Ion-exchanged phyllosilicate particles, catalyst component for olefin polymerization, catalyst for olefin polymerization, process for producing catalyst for olefin polymerization, and process for producing olefin polymer using the same

Abstract

To provide an ion-exchange layered silicate particle for improving catalytic activity.SOLUTION: The ion-exchanged phyllosilicate particles have the following characteristics (I) and (ii): Fitting a base line having a constant height with respect to a peak intensity and a calculated peak created by a sum of two pseudo-Voigt functions to an actually measured peak (X) present in a range of 2 θ = 60.00 ° to 64.00 ° in a range of 2 θ = 60.00 ° to 64.00 ° in X-ray diffraction, separating the peak (X) into two peaks and determining a base line, and when a calculated peak created by a sum of the two pseudo-Voigt functions is (X '), a vertex of the calculated peak (X ') is in a range of 2 θ = 61.66 ° to 61.77 °. (ii) The specific surface area is 250m2 / g or more and 700m2 / g or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to ion-exchange layered silicate particles, a catalyst component for olefin polymerization, an olefin polymerization catalyst, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer using the same. [Background technology]

[0002] Ion-exchangeable layered silicates, such as clay minerals, are widely used as adsorbents, catalysts, catalyst supports, etc. While various factors affect performance in these applications, pore volume, pore distribution, and specific surface area have particularly significant effects. For example, Patent Document 1 exemplifies activated clay with a specific pore distribution and a decolorizing agent for animal and vegetable fats and oils or mineral oils, which comprises the activated clay.

[0003] It is also known to produce an olefin polymer by polymerizing an olefin in the presence of a catalyst that uses clay, a clay mineral, or an ion-exchange layered compound as a catalyst component for olefin polymerization (for example, Patent Document 2). Further, the catalyst component for olefin polymerization is characterized by comprising an ion-exchanged layered silicate in which the sum of the pore volumes of pores having a diameter of 2 to 10 nm is 60 to 100% of the total mesopore volume, and optionally, in X-ray diffraction (XRD), the catalyst component may have a peak (m) at 2θ=19.6 to 20.0 degrees, and when the intensity of the peak (m) is defined as peak intensity (M), no peak (i) other than the peak (m) is present at 2θ=15 to 25 degrees, or may have a peak (i) and the peak intensity (I) of the peak (i) satisfies the relationship 0<(I / M)≦1.6 with respect to the peak intensity (M) (however, there may be a plurality of peaks (i), and when a plurality (n) of peaks (i) are present, the relationship 0<sum of (I / M)≦1.6 with respect to the sum of the intensity ratios (I / M) of the respective peak intensities (I / M) of the n peaks satisfies). 2 A catalyst component for olefin polymerization using an ion-exchanged layered silicate having a molecular weight of 1 / g or more has also been disclosed (Patent Document 3).

[0004] It is also known that ion-exchanged layered silicates contain cations between the layers (hereinafter referred to as interlayer cations), and that these interlayer cations can be exchanged using specific ionic compounds (Non-Patent Document 1). Polymerization catalysts that utilize the exchange reaction of these interlayer cations are known.

[0005] For example, a catalyst for olefin polymerization using a modified clay obtained by treating a clay mineral with a compound capable of introducing cations between its layers has been disclosed (Patent Document 4). Also disclosed is an olefin polymerization catalyst using an ion-exchanged layered silicate in which the interlayer cation contains an alkali metal ion and the content of the alkali metal ion is 0.33 mmol / g or more (Patent Document 5). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2010 / 032568 [Patent Document 2] Japanese Patent Application Publication No. 5-295022 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-108138 [Patent Document 4] Japanese Patent Application Publication No. 7-224106 [Patent Document 5] Japanese Patent Application Publication No. 2018-162391 [Non-patent literature]

[0007] [Non-Patent Document 1] Clay Society of Japan, ed., Clay Handbook, 3rd edition, 2009, p.127 Summary of the Invention [Problem to be solved by the invention]

[0008] In the above-mentioned Patent Documents 2 to 5, the pore volume, pore distribution, specific surface area, and interlayer cations of the ion-exchanged layered silicate are controlled to improve the performance of the catalyst. However, the techniques in these documents do not necessarily provide sufficient catalytic activity, and further improvement in catalytic activity has been desired. The present invention has been made in view of the above-mentioned circumstances, and aims to provide ion-exchanged layered silicate particles that improve catalytic activity, an olefin polymerization catalyst component containing the ion-exchanged 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 problem]

[0009] The present inventors have conducted extensive research to achieve the above object and have found that ion-exchanged layered silicate particles having a specific X-ray diffraction peak and specific surface area improve catalytic activity. The present invention provides ion-exchanged layered silicate particles that improve catalytic activity, as well as an olefin polymerization catalyst component and an olefin polymerization catalyst that contain the ion-exchanged layered silicate particles. That is, the present invention includes the following aspects.

[0010] <1> Ion-exchangeable layered silicate particles having the following properties (i) and (ii): Property (i): In X-ray diffraction, when a measured peak (X) existing in the range of 2θ=60.00° to 64.00° is fitted with a baseline having a constant height relative to the peak intensity and a calculated peak created by the sum of two pseudo-Voigt functions in the range of 2θ=60.00° to 64.00°, the peak (X) is separated into two peaks and a baseline is determined. When the calculated peak (X') is created by the sum of the two pseudo-Voigt functions, the apex of the calculated peak (X') is in the range of 2θ=61.66° to 61.77°. Property (ii): Specific surface area is 250m 2 / g or more, 700m 2 / g or less. <2> Furthermore, the above-mentioned compound having the following characteristic (iii): <1> The ion-exchange layered silicate particles according to claim 1. Property (iii): The lithium atom content is 0.10 mmol / g or more and 5.00 mmol / g or less. <3> Furthermore, the above-mentioned compound having the following characteristic (iv): <1> or the above <2> The ion-exchange layered silicate particles according to claim 1. Property (iv): Swelling power in water is 3 ml / 2 g or more and 20 ml / 2 g or less. <4> Furthermore, the above-mentioned compound having the following characteristic (v): <1> ~ <3> The ion-exchange layered silicate particles according to any one of claims 1 to 4. Characteristic (v): The average particle size is 2 μm or more and 500 μm or less. <5> The aforementioned <1> ~ <4> 10. A catalyst component for olefin polymerization, comprising the ion-exchange layered silicate particles according to any one of claims 1 to 9. <6> An olefin polymerization catalyst comprising the following components [A], [B], and [C]: Component [A]: <1> ~ <4> The ion-exchange layered silicate particles according to any one of claims 1 to 4. Component [B]: Transition metal compound Component [C]: Organoaluminum compound <7> A method for producing an olefin polymerization catalyst, comprising mixing the following components [A], [B], and [C]: Component [A]: <1> ~ <4> The ion-exchange layered silicate particles according to any one of claims 1 to 4. Component [B]: Transition metal compound Component [C]: Organoaluminum compound <8> The aforementioned <6> olefin polymerization in the presence of the olefin polymerization catalyst according to claim 1. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide ion-exchanged layered silicate particles that improve catalytic activity, an olefin polymerization catalyst component containing the ion-exchanged 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. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows an observed peak (X) in an X-ray diffraction measurement of an ion-exchanged layered silicate particle, two calculated peaks (pseudo-Voigt function 1 (X1') and pseudo-Voigt function 2 (X2')) obtained by fitting a calculated peak created by the sum of two pseudo-Voigt functions to the observed peak (X) for peak separation, and a calculated peak (X') created by the sum of the two pseudo-Voigt functions. [Figure 2] FIG. 2 is a diagram in which the apex of the calculated peak (X') in X-ray diffraction is plotted against the BET specific surface area (m2 / g) for the ion-exchanged layered silicate particles described in the Examples and Comparative Examples. [Figure 3] FIG. 3 is a diagram in which the apex of the calculated peak (X1') in X-ray diffraction is plotted against the BET specific surface area (m2 / g) for the ion-exchanged layered silicate particles described in the Examples and Comparative Examples. [Figure 4] FIG. 4 is a graph in which the polymerization activity of the propylene homopolymerization using the olefin polymerization catalysts described in the Examples and Comparative Examples is plotted against the MFR of the resulting polymer. DETAILED DESCRIPTION OF THE INVENTION

[0013] The ion-exchange layered silicate particles, the olefin polymerization catalyst component, the olefin polymerization catalyst, the process for producing the olefin polymerization catalyst, and the process for producing an olefin polymer using the same of the present invention will be described in detail below. In this specification, unless otherwise specified, the use of "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower and upper limits. For example, the expression "10 to 20" includes both the lower limit "10" and the upper limit "20". In other words, "10 to 20" has the same meaning as "10 or more and 20 or less". Furthermore, in the present invention, any combination of upper and lower limits can be used to indicate a numerical range. The properties of the ion-exchanged layered silicate particles described below are properties of an aggregate of ion-exchanged layered silicate particles.

[0014] 1. Ion-exchange layered silicate particles The ion-exchanged layered silicate particles of the present invention are characterized by having the following properties (i) and (ii). Property (i): In X-ray diffraction, when a measured peak (X) existing in the range of 2θ=60.00° to 64.00° is fitted with a baseline having a constant height relative to the peak intensity and a calculated peak created by the sum of two pseudo-Voigt functions in the range of 2θ=60.00° to 64.00°, the peak (X) is separated into two peaks and a baseline is determined. When the calculated peak (X') is created by the sum of the two pseudo-Voigt functions, the apex of the calculated peak (X') is in the range of 2θ=61.66° to 61.77°. Property (ii): Specific surface area is 250m 2 / g or more, 700m 2 / g or less.

[0015] As a result of intensive research to achieve the above object, the present inventors have found that catalytic activity can be improved by substituting lithium ions for the interlayer cations of a specific ion-exchanged phyllosilicate and then subjecting the phyllosilicate to heat treatment under specific conditions, thereby migrating the lithium ions to the octahedral layers. It is believed that the change in the location of the lithium ions from the interlayers to the interior of the octahedral layers in the specific ion-exchanged phyllosilicate results in a structure of the ion-exchanged phyllosilicate that is more likely to form polymerization active sites, resulting in higher catalytic activity. In other words, the ion-exchanged layered silicate particles of the present invention have a peak at the specific position in X-ray diffraction, and have a specific octahedral layer, which causes a specific change in the electronic state of the octahedral layer, resulting in an ion-exchanged layered silicate structure that is prone to forming polymerization active sites.In addition, because they have a specific specific surface area, the amount of active component of the catalyst that can be supported is increased, and it is presumed that the synergistic effect of these factors can improve catalytic activity.

[0016] 1-1. Characteristics of ion-exchange layered silicate particles (1) X-ray diffraction peaks In the ion-exchanged layered silicate particles of the present invention, when an actually measured peak (X) in the range of 2θ=60.00° to 64.00° is measured in X-ray diffraction by fitting a calculated peak created by the sum of two pseudo-Voigt functions and a baseline having a constant height relative to the peak intensity to the measured peak (X) in the range of 2θ=60.00° to 64.00°, the peak (X) is separated into two peaks and a baseline is determined. When the calculated peak (X') is created by the sum of the two pseudo-Voigt functions, the apex of the calculated peak (X') is in the range of 2θ=61.66° to 61.77° (characteristic (i)).

