JP2008162857A - Ion-exchangeable layered silicate particles and their manufacture method, as well as olefin polymerization catalyst comprising the same and method of manufacturing olefin polymer using the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ion-exchangeable layered silicate particles having good particle structure by reducing the size of a basic particle, that is, particle before granulation process, and its manufacturing method, a catalyst for olefin polymerization producing polymer particles good in particle property with high activity, by controlling the structure and the size of an ion-exchangeable layered compound particles being a co-catalyst and also a carrier, and a method of manufacturing an olefin polymer having superior performance by using the catalyst. <P>SOLUTION: The ion-exchangeable layered silicate particles are prepared by a method of manufacturing ion-exchangeable layered silicate particles characterized by including a first granulation process for manufacturing granules having a surface area of 40 m<SP>2</SP>/g or more by granulating the ion-exchangeable layered silicate, and a second granulation process for pulverizing the granules prepared in the first granulation process and re-granulating them, to manufacture granules. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to ion-exchange layered silicate particles and a production method thereof, an olefin polymerization catalyst comprising the same, and an olefin polymer production method using the same. More specifically, the ion-exchanged layered silicate particles having a good particle structure by reducing the size of the basic particles (primary particles) and the production method thereof, the structure and size of the ion-exchangeable layered compound particles as the promoter / support The present invention relates to an olefin polymerization catalyst that gives polymer particles with high activity and good particle properties by controlling the thickness, and a method for producing an olefin polymer having excellent performance using the same.

It is known that an olefin polymer is produced by polymerizing an olefin in the presence of a catalyst using clay or clay mineral as a catalyst component for olefin polymerization (Patent Document 1 and Patent Document 2). In addition, olefin polymerization catalysts containing an ion-exchange layered compound subjected to acid treatment or salt treatment as a component are also known (Patent Documents 3 to 8). Furthermore, an olefin polymerization catalyst containing an ion-exchange layered compound treated in the presence of an acid and a salt as a component is also known (Patent Document 9).
Recently, focusing on the properties of ion-exchange layered silicate as a solid acid, a high activation method by increasing the amount of strong acid sites has been developed (Patent Document 10).

  These ion-exchange layered silicates act not only as a co-catalyst but also as a support, so the control of the particle structure greatly affects the form of the powder particles of the polymer produced, and therefore the productivity of the polymer is influenced. It is an important element to do. Conventionally, chemical treatments such as acid treatment, salt treatment, and alkali treatment have been frequently used as a method for controlling the particle structure of ion-exchanged layered silicate. However, these techniques alone cannot always produce ion-exchange layered silicate particles having a good particle structure.

JP-A-5-295022 Japanese Patent Laid-Open No. 5-301917 JP-A-7-228621 Japanese Patent Laid-Open No. 7-309906 Japanese Patent Laid-Open No. 7-309907 JP-A-7-228621 JP-A-8-127613 JP-A-10-168109 JP-A-10-168110 JP 2002-053609 A

  An object of the present invention is to provide ion-exchange layered silicate particles having a good particle structure by reducing the size of basic particles (primary particles), a method for producing the same, and a promoter / support. A catalyst for olefin polymerization that gives polymer particles with high activity and good particle properties by controlling the structure and size of certain ion-exchange layered compound particles, and a method for producing an olefin polymer having excellent performance using the same. It is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have determined that the important factor controlling the particle structure of the ion-exchange layered silicate (clay mineral) is the amount of the end face of the basic particles (primary particles). As a result of finding out the properties and intensive studies, the present invention has been completed.

  In addition, the present inventors can control the viscosity when the ion-exchange layered silicate is slurried in a liquid such as water by controlling the size of the basic particles of the ion-exchange layered silicate. Has a great influence on the granulated particle structure in the case of granulating an ion-exchange layered silicate slurry in the subsequent process, and an ion-exchange layered silicate that acts as a support and co-catalyst by intensive study of this technology A technique for controlling the granulated particle structure, pore structure, and particle shape was found, thereby completing a technique for producing polymer powder particles having good properties, thereby completing the present invention.

  Furthermore, the present inventors have found that increasing the end surface by reducing the basic particles also leads to an increase in acid sites. Olefin polymerization requires transition metals from Groups 3-12 of the Periodic Table, but the acid sites are believed to activate them. As a result of investigations by the present inventors, it has been clarified that the place that becomes an acid point on the ion-exchange layered silicate is the end face of the basic particle. Therefore, by increasing the end face, it was found that the activation of the transition metal of Group 3-12 of the periodic table serving as the active point can be promoted, and a highly active catalyst can be provided, thereby completing the present invention. It was.

That is, according to 1st invention of this invention, the 1st granulation process of granulating an ion exchange layered silicate and manufacturing the granulated body whose surface area is 40 m < ² > / g or more, A method for producing ion-exchangeable layered silicate particles, comprising a second granulation step of producing a granulated body by pulverizing the granulated body obtained in the granulation step and then granulating again. Provided.

  According to the second invention of the present invention, in the first invention, the first granulation step includes an operation of evaporating a liquid from the slurry of the ion-exchangeable layered silicate. A method for producing layered silicate particles is provided.

  According to a third aspect of the present invention, there is provided the method for producing ion-exchange layered silicate particles according to the second aspect, wherein the operation is a spray granulation method.

  According to a fourth invention of the present invention, in any one of the first to third inventions, the ion-exchangeable layered silicate particle characterized in that the second granulation step includes a spray granulation method. A manufacturing method is provided.

  According to a fifth aspect of the present invention, there is provided the method for producing ion-exchangeable layered silicate particles according to any one of the first to fourth aspects, further comprising a chemical treatment step. .

