Ion-exchangeable layered silicate particles, catalyst components for olefin polymerization, catalyst for olefin polymerization, method for producing the catalyst for olefin polymerization, and method for producing an olefin polymer using the same.

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

[Technical Field]

[0001] The present invention relates to ion-exchange layered silicate particles, catalyst components for olefin polymerization, catalysts for olefin polymerization, methods for producing olefin polymerization catalysts, and methods for producing olefin polymers using the same. [Background technology]

[0002] Ion-exchangeable layered silicates, zirconium phosphate, and clay minerals are widely used as adsorbents, catalysts, catalyst supports, and the like. While various factors influence their performance in these applications, pore volume, pore distribution, and specific surface area have particularly significant effects. For example, Patent Document 1 provides an example of a clay mineral with a specific pore distribution as an adsorbent. Furthermore, it is well known that olefin polymers can be produced by polymerizing olefins in the presence of a catalyst that utilizes clay or clay minerals as a catalyst component for olefin polymerization (for example, Patent Document 2).

[0003] Furthermore, catalysts for olefin polymerization that contain ion-exchangeable layered compounds that have undergone acid treatment or salt treatment as components are also known (for example, Patent Document 3). Patent Document 4 discloses an ion-exchangeable layered silicate with a specific pore distribution as a catalyst support, and a catalyst for olefin polymerization. However, this ion-exchangeable layered silicate with a specific pore distribution has a small specific surface area, which greatly affects its performance as a catalyst or adsorbent, and is not necessarily sufficient.

[0004] On the other hand, as a method for controlling the pore distribution of a solid made of ion-exchangeable layered silicate, for example, Patent Document 5 describes controlling the pore structure by amorphousizing the SiO2 crystalline component contained in clay minerals. However, this method involves including an SiO2 component that does not have catalytic activity, raising concerns about a decrease in catalytic activity.

[0005] In Patent Document 6, after performing dry granulation of clay minerals in a state containing calcium carbonate, magnesium carbonate, calcium hydroxide, etc., which are substantially insoluble salts in a slurry, the pore structure of activated clay particles is controlled by reacting with an acid to generate carbon dioxide gas. Patent Document 6 does not mention the particle size distribution of the insoluble salts, etc., 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 mesopores of 10 to 50 nm.

[0006] In Patent Document 7, a method of controlling the pore structure is disclosed in which a particulate solid compound such as zinc oxide or titania and an ion-exchangeable layered silicate are mixed in a liquid and dried and granulated, and then at least a part of the particulate solid compound is eluted with an acid. Since the average particle diameter of the particulate solid compound used is from 2.25 μm to 2.98 μm, it is presumed to be a technique for controlling the pore structure on the μm order. 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.

[0007] In Patent Document 8, it is disclosed that a specific pore structure is formed by using an ion-exchangeable layered silicate having a specific composition. In Patent Document 9, improvement is attempted by eluting the aluminum component of the ion-exchangeable layered silicate granulated to a specific particle diameter and adjusting it to a specific particle strength. As described above, by controlling the pore distribution, etc. of a solid composed of an ion-exchangeable layered silicate, improvement in catalytic activity, filtration performance, operation performance during polymer production, and product quality is aimed at. However, it is not yet sufficient, and further improvement is required.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0009] In view of the above-described prior art situation, the present invention aims to provide ion-exchangeable layered silicate particles having a novel pore structure that improves catalytic activity and polymer quality, an olefin polymerization catalyst component containing the ion-exchangeable layered silicate particles, an olefin polymerization catalyst, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer using the same.

Means for Solving the Problems

[0010] The present inventors have found novel ion-exchangeable layered silicate particles in which the total pore volume of pores having a diameter of 2 nm to 10 nm has a specific range with respect to 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. That is, the present inventors have found that ion-exchangeable layered silicate particles having a novel pore structure, in which the total pore volume of pores exceeding 10 nm and not exceeding 50 nm in diameter is larger than before with respect to the total mesopore volume and the specific surface area is large within a specific range, improve catalytic activity and polymer quality.

[0011] The ion-exchangeable layered silicate particles of the present invention are characterized by having the following characteristics (i) and (ii). Characteristic (i): In the pore distribution curve calculated by the BJH method from the desorption isotherms measured by the nitrogen adsorption-desorption method, the sum of the pore volumes with diameters of 2 nm to 10 nm is between 40% and 93% of the total mesopore volume. Characteristic (ii): Specific surface area of ​​300 m² 2 / g or more, 700m 2 It is less than / g.

[0012] In the ion-exchangeable layered silicate particles of the present invention, it is preferable that they further possess the following characteristic (iii) from the viewpoint of operability when used as an adsorbent, catalyst, or catalyst support. Characteristic (iii): The average particle size is 2 μm or more and 500 μm or less.

[0013] The catalyst component for olefin polymerization of the present invention is characterized by containing ion-exchangeable layered silicate particles according to the present invention.

[0014] The olefin polymerization catalyst of the present invention is characterized by comprising the following components [A], [B], and [C]. Component [A]: Ion-exchangeable layered silicate particles according to the present invention. Component [B]: Transition metal compound Ingredients [C]: Organoaluminum compounds

[0015] The present invention relates to a method for producing an olefin polymerization catalyst, characterized by mixing the following components [A], [B], and [C]. Component [A]: Ion-exchangeable layered silicate particles according to the present invention. Component [B]: Transition metal compound Ingredients [C]: Organoaluminum compounds

[0016] The present invention provides a method for producing an olefin polymer, characterized by carrying out olefin polymerization using the olefin polymerization catalyst described above. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide ion-exchangeable layered silicate particles having a novel pore structure that improves catalytic activity and polymer quality, a catalyst component for olefin polymerization containing the ion-exchangeable layered silicate particles, a catalyst for olefin polymerization, a method for producing the catalyst for olefin polymerization, and a method for producing an olefin polymer using the same. [Brief explanation of the drawing]

[0018] [Figure 1] Figure 1 shows the ratio of the total pore volume of pores with a diameter of 2 nm to 10 nm to the total mesopore volume of the ion-exchangeable layered silicate particles described in the Examples and Comparative Examples, plotted against the BET specific surface area m2 / g. [Figure 2] Figure 2 shows the polymerization activity of propylene homopolymerization using the olefin polymerization catalysts described in the Examples and Comparative Examples, plotted against the MFR of the obtained polymer. [Figure 3] Figure 3 shows the results of two-stage polymerization of propylene-ethylene using the olefin polymerization catalysts described in the Examples and Comparative Examples, plotting the number of fish eyes contained in the sheet against the molecular weight ratio of the obtained polymers (the molecular weight of the second polymer divided by the molecular weight of the first polymer). [Figure 4] Figure 4 is a plot of the results of crush strength measurements of ion-exchangeable layered silicate particles described in the examples and comparative examples. [Modes for carrying out the invention]

[0019] 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). Characteristic (i): In the pore distribution curve calculated by the BJH method from the desorption isotherms measured by the nitrogen adsorption-desorption method, the sum of the pore volumes with diameters of 2 nm to 10 nm is between 40% and 93% of the total mesopore volume. Characteristic (ii): Specific surface area of ​​300 m² 2 / g or more, 700m 2It is less than / g.

[0020] The pore structure in porous catalysts affects the catalyst's performance, including its activity and strength, and consequently, its economics, operability, and product quality. Through diligent research, the inventors discovered novel ion-exchangeable silicate particles in which, in the pore distribution curve calculated by the BJH method from desorption isotherms measured by nitrogen adsorption-desorption, the sum of pore volumes between 2 nm and 10 nm in diameter is within the aforementioned specific range relative to the total mesopore volume. Specifically, they found that ion-exchangeable layered silicate particles with a novel pore structure in which the sum of pore volumes between 10 nm and 50 nm in diameter is greater than that of conventional particles relative to the total mesopore volume, and which have a large specific surface area within a specific range, improve catalytic activity and polymer quality. 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 olefin polymers with high polymerization activity. Furthermore, the ion-exchangeable layered silicate particles of the present invention can also be used as a catalyst component for olefin polymerization, capable of producing olefin polymers with less "fish-eye" (poor dispersion of incompatible components, gels, or catalyst residues) in the product, which can degrade the product's appearance. The present invention can provide ion-exchangeable layered silicate particles having a novel pore structure that exhibits these effects, as well as a catalyst component for olefin polymerization containing the ion-exchangeable layered silicate particles, and a catalyst for olefin polymerization.

[0021] Conventional ion-exchangeable layered silicate particles have a problem where increasing the proportion of large-diameter mesopores leads to a decrease in specific surface area, resulting in reduced activity. This is because it has been difficult to manufacture ion-exchangeable layered silicate particles with a high proportion of large-diameter mesopores and a large specific surface area. In contrast, the ion-exchangeable layered silicate particles of the present invention have a higher total pore volume of pores with a diameter of 10 nm to 50 nm relative to the total mesopore volume compared to conventional particles, and possess moderately sized pores with a large specific surface area within a specific range. This is thought to increase the number of active sites of the catalyst and improve catalytic activity. Furthermore, the ion-exchangeable layered silicate particles of the present invention also improve monomer diffusion within the particles, reducing the variability of activity at active sites. This reduces the number of active sites that produce extremely high molecular weight polymers, making it easier to produce uniform polymers and enabling the manufacture of olefin polymers with fewer fish eyes in the product.

[0022] The following describes in detail, item by item, the ion-exchangeable layered silicate particles, catalyst component for olefin polymerization, catalyst for olefin polymerization, method for producing the catalyst for olefin polymerization, and method for producing an olefin polymer using the same, according to the present invention. In this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. Furthermore, the properties of the ion-exchangeable layered silicate particles described below, with the exception of the crush strength measured for a single particle, are properties of the aggregate of ion-exchangeable layered silicate particles.

[0023] 1-1. Characteristics of ion-exchangeable layered silicate particles (1) Pore volume The ion-exchangeable layered silicate particles of the present invention, in the pore distribution curve calculated by the BJH method from desorption isotherms measured by nitrogen adsorption-desorption, have a total pore volume of 2 nm to 10 nm (PV(2-10)) that is 40% or more and 93% or less of the total mesopore volume (PV(2-50)) (characteristic (i)). In the ion-exchangeable layered silicate particles of the present invention, the ratio of the sum of the pore volumes with a diameter of 2 nm to 10 nm (PV(2-10) / PV(2-50)) to the total mesopore volume (PV(2-50)) is preferably 45% or more, more preferably 50% or more, even more preferably 60% or more, and even more preferably 65% ​​or more, with an upper limit of preferably 92% or less, and more preferably 90% or less. Any combination of the upper and lower limits can be adopted. Increasing the proportion of small-diameter pores increases the specific surface area, which can increase the number of active sites of the catalyst. However, if the proportion of small-diameter pores increases too much, it can lead to a decrease in the diffusion rate of reaction substrates such as monomers and an excessive increase in particle strength. As a result, in olefin polymerization catalysts that require a support breakdown process during polymerization, polymerization activity decreases, and the quality is negatively affected, such as the appearance of fish eyes in the polymer product. On the other hand, increasing the proportion of large-diameter pores is desirable for the diffusion of reaction substrates. However, if the proportion of large-diameter pores increases too much, it can lead to a decrease in activity due to a decrease in specific surface area, or a decrease in particle strength that makes it easier for fine powder to be generated, which can negatively affect operability and product quality. For these reasons, it is thought that maintaining the PV(2-10) / PV(2-50) within the optimal range results in a catalyst or catalyst component with an excellent balance of catalytic activity, operability, and product quality.

[0024] Here, a mesopore refers to a pore with a diameter of 2 nm to 50 nm, as defined in IUPAC. Various methods are known for measuring pore diameter and pore volume. However, in this invention, the pore diameter and pore volume refer to those calculated by the BJH method from data of desorption isotherms measured by a gas adsorption / desorption method using nitrogen. Pore ​​volume measurement by gas adsorption / desorption is described in standards such as JIS Z8831-2 and ISO 15901-2, and can be performed using commercially available equipment. In this invention, nitrogen is used as the gas, and the sample is heated under reduced pressure (1.3 Pa or less) at 200°C for 2 hours, and then measured at 77K to obtain data from the desorption isotherm. Pore volume can also be calculated from the adsorption isotherm. However, in porous materials, the pore distribution calculated from the desorption isotherm data often does not match the pore distribution calculated from the adsorption isotherm data. This is thought to be due to the fact that thermodynamic equilibrium is not reached within the actual measurement time, and due to the effects of cavitation and pore blocking. Assuming an ink bottle-shaped pore, the pore distribution obtained from the desorption isotherm is said to be influenced by the pore diameter of the bottle neck.

[0025] When using porous materials as catalysts or catalytic components, it is presumed that the reaction substrate is also affected by this "neck region." Therefore, since the pore distribution obtained from desorption isotherms is considered to indirectly represent the performance of the catalyst, the present invention uses the pore distribution obtained from desorption isotherms as the standard. Regarding the method for calculating the pore distribution from desorption isotherm data, the method described in the examples below can be specifically employed.

[0026] Furthermore, in the ion-exchangeable layered silicate particles of the present invention, the sum of the pore volumes {(PV(2-50)-PV(2-10)} of pores with a diameter of more than 10 nm and less than or equal to 50 nm, calculated by the BJH method from the desorption isotherm measured by the nitrogen adsorption-desorption method, may be 0.020 mL / g or more, more preferably 0.030 mL / g or more, and even more preferably 0.040 mL / g or more. The upper limit may be 0.230 mL / g or less. Any combination of the upper and lower limits can be adopted.