[0017] X-ray diffraction is the most effective method for identifying ion-exchanged layered silicates. Inside the crystals of ion-exchanged layered silicates, atoms are regularly and repeatedly arranged, with the period of this arrangement being approximately the same as the wavelength of X-rays. As a result, when X-rays hit the crystal, they are diffracted, and this phenomenon can be described as X-rays coming from the lattice planes of the spatial lattice formed by the three-dimensional atomic arrangement. These behaviors are assumed to satisfy the commonly known Bragg condition, and the lattice indices can be predicted accordingly. On the other hand, even if the indices of the reflections remain unknown, it is possible to identify crystalline materials by comparing the data on the interplanar spacings and intensities of numerous reflections obtained by diffraction with those of known materials. In the present invention, the measurement is carried out by powder X-ray diffraction. The specific powder X-ray diffraction measurement method can be carried out in the same manner as in the examples described below. In the present invention, attention was focused on a specific peak corresponding to the 060 reflection of the crystals of ion-exchanged phyllosilicate. This X-ray diffraction peak is closely related to the atomic composition of the ion-exchanged phyllosilicate and is also used to identify the ion-exchanged phyllosilicate. In the present invention, it was found that ion-exchanged phyllosilicates having a peak at the above-mentioned specific position in X-ray diffraction exhibit high catalytic activity. When lithium cations are inserted into the layers of the dioctahedral ion-exchanged layered silicate, a trioctahedral structure is locally formed, and in X-ray diffraction, the peak corresponding to the 060 reflection of the ion-exchanged layered silicate crystals shifts to a lower 2θ angle. Therefore, it is believed that the ion-exchanged layered silicate particles of the present invention have a peak at the specific position described above. It is presumed that the locally generated trioctahedral structure contributes to improved catalytic activity by changing the electronic state near the Al in the octahedral layer, which is the active site.

[0018] Here, a procedure for determining the baseline and the calculated peak (X') from the measured peak in the measured spectrum obtained by X-ray diffraction measurement will be described. First, the baseline is determined by taking the average intensity value in the ranges of 2θ=60.00° to 60.50° and 63.50° to 64.00°, and using this as the baseline value for 2θ=60.00° to 64.00°. The diffraction intensity obtained by subtracting the baseline obtained above from the measured peak (X) is plotted in the range of 2θ = 60.00 to 64.00. A calculated peak created by the sum of two pseudo-Voigt functions is fitted to the obtained diffraction peak in the range of 2θ = 60.00 to 64.00 degrees to separate the peaks. After separation, the calculated peak on the low-angle 2θ side (pseudo-Voigt function 1 (X1')), the calculated peak on the high-angle 2θ side (pseudo-Voigt function 2 (X2')), and the calculated peak (X') created by the sum of the two pseudo-Voigt functions are obtained (see Figure 1). The pseudo-Voigt function is the sum of a Lorentzian function and a Gaussian function with the same full width at half maximum. The pseudo-Voigt function f(2θ) used in peak separation is shown below.

[0019]

number

[0020] where 2θ jis the diffraction angle at the peak center, A is a scaling factor to fit the actual measurement, η is the mixing ratio of the Lorentzian function (left side of the bracket) and the Gaussian function (right side of the bracket), W is the peak half-width, π is the constant of the circumference, ln is the natural logarithm, and exp is the natural exponential function. In peak separation, the 2θ of each of the two pseudo-Voigt functions is j Using variables W, η, and A, perform fitting using the solver function in Excel so that the mean square deviation between the baseline-subtracted peak (X) and the calculated spectrum in the range of 2θ = 60.00 to 64.00 degrees is minimized.

[0021] In the ion-exchanged layered silicate particles, the lower limit of the apex of the calculated peak (X') is 2θ=61.66°, preferably 2θ=61.70°, more preferably 2θ=61.74°, and may be 2θ=61.75°, and the upper limit of the apex of the calculated peak (X') is 2θ=61.77°, preferably 2θ=61.76°. Any combination of the upper and lower limits can be used.

[0022] Furthermore, in the ion-exchanged layered silicate particles of the present invention, when an observed peak (X) in the 2θ range of 60.00° to 64.00° is subjected to X-ray diffraction analysis by fitting a calculated peak created by the sum of a baseline having a constant height relative to the peak intensity and two pseudo-Voigt functions in the 2θ range of 60.00° to 64.00°, the observed peak (X) is separated into two peaks and a baseline is determined, and the calculated peak on the lower 2θ angle side after separation is designated as (X1'), the apex of the calculated peak (X1') is preferably in the 2θ range of 61.66° to 61.74° (characteristic (vi)). In the ion-exchanged layered silicate particles of the present invention, the apex of the calculated peak (X1') indicates the presence of a locally generated trioctahedral-like structure, and the lower limit of the apex of the calculated peak (X1') is preferably 2θ=61.66°, more preferably 2θ=61.70°, and even more preferably 2θ=61.73°, and the upper limit is preferably 2θ=61.74°. Any combination of the upper and lower limits can be used.

[0023] (2) Specific surface area The ion-exchange layered silicate particles of the present invention have a specific surface area of ​​250 m 2 / g or more, 700m 2 / g or less (property (ii)). In the ion-exchange layered silicate particles of the present invention, the lower limit of the specific surface area is preferably 280 m 2 / g, more preferably 300m 2 / g, more preferably 330m 2 / g, and the upper limit of the specific surface area is preferably 600 m 2 / g, more preferably 550m 2 / g, more preferably 500m 2 / g. Any combination of upper and lower limits can be used. Increasing the specific surface area increases the amount of active component of the catalyst or the amount of active component that can be supported, resulting in higher activity. On the other hand, if the specific surface area is too large, the pore size may become small, which may cause a decrease in the diffusion rate of the reaction substrate, resulting in a decrease in catalytic activity or adsorption performance as an adsorbent. Therefore, the above-mentioned preferred range of the specific surface area is selected from these viewpoints. The specific surface area in the present invention refers to a value calculated by BET multipoint analysis (Rouquerol transformation) from adsorption isotherm data measured using nitrogen gas in a gas adsorption method. The method for measuring specific surface area by the gas adsorption method is explained in, for example, JIS Z8830.

[0024] (3) Lithium content The ion-exchanged layered silicate particles of the present invention preferably contain lithium ions as interlayer ions. The ion-exchanged layered silicate particles of the present invention may be ion-exchanged layered silicate particles that have been chemically treated with a salt containing lithium ions (lithium treatment). From the viewpoint of catalytic activity, the lithium atom content is preferably 0.10 mmol / g or more and 5.00 mmol / g or less (property (iii)). The lower limit of the lithium atom content is preferably 0.30 mmol / g, more preferably 0.40 mmol / g, and even more preferably 0.50 mmol / g, and the upper limit of the lithium atom content is preferably 3.00 mmol / g, more preferably 2.00 mmol / g, and even more preferably 1.00 mmol / g. Any combination of the upper and lower limits can be adopted. When the lithium atom content is within the above preferred range, high polymerization activity is likely to be exhibited. The lithium content in the ion-exchanged layered silicate particles can be determined quantitatively by atomic absorption spectrophotometry (AAS), specifically by the method described in the examples below.

[0025] (4) Swelling power The ion-exchange layered silicate particles of the present invention preferably have a swelling power in water of 3 ml / 2 g or more and 20 ml / 2 g or less (property (iv)). The lower limit of the swelling power in water of the ion-exchanged layered silicate particles is preferably 3 ml / 2 g, more preferably 5 ml / 2 g, and the upper limit of the swelling power in water is preferably 20 ml / 2 g, more preferably 15 ml / 2 g, and even more preferably 10 ml / 2 g. Any combination of the upper and lower limits can be used. The swelling power of the ion-exchangeable layered silicate particles can be determined in accordance with the standard test method for bentonite (JBAS-104-77) of the Japan Bentonite Industry Association, and specifically by the method described in the examples below.

[0026] (5) Average particle size There are no particular restrictions on the particle size of the ion-exchanged layered silicate particles of the present invention, but the average particle size is preferably 2 μm or more and 500 μm or less (property (v)). In the ion-exchanged layered silicate particles of the present invention, the lower limit of the average particle size is more preferably 5 μm, even more preferably 8 μm, and particularly preferably 10 μm, and the upper limit of the average particle size is more preferably 300 μm, even more preferably 100 μm, even more preferably 70 μm, and particularly preferably 55 μm. Any combination of the upper and lower limits can be used. If the particle size is too small, when used as an adsorbent or decolorizing agent, it may reduce the efficiency of solid-liquid separation such as filtration, and when used as a catalyst support, it may cause adhesion inside the reactor or blockage of piping and filters.On the other hand, if the particle size is too large, when used as an adsorbent, decolorizing agent, or catalyst support, it may cause poor dispersion in liquid (slurry state) or during gas-phase reactions. The average particle size of the ion-exchanged layered silicate particles of the present invention is measured using a laser diffraction / scattering particle size distribution analyzer LA-960 manufactured by Horiba, Ltd., after ultrasonic dispersion for 90 seconds at an internal ultrasonic intensity of 5 under the conditions of ethanol as the dispersion solvent, a refractive index real term of 1.490, an imaginary term of 0.000, and a dispersion solvent refractive index real term of 1.360. The average particle size refers to the volume-based median diameter.

[0027] (6) Metal element ratio The ion-exchanged layered silicate particles in the present invention preferably have a structure in which some of the octahedral layers forming the ion-exchanged layered silicate are missing due to weathering, acid treatment, salt treatment, etc. When the ion-exchanged layered silicate is, for example, montmorillonite or beidellite, particles having such a structure are known as acid clay and activated clay, respectively. The ion-exchange layered silicate in the present invention is preferably a layered silicate including montmorillonite and beidellite. The octahedral layers of montmorillonite are composed of metal atoms such as aluminum and magnesium, and it is preferable that the constituent components of these octahedral layers, such as aluminum, are dissolved in an amount of 10% to 75% based on the content before chemical treatment such as acid treatment. It is more preferable that the constituent components of the octahedral layers, such as aluminum, are dissolved in an amount of 15% to 70%, even more preferably 17% to 65%, and particularly preferably 20% to 60% based on the content before chemical treatment such as acid treatment. Furthermore, when the main constituent metal element of the octahedral layer is aluminum and the main constituent metal element of the tetrahedral layer is silicon, the molar ratio of aluminum to silicon is preferably 0.05 to 0.40, more preferably 0.08 to 0.35, even more preferably 0.10 to 0.30, and still more preferably 0.12 to 0.25. If there is too much aluminum relative to the silicon, the pore volume and specific surface area will be small, while if there is too little aluminum relative to the silicon, the number of active sites will be reduced, which may result in a decrease in activity as a catalyst or catalyst support or adversely affect the quality of the product.

[0028] 1-2. Method for producing ion-exchange layered silicate particles The method for producing the ion-exchanged layered silicate particles of the present invention is not particularly limited as long as it can provide ion-exchanged layered silicate particles having the above-mentioned properties. In view of the ease of controlling the specific surface area and of obtaining the properties of the ion-exchanged layered silicate particles of the present invention, a method for producing ion-exchanged layered silicate particles comprising the following steps 1, 2, and 3 is preferably used as the method for producing the ion-exchanged layered silicate particles of the present invention: Step 1: A step of treating an ion-exchanged layered silicate having an average particle size of 0.03 μm to 0.40 μm with an acid to obtain an acid-treated ion-exchanged layered silicate. Step 2: A step of reacting the acid-treated ion-exchanged layered silicate with a compound containing lithium ions to obtain a lithium-treated ion-exchanged layered silicate. Step 3: A step of heating the lithium-treated ion-exchanged layered silicate at a temperature of 130°C to 300°C for 6 hours or longer. In the method for producing ion-exchanged layered silicate particles of the present invention, step 1 may be a step of granulating an ion-exchanged layered silicate having an average particle size of 0.03 μm to 0.40 μm to an average particle size of 2 μm or more and 500 μm or less, and then treating the granulated ion-exchanged layered silicate with an acid to obtain an acid-treated ion-exchanged layered silicate.

[0029] (1) Process 1 Step 1 is a step of treating an ion-exchanged layered silicate having an average particle size of 0.03 μm to 0.40 μm with an acid to obtain an acid-treated ion-exchanged layered silicate. Step 1 may be a step of granulating an ion-exchanged layered silicate having an average particle size of 0.03 μm to 0.40 μm to an average particle size of 2 μm or more and 500 μm or less, and then treating with an acid to obtain an acid-treated ion-exchanged layered silicate.