  Moreover, according to the 6th invention of this invention, the ion exchange layered silicate particle | grains characterized by being obtained by the manufacturing method of the invention in any one of the 1st-5th invention are provided.

  According to the seventh invention of the present invention, in the sixth invention, there is provided ion-exchangeable layered silicate particles characterized by having a compressive fracture strength of 2 MPa or more.

  According to the eighth invention of the present invention, in the sixth or seventh invention, the ion-exchange layered silicate particle characterized in that the ion-exchange layered silicate is mainly composed of montmorillonite. Is provided.

According to the ninth aspect of the present invention, there is provided an olefin polymerization catalyst characterized by contacting the following component [A] and component [B] with an olefin.
Component [A]: Ion-exchangeable layered silicate particle of any of the sixth to eighth inventions Component [B]: Transition metal compound of Groups 3-12 of the periodic table

According to the tenth aspect of the present invention, there is provided an olefin polymerization catalyst characterized by contacting the following component [A], component [B] and component [C] with an olefin.
Component [A]: Ion-exchangeable layered silicate particle of any of the sixth to eighth inventions Component [B]: Transition metal compound of Groups 3-12 of the periodic table Component [C]: Organoaluminum compound

  According to an eleventh aspect of the present invention, there is provided an olefin polymer production method using the olefin polymerization catalyst according to the ninth or tenth aspect of the present invention.

By the method of the present invention, the size of the basic particles can be reduced to produce ion-exchangeable layered silicate particles having a good particle structure, and the structure and size of the ion-exchangeable layered compound particles that are the promoter and support. It is possible to produce ion-exchangeable layered compound particles with controlled thickness.
Further, by using the ion-exchangeable layered compound particles, it is possible to obtain an olefin polymerization catalyst that gives polymer particles having high activity and good particle properties.
Furthermore, by using this catalyst for olefin polymerization, it is possible to produce a polymer with high activity, and the resulting polymer has good particle properties and can be obtained as a high bulk density powder. Can be produced.

  The ion-exchange layered silicate particles and the production method thereof, the olefin polymerization catalyst comprising the same, and the production method of the olefin polymer using the same will be described specifically and in detail below.

1. Manufacturing method of ion-exchange layered silicate particles (1) Ion-exchange layered silicate The ion-exchange layered silicate used in the present invention is a structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bond force. It is a silicate compound that has a crystalline structure and that contains exchangeable ions. Most ion-exchange layered silicates are naturally produced mainly as the main component of clay minerals, but these ion-exchange layered silicates are not limited to natural ones, but are artificially synthesized. Also good. Moreover, the chemical treatment mentioned later may be performed to these ion exchange layered silicates.
In the present invention, if the ion treatment is performed before chemical treatment, the physical and chemical properties are changed by the treatment, and the silicate having no ion exchange property or layer structure is also ionized. Treat as an exchangeable layered silicate.

  Specific examples of the ion-exchange layered silicate include layered silicate having a 1: 1 type structure or a 2: 1 type structure described in “Clay Mineralogy” (Haruo Shiramizu, Asakura Shoten, 1995), for example. Salt. The 1: 1 type structure is based on the stacking of the 1: 1 layer structure in which one layer of tetrahedron sheet and one layer of octahedron sheet are combined as described in the above “clay mineralogy” and the like. The 2: 1 type structure is a structure based on a stack of 2: 1 layer structures in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.

  Specific examples of ion-exchangeable layered silicates in which the 1: 1 layer is the main constituent layer include kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite, chrysotile, risardite, antigolite, etc. Examples include serpentine silicates.

  Specific examples of ion-exchangeable layered silicates with 2: 1 layers as main constituent layers include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, and vermiculite groups such as vermiculite. Examples thereof include mica group silicates such as silicate, mica, illite, sericite, sea chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group and the like. These may form a mixed layer.

  Among these, the main component is preferably an ion-exchange layered silicate having a 2: 1 type structure. More preferably, the main component is a smectite group silicate, and still more preferably, the main component is montmorillonite.

  There are no particular limitations on the type of interlayer cation (cation contained between the layers of the ion-exchange layered silicate), but as a main component, alkali metals of the first group of the periodic table such as lithium and sodium, calcium, magnesium, etc. Alkaline earth metals from Group 2 of the periodic table, or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold are relatively easy as industrial raw materials. It is preferable in that it can be obtained.

  In the present invention, “basic particles” refer to primary particles of an ion-exchange layered silicate granule. The primary particles are the smallest constituent units when solid particles are decomposed into units in which atoms are strongly bonded by covalent bonds or the like and are not easily separated. The ion-exchange layered silicate is a tetrahedral sheet as described in the Japan Clay Society edited by Clay Handbook 2nd Edition. Is shared with the adjacent tetrahedron and the remaining vertex is the same direction and spreads in a hexagonal network), or an octahedron sheet (Al, Mg, Fe, etc.). A sheet in which the surrounding octahedrons share a ridge and spread in a two-dimensional manner) has a structure in which a number of layers are further laminated in a ratio of 1: 1 or 2: 1. The basic particle of the ion-exchange layered silicate is one layer.

  The basic particle (primary particle) particle size and average specific edge area values are obtained by undissolving the ion-exchange layered silicate to the basic particle unit (so-called primary particle) by a method such as water swelling. It is obtained by observing with. If the values of the particle diameter and the average specific end area are outside the preferred ranges, there is a drawback that the activity of the resulting polymerization catalyst does not increase.