[0027] (2) Specific surface area The ion-exchange layered silicate particles of the present invention have a specific surface area of ​​300 m². 2 / g or more, 700m 2is less than or equal to / g (Characteristic (ii)). In the ion-exchangeable layered silicate particles of the present invention, the specific surface area preferably has a lower limit of 325 m 2 / g or more, more preferably 340 m 2 / g or more, still more preferably 355 m 2 / g or more, and the upper limit is preferably 600 m 2 / g or less, more preferably 500 m 2 / g or less. Any combination of the above upper and lower limits can be adopted. Generally, as the specific surface area increases, the amount of the active component of the catalyst or the amount that can support the active component increases, so the activity increases. On the other hand, if the specific surface area is too large, the pore diameter may become small. This may cause a decrease in the diffusion rate of the reaction substrate and the like, leading to a decrease in the activity as a catalyst and the adsorption performance as an adsorbent. The specific surface area in the present invention refers to a value calculated by the BET multipoint method analysis (Rouquerol transformation) from the adsorption isotherm data measured using nitrogen gas in the gas adsorption method. The 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 the examples below can be adopted.

[0028] (3) Particle size There is no particular limitation on the particle size of the ion-exchangeable layered silicate particles of the present invention. Preferably, the average particle size is 2 μm or more and 500 μm or less (Characteristic (iii)). In the ion-exchangeable layered silicate particles of the present invention, the average particle size preferably has a lower limit of more preferably 3 μm or more, still more preferably 8 μm or more, particularly preferably 10 μm or more, and the upper limit is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 70 μm or less, even more preferably 60 μm or less, particularly preferably 55 μm or less. Any combination of the above upper and lower limits can be adopted. Generally, if the particle size is too small, it can cause a decrease in efficiency during solid-liquid separation such as filtration when used as an adsorbent or decolorizing agent, or it can cause adhesion inside the reactor or blockage of piping and filters when used as a catalyst support. On the other hand, if the particle size is too large, it can cause poor dispersion in liquid (slurry state) or during gas-phase reactions when used as an adsorbent, decolorizing agent, or catalyst support. Here, the average particle diameter of the present invention refers to the volume-based median diameter obtained from the spherical equivalent particle diameter distribution. Specifically, the method for measuring the average particle diameter of ion-exchangeable layered silicate particles of the present invention can be the measurement method described in the examples below.

[0029] (4) Crushing strength There are no particular limitations on the crushing strength of the ion-exchangeable layered silicate particles in this invention. However, considering their use as catalyst supports, it is preferable to maintain the crushing strength within an appropriate range. The crushing strength of a single particle can be measured using the method described in JIS R 1639-5:2007 Single or Particle Crushing Strength, etc., and specifically, it can be measured using the measurement method described in the examples below. 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, with a lower limit of more preferably 4.0 MPa or more, even more preferably 5.0 MPa or more, and an upper limit of more preferably 20.0 MPa or less, and even more preferably 15.0 MPa or less. Any combination of the upper and lower limits can be adopted. If the average crushing strength is too low, particle breakage may occur at undesirable times, such as during catalyst preparation, resulting in the generation of fine powder. On the other hand, if the average crushing strength is too high, it may hinder the smooth formation of polymer on the catalyst particles when used as a support for olefin polymerization catalysts.

[0030] Furthermore, it is known that the strength of inorganic brittle materials such as the ion-exchangeable layered silicate particles of the present invention exhibits a so-called size effect. That is, larger particles have a higher probability of containing large defects that are likely to cause fracture, while smaller particles have increased strength. Therefore, the crushing strength S of a particle can generally be expressed by the following equation (1) (Proceedings of the Chemical Engineering Papers 1984, pp. 108-112). S=(S0·V0 1 / m )·V -1 / m ...Equation (1) (In equation (1), S is the crushing strength (MPa) of the ion-exchangeable layered silicate particles, S0 is the crushing strength at a unit volume V0, and V is the volume (μm) of the ion-exchangeable layered silicate particles. 3 ), m is Weibull's coefficient of uniformity. The crush strength S can be measured using the measurement method described above. The volume V of the ion-exchangeable layered silicate particles is calculated using the average value (μm) of the major axis diameter and minor axis diameter of the particle as the diameter d, assuming a perfect sphere of diameter d (unit: μm). 3 ) can be done. m is defined as a number greater than 1. (S0·V0 1 / m As for determining the ratio and 1 / m, they can be determined using the least squares method from the relationship between the measured crushing strength S and the volume V of the ion-exchangeable layered silicate particles.

[0031] In equation (1) above, the larger the value of m, that is, the smaller the value of 1 / m, the more uniform the material is, and the less the crushing strength depends on the size (particle diameter). Therefore, the smaller 1 / m is, the more stable the catalyst support will be and the wider the range of particle sizes that can be used, which is preferable. In equation (1) above, (S0·V0 1 / m The value of ) represents the strength per unit volume. If the size dependence of the crushing strength is sufficiently small, it will be equivalent to the average value of the measured crushing strength S. In the ion-exchange layered silicate particles of the present invention, the (S0·V0 1 / mThere are no particular restrictions on ), and 1 / m. 1 / m is preferably 0.035 or less, more preferably 0.020 or less, and even more preferably 0.010 or less, with smaller values ​​being preferable and the lower limit being 0.000. Also, the above (S0·V0 1 / m The upper limit is preferably 3.0 to 25.0, more preferably 4.0 or higher, even more preferably 5.0 or higher, and more preferably 20.0 or lower, even more preferably 15.0 or lower. Any combination of the upper and lower limits can be adopted. In the ion-exchange layered silicate particles of the present invention, the average crush strength value is the average value of the crush strength measurement S, and the (S0·V0 1 / m The absolute value of the difference between ( ) and ( ) is preferably 8 or less, more preferably 5 or less.

[0032] (5) Metal element ratio In the present invention, it is preferable that the ion-exchangeable layered silicate particles have a structure in which a portion of the octahedral sheet forming the ion-exchangeable layered silicate is missing due to weathering, acid treatment, salt treatment, etc. When the ion-exchangeable layered silicate is of the montmorillonite or bydelite type, such a structure is known as acid clay or activated clay. In the present invention, the ion-exchangeable layered silicate is preferably a montmorillonite or bydelite-type layered silicate. The octahedral sheets of montmorillonite are composed of metal atoms such as aluminum and magnesium. It is preferable that 15% to 75% of these octahedral sheet components are eluted relative to their content before chemical treatment such as acid treatment. More preferably, 15% to 70%, even more preferably 17% to 65%, and particularly preferably 20% to 60% are eluted. Furthermore, 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 to 0.30, even more preferably 0.10 to 0.25, and even more preferably 0.12 to 0.20. When there is too much aluminum relative to silicon, the pore volume and specific surface area tend to decrease. On the other hand, when there is too little aluminum relative to silicon, the number of active sites tends to decrease. This can lead to a decrease in the activity of the catalyst or catalyst support, and can negatively affect the quality of the product. Furthermore, from the viewpoint of ion exchangeability, the molar ratio of iron to silicon is preferably 0 to 0.20, more preferably 0.0005 to 0.10, even more preferably 0.001 to 0.08, and even more preferably 0.005 to 0.05. Furthermore, the molar ratio of magnesium to silicon is preferably 0 to 0.30, more preferably 0.001 to 0.30, even more preferably 0.01 to 0.20, and even more preferably 0.02 to 0.10, from the viewpoint of ion exchangeability.

[0033] 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 it can produce ion-exchangeable layered silicate particles having the above-mentioned characteristics. Because it is easier to control the pore structure and obtain the characteristics of the ion-exchangeable layered silicate particles of the present invention, the method for producing ion-exchangeable layered silicate particles of the present invention is preferably characterized by including the following steps 1, 2, and 3. Step 1: A step of preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and a soluble compound that is solid at 20°C and soluble in the liquid in the slurry, wherein the soluble compound is present in an amount of 10% to 150% by mass relative to the solid component containing the ion-exchangeable layered silicate in the 20°C slurry. Step 2: A step of granulating the slurry prepared in Step 1 to obtain ion-exchange layered silicate composite particles containing the ion-exchange layered silicate and the soluble compound. Step 3: A step of dissolving the soluble compound from the ion-exchangeable layered silicate composite particles obtained in Step 2.

[0034] When a specific amount of soluble compound is added to an ion-exchangeable layered silicate slurry and granulated, the primary silicate particles in the resulting composite particles are thought to have looser bonds due to the soluble compound that solidifies upon drying. Subsequently, when the soluble compound is eluted from the composite particles into a solvent by chemical treatment, appropriate voids are created within the particles, and the pore size of the silicate particles can be controlled. Since the controllable pore size is the size when the soluble compound is dissolved, it is possible to control a smaller pore size than when conventional methods of controlling pores by adding insoluble fine particle solids are used.

[0035] (1) Process 1 Step 1 is a step of preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and the soluble compound.

[0036] (1-1) Ion-exchange layered silicate The ion-exchangeable layered silicate particles of the present invention consist of an ion-exchangeable layered silicate. In this invention, the ion-exchangeable layered silicate is a type of silicate compound that has a crystalline structure in which planes formed by ionic bonds, etc., are stacked parallel to each other with weak bonding forces. In this invention, the ion-exchangeable layered silicate is not limited to naturally occurring materials, but may also be an artificially synthesized material. For example, as described in Haruo Shiramizu's "Clay Mineralogy" (Asakura Shoten, 1995), i) Minerals with a 1:1 layer as the main constituent layer include kaolin group minerals such as deckite, nacrite, kaolinite, and nacrite, serpentine group minerals such as chrysotile, lizardite, and antigorite, and serpentine-related minerals such as amethyst and Al lizardite. ii) Examples of smectite group silicates such as montmorillonite, beiderite, nontronite, saponite, hectorite, and stevensite, whose main constituent layer is a 2:1 layer; vermiculite group silicates such as vermiculite; mica group silicates such as mica, illite, sericite, and erythritol; attapulgite, sepiolite, palygorskite, and chlorite groups. These may form mixed layers. Many smectites occur naturally as mixtures of clay minerals and therefore often contain impurities (such as quartz, cristobalite, opal, and carbonates), but these may also be present. Examples of such impurities include bentonite and acid clay, which are clays mainly composed of montmorillonite. 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 silicate, and even more preferably, montmorillonite. These ion-exchange layered silicates may be used individually or in combination of two or more types.

[0037] In this invention, the compositional analysis of the ion-exchangeable layered silicate and ion-exchangeable layered silicate particles is performed by creating a calibration curve in accordance with JIS R2212 and quantifying them by X-ray fluorescence measurement. Specifically, the method for measuring X-ray fluorescence can be the method described in the examples below.

[0038] Furthermore, it is preferable to purify these natural products by elutriation or efflux. By performing elutriation or efflux, impurities such as quartz and feldspar with high specific gravity can be removed, as can silicates that do not swell, and a desirable ion-exchangeable layered silicate can be obtained. Conventional methods can be used for elutriation or efflux. Drying or grinding may be performed before purification. Grinding methods include dry grinding and wet grinding. Grinding machines include jaw crushers, gyratory crushers, roll crushers, edge runners, hammer mills, ball mills, bead mills, and jet mills.

[0039] Alternatively, ion exchange treatment may be performed beforehand using, for example, a very small amount of sodium carbonate. Examples of this include the conversion of Ca-type bentonite to Na-type activated bentonite (Customs Central Laboratory Bulletin No. 56, p. 85; Clay Science Vol. 21 No. 1 1-13 (1981) Review). This makes it easier to disperse smectite during elutriation, allowing coarse quartz and other particles to settle and separate quickly due to differences in particle size. Known substances may also be added as dispersants, such as sodium silicate and sodium pyrophosphate.

[0040] The ion-exchange layered silicate used in this invention is subjected to granulation and chemical treatment as described later. Furthermore, in this invention, if a silicate has ion-exchange properties before chemical treatment is applied, even if the physical and chemical properties change as a result of the treatment and the ion-exchange properties and layered structure are lost, it will still be treated as an ion-exchangeable layered silicate.

[0041] The type of interlayer cation (cation contained between the layers of the ion-exchangeable layered silicate) of the present invention is not particularly limited. The interlayer cation may contain, as a main component, at least one 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. Alternatively, the interlayer cation may contain transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold. Such ion-exchangeable layered silicates or raw materials required for ion exchange treatment are preferable because they are relatively easily available as industrial raw materials.

[0042] (1-2) Raw material slurry In the method for producing ion-exchangeable layered silicate particles, the raw materials are a slurry containing an ion-exchangeable layered silicate, a solvent, and a soluble compound that is solid at 20°C and soluble in the liquid in the slurry (hereinafter sometimes referred to as the raw material slurry).

[0043] There are no particular restrictions on the shape of the ion-exchange layered silicate before granulation; it may be in its naturally occurring form or in its form at the time of artificial synthesis. Furthermore, ion-exchange layered silicates whose shape has been processed by operations such as crushing, granulation, and classification may be used. In addition, a slurry obtained by purification operations such as elutriation may be used as is. It may also contain impurities (such as quartz, cristobalite, opal, and carbonates). The concentration of the ion-exchangeable layered silicate in the slurry is not particularly limited. The concentration is preferably 0.5% to 60% by mass, more preferably 0.7% to 40% by mass, even more preferably 0.8% to 20% by mass, and most preferably 1% to 10% by mass.

[0044] 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, and more preferably 0.5 μm or less. The particle size referred to here is the equivalent diameter of a circle, measured by the following method. The method for measuring the particle size of the ion-exchangeable layered silicate (raw material) can be specifically the method described in the examples below.

[0045] There are no particular restrictions on the type of solvent that constitutes the slurry. Preferred solvents include water, or organic solvents such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene, with water being even more preferred. These solvents may be used individually or in combination of two or more.

