table 3. The results are shown in Table 3.

[Comparative Examples P1 to P9: Propylene Homopolymerization]
Polymerization was carried out in the same manner as in Example P1 except that the type of catalyst for olefin polymerization, the amount of catalyst and the amount of hydrogenation were set as the conditions shown in Table 3. The results are shown in Table 3.

[Example P27: 1st stage-propylene homopolymerization, 2nd stage-ethylene-propylene copolymerization in 2 stages]
The inside of the stirring autoclave having an internal volume of 3 L was sufficiently replaced with propylene. Then, 5.6 mL (4.04 mmol) of a heptane solution of triisobutylaluminum (TiBA) was added. Next, 528 mL of hydrogen and 750 mL of liquid propylene were introduced, and the temperature was raised to 65 ° C.
The catalyst for olefin polymerization obtained in Example b3 was slurried into heptane. Using this slurry as a solid catalyst (the sum of the amount of ion-exchangeable layered silicate particles and the amount of metallocene complex), 12.7 mg was press-fitted to initiate polymerization.
After polymerization at 65 ° C. for 1 hour, the unreacted propylene remaining in the autoclave was purged. A mixed gas of ethylene and propylene was supplied to this so as to have a molar ratio of 1: 1 in the gas composition in the autoclave, and polymerized at 80 ° C. and 1.9 MPaG for 0.52 hours. The reaction was stopped by press-fitting 5 mL of ethanol, and the residual monomer was purged. The obtained polymer was dried at 90 ° C. for 1 hour. The results are shown in Table 4.

[Examples P28 to P41: 1st stage-propylene homopolymerization, 2nd stage-ethylene-propylene copolymerization in 2 stages]
Polymerization was carried out in the same manner as in Example P27, except that the type of catalyst for olefin polymerization, the amount of catalyst, the amount of hydrogen addition and the copolymerization time of ethylene and propylene were set as the conditions shown in Table 4. The results are shown in Table 4.

[Comparative Examples P10 to P16: 1st stage-propylene homopolymerization, 2nd stage-ethylene-propylene copolymerization in 2 stages]
Polymerization was carried out in the same manner as in Example P27, except that the type of catalyst for olefin polymerization, the amount of catalyst, the amount of hydrogen addition and the copolymerization time of ethylene and propylene were set as the conditions shown in Table 4. The results are shown in Table 4.

[Comparison between Examples and Comparative Examples]
FIG. 1 shows the ratio of the total pore volume having a diameter of 2 nm to 10 nm to the total mesopore volume for the ion-exchangeable layered silicate particles described in Examples a1 to a14 and Comparative Examples a1 to a6, in terms of the BET specific surface area m. It is a figure plotted against ² / g. From FIG. 1, the ion-exchangeable layered silicate particles of the present invention can increase the proportion of large mesopores (more than 10 nm and 50 nm or less) while maintaining the specific surface area, and the pores are different from those in the past. It can be seen that the relationship between volume and specific surface area can be realized.
FIG. 2 is a diagram plotting the polymerization activity of the results of propylene homopolymerization using the olefin polymerization catalysts described in Examples b1 to b11 and Comparative Examples b1 to b3 with respect to the MFR of the obtained polymer. From FIG. 2, it can be seen that the catalyst using the ion-exchangeable layered silicate particles of the present invention exhibits higher catalytic activity than the catalyst of the comparative example in terms of MFR.
FIG. 3 shows the number of fish eyes contained in the sheet for the results of the two-stage polymerization of propylene-ethylene by the olefin polymerization catalysts described in Examples b3, b4, b6 to b8, b11 and Comparative Examples b1 to b3. It is a figure plotted with respect to the molecular weight ratio of the obtained polymer (the value which divided the molecular weight of the polymer of the 2nd stage by the molecular weight of the polymer of the 1st stage). From FIG. 3, it can be seen that the catalyst using the ion-exchangeable layered silicate particles of the present invention has a smaller number of fish eyes than the catalyst of the comparative example in terms of molecular weight ratio.
FIG. 4 is a diagram plotting the results of crushing strength measurement of the ion-exchangeable layered silicate particles according to Examples a1 and a13 and Comparative Examples a1 and a3. Table 5 shows the results of crushing strength measurement of ion-exchangeable layered silicate particles. From FIG. 4, it can be seen that the ion-exchangeable layered silicate particles of the present invention are particle aggregates having a smaller variation in crushing strength and higher uniformity than the ion-exchangeable layered silicate particles of the comparative example even at the same volume. I understand.
Table 6 shows the average crushing strength of the ion-exchangeable layered silicate particles described in Examples a1 and a13 and Comparative Examples a1 and a3, S0 ・ V _{0 1} ^{/ m} and 1 / m, respectively. According to Table 6, the ion-exchangeable layered silicate particles of the present invention have a small 1 / m of 0.000. This indicates that the particles are more uniform. Further, the ion-exchangeable layered silicate particles of the present invention have a small dependence on the size (particle size) of the crushing strength. This shows stable properties as a catalyst carrier. Furthermore, it has been shown that the ion-exchangeable layered silicate particles of the present invention can be used in a wide range of sizes (particle diameters).

According to the present invention, an ion-exchangeable layered silicate particle having a novel pore structure that improves catalytic activity and quality of a polymer, and an olefin polymerization catalyst component containing the ion-exchangeable layered silicate particles, olefin. It is possible to provide a polymerization catalyst, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer using the same, which is highly industrially usable.

Claims (6)

Ion-exchangeable layered silicate particles having the following properties (i) and (ii).
Property (i): In the pore distribution curve calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption and desorption method, the total pore volume with a diameter of 2 nm to 10 nm is 40% of the total mesopore volume. Above, it is 93% or less.
Characteristics (ii): The specific surface area is 300 m ² / g or more and 700 m ² / g or less. The ion-exchangeable layered silicate particles according to claim 1, further having the following characteristics (iii).
Characteristics (iii): The average particle size is 2 μm or more and 500 μm or less. A catalyst component for olefin polymerization, which comprises the ion-exchangeable layered silicate particles according to claim 1 or 2. A catalyst for olefin polymerization, which comprises the following component [A], component [B], and component [C].
Component [A]: Ion-exchangeable layered silicate particle component according to claim 1 or 2. Component [B]: Transition metal compound component [C]: Organoaluminum compound A method for producing a catalyst for olefin polymerization, which comprises mixing the following components [A], component [B], and component [C].
Component [A]: Ion-exchangeable layered silicate particle component according to claim 1 or 2. Component [B]: Transition metal compound component [C]: Organoaluminum compound A method for producing an olefin polymer, which comprises performing olefin polymerization using the catalyst for olefin polymerization according to claim 4.

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