(2) 1st granulation process (1st granulation process)
The effect of the present invention is that the ion-exchange layered silicate particles of the present invention are granulated from the ion-exchange layered silicate as a raw material to produce a granulated body having a specific surface area ("first granulation step" And then the obtained granulated material is pulverized (also referred to as “grinding step”) and then granulated again (also referred to as “second granulation step”). Can be obtained.
Moreover, the catalyst for olefin polymerization catalysts of the present invention is produced using the ion-exchangeable layered silicate particles.
Therefore, the form of the ion-exchange layered silicate before pulverization needs to be a granulated body, and the surface area of the granulated body is preferably 40 m ² / g or more. The surface area is a value measured by the BET three-point method. A preferable surface area is 45 m ² / g or more, more preferably 50 m ² / g or more, particularly preferably 60 m ² / g or more, still more preferably 65 m ² / g or more, and most preferably 70 m ² / g or more. .

When the surface area is small, the distortion of the basic particles of the ion-exchange layered silicate in the granule is small, and it is difficult to obtain the effect of reducing the basic particles by subsequent pulverization. In this case, the granulation is preferably a technique in which a large amount of strain of basic particles of the ion-exchange layered silicate remains.
The value of the surface area is an index of the particle structure in the granulated body, and when the surface area is large, there are many pores in the particle. The reason why there are many pores is that the basic particles of the ion-exchange layered silicate have a structure in which they are gathered together in a random manner.

  The method of giving such a form having a specific surface area is not particularly limited as long as the granulated particles have a specific surface area, but in the present invention, the distortion of the basic particles is reduced. Since a large amount can be left, a method including an operation of evaporating a liquid from the slurry of the ion-exchange layered silicate is preferable. Examples include spray granulation and various granulation operations after freeze-drying.

On the other hand, the method of pulverizing the purified ion-exchanged layered silicate lump is not preferable as the first granulation step in the present invention. In such a method, the surface area does not increase to 40 m ² / g or more, and the effect of subsequent grinding is hardly obtained. For example, the surface area of Kunipia F (ion exchange layered silicate manufactured by Kunimine Industries Co., Ltd.) manufactured by such a method is only 26 m ² / g.

  Preferred granulation techniques in the first granulation step include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method and the like. Particularly preferred are agitation granulation method, spray granulation method, rolling granulation method, and fluidized granulation method. In the present invention, a large amount of basic particle strain remains and the surface area is increased. Therefore, spray granulation is particularly preferable.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as a dispersion medium.

  Since the first granulation step has good handleability, it is desirable that the first granulation step can be granulated spherically. The concentration of the component ion-exchange layered silicate in the spray granulation raw slurry liquid from which spherical particles are obtained is 0.1 to 70% by weight, preferably 1 to 50% by weight, particularly preferably 5 to 30% by weight. is there. The temperature at the inlet of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, Examples thereof include latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate.

  There are no particular restrictions on the shape of the ion-exchange layered silicate as a raw material before granulation, and it may be a naturally produced shape, a shape when artificially synthesized, or operations such as grinding, granulation, and classification. You may use the ion exchange layered silicate which processed the shape by.

(3) Grinding (grinding process)
The ion-exchangeable layered silicate particles of the present invention are obtained after granulating the raw material ion-exchangeable layered silicate to produce a granulated body having a specific surface area and then granulated. It is manufactured through a pulverization process for pulverizing the body.

The meaning of using the product subjected to the first granulation step as a pretreatment before being subjected to the pulverization step is considered as follows.
The basic particles of the ion-exchange layered silicate are very thin plate-like, and several tens or more layers overlap each other. Conventionally, it is difficult to reduce the size of the basic particles, and even if it is simply pulverized, it can only be pulverized in such a direction that several tens of layers are peeled off and the number of layers is decreased. One of the reasons for this was simply selecting an ion-exchange layered silicate mineral mass (clay mineral) as a raw material before grinding.

  According to the study by the present inventors, by carrying out appropriate pretreatment, specifically, granulation after carrying out granulation treatment, not only the direction in which the number of layers is reduced, but also the direction in which the size of the basic particles is reduced. That is, it was found that the surface of the basic particle plate can be pulverized in the direction of decreasing, and the end face is increased. The reason for this is not necessarily clear, but it is because the basic particles of the clay are not stacked in an orderly manner after the granulation process, but the basic particle plates are fixed with some distortion. It is done. Therefore, it is considered preferable to select a technique that leaves a large amount of basic particle strain as the granulation treatment.

Next, the relationship between the pulverization of the basic particles and the particle structure will be described. The higher order structure of the ion-exchange layered silicate particles is composed of the following two adhesion points. The first adhesion is adhesion in a direction in which plate-like basic particles are laminated in parallel. This adhesion increases when the size of the basic particles is large (the area of the plate is large). The second adhesion is an adhesion between the end face of the basic particles (the edge portion of the board) and the board surface, and forms a structure such as a so-called card house structure. This adhesion increases as the size of the basic particles decreases (the area of the plate decreases).
A feature of the present invention is that by controlling the size of the basic particles, the form of adhesion between them can be controlled, thereby providing a carrier that gives good polymer particle properties.

Moreover, it is considered as a mechanochemical effect that a thermodynamic property, a chemical property, and a crystallographic property change when a crystalline substance receives mechanical energy, such as grinding, compression, an impact, and mixing.
Ion exchange layered silicates are also crystalline materials and so far there have been studies of mechanochemical effects on various ion exchange layered silicates (eg Perez-Rodriguez, J. L., Madrid Sanchez del Villar, L.). And Sanches-Soto, P. J. (1988) Clay Miner., 23, 399-401).

However, there have been no examples of pulverizing and grinding ion-exchange layered silicates for olefin polymerization catalyst components using techniques that have developed a mechanochemical effect so far. It was only implemented from the viewpoint of facilitating.
The feature of the present invention is that the mechanochemical effect is expressed by pulverization of the granulated ion-exchange layered silicate, and the end face is increased and the end face property is also controlled. The activity is improved.