[0046] The aforementioned soluble compound is an additive that is solid at 20°C and is soluble in the liquid in the slurry at the granulation temperature, preferably 20°C. Here, "solubility" means that the concentration in the liquid in the slurry is 0.3% by mass or more, preferably 0.5% by mass or more, and more preferably 0.8% by mass or more. The soluble compound is solid at 20°C on its own, is soluble in the liquid in the raw material slurry, and is not particularly limited as long as it can be dissolved by chemical treatment in step 3 described below. Salts are preferred as the soluble compound because they allow for easier control of pore size. Examples of salts include those composed of a cation selected from the group consisting of organic cations and inorganic cations including metal ions, and an anion selected from the group consisting of organic anions and inorganic anions including halide ions. A preferred example of a salt is a compound composed of a cation containing at least one atom selected from groups 1 to 14 of the periodic table, and at least one anion selected from the group consisting of halogen anions, inorganic Brønsted acid anions, and organic Brønsted acid anions. More preferably, the salt is an inorganic salt composed of at least one anion selected from inorganic Brønsted acid anions and halogen anions, and more preferably an inorganic salt that is soluble in water.

[0047] Examples of cations constituting such inorganic salts include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as magnesium ions and calcium ions; aluminum ions, iron ions, strontium ions, cobalt ions, copper ions, nickel ions, zinc ions, ruthenium ions, rhodium ions, palladium ions, silver ions, iridium ions, platinum ions, and ammonium ions. Examples of anions include inorganic acid ions such as sulfate ions, nitrate ions, chloride ions, hydrobromide ions, hydroiodide ions, phosphate ions, pyrophosphate ions, perchlorate ions, molybdate ions, hexafluorosilicate ions, and carbonate ions; organic acid ions such as acetate ions, citrate ions, oxalate ions, formate ions, methanesulfonate ions, trifluoromethanesulfonate ions, toluenesulfonate ions, and taurine ions; and oxygen ions (oxide ions) and hydroxide ions.

[0048] As for soluble compounds, more preferably, from the standpoint of being easily eluted and readily treatable industrially, salts containing at least one cation selected from the group consisting of lithium ions, sodium ions, magnesium ions, aluminum ions, and iron ions are used. Even more preferably, salts containing at least one cation selected from the group consisting of lithium ions, sodium ions, magnesium ions, aluminum ions, and iron ions, and at least one anion selected from the group consisting of sulfate ions, nitrate ions, chloride ions, and phosphate ions are used. Even more preferably, salts containing at least one cation selected from the group consisting of lithium ions, sodium ions, and magnesium ions, and at least one anion selected from the group consisting of sulfate ions, nitrate ions, chloride ions, and phosphate ions are used. Particularly preferred is lithium sulfate.

[0049] These soluble compounds may be used individually or in combination of two or more. It is preferable to add the soluble compound in an amount of 10% to 150% by mass relative to the solid component containing the ion-exchangeable layered silicate in the 20°C slurry, as this makes it easier to obtain the characteristics of the ion-exchangeable layered silicate particles of the present invention. In other words, the amount of soluble compound added is preferably 10% to 150% by mass relative to the total sum of ion-exchangeable layered silicate and non-soluble solid components (solid components different from the ion-exchangeable layered silicate and the soluble compound) in the 20°C slurry. The amount of soluble compound added can be appropriately selected within the above range to control the pore distribution. The lower limit is more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, and the upper limit is more preferably 130% by mass or less, even more preferably 110% by mass or less, and even more preferably 100% by mass or less. Any combination of the upper and lower limits can be adopted. If the aforementioned upper limit exceeds 150% by mass, the strength of the granulated solid may decrease, and fine powder and other particles may be more likely to be generated. On the other hand, if it falls below 10% by mass, the characteristics of the ion-exchangeable layered silicate particles of the present invention may not be obtained. The soluble compound is preferably added to the slurry in an amount of 10% to 150% by mass relative to the ion-exchangeable layered silicate, as this facilitates obtaining the desired pore structure. The lower limit is more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, while the upper limit is more preferably 130% by mass or less, even more preferably 110% by mass or less, and even more preferably 100% by mass or less. Any combination of the upper and lower limits can be adopted.

[0050] On the other hand, the gas generated when carbonates react with acids affects the pore structure. Therefore, the amount of carbonate added as a soluble compound is preferably 0% to 75% by mass, more preferably 0% to 50% by mass, and even more preferably 0% to 30% by mass. If the amount of soluble compound added is insufficient, it is preferable to supplement it with other soluble compounds. When using ion-exchangeable layered silicates containing carbonates as impurities, or ion-exchangeable layered silicates that have been activated to the Na type by treatment with sodium carbonate, etc., it is preferable that the total amount of carbonates is as described above.

[0051] When calculating these additive amounts, salts containing adducts that are liquid on their own, such as hydration water, should be calculated as if they were anhydrous or otherwise without adducts.

[0052] A 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 the solvent is removed. A particularly preferred soluble compound is a substance that is crystalline in its granulated state. A crystalline substance is a substance that possesses some kind of structural order. That is, it is a substance whose diffraction pattern using X-rays or particle beams exhibits discrete diffraction spots. Using a crystalline substance as a soluble compound after drying or granulation is preferable because the pore structure can be adjusted by controlling the crystal size. However, it is not necessary for all of the soluble compound used to become crystalline; some may be crystalline. The presence or absence of crystallinity can be confirmed by the presence or absence of diffraction patterns using X-rays or particle beams, and generally, this can be confirmed by X-ray scattering or diffraction phenomena.

[0053] A binder may be added to improve the shape during granulation, etc. Examples of binders include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcellulose, polyvinyl alcohol, water glass, alcohols, glycol, starch, casein, latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, sodium alginate, etc. Viscosity modifiers may also be added to adjust the pH, viscosity, etc., of the slurry. It is well known that the pH of an ion-exchange layered silicate slurry affects the viscosity of the slurry. In addition to the binders mentioned above, acids such as sulfuric acid, nitric acid, and hydrochloric acid, or bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide may be added to adjust these properties. In addition, known substances may be added as dispersants or flocculants. Examples of dispersants include sodium silicate, sodium pyrophosphate, and aluminum sulfate. If these binders, viscosity modifiers, dispersants, flocculants, etc. satisfy the characteristics of the soluble compounds, it is preferable to treat them as soluble compounds and adjust the amount added to the solid component containing the ion-exchangeable layered silicate in the 20°C slurry.

[0054] There are no particular restrictions on the order in which the ion-exchangeable layered silicate, soluble compound, and solvent are mixed. However, the mixing order may affect the physical properties of the slurry, such as viscosity, and may also affect the drying, granulation, and physical properties of the ion-exchangeable layered silicate particles. The mixing order may be to add the ion-exchangeable layered silicate and the soluble compound to the solvent sequentially or simultaneously. Alternatively, the ion-exchangeable layered silicate and the soluble compound may be dispersed or dissolved in the solvent separately before mixing. Most preferably, the soluble compound is dissolved in the solvent, and then a slurry in which the ion-exchangeable layered silicate is dispersed in the solvent is added to this solution. There are no restrictions on the mixing order when adding binders, dispersants, flocculants, or viscosity modifiers.

[0055] There are no particular restrictions on the mixing temperature, but a temperature below the boiling point of the solvent is preferred. When using water, the temperature 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. Known methods can be used. Mixing methods include stirring and static mixers. Furthermore, to particularly improve dispersibility, high-speed stirrers, media mills, high-pressure homogenizers, ultrasonic dispersers, thin-film swirling high-speed stirrers, etc., can be used. Multiple of the above methods may be combined. Stirring, high-speed stirrers, bead mills, and high-pressure homogenizers are particularly preferred.

[0056] The slurry viscosity is preferably 5 Pa·s to 5,000 Pa·s, and more preferably 8 Pa·s to 3,000 Pa·s. This viscosity can be measured using a B-type viscometer (BROOKFIELD DV-I Viscometer) with an LV-3 spindle at 12 rpm and 20°C.

[0057] (2) Process 2 Step 2 is a step of granulating the slurry prepared in Step 1 to obtain ion-exchange layered silicate composite particles containing the ion-exchange layered silicate and the soluble compound. In step 2, ion-exchangeable layered silicate composite particles are produced by granulation and, if necessary, drying, concentration, filtration, or decantation of the raw material slurry obtained in step 1. Granulation and separation from the solvent may be performed separately or simultaneously. There are no particular restrictions on the method or order of granulation and separation from the solvent. However, it is necessary to include soluble compounds in the particles after granulation. Preferred methods for producing granulated bodies include stirring granulation, spray granulation, rolling granulation, briquetting, compacting, extrusion granulation, fluid bed granulation, jet bed granulation, emulsification granulation, liquid granulation, and compression molding granulation. More preferably, methods include spray drying granulation, spray cooling granulation, fluid bed granulation, jet bed granulation, liquid granulation, and emulsification granulation, with spray drying granulation and spray cooling granulation being particularly preferred.

[0058] When performing spray granulation, there are no particular restrictions on the spraying method. Rotary atomizers, single-fluid nozzles, two-fluid nozzles, or ultrasonic nozzles can be used. There are also no particular restrictions on the drying medium. Examples of drying media include nitrogen, argon, and air. There are no restrictions on the temperature at which the drying medium is supplied during spray drying granulation. The temperature varies depending on the dispersion medium, but taking water as an example, it can be 70°C to 300°C, preferably 80°C to 280°C.

[0059] The particle size distribution of the ion-exchangeable layered silicate composite particles produced can be adjusted by manufacturing conditions such as atomizer and drying medium temperature and flow rate. Alternatively, it may be adjusted using known classification techniques such as sieving or air classification.

[0060] 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, even more preferably 8 μm to 100 μm, and most preferably 20 μm to 70 μm. Here, the average particle size refers to the volume-based median diameter determined from the spherical equivalent particle size distribution measured by laser diffraction, similar to the average particle size of the ion-exchangeable layered silicate particles of the present invention described above.

[0061] 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 crystalline solid. The presence or absence of crystallinity can be confirmed by the presence or absence of diffraction patterns using X-rays or particle beams, and can generally be confirmed by X-ray scattering or diffraction phenomena.

[0062] (3) Process 3 Step 3 is a step of dissolving the soluble compound from the ion-exchangeable layered silicate composite particles obtained in step 2. By performing appropriate chemical treatment on the ion-exchangeable layered silicate composite particles, some or all of the soluble compound is dissolved from the ion-exchangeable layered silicate composite particles and removed from the ion-exchangeable layered silicate particles. As for the chemical treatment, any treatment method that can dissolve the soluble compound from the ion-exchangeable layered silicate composite particles can be appropriately selected and used. Examples include acid treatment by contact with acids, base treatment by contact with bases, salt treatment by contact with salts, elution treatment (washing) with a suitable solvent that dissolves the soluble compound (for example, a mixed solvent of alcohol and water), and other chemical treatments. Each treatment may be performed multiple times. Multiple treatments may also be combined. Hereinafter, ion-exchangeable layered silicate composite particles and ion-exchangeable layered silicate particles that have undergone a process of dissolving soluble compounds are sometimes collectively referred to as ion-exchangeable layered silicate (composite) particles. Ion-exchangeable layered silicate (composite) particles refer to either ion-exchangeable layered silicate composite particles or ion-exchangeable layered silicate particles. In particular, it is preferable to perform an acid treatment in which ion-exchangeable layered silicate composite particles are brought into contact with acids, as this improves the specific surface area, which affects the strength, catalytic activity, and adsorption performance of the particles. It is even more preferable to perform a base treatment in which the ion-exchangeable layered silicate composite particles are brought into contact with bases or a salt treatment in which they are brought into contact with salts after the acid treatment in which the ion-exchangeable layered silicate composite particles are brought into contact with acids.

[0063] (3-1) Acid treatment In the present invention, it is preferable to perform an acid treatment in which ion-exchangeable layered silicate (composite) particles are brought into contact with acids. Acid treatment dissolves soluble compounds and impurities, and facilitates the exchange of cations between the layers of ion-exchangeable layered silicates. Furthermore, acid treatment can alter the pore structure properties and increase the specific surface area by eluting some or all of the cations, such as Al, Fe, and Mg, that constitute the crystalline structure of ion-exchangeable layered silicates. This contributes to increasing the acid strength of the ion-exchangeable layered silicate particles and increasing the amount of acid per unit mass.

[0064] It is preferable to dissolve 15% to 75% of the metal cations constituting the octahedral sheet by acid treatment, more preferably 15% to 70%, even more preferably 17% to 65%, and particularly preferably 20% to 60%. The percentage of metal cations to be dissolved is expressed by the following formula, for example, when the metal cation is aluminum. [Aluminum / Silicon molar ratio before chemical treatment - Aluminum / Silicon molar ratio after chemical treatment] ÷ Aluminum / Silicon molar ratio before chemical treatment × 100 When the elution rate is within the above range, the specific surface area improves, leading to improved adsorption performance and catalytic activity. Furthermore, when used as an olefin polymerization catalyst component, the amount of fisheye in the product tends to decrease.

[0065] Examples of acids used in acid treatment include inorganic 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 these, inorganic acids are preferred, with hydrochloric acid, nitric acid, and sulfuric acid being preferred. More preferably, hydrochloric acid and sulfuric acid are preferred, and particularly preferably, sulfuric acid.

[0066] Contact between ion-exchangeable layered silicate (composite) particles and acids is preferably carried out under a slurry of ion-exchangeable layered silicate (composite) particles, as this allows for an efficient and uniform reaction. There are no particular restrictions on the solvent used for slurry formation. A solvent that does not react during acid treatment is preferred, and organic solvents such as water, methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene are preferred. Water is even more preferred. These solvents may be used individually or in combination of two or more.