[0030] (1-1) Ion-exchange layered silicate The ion-exchangeable layered silicate in the present invention is a type of silicate compound that has a crystalline structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with weak bonding forces, and is not limited to naturally occurring silicates but may also be artificially synthesized compounds. As a specific example, as described in "Clay Mineralogy" by Shiramizu Haruo, Asakura Shoten (1995), i) Kaolin group minerals such as dickite, nacrite, kaolinite, and nacrite, which have a 1:1 layer as the main constituent layer, serpentine group minerals such as chrysotile, lizardite, and antigorite, and serpentine-related minerals such as amesite and Al lizardite, etc. ii) Examples of smectite group silicates, such as montmorillonite, beidellite, nontronite, saponite, hectorite, and stevensite, in which the 2:1 layer is the main constituent layer; vermiculite group silicates, such as vermiculite; mica group silicates, such as mica, illite, sericite, and glauconite; attapulgite, sepiolite, palygorskite, and chlorite groups. These may form mixed layers. Many smectite group silicates are naturally produced as mixtures of clay minerals and often contain impurities (such as quartz, cristobalite, opal, and carbonates). These may also contain impurities. Examples of such impurities include bentonite and acid clay, which are clays containing montmorillonite as the main component. From the standpoint of polymerization activity, the ion-exchangeable layered silicate of the present invention is preferably a layered silicate in which the 2:1 layer is the main constituent layer. The ion-exchanged layered silicate used in the present invention may be an ion-exchanged layered silicate containing a smectite group silicate, more preferably an ion-exchanged layered silicate containing montmorillonite, more preferably a smectite group silicate, and even more preferably montmorillonite. These ion-exchange layered silicates may be used alone or in combination of two or more.

[0031] In the present invention, the composition of the ion-exchanged layered silicate and the ion-exchanged layered silicate particles can be analyzed by preparing a calibration curve in accordance with JIS R2212 and quantifying the content by fluorescent X-ray measurement. Specifically, the composition can be measured by the method described in the examples below.

[0032] These natural products may be purified by elutriation or air elutriation. By performing elutriation or air elutriation, impurities such as quartz and feldspar, which have a high specific gravity, can be removed, and also silicates that do not swell can be removed, thereby obtaining a preferred ion-exchangeable layered silicate. As the elutriation or air elutriation method, a commonly used method can be used. Drying and pulverization may be performed before purification. Examples of pulverization methods include dry pulverization and wet pulverization. Examples of pulverizers include jaw crushers, gyratory crushers, roll crushers, edge runners, hammer mills, ball mills, bead mills, and jet mills.

[0033] Alternatively, ion exchange treatment may be carried out in advance using, for example, a very small amount of sodium carbonate. Examples of such treatments include converting Ca-type bentonite into activated Na-type bentonite (Report of the Central Customs Analysis Laboratory, Vol. 56, p. 85; Clay Science, Vol. 21, No. 1, pp. 1-13 (1981)). This facilitates dispersion of smectite during elutriation, allowing coarse quartz and other particles to be rapidly sedimented and separated due to differences in particle size. A dispersant may also be added during elutriation. Examples of dispersants include sodium silicate and sodium pyrophosphate.

[0034] The ion-exchanged layered silicate used in the production of the ion-exchanged layered silicate particles of the present invention preferably has a lower limit of the average particle diameter of 0.03 μm, more preferably 0.07 μm, even more preferably 0.10 μm, and particularly preferably 0.12 μm, and preferably has an upper limit of 0.40 μm, more preferably 0.35 μm, even more preferably 0.30 μm, and particularly preferably 0.29 μm. Any combination of the upper and lower limits can be adopted. When the average particle diameter is within the above range, the number of end faces of the ion-exchanged layered silicate that serve as active sites for olefin polymerization increases, resulting in a highly active olefin polymerization catalyst component. Furthermore, the smaller the average particle diameter of the ion-exchanged layered silicate, the larger the specific surface area after acid treatment tends to be, making it easier to adjust the specific surface area to the range specified in the present invention. The average particle size of the ion-exchanged layered silicate used in producing the ion-exchanged layered silicate particles refers to the volume-based median diameter determined from the spherical equivalent particle size distribution measured using a HORIBA, Ltd. laser diffraction / scattering particle size distribution analyzer LA-960 under the following conditions: distilled water as the dispersion solvent, refractive index real term 1.490, imaginary term 0.100, dispersion solvent refractive index real term 1.333, transmittance (R) 85% to 99%, transmittance (B) 85% to 90%, and after two minutes of ultrasonic treatment at an internal ultrasonic intensity of "7".

[0035] The ion-exchanged layered silicate preferably used in the method for producing ion-exchanged layered silicate particles of the present invention is preferably subjected to various treatments described below. In the present invention, as long as the silicate has ion-exchange properties and a layer structure prior to the treatment, the physical and chemical properties of the silicate are changed by the treatment, and the silicate no longer has ion-exchange properties or a layer structure, and the silicate is also treated as an ion-exchanged layered silicate.

[0036] The type of interlayer cation (positive ion contained between the layers of the ion-exchanged layered silicate) of the ion-exchanged layered silicate preferably used in the method for producing ion-exchanged layered silicate particles of the present invention is not particularly limited. The interlayer cation is preferably a cation of an alkali metal of Group 1 of the periodic table, such as lithium or sodium, an alkaline earth metal of Group 2 of the periodic table, such as calcium or magnesium, or a transition metal, such as aluminum, silicon, iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, or gold, as a main component, because it is relatively easily available as an industrial raw material.

[0037] (1-2) Granulation In step 1, when used as a catalyst support, in order to prevent adhesion to the inside of a reactor, clogging of piping or filters, and poor dispersion within the reactor, an ion-exchanged layered silicate having an average particle size of 0.03 μm to 0.40 μm may be granulated to an average particle size of 2 μm or more and 500 μm or less, and then subjected to an acid treatment. In the granulation step, a slurry containing an ion-exchanged layered silicate, a solvent, and a soluble compound that is solid at 20°C and is soluble in the liquid in the slurry (hereinafter, sometimes referred to as a raw material slurry) may be prepared, and the slurry may be granulated. In this case, the obtained ion-exchanged layered silicate granulated particles containing the ion-exchanged layered silicate and the soluble compound may be referred to as ion-exchanged layered silicate composite granulated particles.

[0038] The shape of the ion-exchanged layered silicate before granulation is not particularly limited, and may be the shape found in nature or the shape at the time of artificial synthesis. Furthermore, an ion-exchanged layered silicate whose shape has been processed by operations such as pulverization, granulation, and classification may also be used. Furthermore, a slurry obtained by a purification operation such as elutriation may be used as is. Furthermore, it may contain impurities (such as quartz, cristobalite, opal, and carbonates). There are no particular restrictions on the concentration of the ion-exchange layered silicate in the slurry, and 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.

[0039] Although there is no particular limitation on the type of solvent constituting the slurry, water or organic solvents such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, etc. are preferred, and water is more preferred. These solvents may be used alone or in combination of two or more.

[0040] The soluble compound is an additive that is solid at 20° C. and has solubility in the liquid in the slurry at the temperature during granulation, preferably at 20° C. Here, solubility means that the concentration of the compound 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 not particularly limited as long as it is solid at 20°C by itself, has solubility in the liquid in the raw material slurry, and is dissolved by the acid treatment described above. The soluble compound is preferably a salt, as it is easy to control the pores. 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. Preferred examples of salts include compounds 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 a halogen anion, an anion of an inorganic Brønsted acid, and an anion of an organic Brønsted acid. More preferred salts are inorganic salts that are compounds composed of at least one anion selected from an anion of an inorganic Brønsted acid and an anion of a halogen, and more preferably inorganic salts that are soluble in water.

[0041] Examples of cations constituting such inorganic salts include alkali metal ions such as lithium ion, sodium ion, and potassium ion, alkaline earth metal ions such as magnesium ion and calcium ion, aluminum ion, iron ion, strontium ion, cobalt ion, copper ion, nickel ion, zinc ion, ruthenium ion, rhodium ion, palladium ion, silver ion, iridium ion, platinum ion, and ammonium ion. Examples of anions include inorganic acid ions such as sulfate ion, nitrate ion, chloride ion, hydrobromide ion, hydroiodide ion, phosphate ion, pyrophosphate ion, perchlorate ion, molybdate ion, hexafluorosilicate ion, and carbonate ion, organic acid ions such as acetate ion, citrate ion, oxalate ion, formate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, and taurine ion, as well as oxygen ions (oxide ions) and hydroxide ions.

[0042] As the soluble compound, from the viewpoints of ease of appropriate elution and industrial ease of wastewater treatment, more preferred are salts in which the cation is at least one selected from the group consisting of lithium ions, sodium ions, magnesium ions, aluminum ions, and iron ions. Even more preferred are salts in which the cation is at least one selected from the group consisting of lithium ions, sodium ions, magnesium ions, aluminum ions, and iron ions, and the anion is at least one selected from the group consisting of sulfate ions, nitrate ions, chloride ions, and phosphate ions. Even more preferred are salts in which the cation is at least one selected from the group consisting of lithium ions, sodium ions, and magnesium ions, and the anion is at least one selected from the group consisting of sulfate ions, nitrate ions, chloride ions, and phosphate ions. Lithium sulfate is particularly preferred.

[0043] These soluble compounds may be used alone or in combination of two or more. The soluble compound is preferably added in an amount of 10% by mass to 150% by mass relative to the solid components containing the ion-exchanged layered silicate in the slurry at 20°C, since this makes it easier to obtain the properties of the ion-exchanged layered silicate particles of the present invention. That is, the amount of the soluble compound added is preferably 10% by mass to 150% by mass of the total of the ion-exchanged layered silicate and insoluble solid components (solid components other than the ion-exchanged layered silicate and the soluble compound) in the slurry at 20°C. The amount of the soluble compound added may be appropriately selected within the above range so as to adjust the pore structure and specific surface area. The amount of the soluble compound added is more preferably 15% by mass or more, even more preferably 20% by mass or more, still more preferably 25% by mass or more, and more preferably 130% by mass or less, even more preferably 110% by mass or less, and still more preferably 100% by mass or less, of the total. Any combination of the above upper and lower limits can be used. When the content is equal to or less than the upper limit, the strength of the granulated solid increases and the generation of fine powders is reduced, while when the content is equal to or more than the lower limit, the properties of the ion-exchange layered silicate particles of the present invention are easily obtained. The soluble compound is preferably added to the slurry in an amount of 10% to 150% by mass relative to the ion-exchanged layered silicate, since this makes it easier to obtain a desired pore structure and specific surface area. The amount of soluble compound added is more preferably 15% by mass or more, even more preferably 20% by mass or more, still more preferably 25% by mass or more, and more preferably 130% by mass or less, even more preferably 110% by mass or less, and still more preferably 100% by mass or less, relative to the ion-exchanged layered silicate. Any combination of the upper and lower limits can be used.

[0044] On the other hand, when carbonate reacts with acid, the gas generated affects the pore structure. Therefore, the amount of carbonate added as a soluble compound is preferably 0% by mass to 75% by mass, more preferably 0% by mass to 50% by mass, and even more preferably 0% by mass to 30% by mass. If the amount of soluble compound added is insufficient, it is preferable to supplement it with another soluble compound. When using an ion-exchanged layered silicate containing carbonate as an impurity or an ion-exchanged layered silicate that has been activated to the Na type by treatment with sodium carbonate or the like, it is preferable that the total amount of carbonate is the above-mentioned content.

[0045] In calculating the amounts of these additives, in the case of salts containing an adduct that is liquid by itself, such as water of hydration, the amount is calculated as if the salt were an anhydride or the like without the adduct.