  Although there is no restriction | limiting in particular as a grinding | pulverization method in a grinding | pulverization process, It is required that it is the method by which the basic particle of an ion exchange layered silicate becomes small by grinding | pulverization of an ion exchange layered silicate particle.

The particle size of the basic particles (primary particles) of the ion-exchanged layered silicate after pulverization is preferably 5 μm or less. More preferably, it is 2 μm or less, particularly preferably 1 μm or less, still more preferably 0.5 μm or less, and very preferably 0.3 μm or less. In the case of an ion-exchange layered silicate, the basic particles (primary particles) are plate-like (thin sheet-like), but this particle size is calculated by calculating the surface area of the plate and representing the diameter when it is assumed to be a perfect circle.
Moreover, it is preferable that an average specific end area is 10 m < ² > / g or more. More preferably ^{20 m} 2 / g or more, particularly preferably ^{30 m} 2 / g or more, more preferably ^{50 m} 2 / g or more. The average specific edge area of the basic particles of the ion-exchange layered silicate is the surface area of the smectite that is a thin sheet (the part other than the upper and lower surfaces when the sheet is placed on a horizontal substrate, The area of the portion of the outer peripheral portion corresponding to the vertical direction area) is expressed per 1 g of smectite.

  The particle size and average specific edge area of the basic particles (primary particles) described above are obtained by unraveling the ion-exchange layered silicate to a basic particle unit (so-called primary particles) by a method such as water swelling. It can be obtained by observing with TEM or the like. If the values of the particle diameter and the average specific end area are outside the preferred ranges, there is a drawback that the activity of the resulting polymerization catalyst does not increase.

  Specific examples of the pulverizer include a jaw crusher, a gyratory crusher, a roll crusher, an edge runner, a hammer mill, a ball mill, and a jet mill. A ball mill and a jet mill are preferable, and a jet mill is particularly preferable. Further, either dry pulverization or wet pulverization may be used. In the present invention, in order to obtain ion-exchangeable layered silicate particles that can exhibit a mechanochemical effect and are preferable as a carrier for an olefin catalyst, specifically, the average specific area is the above-mentioned by the method of physical pulverization by impact. It is preferable to grind into a size within the preferred range. As a result, in the second granulation step, which is the next step, the productivity of granulation is improved, and a larger particle size ion-exchange layered silicate granule can be obtained. It can be made suitable for a catalyst.

(4) Second granulation step (second granulation step)
In the present invention, the ion-exchange layered silicate after the pulverization step is granulated again in the second granulation step to form particles. There is no particular limitation on the granulation method at this stage, as described above, stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, Examples thereof include an emulsification granulation method, a submerged granulation method, and a compression molding granulation method. Particularly preferred are agitation granulation method, spray granulation method, rolling granulation method and fluidized granulation method, and in the present invention, since spherical particles are easy to produce, spray granulation method is particularly preferred. Can be mentioned.

  After the granulation body having a specific surface area by the first granulation step according to the production method of the present invention, this is pulverized, and then the ion-exchangeable layered silicate particles as the catalyst component are granulated again. The particle structure of the ion-exchanged layered silicate granule serving as the catalyst carrier is a structure suitable as a catalyst carrier for olefin polymerization. Specifically, the shape of the catalyst is close to a true sphere, whereby a powder particle-shaped olefin polymer close to a true sphere is obtained, the bulk density of the powder is improved, and the fluidity of the powder is improved.

  In addition, in order to obtain ion-exchangeable layered silicate particles suitable as a catalyst support for olefin polymerization, granulation so as to have a compressive fracture strength of 2 MPa or more in order to suppress crushing and the like in the polymerization step described later. Is preferred. The lower limit of the preferred compressive fracture strength is 5 MPa or more, more preferably 7 MPa or more, particularly preferably 13 MPa or more, very preferably 15 MPa or more, very preferably 17 MPa or more, and particularly preferably 20 MPa or more. The upper limit is preferably 100 MPa, more preferably 50 MPa. If the upper limit is exceeded, the particles do not grow by the replica effect during the polymerization, and there are problems that strained powder particles are generated, fine powder is generated, and initial activity is lowered.

  The particle size of the ion-exchangeable layered silicate suitable as an olefin polymerization catalyst carrier after being pulverized and granulated again is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. The preferred particle size range depends on the polymerization process.

Therefore, as a technique for satisfying the above requirements and producing ion-exchangeable layered silicate particles suitable as an olefin polymer catalyst carrier, it is preferable to employ a spray granulation method under the following conditions.
As the conditions for spray granulation, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene or the like is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium.
In order to obtain excellent catalytic properties and polymer particle properties, it is desirable that the second granulation step be capable of being granulated spherically. The concentration of the component ion-exchange layered silicate in the spray granulation raw slurry liquid from which spherical particles are obtained is 0.1 to 70% by weight, preferably 1 to 50% by weight, particularly preferably 5 to 30% by weight. is there. The temperature at the inlet of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.
Further, when the pulverization is performed before the granulation by the second granulation step, there is an advantage that the viscosity of the slurry can be reduced when the pulverized ion-exchange layered silicate particles are made into a water slurry. The low slurry viscosity means that the concentration of the ion-exchange layered silicate can be increased in order to achieve the same viscosity, thereby improving the productivity of granulation and increasing the size of the larger particles. A granulated body of ion-exchange layered silicate having a diameter can be obtained, and the grain system can be controlled. The slurry viscosity is preferably 5 wt% or more, more preferably 7 wt% or more.