[0067] There are no particular restrictions on the acid concentration (mass percentage of acid relative to the total mass of the reaction system) during the acid treatment of the present invention. The acid concentration is preferably 3% to 50% by mass, more preferably 4% to 40% by mass, and even more preferably 5% to 20% by mass. Furthermore, there are no restrictions on the temperature during the 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 are no particular restrictions on the solid content concentration in the solvent during acid treatment. The concentration is preferably 3% to 50% by mass, more preferably 5% to 30% by mass, and even more preferably 8% to 20% by mass. There are no restrictions on the duration of the acid treatment. The duration is preferably 5 to 3000 minutes, more preferably 10 to 1500 minutes, and even more preferably 30 to 750 minutes. The degree to which soluble compounds, impurities, cations, etc., are eluted can be adjusted by appropriately selecting the type of acid, the concentration of the acid, the treatment temperature, the treatment time, etc. Furthermore, the acid treatment can be carried out in multiple stages.

[0068] (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. After the acid treatment, the ion-exchangeable layered silicate composite particles may be further subjected to a base treatment in which they are brought into contact with bases. Base treatment dissolves soluble compounds and impurities, and facilitates the exchange of cations between the layers of ion-exchangeable layered silicates. Furthermore, base treatment can alter the pore structure and increase the specific surface area by eluting some or all of the cations, such as Al, Fe, Mg, and Si, that constitute the crystalline structure of ion-exchangeable layered silicates.

[0069] The bases used in base treatment are substances that act as Brønsted bases. Bases are substances that react with protons to produce water (neutralization reaction). Preferably, these are hydroxides of metals selected from the group consisting of alkali metals, alkaline earth metals, and metals from groups 3 to 14 of the periodic table. More preferably, these are hydroxides of alkali metals, alkaline earth metals, Mn, Fe, Ni, Cu, Zn, Al, Sn, and Pb. Even more preferably, these are hydroxides of alkali metals, alkaline earth metals, Mg, Zn, and Al. Bases are not limited to those listed below. 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, Li2CO3, Na2CO3, K2CO3, Cs2CO3, Rb2CO3, BeCO3, MgCO3, CaCO3, MnCO3, CuCO3, Al2(CO)3, ZnCO3, PbCO3, LiHCO3, NaHCO3, RpHCO3, CsHCO3, Ca(HCO3)2, Mg(HCO3)2, and others. Bases may be used individually or in combination. There are no particular restrictions on their use. The state of the bases when they come into contact with ion-exchangeable layered silicate (composite) particles is either dissolved in the solvent or in solid form. When dissolved in the solvent and brought into contact with the bases, there is no limit to the concentration, but it is preferable that the upper limit be below the saturation concentration.

[0070] The base treatment is preferably carried out under an ion-exchangeable layered silicate (composite) particle slurry, as this allows for an efficient and uniform reaction. Suitable solvents for slurry formation include water or organic solvents such as alcohols. Preferably, ethanol, methanol, ethylene glycol, glycerin, or water are used, with water being more preferred. These solvents may be used individually or in combination of two or more.

[0071] The amount of bases used varies depending on the amount of acid contained in the ion-exchangeable layered silicate (composite) particle slurry before contact with the bases, as well as the purpose of the treatment. When using an ion-exchangeable layered silicate (composite) particle slurry after acid treatment with water as the solvent, it is preferable that the amount of bases used is such that the pH is 8 or less during the base treatment process and the pH is 4.5 to 8 when the base treatment process is completed.

[0072] Furthermore, there are no restrictions on the temperature during the 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 are no particular restrictions on the solid content concentration in the solvent during base treatment. The concentration is preferably 1% to 50% by mass, more preferably 2% to 30% by mass, and even more preferably 3% to 20% by mass. There are no restrictions on the duration of the base treatment. The duration is preferably 1 to 600 minutes, more preferably 5 to 300 minutes, and even more preferably 10 to 120 minutes. The degree to which soluble compounds, impurities, cations, etc., are eluted can be adjusted by appropriately selecting the type of base, the concentration of the base, the treatment temperature, the treatment time, etc. Furthermore, the base treatment can be carried out in multiple stages.

[0073] (3) Other chemical treatments In this invention, in addition to acid treatment and base treatment, other chemical treatments may be performed on the ion-exchangeable layered silicate (composite) particles. The ion-exchangeable layered silicate composite particles may be subjected to further chemical treatments after the acid treatment or base treatment described above.

[0074] Other chemical treatments include contact with treatment agents containing salts, oxidizing agents, reducing agents, or compounds that can interlate between the layers of ion-exchangeable layered silicate (composite) particles, as well as washing with solvents. Intercalation refers to the process of introducing another substance between layers of a layered material. The introduced substance is called a guest compound. Furthermore, intercalation, salt treatment, acid treatment, or base treatment can form ionic complexes, molecular complexes, or organic derivatives, thereby altering the surface area and interlayer distance. By utilizing ion exchange, it is also possible to obtain layered materials with expanded interlayers by substituting exchangeable ions between layers with other large, bulky ions. In other words, the bulky ions play a supporting role for the layered structure and are called pillars. Specific examples of treatment agents are shown below.

[0075] Examples of salts include salts composed of a cation selected from the group consisting of organic cations and inorganic cations including metal ions, and an anion selected from the group consisting of organic anions and inorganic anions including halide ions. For example, a compound composed of a cation containing at least one atom selected from groups 1 to 14 of the periodic table and at least one anion selected from the group consisting of halogen anions, inorganic Brønsted acids, and organic Brønsted acid anions is a preferred example. Particularly preferred are compounds in which the anion consists of an inorganic Brønsted acid or a halogen.

[0076] Specific examples of such salts include LiCl, LiBr, Li2SO4, Li3(PO4), LiNO3, Li(OOCCH3), NaCl, NaBr, Na2SO4, Na3(PO4), NaNO3, Na(OOCCH3), KCl, KBr, K2SO4, K3(PO4), KNO3, K(OOCCH3), CaCl2, CaSO4, Ca(NO3)2, Ca3(C6H5O7). 2, Ti(OOCCH3)4, Ti(CO3)2, Ti(NO3)4, Ti(SO4)2, TiF4, TiCl4, TiBr4, TiI4, Zr(OOCCH3)4, Zr(CO3)2, Z r(NO3)4, Zr(SO4)2, ZrF4, ZrCl4, ZrBr4, ZrI4, ZrOCl2, ZrO(NO3)2, ZrO(ClO4)2, ZrO(SO4), Hf(OOCCH3) 4, Hf(CO3)2, Hf(NO3)4, Hf(SO4)2, HfOCl2, HfF4, HfCl4, HfBr4, HfI4, CuCl2, CuBr2, Cu(NO3)2, CuC2O4 , Cu(ClO4)2, CuSO4, Cu(OOCCH3)2, Zn(OOCH3)2, Zn(CH3COCHCOCH3)2, ZnCO3, Zn(NO3)2, Zn(ClO4)2, Zn3 Examples include (PO4)2, ZnSO4, ZnF2, ZnCl2, nBr2, ZnI2, AlF3, AlCl3, AlBr3, AlI3, Al2(SO4)3, Al2(C2O4)3, Al(CH3COCHCOCH3)3, Al(NO3)3, AlPO4, GeCl4, Sn(OOCCH3)4, Sn(SO4)2, SnF4, SnCl4, etc., but are not limited to these.

[0077] Examples of organic cations include 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-dimethyl-p-trimethylsilylanilinium, N,N-dimethyl-1-naphthylanilinium, N,N,2-trimethylanilinium, 2,6-dimethylanilinium Examples include, but are not limited to, ammonium compounds such as tilanilinium, nitrogen-containing aromatic compounds such as pyridinium, quinolinium, N-methylpiperidinium, 2,6-dimethylpyridinium, and 2,2,6,6-tetramethylpiperidinium, oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, and oxolanium, phosphonium compounds such as triphenylphosphonium, tri-o-tolylphosphonium, tri-p-tolylphosphonium, and trimesitylphosphonium, and phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium. Examples of anions include, but are not limited to, those composed of boron compounds and phosphorus compounds, such as hexafluorophosphate, tetrafluoroborate, and tetraphenylborate. These salts may be used individually or in combination of two or more types.

[0078] Salts may also be used in combination with acids, bases, oxidizing agents, reducing agents, or compounds that intercalate between the layers of ion-exchangeable layered silicates. These combinations may be used in combination with treatment agents added at the start of the process. They may also be used in combination with treatment agents added during the process.

[0079] The salt treatment described above may be carried out using a suitable solvent in which the treatment agent is dissolved to form a treatment agent solution. Alternatively, the treatment agent itself may be used as the solvent. Suitable solvents include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethylformamide. Preferably, water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers are used; more preferably, water, alcohols, aliphatic hydrocarbons, and ethers; and most preferably, water and alcohols. Furthermore, the concentration of the treatment agent in the treatment solution is preferably about 0.1% to 100% by mass, and more preferably about 5% to 50% by mass. A benefit of this concentration range is that the processing time is shortened, enabling more efficient production.

[0080] Furthermore, it is preferable to perform washing with a solvent as a chemical treatment. Washing dissolves soluble compounds and impurities, and exchanges cations present between the layers of the ion-exchangeable layered silicate. Washing can also remove any remaining acids, bases, salts, or solvents from the aforementioned treatment with acids, bases, or salts.

[0081] Solvents used for washing include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethylformamide. Two or more of these may be used in mixture form. Preferably, the solvents are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers; more preferably, water, alcohols, aliphatic hydrocarbons, and ethers; more preferably, water, alcohols, and mixed solvents thereof; particularly preferably, water. Furthermore, there are no restrictions on the temperature during washing. The temperature is preferably 0°C to 100°C, more preferably 50°C to 95°C, and even more preferably 10°C to 60°C. There are no particular restrictions on the solid content concentration in the solvent during washing. The concentration is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 8% to 30% by mass. There are no restrictions on the washing time. The washing time is preferably 1 minute to 3000 minutes, more preferably 3 minutes to 1500 minutes, and even more preferably 5 minutes to 750 minutes.

[0082] There are no particular restrictions on the solid-liquid separation method used to separate the solvent from the ion-exchangeable layered silicate (composite) particles. Examples include sedimentation separation, filtration separation, centrifugal sedimentation separation, and centrifugal filtration. These methods may be performed multiple times, or multiple methods may be combined. The cleaning rate is preferably 1 / 5 to 1 / 10000, more preferably 1 / 10 to 1 / 1000. Here, the cleaning rate represents the percentage of solvent remaining at the start of cleaning. For example, if cleaning is performed by contacting 100 L of solvent with ion-exchangeable layered silicate (composite) particles and then removing 90 L of solvent, the cleaning rate will be (100-90) / 100 = 1 / 10. Furthermore, the supernatant liquid, which indicates the amount of remaining ions, can be washed until its electrical conductivity is preferably 1000 mS / cm or less, more preferably 100 mS / cm or less, even more preferably 10 mS / cm or less, and most preferably 1 mS / cm or less.

[0083] (4) Other processes After performing 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. It is preferable to dry the material in a way that does not cause structural damage to the ion-exchangeable layered silicate particles. The drying temperature can generally be 100°C to 800°C, preferably 120°C to 600°C, and is 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 reduced pressure.

[0084] These ion-exchangeable layered silicate particles change their properties depending on the drying temperature, even without structural breakdown; therefore, it is preferable to vary the drying temperature depending on the application. When used as a component of an olefin polymerization catalyst, the moisture content after removal is preferably 3% by mass or less, more preferably 1% by mass or less, when the moisture content after dehydration at a temperature of 200°C and a pressure of 1 mmHg for 2 hours is considered to be 0% by mass.

[0085] 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 described above. Therefore, the ion-exchangeable layered silicate particles of the present invention are widely used as a support for olefin polymerization catalysts, a catalyst for organic chemical reactions, for dehydration, decolorization, and purification of petroleum and oils, as well as as a drying agent, adsorbent, bleaching agent, and the like.

[0086] 2. Catalyst components for olefin polymerization The catalyst component for olefin polymerization 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 support, co-catalyst, etc. The pore structure in ion-exchange layered silicate particles affects the performance of the catalyst, including its activity and strength. Furthermore, this pore structure also influences economic efficiency, operability, and product quality. The ion-exchangeable layered silicate particles of the present invention, as shown above, have a pore distribution curve calculated by the BJH method from desorption isotherms measured by nitrogen adsorption-desorption, in which the sum of pore volumes with diameters of 2 nm to 10 nm has a specific range relative to the total mesopore volume. That is, the sum of pore volumes with diameters exceeding 10 nm and less than or equal to 50 nm is larger than conventional pores relative to the total mesopore volume, and the specific surface area is large within a specific range. Because they have a novel pore structure, the ion-exchangeable layered silicate particles of the present invention 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, olefin polymers can be produced with high polymerization activity. Furthermore, when the ion-exchangeable layered silicate particles of the present invention are used as a catalyst component for olefin polymerization, it is also possible to produce olefin polymers with fewer fish-eye particles in the product, which can degrade the product's appearance.

[0087] The method of using the catalyst component for olefin polymerization of the present invention is not particularly limited. For example, the method described in Japanese Patent Publication No. 2002-053611 and Japanese Patent Publication No. 2009-280443 can be used. In particular, using it as a catalyst for olefin polymerization, as described later, is preferable because it is easier to obtain improved catalytic performance.

[0088] 3. Catalysts for olefin polymerization The olefin polymerization catalyst of the present invention is characterized by comprising the following components [A], [B], and [C]. Component [A]: Ion-exchangeable layered silicate particles of the present invention. Component [B]: Transition metal compound from Group 4 of the periodic table Ingredients [C]: Organoaluminum compounds

[0089] 3-1. Components of Catalysts for Olefin Polymerization <Ingredients [A]> 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 those described above, so their explanation is omitted here.