[0046] The soluble compound is a substance that is dissolved in a solvent-containing slurry and does not exist as a solid, but becomes a solid when the slurry is dried to remove the solvent. The soluble compound is particularly preferably a substance that is crystalline in a granulated state. A crystalline substance is a substance that has some structural order. In other words, it is a substance that shows discrete diffraction spots in the diffraction pattern of X-rays or particle beams. Using a substance that is crystalline after drying or granulation as a soluble compound is preferable because it allows the pore structure to 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 a diffraction pattern using X-rays or particle beams, and generally by the scattering or diffraction phenomenon of X-rays.

[0047] A binder may be added for the purpose of improving the shape of the granules during granulation, etc. Examples of binders include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, alcohols, glycol, starch, casein, latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate. A viscosity modifier may be added to adjust the pH, viscosity, etc. of the slurry. It is known that the pH of the ion-exchange layered silicate slurry affects the viscosity of the slurry. In order to adjust these, in addition to the binders mentioned above, acids such as sulfuric acid, nitric acid, and hydrochloric acid, and bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide may be added. Also, known substances may be added as dispersants or flocculants, such as sodium silicate, sodium pyrophosphate, and aluminum sulfate. When these binders, viscosity modifiers, dispersants, flocculants, etc. satisfy the properties of the soluble compounds, it is preferable to treat them as soluble compounds and adjust the amount added relative to the solid components containing the ion-exchangeable layered silicate in the 20°C slurry.

[0048] The order in which the ion-exchanged layered silicate, the soluble compound, and the solvent are mixed is not particularly limited, but the mixing order may affect the physical properties such as the viscosity of the slurry, which may affect the drying and granulation steps and the physical properties of the ion-exchanged layered silicate particles. As for the mixing order, the ion-exchanged layered silicate and the soluble compound may be added to the solvent sequentially or simultaneously. The ion-exchanged layered silicate and the soluble compound may be dispersed or dissolved in a solvent, respectively, and then mixed. Most preferably, the soluble compound is dissolved in a solvent, and a slurry of the ion-exchanged layered silicate dispersed in the solvent is added to this solution. There are no limitations on the mixing order when adding a binder, dispersant, flocculant, or viscosity modifier.

[0049] The temperature during mixing is not particularly limited, but is preferably below the boiling point of the solvent. When water is used, the temperature is 0 to 80°C, more preferably 10 to 70°C, and even more preferably 20 to 60°C. There are no particular limitations on the mixing method. Known methods can be used. Examples of mixing methods include stirring and using a static mixer. Furthermore, to particularly improve dispersibility, a high-speed stirrer, a media mill, a high-pressure homogenizer, an ultrasonic disperser, a thin film rotary high-speed stirrer, etc. can be used. A combination of the above methods may also be used. Stirring, a high-speed stirrer, a bead mill, and a high-pressure homogenizer are particularly preferred.

[0050] The viscosity of the slurry is not particularly limited. The viscosity of the slurry is preferably 5 Pa·s to 5,000 Pa·s, and more preferably 8 Pa·s to 3,000 Pa·s. The viscosity here refers to a value measured at 12 rpm and 20°C using a Brookfield DV-I Viscometer (LV-1, LV-2, or LV-3 spindle, depending on the viscosity).

[0051] The ion-exchanged layered silicate or the raw material slurry is granulated and, if necessary, subjected to solid-liquid separation such as drying, concentration, filtration, or decantation to produce ion-exchanged layered silicate granulated particles. Granulation and solvent separation may be carried out separately or simultaneously. There are no particular limitations on the method or order of granulation and solvent separation. However, when a soluble compound is used, it is necessary to incorporate the soluble compound into the particles after granulation. Preferred methods for producing granules include agitation granulation, spray granulation, tumbling granulation, briquetting, compaction, extrusion granulation, fluidized bed granulation, spouted bed granulation, emulsion granulation, submerged granulation, and compression molding granulation. More preferred are spray drying granulation, spray cooling granulation, fluidized bed granulation, spouted bed granulation, submerged granulation, and emulsion granulation, with spray drying granulation and spray cooling granulation being particularly preferred.

[0052] When spray granulation is performed, there are no particular limitations on the spraying method. A rotary atomizer, a one-fluid nozzle, a two-fluid nozzle, an ultrasonic nozzle, or the like can be used. There are also no particular limitations on the drying medium. Examples of drying media include nitrogen, argon, and air. There is no limitation on the temperature at which the drying medium is supplied for spray-drying granulation. The temperature varies depending on the dispersion medium, but for water, for example, the temperature is 70°C to 300°C, preferably 80°C to 280°C.

[0053] The particle size distribution of the ion-exchanged layered silicate granulated particles to be produced can be adjusted by the production conditions such as the atomizer, the temperature of the drying medium, the flow rate, etc. It may also be adjusted by using a known classification technique such as sieving or air classification.

[0054] The average particle size of the ion-exchanged layered silicate granulated particles obtained through the granulation step is preferably 2 μm to 500 μm. The lower limit of the average particle size of the ion-exchanged layered silicate granulated particles obtained through the granulation step is more preferably 5 μm, even more preferably 8 μm, and particularly preferably 10 μm, and the upper limit of the average particle size is more preferably 300 μm, even more preferably 100 μm, even more preferably 70 μm, and particularly preferably 55 μm. Any combination of the upper and lower limits can be adopted. Note that the average particle size here refers to the volume-based median size determined from the spherical equivalent particle size distribution measured by laser diffraction, as with the average particle size of the ion-exchanged layered silicate particles of the present invention.

[0055] When a soluble compound is used for granulation, the ion-exchanged layered silicate granulated particles are particles containing the ion-exchanged layered silicate and the soluble compound. The soluble compound in the particles is a solid, preferably a crystalline solid. The presence or absence of crystallinity can be confirmed by the presence or absence of a diffraction pattern using X-rays or particle beams, and can generally be confirmed by X-ray scattering or diffraction.

[0056] (1-3) Acid treatment Step 1 is a step of treating an ion-exchanged layered silicate with an acid to obtain an acid-treated ion-exchanged layered silicate. In this step, the ion-exchanged layered silicate may be in the form of granulated particles of the ion-exchanged layered silicate. The acid treatment in step 1 dissolves soluble compounds and impurities, and also dissolves cations present between the layers of the ion-exchanged layered silicate, which are exchanged with hydrogen cations, followed by dissolution of the cations constituting the octahedral layers. The acid treatment dissolves some or all of the cations, such as Al, Fe, and Mg, that make up the crystal structure of the ion-exchanged layered silicate, thereby changing the characteristics of the pore structure and increasing the specific surface area. The acid treatment increases the acid strength of the ion-exchanged layered silicate and contributes to increasing the number of acid sites per unit mass.

[0057] Examples of acids used in the acid treatment include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propionic acid, fumaric acid, maleic acid, and phthalic acid, and organic acids. Among these, inorganic acids are preferred, and hydrochloric acid, nitric acid, and sulfuric acid are more preferred. Hydrochloric acid and sulfuric acid are even more preferred, and sulfuric acid is particularly preferred.

[0058] The acid treatment of the ion-exchanged layered silicate is preferably carried out by contacting the ion-exchanged layered silicate with a solution of an acid, from the viewpoint of efficient and uniform reaction. When the acid is solid, the solvent for dissolving it is not particularly limited. When the acid is liquid to begin with, it may be used as is or may be diluted with a solvent, and the solvent is also not particularly limited. The solvent is preferably a solvent that does not undergo a reaction during the acid treatment, and is preferably water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene, and more preferably water. These solvents may be used alone or in combination of two or more.

[0059] The acid concentration during the acid treatment (mass percentage of acids relative to the total mass of the slurry during the acid treatment) is not particularly limited and is preferably 3 mass % to 50 mass %, more preferably 4 mass % to 40 mass %, and even more preferably 5 mass % to 30 mass %. The temperature during the acid treatment is not particularly limited, and is preferably 30°C to 102°C, more preferably 40°C to 100°C, and even more preferably 50°C to 97°C. The concentration of the ion-exchanged layered silicate in the solvent during the acid treatment (the concentration of the ion-exchanged layered silicate in the slurry, where the entire slurry containing the ion-exchanged layered silicate is taken as 100% by mass) is not particularly limited, and is preferably 3% to 50% by mass, more preferably 5% to 30% by mass, and even more preferably 8% to 20% by mass. The time for the acid treatment is not particularly limited, and 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. The acid treatment may be carried out in one step or in multiple steps.

[0060] The acid treatment preferably dissolves 10% to 75% of the metal cations that make up the octahedral layer, based on the content before the chemical treatment, more preferably 15% to 70%, even more preferably 17% to 65%, and particularly preferably 20% to 60%. Here, the proportion (mol %) of the eluted metal cations is expressed by the following formula, for example, when the metal cations are aluminum. [Aluminum / silicon (molar ratio) before chemical treatment - Aluminum / silicon (molar ratio) after chemical treatment] ÷ Aluminum / silicon (molar ratio) before chemical treatment × 100 When the elution rate is within the above range, the specific surface area is likely to be improved, and the adsorption performance and catalytic activity are likely to be improved.

[0061] In step 1, an ion-exchange layered silicate having an average particle size of 0.03 μm to 0.40 μm is granulated, optionally to an average particle size of 2 μm or more and 500 μm or less, and then acid-treated to form a granule having a specific surface area of ​​250 m 2 / g or more 700m 2 The step may be a step of obtaining an acid-treated ion-exchanged layered silicate having a pore size of 1 / g or less. The lower limit of the specific surface area of ​​the acid-treated ion-exchanged layered silicate is preferably 280 m 2 / g, more preferably 300m 2 / g, particularly preferably 330m 2 / g, and the upper limit of the specific surface area of ​​the acid-treated ion-exchanged layered silicate is more preferably 600 m 2 / g, more preferably 550m 2 / g, particularly preferably 500m 2 / g. Any combination of upper and lower limits can be used. The specific surface area of ​​the acid-treated ion-exchanged layered silicate can be measured in the same manner as the specific surface area of ​​the ion-exchanged layered silicate particles of the present invention. Ion-exchange layered silicate having an average particle size of 0.03 μm to 0.40 μm is optionally granulated to an average particle size of 2 μm or more and 500 μm or less, and then acid-treated to form a powder having a specific surface area of ​​250 m 2 / g or more 700m 2 In the step of obtaining an acid-treated ion-exchanged layered silicate having a SiO 2 content of 0.1 to 1.0 wt %, it is preferable to adjust the acid concentration and the acid treatment time during the acid treatment.

[0062] (1-4) Cleaning process Step 1 may include a step of washing with a solvent. For example, washing may be performed following the acid treatment. Step 1 may be a step of optionally granulating an ion-exchanged layered silicate having an average particle size of 0.03 μm to 0.40 μm to an average particle size of 2 μm or more and 500 μm or less, and then treating the granules with an acid and washing the granules to obtain an acid-treated ion-exchanged layered silicate. The washing serves to dissolve soluble compounds and impurities, exchange cations present between layers of the ion-exchangeable layered silicate, and also to remove the acid and solvent remaining from the acid treatment described above.

[0063] Examples of solvents used for washing include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethylformamide. These may be used in combination of two or more. Preferred are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers, more preferred are water, alcohols, aliphatic hydrocarbons, and ethers, more preferred are water, alcohols, and mixed solvents thereof, and particularly preferred is water. There are no limitations on the temperature during washing, but it 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 concentration of the acid-treated ion-exchanged layered silicate in the solvent, but it is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 8% to 30% by mass. There is no limitation on the washing time, but it is preferably 1 to 3000 minutes, more preferably 3 to 1500 minutes, and even more preferably 5 to 750 minutes.