(5) Ion exchange layered silicate chemical treatment step (i) Chemical treatment agent The ion exchange layered silicate particles of the present invention are desirably subjected to chemical treatment. The chemical treatment step is preferably performed in a step after the pulverization step. The reason for this is that the part that changes greatly in the chemical treatment is the end face of the ion-exchange layered silicate, and the end face can be increased by grinding, so the chemical treatment proceeds more efficiently after grinding. is there. The chemical treatment is more preferably performed after the second granulation step. The reason is that it gives a highly active catalyst, and after granulation, the particle size of the particles is larger, so that the ion-exchange layered silicate tends to settle during chemical treatment and washing in post-treatment. Further, it is easy to filter. Chemical treatment of ion-exchangeable layered silicate particles means treatment agents and ions containing acids, salts, alkalis, oxidizing agents, reducing agents, or compounds that can intercalate between the layers of ion-exchangeable layered silicate. This refers to contacting with an exchangeable layered silicate. Intercalation refers to introducing another substance between layers of a layered substance, and the introduced substance is called a guest compound. Among these treatments, acid treatment or salt treatment is particularly preferable.

  A common effect of chemical treatment is to exchange interlayer cations. In addition, various chemical treatments have the following various effects. For example, according to the acid treatment with acids, impurities on the silicate surface can be removed and the surface area can be increased by eluting cations such as Al, Fe, and Mg in the crystal structure. This contributes to increasing the acid strength of the silicate and increasing the amount of acid sites per unit weight.

  In alkali treatment with alkalis, the crystal structure of the clay mineral is destroyed, resulting in a change in the structure of the clay mineral. In intercalation or salt treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed to change the surface area or interlayer distance. By using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material with the layers expanded. That is, the bulky ions play a role of supporting pillars and support the layered structure, and are called pillars.

  Below, the specific example of a processing agent is shown. In the present invention, the following acids, salts, alkalis, oxidizing agents, reducing agents, and combinations of two or more selected from the group consisting of compounds capable of intercalating between the layers of the ion-exchange layered silicate are combined. May be used as a treating agent. Further, these acids, salts, alkalis, oxidizing agents, reducing agents, and compounds capable of intercalating between the layers of the ion-exchange layered silicate may each be a combination of two or more. Among these, a combination of salt treatment and acid treatment is particularly preferable.

(A) Acids In addition to removing impurities on the surface or exchanging cations existing between layers, acid treatment removes some or all of cations such as Al, Fe, Mg, etc. incorporated in the crystal structure. Can be eluted. Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Of these, inorganic acids are preferred.

(B) Salts Salts are composed of a cation selected from the group consisting of an organic cation, an inorganic cation, and a metal ion, and an anion selected from the group consisting of an organic anion, an inorganic anion, and a halide ion. Examples of such salts are exemplified. For example, at least one selected from the group consisting of a cation containing at least one atom selected from Groups 1 to 14 of the periodic table, a halogen anion, an inorganic Bronsted acid, and an organic Bronsted acid anion. A preferred example is a compound composed of an anion. Particularly preferably, the anion is a compound composed of an inorganic Bronsted acid or a halogen.

Specific examples of such salts include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, Na ₂ SO ₄ , and Na ₃ (PO ₄ ). , NaNO ₃ , Na (OOCCH ₃ ), KCl, KBr, K ₂ SO ₄ , K ₃ (PO ₄ ), KNO ₃ , K (OOCCH ₃ ), CaCl ₂ , CaSO ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , Sc (OOCCH ₃ ) ₂ , Sc ₂ (CO ₃ ) ₃ , Sc ₂ (C ₂ O ₄ ) ₃ , Sc (NO ₃ ) ₃ , Sc ₂ (SO ₄ ) ₃ , _{ScF 3, ScCl 3, ScBr 3} , ScI 3, Y (OOCCH 3) 3, Y (CH 3 COCHCOCH 3) 3, Y 2 (CO 3) 3, Y 2 (C 2 O 4) 3, Y _{NO 3) 3, Y (ClO} 4) 3, YPO 4, Y 2 (SO 4) 3, YF 3, YCl 3, La (OOCH 3) 3, La (CH 3 COCHCOCH 3) 3, La 2 (CO 3 ) ₃ , La (NO ₃ ) ₃ , La (ClO ₄ ) ₃ , La ₂ (C ₂ O ₄ ) ₃ , LaPO ₄ , La ₂ (SO ₄ ) ₃ , LaF ₃ , LaCl ₃ , LaBr ₃ , LaI ₃ etc. .

Sm (OOCCH ₃ ) ₃ , Sm (CH ₃ COCHCOCH ₃ ) ₃ , Sm ₂ (CO ₃ ) ₃ , Sm (NO ₃ ) ₃ , Sm (ClO ₄ ) ₃ , Sm ₂ (C ₂ O ₄ ) ₃ , SmPO ₄ , Sm ₂ (SO ₄ ) ₃ , SmF ₃ , SmCl ₃ , SmBr ₃ , SmI ₃ , Yb (OOCCH ₃ ) ₃ , Yb (NO ₃ ) ₃ , Yb (ClO ₄ ) ₃ , Yb ₂ (C ₂ O ₄ ) ₃ , Yb ₂ (SO ₄ ) ₃ , YbF ₃ , YbCl ₃ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , _{TiBr 4, TiI 4, Zr (} OOCCH 3) 4, Zr (CO 3) 2, Zr (NO 3) 4, Zr (SO 4) 2, ZrF 4, ZrCl 4, ZrBr 4, ZrI _{, ZrOCl 2, ZrO (NO 3} ) 2, ZrO (ClO 4) 2, ZrO (SO 4), Hf (OOCCH 3) 4, Hf (CO 3) 2, Hf (NO 3) 4, Hf (SO 4) _{2, HfOCl 2, HfF 4,} HfCl 4, HfBr 4, HfI 4, V (CH 3 COCHCOCH 3) 3, VOSO 4, VOCl 3, VCl 3, VCl 4, VBr 3, Nb (CH 3 COCHCOCH 3) 5, Nb ₂ (CO ₃ ) ₅ , Nb (NO ₃ ) ₅ , Nb ₂ (SO ₄ ) ₅ , ZrF ₅ , ZrCl ₅ , NbBr ₅ , NbI ₅ , Ta (OOCCH ₃ ) ₅ , Ta ₂ (CO ₃ ) ₅ , Ta (NO ₃ ) ₅ , Ta ₂ (SO ₄ ) ₅ , TaF ₅ , TaCl ₅ , TaBr ₅ , TaI _{5 and the} like.