[0090] <Ingredient [B]> The preferred Group 4 transition metal compound of component [B] used in the present invention is a metallocene compound having at least one conjugated five-membered ring ligand. Preferred such transition metal compounds are those represented by the following general formulas (1) to (4).

[0091] [ka] [In the above general formulas (1) to (4), A and A' represent conjugated five-membered ring ligands which may have substituents (A and A' may be the same or different within the same compound), Q represents a bonding group that bridges two conjugated five-membered ring ligands at any position, Z represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, hydrogen atom, halogen atom, or hydrocarbon group, and Z' represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, or hydrocarbon group. Q' represents a bonding group that bridges Z at any position on the conjugated five-membered ring ligand, M represents a metal atom selected from Group 4 of the periodic table, and X and Y represent a hydrogen atom, 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 within the same compound).

[0092] Examples of conjugated five-membered ring ligands for A and A' include substituents derived from cyclopentadiene, indene, tetrahydroindene, fluorene, azulene, and tetrahydroazulene. These substituents may be unsubstituted or substituted. Of these, substituted or unsubstituted indenyl or azulenyl groups are particularly preferred.

[0093] Substituents on the conjugated five-membered ring ligand include, in addition to the aforementioned hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, hydrocarbon groups having 1 to 30 carbon atoms substituted with halogens such as fluorine, chlorine, and bromine, halogen atom groups such as fluorine, chlorine, and bromine, and alkoxy groups having 1 to 12 carbon atoms, for example, -Si(R 1 )(R 2 )(R 3 Silicon-containing hydrocarbon groups represented by ), -P(R 1 )(R 2 A phosphorus-containing hydrocarbon group represented by ), or -B(R 1 )(R 2 Examples include boron-containing hydrocarbon groups represented by ). If there are multiple substituents, each substituent may be the same or different. The above R 1 , R2 , R 3 These may be the same or different, and represent an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms. Furthermore, substituents on the conjugated five-membered ring ligand may have at least one group 15-16 element (i.e., a heteroatom). Preferred examples of such substituents include monocyclic or polycyclic substituents containing at least one heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, and phosphorus atoms in the five-membered or six-membered ring. More preferably, substituents are derived from optionally substituted heteroaromatic compounds, and particularly preferably are optionally substituted furyl groups and optionally substituted thienyl groups. In the case of compounds having a bridging group represented by general formula (2) or (4), these substituents are not particularly limited, but are preferably located at the α-position (relative to the bonding site with the bridging group) on the conjugated five-membered ring ligand.

[0094] Q represents a bonding group that bridges two conjugated five-membered ring ligands at any position, and Q' represents a bonding group that bridges any position of a conjugated five-membered ring ligand with the group indicated by Z. The following are specific examples of Q and Q': (a) Alkylene groups such as methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, and cyclohexylene group. (b) Silylene groups such as dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disylylene group, tetramethyldisylylene group, and silaciclobutylene group. (h) Hydrocarbon groups containing germanium, phosphorus, nitrogen, boron, or aluminum

[0095] More specifically, these include groups represented by (CH3)2Ge, (C6H5)2Ge, (CH3)P, (C6H5)P, (C4H9)N, (C6H5)N, (C4H9)B, (C6H5)B, (C6H5)Al, and (C6H5O)Al. Preferably, alkylene groups or silylene groups.

[0096] Furthermore, M represents a metal atom, specifically a transition metal atom selected from Group 4 of the periodic table. Examples of M include titanium, zirconium, and hafnium. Zirconium and hafnium are particularly preferred. Furthermore, Z represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, a hydrogen atom, a halogen atom, or a hydrocarbon group, and Z' represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, or a hydrocarbon group. Preferred specific examples of Z and Z' include oxygen-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; sulfur-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; silicon-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; nitrogen-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; phosphorus-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; and hydrocarbon groups having 1 to 20 carbon atoms. Further preferred specific examples of Z include hydrogen atoms, chlorine atoms, and bromine atoms.

[0097] X and Y are, respectively, 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 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a diphenylphosphono group, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a trimethylsilyl group or a bis(trimethylsilyl)methyl group. X and Y may be the same or different. Of these, halogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, and amino groups having 1 to 12 carbon atoms are particularly preferred.

[0098] Examples of compounds represented by general formula (1) include: (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, These are some examples.

[0099] Examples of compounds represented by general formula (2) include: (1) Dimethylsilylenebis{1-(2-methyl-4-isopropyl-4H-azlenyl)}zirconium dichloride, (2) Dimethylsilylenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (3) Dimethylsilylenebis[1-{2-methyl-4-(4-fluorophenyl)-4H-azlenyl}]zirconium dichloride, (4) Dimethylsilylenebis[1-{2-methyl-4-(2,6-dimethylphenyl)-4H-azlenyl}]zirconium dichloride, (5) Dimethylsilylenebis{1-(2-methyl-4,6-diisopropyl-4H-azlenyl)}zirconium dichloride, (6) Diphenylsilylenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (7) Dimethylsilylenebis{1-(2-ethyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (8) Ethylene bis{1-[2-methyl-4-(4-biphenylyl)-4H-azlenyl]}zirconium dichloride, (9) Dimethylsilylenebis{1-[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azlenyl]}zirconium dichloride, (10) Dimethylsilylenebis{1-[2-methyl-4-(2',6'-dimethyl-4-biphenylyl)-4H-azlenyl]}zirconium dichloride, (11) Dimethylsilylene {1-[2-methyl-4-(4-biphenylyl)-4H-azlenyl]}{1-[2-methyl-4-(4-biphenylyl)indenyl]} zirconium dichloride, (12) Dimethylsilylene {1-(2-ethyl-4-phenyl-4H-azlenyl)}{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride, (13) Dimethylsilylenebis{1-(2-ethyl-4-phenyl-7-fluoro-4H-azlenyl)}zirconium dichloride, (14) Dimethylsilylenebis{1-(2-ethyl-4-indolyl-4H-azlenyl)}zirconium dichloride, (15) Dimethylsilylenebis[1-{2-ethyl-4-(3,5-bistrifluoromethylphenyl)-4H-azlenyl}]zirconium dichloride, (16) Dimethylsilylenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}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,

[0100] (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-azlenyl)}zirconium dichloride, (26) Isopropylidenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (27) Dimethylgermylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, (28) Dimethylgermylenebis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride, (29) Phenylphosphinobis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride, (30) Dimethylsilylenebis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride, (31) Dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride, (32) Dimethylsilylenebis[2-(2-furyl)-indenyl]zirconium dichloride, (33) Dimethylsilylenebis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, (34) Dimethylsilylenebis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, (35) Dimethylsilylene bis[2-(2-thienyl)-indenyl]zirconium dichloride, (36) Dimethylsilylene [2-(2-(5-methyl)furyl)-4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride, (37) Dimethylsilylene bis(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) Silacylbutylenebis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride,

[0101] (41) Silacic butylene bis[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (42) Silacylbutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (43) Silacic butylene bis[2-(5-t-butyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (44) Silacic butylene bis[2-(5-phenyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (45) Silacic butylene bis[2-(2-thienyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (46) Silacic butylene bis[2-(5-methyl-2-thienyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (47) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-5-methyl-1-indenyl]zirconium dichloride, (48) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-5-methyl-1-indenyl]zirconium dichloride, (49) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-5-methyl-1-indenyl] zirconium dichloride, (50) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (51) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-5-methyl-1-indenyl] zirconium dichloride, (52) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (53) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-5-methyl-1-indenyl]zirconium dichloride, (54) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-5-methyl-1-indenyl]zirconium dichloride, (55) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-5-methyl-1-indenyl]zirconium dichloride, (56) Silacic butylene bis[2-(2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (57) Silacic butylene bis[2-(5-methyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (58) Silacic butylene bis[2-(4,5-dimethyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (59) Silacic butylene bis[2-(5-t-butyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (60) Silacic butylene bis[2-(5-phenyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride,

[0102] (61) Silacic butylene bis[2-(2-thienyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (62) Silacic butylene bis[2-(5-methyl-2-thienyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (63) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (64) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (65) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (66) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (67) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (68) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (69) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (70) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (71) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (72) Silacylbutylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (73) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (74) Silacylbutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (75) Silacylbutylenebis[2-(5-t-butyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (76) Silacylbutylenebis[2-(5-phenyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (77) Silacic butylene bis[2-(2-thienyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (78) Silacic butylene bis[2-(5-methyl-2-thienyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (79) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (80) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride,

[0103] (81) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (82) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (83) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (84) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (85) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (86) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (87) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (88) Silacic butylene bis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indasen-1-yl]zirconium dichloride, (89) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indasen-1-yl]zirconium dichloride, (90) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2,5-dimethyl-4-phenyl-1-indenyl] zirconium dichloride, (91) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(2-furyl)-4-phenyl-5-methyl-1-indenyl] zirconium dichloride, (92) Silacic butylene [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) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-1-indenyl] zirconium dichloride, (94) Silacic butylene [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) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride, (96) Silacycyclopentylenebis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (97) Silacycyclopentylenebis[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-indacen-1-yl]zirconium dichloride, (99) Silacicopentylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, etc.

[0104] Examples of compounds represented by general formula (3) include: (1) (Tetramethylcyclopentadienyl)titanium (bis-t-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-azlenyl)titanium {bis(trimethylsilyl)amide}dichloride, (6) (2-methylindenyl)titanium (bis-t-butylamide) dichloride, (7) (Fluorenyl)titanium (bis-t-butylamide) dichloride, (8) (3,6-diisopropylfluorenyl)titanium(bis-t-butylamide)dichloride, (9) (Tetramethylcyclopentadienyl)titanium (phenoxide) dichloride, (10) (Tetramethylcyclopentadienyl)titanium (2,6-diisopropylphenoxide) dichloride, These are some examples.

[0105] Examples of compounds represented by general formula (4) include: (1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamide) titanium dichloride, (2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride, (3) Dimethylsilanediyl (2-methylindenyl)(t-butylamide)titanium dichloride, (4) Examples include dimethylsilanediyl (fluorenyl) (t-butylamide) titanium dichloride.

[0106] Compounds in which the dichloride in these example compounds is replaced with dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide, etc., are also similarly exemplified. Furthermore, compounds in which zirconium in the example compounds is replaced with hafnium or titanium, and titanium is replaced with hafnium or zirconium, are also similarly exemplified.

[0107] The transition metal compound used in this invention is preferably the compound represented by general formula (2). Furthermore, metallocene compounds can be used individually or in combination of two or more.

[0108] When using two or more types in combination, you can choose two or more compounds from the group of compounds included in any one of the general formulas (1) to (4) above. Furthermore, you can also choose one or more compounds selected from the group of compounds included in one general formula and one or more compounds selected from the group of compounds included in another general formula.

[0109] <Ingredient [C]> The component [C] is the general formula (AlR n X 3-n ) m The organoaluminum compounds represented by the formula are used. In the formula, R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, alkoxy group, or amino group, n represents an integer from 1 to 3, and m represents an integer from 1 to 2. Organoaluminum compounds can be used individually or in combination.

[0110] Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, trin-n-propylaluminum, trin-n-butylaluminum, triisobutylaluminum, trin-n-hexylaluminum, trin-n-octylaluminum, trin-n-decylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, the preferred are trialkylaluminum and alkylaluminum hydride with m=1 and n=3. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

[0111] 3-2. Preparation of catalysts for olefin polymerization and prepolymerization The present invention relates to a method for producing an olefin polymerization catalyst, characterized by mixing the following components [A], [B], and [C]. The olefin polymerization catalyst of the present invention is formed by contacting component [B] with component [A] and component [C]. The method of contact is not particularly limited, but contact can be made in the following order. Furthermore, this contact may be carried out not only during catalyst preparation, but also during prepolymerization with olefins or during polymerization of olefins. A solvent may be used to ensure sufficient contact during these interactions. 1) Bring component [B] and component [A] into contact. 2) After bringing component [B] and component [A] into contact, add component [C]. 3) After bringing component [B] and component [C] into contact, add component [A]. 4) After bringing components [A] and [C] into contact, add component [B]. Alternatively, the three components may be brought into contact simultaneously.

[0112] A preferred contact method is to bring component [A] and component [C] as described in 4) above into contact, remove any unreacted component [C] by washing or the like, then bring the minimum necessary amount of component [C] into contact with component [A] again, and then bring component [B] into contact.

[0113] The molar ratio of Al in component [C] to the transition metal in component [B] is in the range of 0.1 to 1,000, preferably 1 to 100, and more preferably 4 to 50.

[0114] There are no particular restrictions on the contact temperature, but it is preferably 0°C to 100°C, more preferably 10°C to 80°C, and most preferably 20°C to 60°C.

[0115] Organic solvents are preferred as solvents. Saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, and olefins (described later) are more preferred. These may be used individually or in combination. There are no restrictions on the concentration of component [B] in the solvent, but it is preferably 3 mmol / L to 50 mmol / L, more preferably 4 mmol / L to 40 mmol / L, and even more preferably 6 mmol / L to 30 mmol / L. The amount of component [B] used is preferably in the range of 0.001 mmol to 10 mmol, more preferably 0.001 mmol to 1 mmol, per 1 g of component [A].

[0116] The olefin polymerization catalyst of the present invention may undergo a prepolymerization treatment, which involves contacting an olefin and polymerizing a small amount of it. The olefin used is not particularly limited. It is possible to use ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, or styrene, with ethylene or propylene being particularly preferred. Any method can be used to supply the olefin. For example, methods include supplying the olefin to the reaction vessel at a constant rate or under constant pressure, or a combination of these methods, or by introducing stepwise changes.