[0064] The method of solid-liquid separation for separating the solvent from the acid-treated ion-exchanged layered silicate is not particularly limited, and examples thereof include sedimentation separation, filtration separation, centrifugal sedimentation separation using centrifugal force, centrifugal filtration, etc. These may be carried out multiple times, or multiple methods may be combined. The cleaning ratio is preferably 1 / 5 to 1 / 10,000, more preferably 1 / 10 to 1 / 1,000. Here, the cleaning ratio refers to the ratio of the solvent remaining at the start of cleaning. For example, if 100 L of solvent is brought into contact with the acid-treated ion-exchanged layered silicate and then 90 L of the solvent is removed to perform cleaning, the cleaning ratio is (100-90) / 100=1 / 10. Furthermore, washing can be carried out until the electrical conductivity of the supernatant, which indicates the amount of remaining ions, 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.

[0065] (2) Process 2 Step 2 is a step of reacting the acid-treated ion-exchanged layered silicate with a compound containing lithium ions (hereinafter, sometimes referred to as lithium treatment) to obtain a lithium-treated ion-exchanged layered silicate. The lithium treatment exchanges cations present between layers of the ion-exchangeable layered silicate with lithium ions. The lithium ion-containing compound may contain lithium ions as cations, and the anions are not particularly limited. The lithium ion-containing compound may contain, for example, an anion selected from the group consisting of organic anions and inorganic anions including metal ions, or an anion selected from the group consisting of organic anions and inorganic anions including halide ions. Examples of anions include inorganic acid ions such as sulfate, nitrate, chloride, hydrobromide, hydroiodide, phosphate, pyrophosphate, perchlorate, molybdate, hexafluorosilicate, and carbonate; organic acid ions such as acetate, citrate, oxalate, formate, methanesulfonate, trifluoromethanesulfonate, toluenesulfonate, and taurine; and oxygen ions (oxide ions), hydroxide ions, and the like. The lithium ion-containing compound may be used alone or in combination. There are no particular limitations on the method of use.

[0066] The state of the lithium ion-containing compound when contacted with the acid-treated ion-exchanged layered silicate may be in a state of being dissolved in a solvent or in a solid state. When contacted with the acid-treated ion-exchanged layered silicate after being dissolved in a solvent, there is no limitation on the concentration, and the upper limit is preferably equal to or lower than the saturation concentration.

[0067] From the viewpoint of efficient and uniform reaction, the lithium treatment may be a method of contacting the acid-treated ion-exchanged layered silicate with a solution of a base. When the lithium ion-containing compound is solid, the solvent used to form the solution is not particularly limited. Furthermore, when the lithium ion-containing compound is liquid, it may be diluted with a solvent before use, and the solvent is not particularly limited. Furthermore, the solvent used to form a slurry of the acid-treated ion-exchanged layered silicate is not particularly limited. Examples of the solvent include water and organic solvents such as alcohol, and preferably ethanol, methanol, ethylene glycol, glycerin, and water, and more preferably water. These solvents may be used alone or in combination.

[0068] The temperature during the lithium treatment is not particularly limited, and is preferably from -20°C to 120°C, more preferably from 0°C to 105°C, and even more preferably from 10°C to 80°C. The concentration of the compound containing lithium ions in the solution during the lithium salt treatment is not particularly limited, but is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, and even more preferably 3% by mass to 20% by mass. The concentration here refers to the mass percentage of the compound containing lithium ions relative to the total mass of the solution during the lithium salt treatment. The time for the lithium treatment is not particularly limited, and is preferably 1 to 600 minutes, more preferably 5 to 300 minutes, and even more preferably 10 to 120 minutes. The lithium salt treatment may be carried out in one step or in multiple steps.

[0069] Step 2 may include a step of washing with a solvent. For example, washing may be performed following the lithium treatment. Step 2 may be a step of reacting the acid-treated ion-exchanged layered silicate with a compound containing lithium ions and washing the reaction product to obtain a lithium-treated ion-exchanged layered silicate. Washing can dissolve impurities and remove salts and solvents remaining from the lithium treatment described above. The washing method may be the same as that described in the washing step (1-4) of step 1 above.

[0070] (3) Process 3 Step 3 is a step of heating the lithium-treated ion-exchanged layered silicate at a temperature of 130° C. to 300° C. for 6 hours or longer. By subjecting the lithium-treated ion-exchanged layered silicate to a heat treatment, lithium ions can be moved into the voids in the octahedral layers of the ion-exchanged layered silicate crystals. To obtain a crystal structure that improves polymerization activity, the lower limit of the heating temperature is 130° C., preferably 150° C., and more preferably 180° C., and the upper limit of the heating temperature is 300° C., preferably 270° C., and more preferably 240° C. Any combination of the upper and lower limits can be used. In order to obtain a crystal structure that improves polymerization activity, the lower limit of the heating time is 6 hours, preferably 9 hours, and more preferably 12 hours, and the upper limit of the heating time is preferably 48 hours, more preferably 36 hours, and even more preferably 24 hours. The atmosphere during the heat treatment is preferably dry air, dry nitrogen, dry argon, or reduced pressure, and may be reduced pressure in order to remove moisture contained in the lithium-treated ion-exchanged layered silicate.

[0071] The heat treatment of the lithium-treated ion-exchanged layered silicate in step 3 may be a single treatment or a plurality of separate treatments. The average particle size of the ion-exchanged layered silicate particles obtained after the heat treatment is preferably 2 μm or more and 500 μm or less. The average particle size is more preferably 5 μm or more, even more preferably 8 μm or more, and even more preferably 10 μm or more, with the upper limit being more preferably 300 μm or less, even more preferably 100 μm or less, still more preferably 70 μm or less, and particularly preferably 55 μm or less. Any combination of the upper and lower limits can be used.

[0072] 1-3. Uses of ion-exchange layered silicate particles The ion-exchanged layered silicate particles of the present invention are widely used as supports for olefin polymerization catalysts and the like because they improve catalytic activity. Furthermore, since the ion-exchangeable layered silicate particles of the present invention have the above-mentioned specific crystal structure and specific surface area, they may be widely used as catalysts for organic chemical reactions, for dehydrating, decolorizing, and refining petroleum and oils and fats, as drying agents, adsorbents, bleaching agents, etc.

[0073] 2. Olefin polymerization catalyst components The catalyst component for olefin polymerization of the present invention is characterized by containing the ion-exchange layered silicate particles of the present invention. In one embodiment of the present invention, the ion-exchanged phyllosilicate particles of the present invention can be used as a catalyst component for olefin polymerization or copolymerization, and function as a catalyst support, co-catalyst, etc. The pore structure and crystalline structure of the ion-exchange layered silicate particles affect the performance such as the activity and strength of the catalyst, and further affect the economy, operability, and product quality. When the ion-exchange layered silicate particles obtained by the present invention are used as a catalyst component for olefin polymerization, olefin polymers can be produced with high polymerization activity.

[0074] The method for using the olefin polymerization catalyst component obtained by the present invention is not particularly limited, and examples of the method for use include those described in JP-A Nos. 2002-053611 and 2009-280443. In particular, when used as a catalyst for olefin polymerization, which will be described later, the catalytic performance is likely to be improved.

[0075] 3. Olefin polymerization catalysts The olefin polymerization catalyst of the present invention is characterized by containing the following components [A], [B], and [C]: Component [A]: the ion-exchangeable layered silicate particles of the present invention Component [B]: Transition metal compound Component [C]: Organoaluminum compound

[0076] 3-1. Components of olefin polymerization catalysts <Component [A]> Component [A] is the ion-exchangeable layered silicate particles of the present invention, and may be the same as described above, so a description thereof will be omitted here.

[0077] <Ingredient [B]> Component [B] used in the present invention is a transition metal compound. Among transition metal compounds, a transition metal compound of Group 4 of the periodic table is preferred. An example of a transition metal compound of Group 4 of the periodic table is a metallocene compound having at least one conjugated five-membered ring ligand. Suitable examples of this transition metal compound include compounds represented by the following general formulas (1) to (4).

[0078] [ka] [In the above general formulas (1) to (4), A and A' represent a conjugated five-membered ring ligand which may have a substituent (A and A' may be the same or different in 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, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom, a hydrogen atom, a halogen atom, or a hydrocarbon group; and Z′ represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom, or a hydrocarbon group. Q' represents a bonding group bridging any position of the conjugated five-membered ring ligand with Z, 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).

[0079] Examples of the conjugated five-membered ring ligands A and A' include substituents derived from cyclopentadiene, indene, tetrahydroindene, fluorene, azulene, and tetrahydroazulene, which may be unsubstituted or substituted. Among these, particularly preferred are substituted or unsubstituted indenyl or azulenyl groups.

[0080] Examples of the substituent on the conjugated five-membered ring ligand include the hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, as well as hydrocarbon groups having 1 to 30 carbon atoms substituted with halogen such as fluorine, chlorine, or bromine, halogen atom groups such as fluorine, chlorine, or bromine, and alkoxy groups having 1 to 12 carbon atoms, for example, -Si(R 1 )(R 2 )(R 3 ), a silicon-containing hydrocarbon group represented by -P(R 1 )(R 2 ) or -B(R 1 )(R 2 When a plurality of these substituents are present, the respective substituents may be the same or different. The above-mentioned R 1 , R 2 , R 3 may be the same or different and represent an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms. The substituent on the conjugated five-membered ring ligand may have at least one Group 15-16 element (i.e., a heteroatom). Such a substituent is preferably a monocyclic or polycyclic substituent containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, and phosphorus atoms in a five- or six-membered ring. More preferably, it is a substituent derived from an optionally substituted heteroaromatic compound. An optionally substituted furyl group or an optionally substituted thienyl group is particularly preferred. In the case of a compound having a bridging group represented by general formula (2) or (4), the substituent is not particularly limited, but is preferably located at the α-position (based on the bonding site with the bridging group) on the conjugated five-membered ring ligand.

[0081] 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 the conjugated five-membered ring ligand with the group represented by Z. Specific examples of Q and Q' include the following groups. <1> Alkylene groups such as methylene, ethylene, isopropylene, phenylmethylmethylene, diphenylmethylene, and cyclohexylene groups <2> Silylene groups such as dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisilylene group, and silacyclobutylene group <3> A germanium atom, a phosphorus atom, a nitrogen atom, a boron atom, or an aluminum atom substituted with a hydrocarbon group

[0082] More specifically, groups represented by (CH3)2Ge, (C6H5)2Ge, (CH3)P, (C6H5)P, (C4H9)N, (C6H5)N, (C4H9)B, (C6H5)B, (C6H5)Al, (C6H5O)Al, etc. Preferred are alkylene groups or silylene groups.

[0083] Furthermore, M represents a metal atom, particularly a transition metal atom selected from Group 4 of the periodic table, such as titanium, zirconium, hafnium, etc. Zirconium and hafnium are particularly preferred. Furthermore, Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom, a hydrogen atom, a halogen atom, or a hydrocarbon group, and Z' represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom, or a hydrocarbon group. Specific preferred examples of Z and Z' include an oxygen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a sulfur-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms, and specific preferred examples of Z further include a hydrogen atom, a chlorine atom, and a bromine atom.

[0084] X and Y each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkoxy group, amino group, or diphenylphosphino group, having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a trimethylsilyl group or bis(trimethylsilyl)methyl group. X and Y may be the same or different. Among these, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an amino group having 1 to 12 carbon atoms are particularly preferred.

[0085] Examples of the compound 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, etc.