Cr (OOCH ₃ ) ₂ OH, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₃ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , MoOCl ₄ , MoCl ₃ , MoCl ₄ , MoCl ₅ , MoF ₆ , MoI ₂ , WCl ₄ , WCl ₆ , WF ₆ , WBr ₅ , Mn (OOCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₃ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , MnBr ₂ , MnI ₂ , Fe (OOCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) _{3, FeCO 3, Fe (NO} 3) 3, Fe (ClO 4) 3, FePO 4, FeSO 4, _{e 2 (SO 4) 3,} FeF 3, FeCl 3, MnBr 3, FeI 3, FeC 6 H 5 O 7, Co (OOCH 3) 2, Co (CH 3 COCHCOCH 3) 3, CoCO 3, Co (NO 3 ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , CoBr ₂ , CoI ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _2, etc.

CuCl ₂ , CuBr ₂ , Cu (NO ₃ ) ₂ , CuC ₂ O ₄ , Cu (ClO ₄ ) ₂ , CuSO ₄ , Cu (OOCCH ₃ ) ₂ , Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , Sn (OOCCH ₃ ) ₄ , _{sn (SO 4) 2, SnF} 4, SnCl 4 and the like.

  Examples of organic cations include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5- Pentamethylanilinium, N, N-dimethyloctadecylammonium, octadodecylammonium, N, N-2,4,5-pentamethylanilinium, N, N-dimethyl-pn-butylanilinium, N, N- Ammonium compounds such as dimethyl-p-trimethylsilylanilinium, N, N-dimethyl-1-naphthylanilinium, N, N, 2-trimethylanilinium, 2,6-dimethylanilinium, pyridinium, quinolinium, N-methylpi Peridinium, 2,6-dimethyl Nitrogen-containing aromatic compounds such as pyridinium, 2,2,6,6-tetramethylpiperidinium, oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, oxolanium, triphenylphosphonium, tri-o Examples include, but are not limited to, phosphonium compounds such as -tolylphosphonium, tri-p-tolylphosphonium, and trimesitylphosphonium, and phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium.

  Examples of the anion include, in addition to the anions exemplified above, anions composed of boron compounds and phosphorus compounds such as hexafluorophosphate, tetrafluoroborate, tetraphenylborate and the like. Is not to be done.

  Moreover, these salts may be used independently and may be used in combination of 2 or more types. Further, it may be used in combination with acids, alkalis, oxidizing agents, reducing agents, compounds that intercalate between the layers of the ion-exchange layered silicate, and the like. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment.

(C) Alkaline Examples of the treatment agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , and Ba (OH) ₂ . In addition, since the loss of the acid point of the ion-exchange layered silicate due to the alkali treatment is considered, it is preferable to perform the acid treatment after achieving the structural change of the clay mineral by the alkali treatment. Or even if it is after performing an alkali treatment, if the intensity | strength and quantity of an acid point satisfy | fill the above-mentioned range, the effect of this invention will not be impaired at all. Among these, LiOH, NaOH, KOH, and Mg (OH) ₂ are preferable.

(D) Oxidizing agent As the oxidizing agent, permanganic acids such as HMnO ₄ , NaMnO ₄ , and KMnO ₄ , HNO ₃ , N ₂ O ₄ , N ₂ O ₃ , N ₂ O, Cu (NO ₃ ) ₂ , Pb ( NO ₃ ) ₂ , AgNO ₃ , KNO ₃ , NH ₄ NO ₃ and other nitrate compounds, F ₂ , Cl ₂ , Br ₂ , I ₂ and other halogens, H ₂ O ₂ , Na ₂ O ₂ , BaO ₂ , (C _{6 H 5 CO) 2 O 2} , K 2 S 2 O 8, K 2 SO 5, HCO 3 H, CH 3 CO 3 H, C 6 H 5 CO 3 H, C 6 H 4 (COOH) CO 3 H, Peroxides such as CF ₃ CO ₃ H, oxygen acids such as KIO, KClO, KBrO, KClO ₃ , KBrO ₃ , KIO ₃ , HIO ₄ , Na ₃ H ₂ I ₆ , KIO ₄ , CeO ₂ , Ag ₂ O, CuO, HgO, Pb O ₂ , Bi ₂ O ₃ , OsO ₄ , RuO ₄ , SeO ₂ , MnO ₂ , As ₂ O ₅ and other oxides, oxygen, oxygen such as ozone, hot concentrated sulfuric acid, fuming sulfuric acid and concentrated nitric acid mixture, nitrobenzene And iodoso compounds.

(E) Reducing agent Examples of the reducing agent include hydrogen and hydrogen compounds such as H ₂ , HI, H ₂ S, LiAlH ₄ and NaBH ₄ , sulfur compounds such as SO ₂ and Na ₂ S, alkali metals, alkaline earth metals, Metals such as transition metals of Group 3 to 10 of the periodic table or alloys thereof, salts of metals in a low valence state such as Fe (II), Sn (II), Ti (II), Cr (II), CO, etc. Is exemplified.