[0117] The pre-polymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. Furthermore, the amount of prepolymerization is preferably 0.01 to 100, and more preferably 0.1 to 50, of the amount of prepolymerized polymer per part of 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. Prepolymerization can be carried out in a liquid such as an organic solvent, and this is preferable. There are no particular restrictions on the concentration of the solid catalyst during prepolymerization, but it is preferably 10 g / L to 300 g / L, more preferably 20 g / L to 200 g / L, and especially preferably 25 g / L to 150 g / L.

[0118] The catalyst may be dried after contact with each component. There are no particular restrictions on the drying method. Examples include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used individually or in combination of two or more methods. During the drying process, the catalyst may be stirred, vibrated, or allowed to flow, or it may be left to stand still.

[0119] Furthermore, it is possible to include polymers such as polyethylene, polypropylene, and polystyrene, or inorganic oxide solids such as silica and titania, during or after contact with each of the above components. Additionally, various surfactants, antistatic agents, and donors known in olefin polymerization catalysts such as alkoxysilanes, aminosilanes, ethers, phthalates, and carboxylic acid esters can be added.

[0120] 4. Method for producing olefin polymers The present invention provides a method for producing an olefin polymer, characterized by carrying out olefin polymerization using the olefin polymerization catalyst of the present invention. The method for producing an olefin (co)polymer involves homopolymerizing or copolymerizing 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 type of α-olefin is polymerized, or two or more types of α-olefins are copolymerized. In this specification, (co)polymer means at least one of a homopolymer and a copolymer.

[0121] In copolymerization, the relative amounts of each monomer in the reaction system do not need to remain constant over time; it is possible to supply each monomer in a constant mixing ratio. Furthermore, it is possible to change the mixing ratio of the supplied monomers over time. Additionally, it is possible to add one of the monomers in stages, taking into account the copolymerization reaction ratio.

[0122] Polymerizable α-olefins are preferably those having 2 to 20 carbon atoms, specifically including ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1, 7-octadiene, cyclopentene, norbornene, and ethylidenenorbornene. Preferably, they are α-olefins having 2 to 8 carbon atoms, and more preferably ethylene or propylene.

[0123] In copolymerization, the type of comonomer used can be selected from the above-mentioned α-olefins, with the exception of the main component, by selecting one or more α-olefins. The preferred main component of the comonomer is propylene.

[0124] Any polymerization method can be employed, as long as the catalyst component and each monomer can come into efficient contact. Specifically, methods such as slurry methods using inert solvents, methods using monomers such as propylene as solvents without substantially using inert solvents, solution polymerization, or gas-phase methods that keep each monomer in gaseous form without substantially using liquid solvents can be employed. In addition, methods involving continuous polymerization, batch polymerization, or prepolymerization can also be applied.

[0125] In slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, either alone or in mixtures, are used as polymerization solvents. The polymerization temperature is typically between 0°C and 150°C.

[0126] Hydrogen can also be used as a molecular weight modifier. Furthermore, compounds that deactivate the catalyst, such as oxygen or alcohol, may be supplied to adjust the reaction rate. Known additives such as oxygen, alcohol, alkoxysilane, and surfactants may be added to improve operability. Polymerization pressure is 0 kg / cm² 2 ~2000 kg / cm 2 G (≒0MPaG~196.14MPaG), preferably 0kg / cm 2 ~60kg / cm 2 A suitable pressure range is G (approximately 0 MPa G to 5.88 MPa G).

[0127] The olefin (co)polymer obtained by the method for producing olefin (co)polymers is not particularly limited. For example, ethylene homopolymers, propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, and propylene / ethylene-α-olefin copolymers are preferred.

[0128] The olefin polymer obtained by the manufacturing method of the present invention has fewer fish-eyes that degrade the appearance of the product. The olefin polymer obtained by the manufacturing method of the present invention is preferable as it has fewer fisheyes. The ideal number of fisheyes is 0 per 900 mm. 2 ~100 pieces / 900mm 2 It may be 0 pieces / 900mm, preferably 0 pieces / 900mm 2 ~70 pieces / 900mm 2 That's fine. Mixtures of incompatible polymers are called impact copolymers or block copolymers. These are obtained by multi-stage polymerization or polymer compounding. Fish eyes in these mixtures can occur due to poor dispersion caused by the compatibility (composition), mixing ratio, and molecular weight differences (viscosity differences) of the polymers. Generally, fish eyes tend to increase when compatibility is low or when there are large differences in molecular weight and viscosity of each component. The measurement methods for each of the above characteristics will be described later, so they are omitted here. [Examples]

[0129] The present invention will now be specifically described with reference to examples, but the present invention is not limited by these examples as long as it does not depart from its essence. The measurement method in these examples is as follows.

[0130] (Various physical property measurement methods) [Compositional analysis of ion-exchange layered silicates and ion-exchange layered silicate particles] A calibration curve was created in accordance with JIS R2212, and the composition of ion-exchangeable layered silicate and ion-exchangeable layered silicate particles was quantified by X-ray fluorescence measurement. The equipment used was the Rigaku ZSX Primus IV. The sample was prepared by firing it at 1050°C for 1 hour, then separating 0.4g, mixing it with 4g of flux (Li2B4O7) and 15μL of 50% LiBr aqueous solution (release agent), and creating a glass bead.

[0131] [Method for calculating the elution rate of Al (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.

[0132] [Particle size of ion-exchange layered silicate (raw material)] The equivalent circle diameter measured by the following method was defined as the particle size. The procedure was carried out according to the method described in SCANNING VOL.26, 131-134 (2004). A high-resolution graphite surface was treated with polydiallyldimethylammonium chloride to prepare the substrate. An aqueous slurry of ion-exchangeable layered silicate, adjusted to 0.001 wt% and thoroughly dispersed by ultrasonic irradiation for 30 minutes, was applied to this substrate. Subsequently, the moisture was adsorbed with filter paper, and the sample was prepared by blowing air onto it. Secondary electron images of the ion-exchangeable silicate on this substrate were taken by SEM. After imaging, the images were binarized by image processing, and the area of ​​each particle was determined. After imaging until the number of particles exceeded 10,000, the particle size was defined as the diameter at which the area integrated value relative to the equivalent circle diameter was 50%. The SEM imaging conditions are as follows: Equipment used: Hitachi High-Technologies Corporation SU8020 Field Emission Scanning Electron Microscope. Measurement conditions: Data Size: 1280x960 Acceleration voltage: 800 Volts Working distance: 3mm Device magnification: 10K

[0133] [Pore distribution measurement and specific surface area measurement] The adsorption and desorption isotherms of ion-exchangeable layered silicate particles were measured using the nitrogen adsorption method. Using the obtained adsorption isotherms, BET multipoint analysis (Rouquerol transformation) was performed to determine the specific surface area of ​​the ion-exchangeable layered silicate particles. Furthermore, the pore distribution was calculated using the BJH (Barrett, Joyner, Hallender, J.Am.Chem. Soc.1951, P373) method analysis with desorption isotherms. The c value was not kept constant, and calculations were performed for each measured value. The thickness t (Å) of the adsorption layer was determined using de Boer's formula. t(Å)=[13.99 / (log(P0 / P)+0.034)] 1 / 2 The specific measurement conditions were as follows: Equipment: Anton-Paar Autosorb-iQ3 gas adsorption measurement device Measurement method: Nitrogen gas adsorption method Pretreatment conditions: Heat the sample under reduced pressure (1.3 Pa or less) at 200°C for 2 hours. Sample quantity: Approximately 0.2g Gas liquefaction temperature: 77K

[0134] [Measurement of average particle size] The average particle diameter was measured using a HORIBA LA-960 laser diffraction / scattering particle size distribution analyzer, after ultrasonic dispersion under the following conditions: ethanol as the dispersion solvent, real refractive index term 1.490, imaginary term 0.000, and real refractive index term 1.360 for the dispersion solvent. The average particle diameter refers to the median diameter based on volume.

[0135] [X-ray diffraction (XRD)] X-ray diffraction measurements were performed under atmospheric conditions as follows: • Instrument: Rigaku X-ray Diffractometer Smartlab • X-ray source: Cu-Kα rays (using Kβ absorption plate), tube voltage 40kV, tube current 30mA • Optical system: Focusing method • Divergence slit 2 / 3 degrees, scattering slit 2 / 3 degrees, receiving slit 0.300mm • Scan mode: 2θ / θ scan • 2θ scan range: 1.0000° to 70.0000° • Angle step size: 0.0200° • Scan speed: 4.0000° / min • Detector: Scintillation counter • Sample holder: Glass holder with a depth of 0.2mm

[0136] [Crushing strength] Using the Shimadzu Corporation's "MCT-210" crushing tester, and referring to JIS R 1639-5:2007, 20 particles selected to avoid size bias were measured at a temperature of 23°C, humidity of 35%, and a loading speed of 1.9 mN / sec. The crushing strength of the particles was then calculated according to the following formula. S = 2.48·P / (π·d 2 ) (S: Crushing strength (MPa), P: Test pressure at fracture (N), d: Diameter = Average value of the major axis diameter and minor axis diameter of the particle (μm)) Note that 'd' was measured using an optical microscope. The average of the crushing intensities of the 20 obtained particles was defined as the average crushing intensity. Furthermore, for the 20 obtained particles, the crushing strength S (MPa) and volume V (volume was calculated assuming a perfect sphere with the aforementioned diameter d; the unit is μm) were determined. 3 From the results of ), the coefficient 1 / m in equation (1) below and S0·V0 can be obtained by the least squares method. 1 / m The result was calculated. S=(S0·V0 1 / m )·V -1 / m ...Equation (1) (In equation (1), S is the crushing strength (MPa) of the ion-exchangeable layered silicate particles, S0 is the crushing strength at a unit volume V0, and V is the volume (μm) of the ion-exchangeable layered silicate particles. 3 ), m is Weibull's coefficient of uniformity.

[0137] [MFR (Meltmass Flow Rate)] The measurements were taken using a melt indexer manufactured by Takara Corporation, in accordance with the test conditions of JIS K7210, "Plastics - Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastic plastics": 230°C, 2.16 kg load.

[0138] [Measuring the number of fisheyes] To 20 g of polymer, 10 mg each of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), tris(2,4-di-tert-butylphenyl) phosphite, and calcium stearate were added. The mixture was kneaded using an Xplore microcompounder (DSM) at 200°C, 50 rpm, and 2 min, and then pressed to a thickness of 0.2 mm at 190°C, 10 MPa to obtain a sheet. The sheet was scanned using a Canon Cano Scan 9000F Mark II as a 1200 dpi, 8-bit grayscale image, and then the image was binarized. For this binarized image, a 30mm x 30mm area (square area: 900mm) was then examined. 2 The number of fisheyes was measured at three locations in the image, and the average value of the three locations was used as the number of fisheyes (unit: fisheyes / 900mm). 2 Points with 3 pixels or less were considered noise and were excluded from the measurement.

[0139] [Analytical methods for polymers containing ethylene-propylene copolymers] The determination was made using a method combining the cross-sorting method and the FT-IR method described in Japanese Patent Publication No. 2015-193605.

[0140] (Synthesis Example 1) Silacicbutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride was synthesized in the same manner as described in Example 7 of Japanese Patent Application Publication No. 2015-193605.

[0141] [Example a1: Production of ion-exchange layered silicate particles] (a1-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, a 5.0 wt% aqueous slurry of "Benclay KK" (main component: smectite montmorillonite with a 2:1 layered structure), manufactured by Mizusawa Chemical Industries, Ltd., 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 form a solution. 2,000 g of Benclay KK aqueous slurry (5.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 28,000 rpm • Cyclone differential pressure: 1.05 kPa • Dry air inlet temperature: 110℃ The slurry supply time was 202 minutes. 255 g of granules were obtained from the bottom of the cyclone and the main body. Coarse material was removed by passing this through a sieve with a mesh size of 75 μm. The sieved material 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 carried out by XRD, peaks derived from lithium sulfate monohydrate crystals were observed in addition to the peaks derived from ion-exchangeable layered silicate (montmorillonite).

[0142] (a1-2) Chemical treatment (1) of ion-exchangeable layered silicate composite particles 350 g of distilled water was charged 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 sulfuric acid aqueous 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 the above (a1-1) 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 500 mL of distilled water. The obtained slurry was suction filtered to obtain 151.3 g of the remaining solid content.

[0143] (a1-3) Chemical treatment (2) of ion-exchangeable layered silicate composite particles 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 for the reaction. The pH of the slurry after 90 minutes was 5.8. After pouring the reaction slurry into 450 mL of distilled water, it was suction filtered. The recovered solid content was washed three times with 450 mL of distilled water. After washing, the solid content was dried at 110°C overnight, and coarse materials were removed through a sieve with a mesh size of 75 μm. The fraction passing through the sieve was dried at 200°C under reduced pressure for 2 hours to obtain 38.6 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0144] [Example a2: Production of ion-exchangeable layered silicate particles] (a2-1) Production of ion-exchangeable layered silicate composite particles As the ion-exchangeable layered silicate, an aqueous slurry (5.0 wt%) of "Benclay KK" manufactured by Mizusawa Chemical Industry Co., Ltd. (the main component is smectite group montmorillonite with a 2:1 type layer structure) was used. 50.0 g of lithium sulfate monohydrate and 500 g of distilled water were added to a 5 L beaker and stirred to form a solution. To this solution, 2,000 g of a water slurry (5.0 wt%) of Benclay KK was slowly added while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. The above operations were carried out twice. Using the obtained two batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulation apparatus (L-8, manufactured by Okawara Chemical Industries Co., Ltd.). · Atomizer type: M type rotary disk · Atomizer rotation speed: 28,000 rpm · Cyclone differential pressure: 1.05 kPa · Dry air inlet temperature: 150 °C The supply time of the slurry was 195 minutes. The granulated product obtained at the lower part of the cyclone and the lower part of the main body was 304 g. Coarse particles were removed by passing this through a sieve with a mesh opening of 75 μm. The fraction passing through the sieve was dried at 200 °C under reduced pressure for 2 hours to obtain 255 g of ion-exchangeable layered silicate composite particles. When analysis was performed by XRD, peaks derived from lithium sulfate monohydrate crystals were observed in addition to the peaks derived from the ion-exchangeable layered silicate (montmorillonite).