[0086] Examples of the compound represented by general formula (2) include: (1) dimethylsilylenebis{1-(2-methyl-4-isopropyl-4H-azulenyl)}zirconium dichloride, (2) dimethylsilylenebis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium dichloride, (3) dimethylsilylenebis[1-{2-methyl-4-(4-fluorophenyl)-4H-azulenyl}]zirconium dichloride, (4) dimethylsilylenebis[1-{2-methyl-4-(2,6-dimethylphenyl)-4H-azulenyl}]zirconium dichloride, (5) dimethylsilylenebis{1-(2-methyl-4,6-diisopropyl-4H-azulenyl)}zirconium dichloride, (6) diphenylsilylenebis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium dichloride, (7) dimethylsilylenebis{1-(2-ethyl-4-phenyl-4H-azulenyl)}zirconium dichloride, (8) ethylenebis{1-[2-methyl-4-(4-biphenylyl)-4H-azulenyl]}zirconium dichloride, (9) dimethylsilylenebis{1-[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]}zirconium dichloride, (10) dimethylsilylenebis{1-[2-methyl-4-(2',6'-dimethyl-4-biphenylyl)-4H-azulenyl]}zirconium dichloride, (11) dimethylsilylene{1-[2-methyl-4-(4-biphenylyl)-4H-azulenyl]}{1-[2-methyl-4-(4-biphenylyl)indenyl]}zirconium dichloride, (12) dimethylsilylene{1-(2-ethyl-4-phenyl-4H-azulenyl)}{1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride, (13) dimethylsilylenebis{1-(2-ethyl-4-phenyl-7-fluoro-4H-azulenyl)}zirconium dichloride, (14) dimethylsilylenebis{1-(2-ethyl-4-indolyl-4H-azulenyl)}zirconium dichloride, (15) dimethylsilylenebis[1-{2-ethyl-4-(3,5-bistrifluoromethylphenyl)-4H-azulenyl}]zirconium dichloride, (16) dimethylsilylenebis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium bis(trifluoromethanesulfonate), (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,

[0087] (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-azulenyl)}zirconium dichloride, (26) Isopropylidenebis{1-(2-methyl-4-phenyl-4H-azulenyl)}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-dimethyl-cyclopentadienyl]zirconium dichloride, (31) dimethylsilylenebis[2-(2-furyl)-3,5-dimethyl-cyclopentadienyl]zirconium dichloride, (32) dimethylsilylenebis[2-(2-furyl)-indenyl]zirconium dichloride, (33) dimethylsilylenebis[2-(2-(5-methyl)furyl)-4,5-dimethyl-cyclopentadienyl]zirconium dichloride, (34) dimethylsilylenebis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethyl-cyclopentadienyl]zirconium dichloride, (35) dimethylsilylenebis[2-(2-thienyl)-indenyl]zirconium dichloride, (36) dimethylsilylene[2-(2-(5-methyl)furyl)-4-phenylindenyl][2-methyl-4-phenylindenyl]zirconium dichloride, (37) dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)zirconium dichloride, (38) dimethylsilylenebis(2,3-dimethyl-5-ethylcyclopentadienyl)zirconium dichloride, (39) dimethylsilylenebis(2,5-dimethyl-3-phenylcyclopentadienyl)zirconium dichloride, (40) Silacyclobutylenebis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride,

[0088] (41) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (42) Silacyclobutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride (43) Silacyclobutylenebis[2-(5-t-butyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (44) Silacyclobutylenebis[2-(5-phenyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (45) Silacyclobutylenebis[2-(2-thienyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (46) Silacyclobutylenebis[2-(5-methyl-2-thienyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (47) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-5-methyl-1-indenyl]zirconium dichloride, (48) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-5-methyl-1-indenyl]zirconium dichloride, (49) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (50) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (51) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (52) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (53) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-5-methyl-1-indenyl]zirconium dichloride, (54) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-5-methyl-1-indenyl]zirconium dichloride, (55) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-5-methyl-1-indenyl]zirconium dichloride, (56) Silacyclobutylenebis[2-(2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (57) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (58) Silacyclobutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (59) Silacyclobutylenebis[2-(5-t-butyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (60) Silacyclobutylenebis[2-(5-phenyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride,

[0089] (61) Silacyclobutylenebis[2-(2-thienyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (62) Silacyclobutylenebis[2-(5-methyl-2-thienyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (63) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (64) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (65) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (66) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (67) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (68) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (69) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (70) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (71) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (72) Silacyclobutylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (73) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (74) Silacyclobutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (75) Silacyclobutylenebis[2-(5-t-butyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (76) Silacyclobutylenebis[2-(5-phenyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (77) Silacyclobutylenebis[2-(2-thienyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (78) Silacyclobutylenebis[2-(5-methyl-2-thienyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (79) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (80) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,

[0090] (81) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (82) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (83) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (84) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (85) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (86) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (87) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (88) Silacyclobutylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacen-1-yl]zirconium dichloride, (89) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacen-1-yl]zirconium dichloride, (90) Silacyclobutylene[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl][2,5-dimethyl-4-phenyl-1-indenyl]zirconium dichloride, (91) Silacyclobutylene[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl][2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (92) Silacyclobutylene[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl][2-(5-t-butyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (93) Silacyclobutylene[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl][2-(5-methyl-2-furyl)-4-phenyl-1-indenyl]zirconium dichloride, (94) Silacyclobutylene[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl][2-(5-methyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (95) Silacyclobutylene[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl][2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (96) Silacyclopentylenebis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (97) Silacyclopentylenebis[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (98) Silacyclopentylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (99) Silacyclopentylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (100) dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}zirconium dichloride, (101) Dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}zirconium dichloride, etc.

[0091] Examples of the compound represented by general formula (3) include: (1) (Tetramethylcyclopentadienyl)titanium(bis-t-butylamido)dichloride, (2) (Tetramethylcyclopentadienyl)titanium(bisisopropylamido)dichloride, (3) (Tetramethylcyclopentadienyl)titanium(biscyclododecylamide)dichloride, (4) (Tetramethylcyclopentadienyl)titanium {bis(trimethylsilyl)amide)} dichloride, (5) (2-methyl-4-phenyl-4H-azulenyl)titanium{bis(trimethylsilyl)amide} dichloride, (6) (2-methylindenyl)titanium(bis-t-butylamido)dichloride, (7) (Fluorenyl)titanium(bis-t-butylamido)dichloride, (8) (3,6-diisopropylfluorenyl)titanium(bis-t-butylamido)dichloride, (9) (Tetramethylcyclopentadienyl)titanium(phenoxide) dichloride, (10) (Tetramethylcyclopentadienyl)titanium(2,6-diisopropylphenoxide) dichloride, etc.

[0092] Examples of the compound represented by general formula (4) include: (1) dimethylsilanediyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride, (2) dimethylsilanediyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride, (3) dimethylsilanediyl(2-methylindenyl)(t-butylamido)titanium dichloride, (4) Dimethylsilanediyl(fluorenyl)(t-butylamido)titanium dichloride, etc.

[0093] Similarly, compounds in which the dichloride of these exemplary compounds is replaced with dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide, etc. Furthermore, similarly, compounds in which the zirconium in the exemplary compounds is replaced with hafnium or titanium, and the titanium with hafnium or zirconium are also exemplified.

[0094] The transition metal compound used in the present invention is preferably a compound represented by the general formula (2). The metallocene compounds may be used alone or in combination of two or more.

[0095] When two or more types are used in combination, two or more types can be selected from the group of compounds included in any one of the above general formulas (1) to (4). Alternatively, one or more types selected from the group of compounds included in one general formula and one or more types selected from the group of compounds included in another general formula can be selected.

[0096] <Ingredient [C]> Component [C] is an organoaluminum compound. The component [C] is a compound of the general formula (AlR n X 3-n ) m In the formula, R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2. The organoaluminum compounds can be used alone or in combination of two or more.

[0097] Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-normal propylaluminum, tri-normal butylaluminum, triisobutylaluminum, tri-normal hexylaluminum, tri-normal octylaluminum, tri-normal decylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminums and alkylaluminum hydrides in which m=1 and n=3 are preferred. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

[0098] 3-2. Preparation of olefin polymerization catalysts and prepolymerization The method for producing an olefin polymerization catalyst of the present invention is characterized by mixing the above-mentioned component [A], component [B], and component [C]. The olefin polymerization catalyst of the present invention is prepared by contacting component [B] with component [A] and component [C]. The mixing (contact) method is not particularly limited, but the contact can be carried out in the following order. This mixing may be carried out not only during catalyst preparation but also during prepolymerization with an olefin or during olefin polymerization. A solvent may be used in these mixing steps to ensure sufficient mixing. 1) Mix component [B] and component [A]. 2) Mix component [B] and component [A], then mix component [C]. 3) Mix component [B] and component [C], then mix component [A]. 4) Mix component [A] and component [C], then mix component [B]. Alternatively, the three components may be mixed simultaneously.

[0099] A preferred mixing method is to mix component [A] and component [C] in 4) above, remove unreacted component [C] by washing or the like, mix again with the minimum necessary amount of component [C], and then mix with component [B].

[0100] The molar ratio (Al / M) of Al in the component [C] to the transition metal (M) in the component [B] may be 0.1-1,000, 1-100, or 4-50.

[0101] There are no particular restrictions on the mixing (contact) temperature, but it is preferably 0°C to 100°C, more preferably 10°C to 80°C, and particularly preferably 20°C to 60°C.

[0102] The solvent is preferably an organic solvent, and more preferably a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene, or an olefin described below. These may be used alone or in combination. There are no limitations on the concentration of component [B] in the solvent, but it is preferably 3 mM to 50 mM, more preferably 4 mM to 40 mM, and even more preferably 6 mM to 30 mM. The amount of component [B] used may be 0.001 mmol to 10 mmol, or may be 0.001 mmol to 1 mmol, per 1 g of component [A].

[0103] The olefin polymerization catalyst of the present invention may be subjected to a prepolymerization treatment in which a small amount of olefin is polymerized by contacting the catalyst with the olefin. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc. can be used, and it is particularly preferable to use ethylene and propylene. The olefin may be fed to the reactor at a constant rate or at a constant pressure, or by any method, such as a combination of these, or by a stepwise change in the rate.

[0104] The amount of the prepolymerization may be 0.01 to 100 parts by mass, or may be 0.1 to 50 parts by mass, per part by mass of the component [A]. The prepolymerization temperature is not particularly limited, but may be from 0°C to 100°C, from 10°C to 70°C, from 20°C to 60°C, or from 30°C to 50°C. Prepolymerization is preferably carried out in a liquid such as an organic solvent. As the solvent used in prepolymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, and olefins described below are more preferred. These may be used alone or in combination. Furthermore, the solvent used when mixing the components may be used as is. The concentration of the solid catalyst during prepolymerization is not particularly limited, but may be 10 g / L to 300 g / L, 20 g / L to 200 g / L, or 25 g / L to 150 g / L.

[0105] After mixing of the components and prepolymerization, the olefin polymerization catalyst may be dried. The drying method is not particularly limited, but examples include drying under reduced pressure, drying by heating, and drying by passing a dry gas through the substrate. These methods may be used alone or in combination of two or more. In the drying step, the catalyst may be stirred, vibrated, fluidized, or left to stand.

[0106] Furthermore, during or after mixing of the above components, polymers such as polyethylene, polypropylene, polystyrene, etc., and inorganic oxide solids such as silica, titania, etc. may be added. Also, various surfactants, antistatic agents, and alkoxysilanes, aminosilanes, ethers, phthalates, carboxylates, etc., which are known as donors in olefin polymerization catalysts, may be added.

[0107] 4. Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention is characterized by carrying out olefin polymerization in the presence of the olefin polymerization catalyst of the present invention. In the present invention, the term "olefin polymer" also includes "olefin copolymer." To indicate that the term also includes olefin copolymer, it may be written as "olefin (co)polymer." In other words, the olefin (co)polymer means at least one of a homopolymer and a copolymer. The method for producing an olefin (co)polymer preferably involves homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention, i.e., in this production method, at least one olefin is polymerized or two or more olefins are copolymerized.

[0108] In the case of copolymerization, the ratio of the amounts of the olefin monomers in the reaction system does not need to be constant over time. The monomers may be supplied at a constant mixing ratio. Alternatively, the mixing ratio of the supplied monomers may be changed over time. Alternatively, one of the monomers may be added in portions, taking into account the copolymerization reaction ratio.