(F) Compound for intercalation As a guest compound used for intercalating between the layers of the ion-exchange layered silicate, cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR) ₃ [R is an alkyl group, aryl group, etc.] and other metal alcoholates, [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) _{14 ^{] 2+, [Fe 3 O (}} OCOCH 3) 6] + or the like of metal hydroxide ions, ethylene glycol, glycerol, urea, organic compounds such as hydrazine, organic cations such as alkyl ammonium ion.

When intercalating these compounds, polymers obtained by hydrolyzing metal alcoholates such as Si (OR) ₄ , Al (OR) ₃ and Ge (OR) ₄ , colloidal inorganic such as SiO ₂ A compound or the like can also coexist. Examples of pillars include oxides produced by heat dehydration after intercalation of the hydroxide ions between layers. As a method of using the guest compound, it may be used as it is, or it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Moreover, even if it uses independently, 2 or more types of the said solid may be mixed and used.

  The various treatment agents described above may be dissolved in a suitable solvent and used as a treatment agent solution, or the treatment agent itself may be used as a solvent. Solvents that can be used include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide, carbon disulfide, nitrobenzene Pyridines and their halides. Further, the concentration of the treatment agent in the treatment agent solution is preferably about 0.1 to 100% by weight, more preferably about 5 to 50% by weight. If the concentration of the treatment agent is within this range, there is an advantage that the time required for the treatment is shortened and the production can be efficiently performed.

(Ii) Chemical treatment process conditions The treatment conditions are not particularly limited. Usually, the treatment temperature is selected from room temperature to the boiling point of the treatment agent solution, and the treatment time is from 5 minutes to 24 hours. It is preferable to carry out the conditions under which at least a part of the substance constituting the material is removed or exchanged. The ratio of the ion-exchange layered silicate and the treatment agent in the chemical treatment step is not particularly limited, but preferably the ion-exchange layered silicate [g]: treatment agent [mol] = 1: 0.001-1: It is about 0.1.

  After carrying out the chemical treatment, it is possible to remove excess treatment agent and ions eluted by the treatment, which is preferable. At this time, generally, a liquid such as water or an organic solvent is used. After the dehydration, drying is performed. Generally, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C. If the temperature exceeds 800 ° C., the silicate structure may be destroyed, which is not preferable.

  Since the characteristics of these ion-exchangeable layered silicate particles change depending on the drying temperature even if they are not structurally broken, it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.

  Silicates contain various metals in the form of guest compounds, pillars, etc., but those containing aluminum in the state after chemical treatment are preferred, and the atomic ratio of Al / Si is 0.05 to 0.4. , Preferably 0.05 to 0.25, and more preferably 0.07 to 0.23. The Al / Si atomic ratio is considered to be an index for acid treatment of the clay portion.

2. Olefin Polymerization Catalyst (1) Catalyst Component The olefin polymerization catalyst of the present invention is characterized in that the following component [A], component [B], and optionally component [C] are brought into contact with an olefin. It is a catalyst for olefin polymerization.
Component [A]: Ion exchange layered silicate particles obtained by the production method of the present invention Component [B]: Transition metal compound of Groups 3 to 12 of the periodic table,
Component [C]: an organoaluminum compound,

<Component A>
Above 1. It is an ion exchange layered silicate particle obtained by the method explained in 1. above. These particles preferably have a compressive fracture strength of 2 MPa or more in order to suppress crushing and fine powder generation in the polymerization process. The lower limit of the preferred compressive fracture strength is 5 MPa or more, more preferably 7 MPa or more, particularly preferably 13 MPa or more, very preferably 15 MPa or more, very preferably 17 MPa or more, and particularly preferably 20 MPa or more. The upper limit is preferably 100 MPa, more preferably 50 MPa. If the upper limit is exceeded, the particles do not grow by the replica effect during the polymerization, and there are problems that strained powder particles are generated, fine powder is generated, and initial activity is lowered.

  The particle size of the ion-exchange layered silicate particles granulated again after pulverization is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. The preferred particle size range depends on the polymerization process. When the polymerization process is a gas phase method, a larger particle size is preferable because adhesion and fluidity are improved. In the case of the gas phase method, it is preferably 10 μm or more, more preferably 30 μm or more, particularly preferably 46 μm or more, and further preferably 51 μm or more. On the other hand, when the polymerization process is a slurry method (including a bulk method in which the solvent is propylene), it is not preferable that the particle size is too large because the generated powder will settle out. In the case of the bulk method, the particle size is preferably 3 to 40 μm, more preferably 5 to 20 μm.

<Ingredient [B]>
Component [B] used in the present invention is a transition metal compound of Groups 3 to 12 of the periodic table. Specifically, a Group 3-10 transition metal halide, a Group 3-6 transition metal metallocene compound, a Group 4 transition metal bisamide or bisalkoxide compound, a Group 8-10 transition metal bisimide compound, Examples thereof include phenoxyimine compounds of Group 3-11 transition metals.

  Among these, metallocene compounds of Group 4 transition metals are preferred, and specifically, compounds represented by the following general formulas (I) to (VI) are used.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY ··· (I)
^{_{Q (C 5 H 4-c}} R 1 c) (C 5 H 4-d R 2 d) MXY ··· (II)
^{_{Q '(C 5 H 4-}} e R 3 e) ZMXY ··· (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY ··· (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW ··· (V)
Q ″ (C ₅ H _5-g R ⁴ _g ) (C ₅ H _5-h R ⁵ _h ) MXY (VI)

Here, Q is a bonding group that bridges two conjugated five-membered ring ligands, Q ′ is a bonding group that bridges the conjugated five-membered ring ligand and the Z group, and Q ″ is R ⁴ and R. ⁵ is a bonding group that crosslinks ⁵ ; M is a group 3-12 transition metal of the periodic table; X, Y, and W are each independently hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, Z is oxygen , A sulfur-containing ligand, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. Group 4 transition metals such as Zr, Zr and Hf are preferred.