[0145] (a2-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was charged 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 sulfuric acid aqueous 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 obtained in (a2-1) 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 800 mL of distilled water. The obtained slurry was suction filtered, and the remaining solid content was washed with 400 mL of distilled water.

[0146] (a2-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) The 123.7 g of solid obtained in (a2-2) above and 262.3 g of distilled water were added to a 1 L flask and stirred. The slurry was heated to 40°C, and 9.7 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.81. The reaction slurry was poured into 450 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 300 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 34.6 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0147] [Example a3: Production of ion-exchange layered silicate particles] (a3-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used a 5.0 wt% aqueous slurry of "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (whose main component is montmorillonite of the smectite group with a 2:1 layered structure). 30.6 g of lithium sulfate monohydrate and 240 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,100 g of Benclay KK aqueous slurry (5.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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. 214 g of granules were obtained from the lower part of the cyclone and the lower part of the main unit. Of these, the granules obtained from the lower part of the main unit were passed through a sieve with a mesh size of 75 μm to remove coarse material. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 94.5 g of ion-exchangeable layered silicate composite particles.

[0148] (a3-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 225 g of distilled water was added to a 500 mL flask equipped with a stirring blade and reflux apparatus, and 57 g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 45 g of the ion-exchangeable layered silicate composite particles described in (a3-1) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 500 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed twice with 500 mL of distilled water.

[0149] (a3-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 66.6 g of the solid component from (a3-2) above and 181.4 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 4.7 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.57. The reaction slurry was poured into 450 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 300 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 23.8 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0150] [Example a4: Production of ion-exchange layered silicate particles] (a4-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used a 5.0 wt% aqueous slurry of "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (whose main component is montmorillonite of the smectite group with a 2:1 layered structure). 58.0 g of lithium sulfate monohydrate and 440 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,000 g of Benclay KK aqueous slurry (5.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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. 258 g of granules were obtained from the lower part of the cyclone and the lower part of the main body. Of these, the granules obtained from the lower part of the main body were passed through a sieve with a mesh size of 75 μm to remove coarse material. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 166.3 g of ion-exchangeable layered silicate composite particles.

[0151] (a4-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux device, and 88 g of 96% sulfuric acid was added dropwise. This 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 described in (a4-2) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed with 400 mL of distilled water.

[0152] (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 slurry was heated to 40 °C, and 10.1 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto. Then, stirring was continued for 90 minutes to cause a reaction. The pH of the slurry after 90 minutes was 5.63. The reaction slurry was poured into 800 mL of distilled water and then subjected to suction filtration. The recovered solid content was washed three times with 450 mL of distilled water. After washing, the solid content was dried at 110 °C overnight, and coarse materials were removed through a sieve with a mesh size of 75 μm. The fraction passing through the sieve was dried at 200 °C under reduced pressure for 2 hours to obtain 33.0 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0153] [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 (1) of ion-exchangeable layered silicate composite particles 350 g of distilled water was charged 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. At 95 °C, 70 g of the ion-exchangeable layered silicate composite particles of (a5-1) was added, and 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 subjected to suction filtration, and the remaining solid content was washed with 400 mL of distilled water.

[0154] (a5-3) Chemical treatment (2) of ion-exchangeable layered silicate composite particles 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 slurry was heated to 40 °C, and 8.9 g of a 4.43 wt% lithium hydroxide aqueous solution was added dropwise thereto. Then, stirring was continued for 90 minutes to cause a reaction. The pH of the slurry after 90 minutes was 5.48. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 31.6 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0155] [Example a6: Production of ion-exchange layered silicate particles] (a6-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry of purified clay mineral from Nakajo, Niigata Prefecture, manufactured by Mizusawa Chemical Industry Co., Ltd., which was purified by elutriation and centrifugation (main component: montmorillonite of the smectite group with a 2:1 layered structure, solid content 4.0 wt%). 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 form a solution. 2,000 g of the aforementioned aqueous slurry (4.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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 slurry supply time was 333 minutes. The amount of granules obtained at the bottom of the main body was 164 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 113.1 g of ion-exchangeable layered silicate composite particles.

[0156] (a6-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350g of distilled water was added to a 1L flask equipped with a stirring blade and reflux apparatus, and 88g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 100g of the ion-exchangeable layered silicate composite particles described in (a6-1) above was added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water.

[0157] (a6-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 110.7 g of the solid component from (a6-2) above and 265.5 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 7.5 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.52. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 33.7 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0158] [Example a7: Production of ion-exchange layered silicate particles] (a7-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry of a purified product manufactured by Mizusawa Chemical Industry Co., Ltd., which was produced by kneading 3 wt% sodium carbonate with clay minerals from Nakajo, Niigata Prefecture, and then purifying it by elutriation and centrifugation (the main component was montmorillonite of the smectite group with a 2:1 layered structure, and the solid content was 3.8 wt%). 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 form a solution. 2,500 g of the aforementioned aqueous slurry (3.8 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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 slurry supply time was 317 minutes. The amount of granules obtained at the bottom of the main body was 176 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 122.6 g of ion-exchangeable layered silicate composite particles. XRD analysis revealed peaks originating from ion-exchange layered silicate (montmorillonite) as well as peaks originating from lithium sulfate monohydrate crystals.

[0159] (a7-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux apparatus, and 88 g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 100 g of the ion-exchangeable layered silicate composite particles described in (a7-1) above was added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water.

[0160] (a7-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 123.4 g of the solid component from (a7-2) above and 252.8 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 6.8 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.49. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 30.9 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0161] [Example a8: Production of ion-exchange layered silicate particles] (a8-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry of a purified product manufactured by Mizusawa Chemical Industry Co., Ltd., which was produced by kneading 3 wt% sodium carbonate with clay minerals from Nakajo, Niigata Prefecture, and then purifying it by elutriation and centrifugation (the main component is montmorillonite of the smectite group with a 2:1 layered structure, and the solid content is 3.8 wt%). 75.0 g of lithium sulfate monohydrate and 333 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,500 g of the aforementioned aqueous slurry (3.8 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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 slurry supply time was 320 minutes. 200 g of granules were obtained at the bottom of the main body. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 115.5 g of ion-exchangeable layered silicate composite particles. XRD analysis revealed peaks originating from ion-exchange layered silicate (montmorillonite) as well as peaks originating from lithium sulfate monohydrate crystals.

[0162] (a8-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux apparatus, and 93 g of 96% sulfuric acid was added dropwise. This 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 described in (a8-1) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water.

[0163] (a8-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 113.2 g of the solid component from (a8-2) above and 263.0 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 6.6 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.51. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 23.2 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0164] [Example a9: Production of ion-exchange layered silicate particles] (a9-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry of a purified product manufactured by Mizusawa Chemical Industry Co., Ltd., which was produced by kneading 3 wt% sodium carbonate with clay minerals from Nakajo, Niigata Prefecture, and then purifying it by elutriation and centrifugation (the main component is montmorillonite of the smectite group with a 2:1 layered structure, and the solid content is 3.8 wt%). 37.0 g of lithium sulfate monohydrate and 225 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,500 g of the aforementioned aqueous slurry (3.8 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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 slurry supply time was 350 minutes. The amount of granules obtained at the bottom of the main body was 163 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 110.2 g of ion-exchangeable layered silicate composite particles.

[0165] (a9-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux apparatus, and 80 g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 65 g of the ion-exchangeable layered silicate composite particles described in (a9-1) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water.

[0166] (a9-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 97.5 g of the solid component from (a9-2) above and 279.3 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 8.1 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.44. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 28.9 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0167] [Example a10: Production of ion-exchange layered silicate particles] (a10-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry of a purified product manufactured by Mizusawa Chemical Industry Co., Ltd., which was produced by kneading 3 wt% sodium carbonate with clay minerals from Nakajo, Niigata Prefecture, and then purifying it by elutriation and centrifugation (the main component is montmorillonite of the smectite group with a 2:1 layered structure, and the solid content is 3.8 wt%). 25.5 g of lithium sulfate monohydrate and 155 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,500 g of the aforementioned aqueous slurry (3.8 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the obtained slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: 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 slurry supply time was 340 minutes. The amount of granules obtained at the bottom of the main body was 153 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 81.8 g of ion-exchangeable layered silicate composite particles.

[0168] (a10-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux apparatus, and 75 g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 60 g of the ion-exchangeable layered silicate composite particles described in (a10-1) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water.

[0169] (a10-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 136.6 g of the solid component from (a10-2) above and 240.8 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 7.1 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.68. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 29.5 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0170] [Example a11: Production of ion-exchange layered silicate particles] (a11-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry (4.5 wt%) of "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (the main component is montmorillonite of the smectite group with a 2:1 layered structure). 94.0 g of lithium sulfate and 800 g of distilled water were added to a 5 L beaker and stirred to form a solution. To this solution, 1,800 g of Benclay KK aqueous slurry (4.5 wt%) was slowly added while stirring. After stirring for 10 minutes, the mixture was stirred again for 10 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two batches of slurry obtained, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 8000 rpm • Cyclone differential pressure: 1.10 kPa • Dry air inlet temperature: 110℃ The slurry was supplied for 307 minutes. The amount of granules obtained at the bottom of the main body was 214 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 93.7 g of ion-exchangeable layered silicate composite particles.

[0171] (a11-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 200 g of distilled water was added to a 500 mL flask equipped with a stirring blade and reflux apparatus, and 70 g of 96% sulfuric acid was added dropwise. This 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 described in (a11-1) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water.

[0172] (a11-3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 138.3 g of the solid component from (a11-2) and 146.7 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and 5.8 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.91. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 450 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 23.1 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0173] [Example a12: Production of ion-exchange layered silicate particles] (a12-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used a 5.0 wt% aqueous slurry of "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (whose main component is montmorillonite of the smectite group with a 2:1 layered structure). 30.0 g of lithium sulfate monohydrate and 500 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,000 g of Benclay KK aqueous slurry (5.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 28,000 rpm • Cyclone differential pressure: 1.05 kPa • Dry air inlet temperature: 110℃ The slurry supply time was 202 minutes. 255 g of granules were obtained from the lower part of the cyclone and the lower part of the main body. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 229 g of ion-exchangeable layered silicate composite particles. XRD analysis revealed peaks originating from ion-exchange layered silicate (montmorillonite) as well as peaks originating from lithium sulfate monohydrate crystals.

[0174] (a12-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 350 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux apparatus, and 88 g of 96% sulfuric acid was added dropwise. This 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 described in (a12-1) above were added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 500 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 500 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 39.0 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0175] [Example a13: Production of ion-exchange layered silicate particles] (a13-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used a 5.0 wt% aqueous slurry of "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (whose main component is montmorillonite of the smectite group with a 2:1 layered structure). 77.0 g of magnesium sulfate heptahydrate and 420 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,000 g of Benclay KK's aqueous slurry (5.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 28,000 rpm • Cyclone differential pressure: 1.05 kPa • Dry air inlet temperature: 110℃ The slurry supply time was 221 minutes. The amount of granules obtained in the lower part of the cyclone and the lower part of the main body was 298 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 250.3 g of ion-exchangeable layered silicate composite particles. XRD analysis revealed peaks originating from ion-exchange layered silicate (montmorillonite), as well as peaks originating from magnesium sulfate hexahydrate crystals.

[0176] (a13-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 500g of distilled water was added to a 1L flask equipped with a stirring blade and reflux apparatus, and 126g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 100g of the ion-exchangeable layered silicate composite particles described in (a13-1) above was added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and 109 g of the remaining solid was removed. The remaining solid was washed three times with 400 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 24.4 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0177] [Example a14: Production of ion-exchange layered silicate particles] (a14-1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used a 5.0 wt% aqueous slurry of "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (whose main component is montmorillonite of the smectite group with a 2:1 layered structure). 38.0 g of sodium sulfate and 460 g of distilled water were added to a 5 L beaker and stirred to form a solution. 2,000 g of Benclay KK aqueous slurry (5.0 wt%) was slowly added to this solution while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This procedure was repeated twice. Using the two resulting batches of slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 28,000 rpm • Cyclone differential pressure: 1.05 kPa • Dry air inlet temperature: 110℃ The slurry supply time was 192 minutes. The amount of granules obtained in the lower part of the cyclone and the lower part of the main body was 292 g. Coarse material was removed from these granules by passing them through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 247.1 g of ion-exchangeable layered silicate composite particles. XRD analysis revealed peaks originating from ion-exchange layered silicate (montmorillonite) as well as peaks originating from sodium sulfate crystals.

[0178] (a14-2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 500g of distilled water was added to a 1L flask equipped with a stirring blade and reflux apparatus, and 126g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 100g of the ion-exchangeable layered silicate composite particles described in (a14-1) above was added. The reaction was then carried out for 240 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 800 mL of distilled water. The resulting slurry was filtered by suction, and 102.9 g of the remaining solid was removed. The remaining solid was washed three times with 400 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 24.2 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 1.