[0109] The polymerizable olefin is preferably ethylene or an α-olefin having 3 to 20 carbon atoms, and specific examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7-octadiene, cyclopentene, norbornene, ethylidene norbornene, etc. Ethylene or an α-olefin having 3 to 8 carbon atoms is preferred, and ethylene and propylene are more preferred.

[0110] In the case of copolymerization, the type of comonomer used can be one or more olefins selected from the above-mentioned olefins other than the main component, and the preferred main component of the comonomer is propylene.

[0111] Any polymerization method can be used as long as the catalyst components and each monomer are efficiently contacted. Specifically, a slurry method using an inert solvent, a method using a monomer such as propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas-phase method in which each monomer is kept in a gaseous state without substantially using a liquid solvent can be used. Furthermore, continuous polymerization, batch polymerization, or prepolymerization can also be used.

[0112] In the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, etc., may be used alone or in mixture as the polymerization solvent. The polymerization temperature is not particularly limited, but is usually 0°C to 150°C.

[0113] Hydrogen may be used as a molecular weight modifier. In order to adjust the reaction amount, a compound that has the effect of deactivating the catalyst, such as oxygen or alcohol, may be supplied, and known additives, such as oxygen, alcohol, alkoxysilane, or surfactant, may be added for the purpose of improving operability. The polymerization pressure is not particularly limited, but is preferably 0 kg / cm 2 ~2000kg / cm 2 G (≒0 MPaG to 196.14 MPaG), preferably 0 kg / cm2 ~60kg / cm 2 G (≒0MPaG to 5.88MPaG) is appropriate.

[0114] The olefin (co)polymer obtained by the method for producing an olefin (co)polymer of the present invention is not particularly limited, but suitable examples include ethylene homopolymer, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, and block copolymer of propylene homopolymer and ethylene-α-olefin random copolymer. [Example]

[0115] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples as long as they do not deviate from the gist of the invention. The measurement methods used in these examples are as follows.

[0116] 1.Various physical property measurement methods (1) Composition analysis of ion-exchange layered silicate (raw material) and particles A calibration curve was prepared in accordance with JIS R2212, and quantitative determination was performed by fluorescent X-ray measurement. The apparatus used was a ZSX Primus IV manufactured by Rigaku Corporation. The sample was prepared by firing at 1050°C for 1 hour, then taking 0.4 g of the sample and mixing it with 4 g of flux (Li2B4O7) and 15 μL of 50% LiBr aqueous solution (mold release agent) to create glass beads. The Al elution rate (ΔAl amount) was calculated using the following formula. 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

[0117] (2) Measurement of lithium atom content in ion-exchanged layered silicate particles Quantitative determination was performed using an atomic absorption spectrophotometer (AAS). The apparatus used was a Hitachi Z-5310. The sample was fired at 700°C, placed in a platinum crucible, and decomposed by heating with sulfuric acid and hydrofluoric acid. After the volume of the solution was measured, the content of the solution was measured by atomic absorption spectrophotometry (AAS).

[0118] (3) Measurement of the specific surface area of ​​ion-exchange layered silicate particles Adsorption and desorption isotherms were measured by nitrogen adsorption method. The obtained adsorption isotherm was used to carry out BET multipoint analysis (Rouquerol transformation) to determine the specific surface area. The specific measurement conditions were as follows: Equipment: Anton-Paar gas adsorption measurement device Autosorb-iQ3 Measurement method: Nitrogen gas adsorption method Pretreatment conditions: Samples were heated at 200°C under vacuum (1.3 Pa or less) for 2 hours. Sample amount: approx. 0.2g Gas liquefaction temperature: 77K

[0119] (4) Measurement of the average particle size of ion-exchange layered silicate (raw material) The average particle size of the ion-exchange layered silicate (raw material) was measured using a Horiba, Ltd. laser diffraction / scattering particle size distribution analyzer LA-960 under the following conditions: distilled water as the dispersion solvent, refractive index real term 1.490, imaginary term 0.100, dispersion solvent refractive index real term 1.333, transmittance (R) 85%-99%, transmittance (B) 85%-90%, and after 2 minutes of ultrasonic treatment at an internal ultrasonic intensity of "7." The average particle size refers to the volume-based median diameter. Even in the case of granulated particles, the average particle size of the ion-exchanged layered silicate (raw material) before granulation can be measured under the above measurement conditions.

[0120] (5) Measurement of the average particle size of ion-exchange layered silicate particles The average particle size of the ion-exchanged layered silicate particles was measured using a laser diffraction / scattering particle size distribution analyzer LA-960 manufactured by Horiba, Ltd., after ultrasonic dispersion for 90 seconds at an internal ultrasonic intensity of 5 under the conditions of ethanol as the dispersion solvent, a refractive index real term of 1.490, an imaginary term of 0.000, and a dispersion solvent refractive index real term of 1.360. The average particle size refers to the volume-based median diameter.

[0121] (6) X-ray diffraction measurement of ion-exchanged layered silicate particles and determination of calculated peaks (X1') and (X') from measured peaks X-ray diffraction measurements were performed under the following conditions in air: Apparatus: Rigaku Smartlab X-ray Diffractometer; X-ray source: Cu-Kα radiation (using a Kβ absorber plate), tube voltage: 40 kV, tube current: 30 mA; Optical system: focusing method; Divergence slit: 2 / 3°, scattering slit: 2 / 3°, receiving slit: 0.300 mm; Scan mode: 2θ / θ scan; 2θ scan range: 60.0000°–64.0000°; Angle step width: 0.0200°; Scan speed: 0.0500° / min; Detector: Scintillation counter; Sample holder: Glass holder with a depth of 0.2 mm.

[0122] The procedure for determining the baseline and the calculated peak (X1') and calculated peak (X') from the measured peaks in the measured spectrum obtained from X-ray diffraction (XRD) measurement will be described. First, the baseline was determined by taking the average intensity value in the ranges of 2θ=60.00° to 60.50° and 63.50° to 64.00°, and using this as the baseline value in 2θ=60.00° to 64.00°. The diffraction intensity obtained by subtracting the baseline obtained above from the measured peak (X) was plotted in the range of 2θ = 60.00 to 64.00. A calculated peak created by the sum of two pseudo-Voigt functions was fitted to the obtained diffraction peak in the range of 2θ = 60.00 to 64.00 degrees to perform peak separation, and the calculated peak (X1') at the lower 2θ angle after separation and the calculated peak (X') created by the sum of two pseudo-Voigt functions were obtained. The pseudo-Voigt function is the sum of a Lorentzian function and a Gaussian function with the same full width at half maximum. The pseudo-Voigt function f(2θ) used in peak separation is shown below.

[0123]

number

[0124] where 2θ j is the diffraction angle at the peak center, A is a scaling factor to fit the actual measurement, η is the mixing ratio of the Lorentzian function (left side of the bracket) and the Gaussian function (right side of the bracket), W is the peak half-width, π is the constant of the circumference, ln is the natural logarithm, and exp is the natural exponential function. In peak separation, the 2θ of each of the two pseudo-Voigt functions is j Fitting was performed using Excel's Solver function to minimize the mean square deviation between the baseline-subtracted peak (X) and the calculated spectrum in the range of 2θ = 60.00 to 64.00 degrees, with W, η, and A as variables.

[0125] (7) Measurement of swelling force The test was conducted in accordance with the Japan Bentonite Industry Association's standard test method for testing the swelling of bentonite (JBAS-104-77). 2.0 g of sample was taken and added in 10 batches to a measuring cylinder containing 100 ml of water. The next batch was added after the first batch had mostly settled. The mixture was left for 24 hours, and the apparent volume of the settled mass at the bottom of the container was read.

[0126] (8) MFR (Melt Mass Flow Rate) Measurements were taken using a Takara melt indexer under the test conditions of JIS K7210 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics - thermoplastics" at 230°C and a load of 2.16 kg.

[0127] 2. Production of ion-exchangeable layered silicate particles In the following examples, the particle size analysis results of the ion-exchanged layered silicate, the preparation conditions of the ion-exchanged layered silicate particles and the results of various analyses are shown in Table 1, and the polymerization results are shown in Table 2.

[0128] [Example a1: Production of ion-exchange layered silicate particles] (a1-1) Production of ion-exchange layered silicate composite granules The ion-exchange layered silicate used was a water slurry (solid content 5.3% by mass, mainly smectite-group montmorillonite with a 2:1 layer structure) obtained by mixing 2.4% by mass of sodium carbonate with clay mineral produced by Mizusawa Industrial Chemicals, Nakajo, Niigata Prefecture, and then purifying the mixture using elutriation and centrifugation. The average particle size of the ion-exchange layered silicate (clay mineral) was 0.27 μm. 73.5 g of lithium sulfate monohydrate and 511.5 g of distilled water were added to a 5 L beaker and stirred to form a solution. 1,800 g of the above water slurry (5.3 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 mixer. This procedure was repeated four times. Using the four batches of slurry obtained, spray drying granulation was carried out using a spray drying granulation apparatus (Okawahara Kakoki Co., Ltd. "L-8") under the following conditions: Atomizer type: M type rotary disc Atomizer rotation speed: 8,000 rpm Cyclone differential pressure: 1.08kPa Dry air inlet temperature: 110℃ The slurry supply time was 498 minutes. The granulated material was collected in the lower part of the granulator body and the lower part of the cyclone. A total of 203.6 g of the granulated material collected in the lower part of the body and the cyclone was passed through a sieve with 75 μm openings to remove coarse particles, and then dried at 200°C under reduced pressure for 2 hours to obtain 141.6 g of ion-exchanged layered silicate composite granulated particles.

[0129] (a1-2) Step of Obtaining Acid-Treated Ion-Exchanged Layered Silicate A 2 L flask equipped with a stirring blade and a reflux device was charged with 604.1 g of distilled water, and 169.2 g of 96% sulfuric acid was added dropwise. The aqueous solution was heated in an oil bath until the internal temperature reached 95°C. When the target temperature was reached, 140.0 g of the ion-exchanged layered silicate composite granulated particles obtained in (a1-1) above was added, and the mixture was allowed to react for 240 minutes. The reaction was stopped by pouring the reaction solution into 1500 mL of distilled water. The resulting slurry was filtered using an apparatus consisting of a Nutsche filter and a suction bottle connected to an aspirator. The filter cake was slurried with 1200 mL of distilled water and filtered again for washing. This washing with distilled water was carried out three times in total. 227.6 g of solids were obtained as a filter cake of acid-treated ion-exchangeable layered silicate.

[0130] (a1-3) Step of obtaining lithium-treated ion-exchanged layered silicate 227.6 g of the solid obtained from (a1-2) above and 442.0 g of distilled water were added to a 1 L flask and stirred. The slurry was heated to 40°C, and 10.0 g of a 4.43 wt% aqueous solution of lithium hydroxide was added dropwise. Stirring was then continued for 90 minutes to allow the reaction to proceed. The reaction was stopped by pouring the reaction solution into 1500 mL of distilled water. The resulting slurry was filtered using an apparatus consisting of a Nutsche filter and a suction bottle connected to an aspirator. The filtered cake was slurried with 1200 mL of distilled water and then filtered again for washing. This washing with distilled water was performed a total of three times. 214.5 g of solids were obtained as a filtered cake. The collected cake was dried overnight at 110 °C. The dried cake was then passed through a sieve with 75 μm openings to remove coarse particles, yielding 49.3 g of lithium-treated ion-exchanged layered silicate.

[0131] (a1-4) Heat treatment of lithium-treated ion-exchanged layered silicate 21.4 g of the lithium-treated ion-exchanged layered silicate obtained from (a1-3) above was heat-treated at 200° C. under reduced pressure for 12 hours to obtain 19.6 g of ion-exchanged layered silicate particles.