[0179] [Table 1] mr represents the molar ratio.

[0180] [Comparative Example a1: Production of comparative ion-exchangeable layered silicate particles] (a1-i) As an ion-exchangeable layered silicate, we used "Benclay KK" manufactured by Mizusawa Chemical Industries Co., Ltd. (the main component being montmorillonite of the smectite group with a 2:1 layered structure). Granulated products of this product (median diameter 33.0 μm) were prepared as ion-exchangeable layered silicate particles. (a1-ii) Chemical treatment of ion-exchangeable layered silicate particles (1) 585g of distilled water was added to a 1L flask equipped with a stirring blade and reflux apparatus, and 75g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 90g of the aforementioned ion-exchangeable layered silicate particles were added. The reaction was then carried out for 505 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 900 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid 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 component from (a1-ii) above and 357.6 g of distilled water were added to a 1 L flask and stirred. The slurry was heated to 40°C, and 22.1 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.50. The reaction slurry was poured into 900 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 900 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 59.9 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 2.

[0181] [Comparative Example a2: Production of comparative ion-exchangeable layered silicate particles] (a2-i) As the ion-exchangeable layered silicate, we used an aqueous slurry of a purified clay mineral from Nakajo, Niigata Prefecture, manufactured by Mizusawa Chemical Industry Co., Ltd., which was purified by elutriation and centrifugation (the main component being montmorillonite of the smectite group with a 2:1 layered structure). 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) 585g of distilled water was added to a 1L flask equipped with a stirring blade and reflux apparatus, and 76g of 96% sulfuric acid was added dropwise. This sulfuric acid solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 90g of the aforementioned ion-exchangeable layered silicate particles were added. The reaction was then carried out for 360 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 900 mL of distilled water. The resulting slurry was filtered by suction, and the remaining solid was washed three times with 450 mL of distilled water. (a2-iii) Chemical treatment of ion-exchangeable layered silicate particles (2) 270.9 g of the solid component from (a2-ii) above and 355.1 g of distilled water were added to a 1 L flask and stirred. The slurry was heated to 40°C, and 20.6 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.51. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 900 mL of distilled water. After washing, the solid was dried overnight at 110°C, and coarse particles were removed by passing it through a sieve with a mesh size of 75 μm. The sieved material was dried at 200°C under reduced pressure for 2 hours to obtain 68.8 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 2.

[0182] [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 Japanese Patent Publication No. 2019-172958. The results of various analyses are shown in Table 2.

[0183] [Comparative Example a4: Production of comparative ion-exchangeable layered silicate particles] As the ion-exchangeable layered silicate, "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (main component is montmorillonite of the smectite group with a 2:1 layered structure) was used, and chemical treatment was carried out according to Example 5, Section 1 of Japanese Patent Application Publication No. 2015-108138 to obtain ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 2.

[0184] [Comparative Example a5: Production of comparative ion-exchangeable layered silicate particles] As the ion-exchangeable layered silicate, "Benclay KK" manufactured by Mizusawa Chemical Industries, Ltd. (main component is montmorillonite of the smectite group with a 2:1 layered structure) was used, and chemical treatment was carried out according to Example 4, Section 1 of Japanese Patent Application Publication No. 2015-108138 to obtain ion-exchangeable layered silicate particles. The results of various analyses are shown in Table 2.

[0185] [Comparative Example a6: Production of comparative ion-exchangeable layered silicate particles] Comparative ion-exchangeable layered silicate particles were produced in the same manner as in Comparative Example 3 of Japanese Patent Publication No. 2002-088114. The results of various analyses are shown in Table 2.

[0186] [Table 2] In the table, "mr" represents the molar ratio, and "-" indicates that the measurement was not taken.

[0187] [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 1000 mL flask and stirred. Then, 34 mL (24.5 mmol-Al) of triisobutylaluminum (TiBA) heptane solution was added and the mixture was stirred at room temperature for 1 hour. Subsequently, the obtained slurry was washed with heptane until the residual liquid volume was reduced to 1 / 100, and finally the slurry volume was adjusted to 50 mL. To this, 31 mL (12.2 mmol) of trin-normal octylaluminum heptane solution was added to obtain an ion-exchangeable layered silicate particle slurry. In a separate flask (200 mL), a solution was prepared by mixing 287 μmol of (r)-silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride with 30 mL of toluene. This 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 1 L stirring autoclave that had been thoroughly purged with nitrogen. The slurry temperature was set to 40°C, and propylene was supplied at a rate of 10 g / hour for 2 hours. After the supply of propylene was stopped, the reaction was carried out until the pressure reached 0.025 MPaG. Subsequently, the remaining monomers were purged and the prepolymerization catalyst slurry was recovered from the autoclave. The recovered prepolymerization catalyst slurry was allowed to stand, and the supernatant was removed. 8.5 mL (6 mmol) of heptane solution of triisobutylaluminum was added at room temperature. Subsequently, the prepolymerization catalyst slurry was dried under reduced pressure to obtain a catalyst for olefin polymerization. The preliminary polymerization ratio (catalyst yield ÷ (ion-exchangeable layered silicate particles + metallocene complex amount) - 1) was 2.43 g / g-catalyst.

[0188] [Example b2: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a2 were used. The pre-polymerization ratio was 2.37 g / g-catalyst.

[0189] [Example b3: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a3 were used. The pre-polymerization ratio was 2.31 g / g-catalyst.

[0190] [Example b4: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a4 were used. The pre-polymerization ratio was 2.31 g / g-catalyst.

[0191] [Example b5: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a5 were used. The pre-polymerization ratio was 2.37 g / g-catalyst.

[0192] [Example b6: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a6 were used. The pre-polymerization ratio was 2.39 g / g-catalyst.

[0193] [Example b7: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a7 were used. The pre-polymerization ratio was 2.40 g / g-catalyst.

[0194] [Example b8: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a8 were used. The pre-polymerization ratio was 2.40 g / g-catalyst.

[0195] [Example b9: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a9 were used. The pre-polymerization ratio was 2.33 g / g-catalyst.

[0196] [Example b10: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a10 were used. The pre-polymerization ratio was 2.36 g / g-catalyst.

[0197] [Example b11: Production of catalyst for olefin polymerization] The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a11 were used. The pre-polymerization ratio was 2.31 g / g-catalyst.

[0198] [Comparative Example b1: Production of Catalyst for Olefin Polymerization] Comparative Example a The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in 1 were used. The pre-polymerization ratio was 2.36 g / g-catalyst.

[0199] [Comparative Example b2: Production of Catalyst for Olefin Polymerization] Comparative Example a The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchangeable layered silicate particles obtained in 2 were used. However, because the rate of pressure decrease after the propylene supply was stopped was small, the reaction was stopped at a pressure of 0.075 MPaG 150 minutes after the propylene supply was stopped. The pre-polymerization ratio was 2.06 g / g-catalyst.

[0200] [Comparative Example b3: Production of Catalyst for Olefin Polymerization] Comparative Example a The catalyst for olefin polymerization was produced in the same manner as in Example b1, except that the ion-exchange layered silicate particles obtained in 3 were used. The pre-polymerization ratio was 2.36 g / g-catalyst.

[0201] [Example P1: Propylene homopolymerization] The contents of a 3 L stirring autoclave were thoroughly replaced with propylene. Then, 5.6 mL (4.04 mmol) of 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 olefin polymerization catalyst obtained in Example b1 above was slurryed with heptane. 11.1 mg of this slurry (sum of ion-exchangeable layered silicate particles and metallocene complex) was injected under pressure as a solid catalyst 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.

[0202] [Examples P2-P26: Propylene homopolymerization] Polymerization was carried out in the same manner as in Example P1, except that the type of catalyst, catalyst amount, and hydrogenation amount for olefin polymerization were as described in Table 3. The results are shown in Table 3.

[0203] [Comparative Examples P1-P9: Propylene Homopolymerization] Polymerization was carried out in the same manner as in Example P1, except that the type of catalyst, catalyst amount, and hydrogenation amount for olefin polymerization were as described in Table 3. The results are shown in Table 3.

[0204] [Table 3]

[0205] [Example P27: Two-step polymerization: 1st stage - propylene homopolymerization, 2nd stage - ethylene-propylene copolymerization] The contents of a 3 L stirring autoclave were thoroughly replaced with propylene. Then, 5.6 mL (4.04 mmol) of 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 olefin polymerization catalyst obtained in Example b3 above was slurryed with heptane. 12.7 mg of this slurry (sum of ion-exchangeable layered silicate particles and metallocene complex) was injected under pressure as a solid catalyst 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 then supplied to the autoclave in a molar ratio of 1:1, and polymerization was carried out at 80°C and 1.9 MPaG for 0.52 hours. The reaction was stopped by injecting 5 mL of ethanol, and the remaining monomer was purged. The resulting polymer was dried at 90°C for 1 hour. The results are shown in Table 4.

[0206] [Examples P28~P41: Two-step polymerization: 1st stage - propylene homopolymerization, 2nd stage - ethylene-propylene copolymerization] 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 hydrogenation, and the copolymerization time of ethylene and propylene were as described in Table 4. The results are shown in Table 4.

[0207] [Comparative Examples P10~P16: Two-step polymerization: 1st stage - propylene homopolymerization, 2nd stage - ethylene-propylene copolymerization] 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 hydrogenation, and the copolymerization time of ethylene and propylene were as described in Table 4. The results are shown in Table 4.

[0208] [Table 4]

[0209] [Comparison of Examples and Comparative Examples] Figure 1 shows the ratio of the total volume of pores with a diameter of 2 nm to 10 nm to the total mesopore volume for the ion-exchange layered silicate particles described in Examples a1 to a14 and Comparative Examples a1 to a6, and the BET specific surface area m². 2This figure plots the particles against / g. From Figure 1, it can be seen that the ion-exchangeable layered silicate particles of the present invention can increase the proportion of large mesopores (greater than 10 nm and less than or equal to 50 nm) while maintaining the specific surface area, thereby achieving a relationship between pore volume and specific surface area that was not possible with conventional methods. Figure 2 shows the polymerization activity of propylene homopolymerization using the olefin polymerization catalysts described in Examples b1-b11 and Comparative Examples b1-b3, plotted against the MFR of the obtained polymer. From Figure 2, it can be seen that the catalyst using ion-exchangeable layered silicate particles of the present invention exhibits higher catalytic activity relative to the MFR than the catalysts of the comparative examples. Figure 3 shows the results of two-stage polymerization of propylene-ethylene using the olefin polymerization catalysts described in Examples b3, b4, b6-b8, b11 and Comparative Examples b1-b3, plotting the number of fish eyes contained in the sheet against the molecular weight ratio of the obtained polymers (the molecular weight of the second polymer divided by the molecular weight of the first polymer). From Figure 3, it can be seen that the catalyst using the ion-exchangeable layered silicate particles of the present invention reduces the number of fish eyes compared to the catalysts of the comparative examples in relation to the molecular weight ratio. Figure 4 is a plot of the crush strength measurements of the ion-exchangeable layered silicate particles described in Examples a1, a13 and Comparative Examples a1, a3. Table 5 shows the results of the crush strength measurements of the ion-exchangeable layered silicate particles. From Figure 4, it can be seen that the ion-exchangeable layered silicate particles of the present invention are particle aggregates with less variation in crush strength and higher uniformity compared to the ion-exchangeable layered silicate particles of the comparative examples, even at the same volume. Table 6 shows the average crush strength and S0·V0 of the ion-exchange layered silicate particles described in Examples a1, a13 and Comparative Examples a1, a3. 1 / m Table 6 shows the values ​​for 1 / m, respectively. According to Table 6, the ion-exchangeable layered silicate particles of the present invention all have a small 1 / m value of 0.000. This indicates that the particles are more uniform. Furthermore, the ion-exchangeable layered silicate particles of the present invention have little dependence of crush strength on size (particle diameter). This indicates stable properties as a catalyst support. In addition, 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).

[0210] [Table 5]

[0211] [Table 6] [Industrial applicability]

[0212] According to the present invention, it is possible to provide ion-exchangeable layered silicate particles having a novel pore structure that improves catalytic activity and polymer quality, a catalyst component for olefin polymerization containing said ion-exchangeable layered silicate particles, a catalyst for olefin polymerization, a method for producing the catalyst for olefin polymerization, and a method for producing an olefin polymer using the same, all of which have high industrial applicability.

Claims

1. Ion-exchangeable layered silicate particles having the following characteristics (i) and (ii). Characteristic (i): In the pore distribution curve calculated by the BJH method from the desorption isotherms measured by the nitrogen adsorption-desorption method, the sum of the pore volumes with diameters from 2 nm to 10 nm is 65% or more and 90% or less of the total mesopore volume. Characteristic (ii): Specific surface area is 325 m² ２ / g or more, 500m ２ It is less than / g.

2. Furthermore, the ion-exchangeable layered silicate particles according to claim 1 are characterized by having the following characteristic (iii). Characteristics (iii): The average particle size is 2 μm or more and 500 μm or less.

3. A catalyst component for olefin polymerization comprising ion-exchangeable layered silicate particles according to claim 1 or 2.

4. A catalyst for olefin polymerization, characterized by containing the following components [A], [B], and [C]. Component [A]: Ion-exchangeable layered silicate particles according to claim 1 or 2 Component [B]: Transition metal compound Component [C]: Organoaluminum compound

5. A method for producing an olefin polymerization catalyst, characterized by mixing the following components [A], [B], and [C]. Component [A]: Ion-exchangeable layered silicate particles according to claim 1 or 2 Component [B]: Transition metal compound Component [C]: Organoaluminum compound

6. A method for producing an olefin polymer, characterized by carrying out olefin polymerization using the olefin polymerization catalyst described in claim 4.

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