[0132] [Example a2: Production of ion-exchange layered silicate particles] (a2-1) Production of ion-exchange layered silicate granules As the ion-exchange layered silicate, the same water slurry as in Example a1 (solid content 5.3 mass %, main component smectite group montmorillonite with a 2:1 layer structure) was used. 457 g of distilled water and 1343.2 g of the above water slurry (5.3% by mass) were slowly added to a 5 L beaker while stirring. After stirring for 10 minutes, the mixture was further stirred for 15 minutes using a high-speed stirrer. This operation was repeated four times. Using the resulting four batches of slurry, spray drying granulation was carried out using a spray drying granulation apparatus (Okawahara Kakoki Co., Ltd. "L-8") under the same conditions as in Example a1. The slurry supply time was 264 minutes. The granulated material was collected in the lower part of the granulator body and the lower part of the cyclone. A total of 338.0 g of the granulated material collected in the lower part of the body and the cyclone was passed through a sieve with 75 μm openings to remove coarse particles, and then dried at 200°C under reduced pressure for 2 hours to obtain 285.6 g of ion-exchange layered silicate granulated particles.

[0133] (a2-2) Step of obtaining acid-treated ion-exchanged layered silicate The same procedure as in Example a1 (a1-2) was repeated except that the distilled water was 910.4 g, the 96% sulfuric acid was 116.3 g, the ion-exchanged layered silicate composite granules were 140.0 g of the ion-exchanged layered silicate granules described in (a2-1) above, and the reaction time was 300 minutes. 335.2 g of solids was obtained as a filter cake of acid-treated ion-exchanged layered silicate.

[0134] (a2-3) Step of obtaining lithium-treated ion-exchanged layered silicate (a1-3) of Example a1 was carried out in the same manner as (a1-3) of Example a1, except that the filter cake of the acid-treated ion-exchanged layered silicate obtained from (a1-2) was replaced with 230.4 g of the filter cake of the acid-treated ion-exchanged layered silicate obtained from (a2-2) above. 216.2 g of solids were obtained as a filter cake. The collected cake was dried overnight at 110° C. Furthermore, the dried cake was passed through a sieve with 75 μm openings to remove coarse particles, yielding 51.2 g of lithium-treated ion-exchanged layered silicate.

[0135] (a2-4) Heat treatment of lithium-treated ion-exchanged layered silicate 3.0 g of the lithium-treated ion-exchanged layered silicate obtained from (a2-3) above was heat-treated at 200° C. under reduced pressure for 12 hours to obtain 2.9 g of ion-exchanged layered silicate particles.

[0136] [Comparative Example a1: Production of Comparative Ion-Exchanged Layered Silicate Particles] In (a1-4) of Example a1, 22.5 g of the lithium-treated ion-exchanged layered silicate obtained from (a1-3) of Example a1 was used, and the same operations as in (a1-1) to (a1-4) of Example a1 were carried out, except that the heat treatment time was 2 hours, to obtain 20.5 g of ion-exchanged layered silicate particles.

[0137] [Comparative Example a2: Production of Comparative Ion-Exchanged Layered Silicate Particles] The same operations as in (a1-1) to (a1-3) of Example a1 were carried out, and the lithium-treated ion-exchanged layered silicate obtained from (a1-3) of Example a1 was used as comparative ion-exchanged layered silicate particles of Comparative Example a2.

[0138] [Comparative Example a3: Production of Comparative Ion-Exchanged Layered Silicate Particles] In (a2-4) of Example a2, 20.0 g of the lithium-treated ion-exchanged layered silicate obtained from (a2-3) of Example a2 was used, and the same operations as in (a2-1) to (a2-4) of Example a2 were carried out, except that the heat treatment time was 2 hours, to obtain 19.3 g of ion-exchanged layered silicate particles.

[0139] [Comparative Example a4: Production of Comparative Ion-Exchanged Layered Silicate Particles] (i) Preparation of ion-exchange layered silicate granules As granulated particles of ion-exchanged layered silicate, granulated particles of ion-exchanged layered silicate (Benclay SL, average particle size of ion-exchanged layered silicate before granulation: 0.45 μm) manufactured by Mizusawa Chemical Industries, Ltd. were prepared. (ii) Step of Obtaining Acid-Treated Ion-Exchanged Layered Silicate The same procedure as in Example a1(a1-2) was repeated, except that 912.0 g of distilled water, 115.2 g of 96% sulfuric acid, 139.4 g of ion-exchange layered silicate particles (Benclay SL) manufactured by Mizusawa Chemical Industries, Ltd. were used as the ion-exchange layered silicate composite particles, and the reaction time was 300 minutes. 342.6 g of solids were obtained as a filter cake of acid-treated ion-exchange layered silicate.

[0140] (iii) A step of obtaining a lithium-treated ion-exchanged layered silicate (a1-3) of Example a1 was carried out in the same manner as (a1-3) of Example a1, except that the filter cake of the acid-treated ion-exchanged layered silicate obtained from (a1-2) was replaced with 225.8 g of the filter cake of the acid-treated ion-exchanged layered silicate obtained from (ii) above. 212.2 g of solids were obtained as a filter cake. The collected cake was dried overnight at 110° C. Furthermore, the dried cake was passed through a sieve with 75 μm openings to remove coarse particles, yielding 47.9 g of lithium-treated ion-exchanged layered silicate.

[0141] (iv) Heat treatment of lithium-treated ion-exchanged layered silicate 27.5 g of the lithium-treated ion-exchanged layered silicate obtained in (iii) above was heat-treated at 200° C. under reduced pressure for 12 hours to obtain 25.0 g of ion-exchanged layered silicate particles.

[0142] [Table 1]

[0143] In addition, in FIG. 2, the apex of the calculated peak (X') in X-ray diffraction is plotted against the BET specific surface area m 2 3 shows a graph plotting the apex of the calculated peak (X1') in X-ray diffraction for the ion-exchanged layered silicate particles described in Examples and Comparative Examples against the BET specific surface area m 2 A plot of the α-to-β ratio against / g is shown.

[0144] 3. Production of olefin polymerization catalysts [Example b1: Production of olefin polymerization catalyst] 10.0 g of the ion-exchangeable layered silicate particles obtained in Example a1 and 66 mL of heptane were added to a 1000 mL flask and stirred. 34 mL of a heptane solution of triisobutylaluminum (TiBA) (24.5 mmol-Al) was then added and stirred at room temperature for 1 hour. After that, the mixture was washed with heptane until the residual liquid ratio was 1 / 100, and finally the slurry volume was adjusted to 50 mL, to which 31 mL (12.2 mmol) of a heptane solution of tri-normal octylaluminum was added. In a separate flask (volume: 200 mL), (r)-silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride was synthesized with reference to Example 7 of JP 2015-193605 A. A solution of 285 μmol of (r)-silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride and 30 mL of toluene was prepared, and added to the ion-exchange layered silicate particle slurry and stirred at 40°C for 60 minutes. After the reaction, heptane was added to bring the total volume to 300 mL, and the mixture was transferred to a stirring autoclave with an internal volume of 1 L that had been thoroughly purged with nitrogen. The temperature of the slurry was set to 40° C., and propylene was fed at a rate of 10 g / hour for 2 hours. After the propylene feed was stopped, the reaction was continued until the pressure reached 0.025 MPaG. Thereafter, the remaining monomer was purged and the polymerization catalyst slurry was recovered from the autoclave. The recovered polymerization catalyst slurry was allowed to stand, and the supernatant was removed. 8.5 mL (6 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, followed by drying under reduced pressure to obtain an olefin polymerization catalyst. The prepolymerization ratio (yield of catalyst for olefin polymerization ÷ (amount of ion-exchanged layered silicate particles + amount of metallocene complex) - 1) was 2.32 g / g-catalyst.

[0145] [Comparative Example b1: Production of olefin polymerization catalyst] The same procedure as in Example b1 was carried out except that the ion-exchange layered silicate particles obtained in Comparative Example a1 were used. The prepolymerization rate was 2.32 g / g of catalyst.

[0146] 4. Polymer production [Example P1: Propylene homopolymerization] After thoroughly replacing the inside of a 3 L stirred autoclave with propylene, 2.8 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (TiBA) was added to the autoclave, and then 242 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 slurried in heptane, and 9.7 mg of the pure catalyst (the sum of the amount of ion-exchanged layered silicate particles and the amount of metallocene complex) was pressure-charged into an autoclave to initiate polymerization. After polymerization at 65°C for 1 hour, 5 mL of ethanol was added to the autoclave to terminate the polymerization reaction. After purging the remaining propylene in the autoclave, the polymer was recovered and dried at 90°C for 1 hour.

[0147] [Examples P2 to P3, Comparative Examples P1 to P3: Propylene Homopolymerization] Polymerization was carried out in the same manner as in Example P1, except that the type of olefin polymerization catalyst, the amount of pure catalyst, and the amount of hydrogen added were set as shown in Table 2.

[0148] [Table 2]

[0149] 5. Results and Discussion Figure 4 is a graph plotting the polymerization activity versus the MFR of the resulting polymer for the results of propylene homopolymerization using the olefin polymerization catalysts of Example b1, which used the ion-exchanged layered silicate particles of Example a1, and Comparative Example b1, which used the ion-exchanged layered silicate particles of Comparative Example a1. Figure 4 shows that the catalysts using the ion-exchanged layered silicate particles of the Examples exhibit higher catalytic activity than the catalysts of the Comparative Examples, relative to their MFRs. That is, when compared at similar MFRs, the catalysts of the Examples exhibit higher catalytic activity than the catalysts of the Comparative Examples.

[0150] The present invention is not limited to the above-described embodiments, and various modifications and variations are possible within the scope of the claims of the present invention. [Industrial Applicability]

[0151] According to the present invention, it is possible to provide ion-exchanged layered silicate particles that improve catalytic activity, an olefin polymerization catalyst component containing the ion-exchanged 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, and these have high industrial applicability.

Claims

1. Ion-exchangeable layered silicate particles having the following properties (i) and (ii): Property (i): In X-ray diffraction, when a measured peak (X) existing in the range of 2θ = 60.00° to 64.00° is fitted with a baseline having a constant height relative to the peak intensity and a calculated peak created by the sum of two pseudo-Voigt functions in the range of 2θ = 60.00° to 64.00° to separate the peak (X) into two peaks and determine a baseline, and the calculated peak created by the sum of the two pseudo-Voigt functions is designated as (X'), the apex of the calculated peak (X') is in the range of 2θ = 61.66° to 61.77°. Property (ii): specific surface area is 250 m ２ / g or more, 700m ２ / g or less.

2. The ion-exchange layered silicate particles according to claim 1, further having the following property (iii): Property (iii): The content of lithium atoms is 0.10 mmol / g or more and 5.00 mmol / g or less.

3. The ion-exchangeable layered silicate particles according to claim 1 or 2, further having the following property (iv): Property (iv): Swelling power in water is 3 ml / 2 g or more and 20 ml / 2 g or less.

4. The ion-exchangeable layered silicate particles according to claim 1 or 2, further having the following property (v): Property (v): The average particle size is 2 μm or more and 500 μm or less.

5. A catalyst component for olefin polymerization, comprising the ion-exchange layered silicate particles according to claim 1 or 2.

6. An olefin polymerization catalyst comprising the following components [A], [B], and [C]: Component [A]: ion-exchange layered silicate particles according to claim 1 or 2 Component [B]: Transition metal compound Component [C]: organoaluminum compound

7. A method for producing an olefin polymerization catalyst, comprising mixing the following components [A], [B], and [C]: Component [A]: ion-exchange layered silicate particles according to claim 1 or 2 Component [B]: Transition metal compound Component [C]: organoaluminum compound

8. A method for producing an olefin polymer, comprising carrying out olefin polymerization in the presence of the olefin polymerization catalyst according to claim 6.

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