R ^{1 to} R ⁵ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, phosphorus A hydrocarbon-containing group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; Two adjacent R ^{1 s} , 2 R ^{2 s} , 2 R ^{3 s} , 2 R ^{4 s} , or 2 R ^{5 s} combine to form a ring having 4 to 10 carbon atoms. You may do it. a, b, c, d, e, and f are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 0 ≦ e ≦ 4, and 0 ≦ f ≦ 5, respectively. , 0 ≦ g ≦ 5, 0 ≦ h ≦ 5.

A bridging group Q that bridges between two conjugated five-membered ring ligands, a bridging group Q ′ that bridges a conjugated five-membered ring ligand and a Z group, and R ⁴ and R ⁵ are bridged. Specific examples of Q ″ include the following: alkylene groups such as methylene groups and ethylene groups, ethylidene groups, propylidene groups, isopropylidene groups, phenylmethylidene groups, and diphenylmethylidene groups. Silicon such as alkylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisiylene group -Containing crosslinking group, germanium-containing crosslinking group, alkylphosphine, amine, etc. Among these, alkylene group, alkylidene group, silicon Yes bridging groups, and germanium-containing crosslinking group are particularly preferably used.

  Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V) and (VI) are exemplified below, but Zr is replaced with Hf or Ti. The same compounds can be used as well. In addition, the component [B] represented by the general formulas (I), (II), (III), (IV), (V) and (VI) is a compound represented by the same general formula or a different general formula. It can be used as a mixture of two or more of the compounds shown.

Formula (I)
Biscyclopentadienylzirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-methyl-4,5benzoindenyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azurenyl) zirconium dichloride Bis (2-methyl-4H-azurenyl) cyclopentadienylzirconium dichloride, bis (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H -Azulenyl) zirconium dichloride.

Formula (II)
Dimethylsilylenebis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-methylindenyl)} zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-methyl) Indenyl)} ethylenebis {1,1 ′-(2-methyl-4,5benzoindenyl)} zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-methyl-4-hydroazurenyl)} zirconium dichloride, Dimethylsilylenebis {1,1 '-(2-methyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride, dimethylsilylenebis [1,1'-{2-methyl-4- (4-chlorophenyl) -4- Hydroazurenyl}] zirconium dichloride, dimethylsilylene bis {1,1 '-(2- Ethyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride, ethylenebis {1,1 ′-(2-methyl-4-hydroazurenyl)} zirconium dichloride.

Formula (III)
(Tertiary butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl-zirconium Dichloride, (Ethylamide) (tetramethyl-η5-cyclopentadienyl) -methylenezirconium dichloride, (Tertiary butyramide) Dimethyl- (tetramethyl-η5-cyclopentadienyl) Silane zirconium dichloride, (Tertiary butyramide) Dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride, (phenylphosphide) dimethyl (te Ramechiru -η5- cyclopentadienyl) silane zirconium dibenzyl.

Formula (IV)
(Cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, (cyclopentadienyl) ( 2,6-di-t-butylphenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride.

General formula (V)
(Cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) zirconium triisopropoxide, ( Pentamethylcyclopentadienyl) zirconium triisopropoxide.

Formula (VI)
Ethylene bis (7,7'-indenyl) zirconium dichloride, dimethylsilylene bis {7,7 '-(1-methyl-3-phenylindenyl)} zirconium dichloride, dimethylsilylene bis [7,7'-{1-methyl -4- (1-naphthyl) indenyl}] zirconium dichloride, dimethylsilylene bis {7,7 '-(1-ethyl-3-phenylindenyl)} zirconium dichloride, dimethylsilylene bis {7,7'-(1- Isopropyl-3- (4-chlorophenyl) indenyl)} zirconium dichloride.

A compound in which the silylene group of the compound of these specific examples is replaced with a germylene group is also exemplified as a suitable compound.
Among the transition metal compound components [B] described above, preferred for the production of the propylene-based polymer of the present invention is a substituted cyclohexane crosslinked with a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. It is a transition metal compound comprising a ligand having a pentadienyl group, a substituted indenyl group, a substituted fluorenyl group, and a substituted azulenyl group. Particularly preferred is a transition metal compound crosslinked with a silylene group having a hydrocarbon substituent or a germylene group. Further, those having a substituted indenyl group and a substituted azulenyl group are preferred, and transition metal compounds having a substituent at the 2-position, 4-position, or 2,4-position are particularly preferred.

  Further, as specific examples of metallocene compounds, JP-A-7-188335, Journal of American Chemical Society, 1996, Vol. Transition metal compounds having a ligand containing one or more elements other than carbon in a 5-membered ring or 6-membered ring disclosed in 118, 2291 can also be used.

  Suitable examples of the bisamide compounds belonging to Group 4 of the periodic table include those described in Macromolecules, Vol. 29, 5241 (1996) and Journal of American Chemical Society, Vol. 119, no. 16, 3830 (1997), Journal of American Chemical Society, Vol. 121, no. 24, 5798 (1999), a bridged transition metal compound having a bulky substituent on the nitrogen atom can be given.

  Moreover, as a suitable example of the bisalkoxide compound of Group 4 of the periodic table, a transition metal compound of Group 4 of the Periodic Table disclosed in WO87 / 02370, preferably two aryloxy ligands are cross-linking groups. More preferable examples include a bridged transition metal compound that can be bonded to each other and that can be coordinated with the transition metal by the crosslinking group.

  Further, bisimide compounds of Group 8 to 10 transition metals in the periodic table can be found in Journal of American Chemical Society, Vol. 117, 6414, WO96 / 23010, Chemical Communication, page 849, Journal of American Chemical Society, Vol. 120, 4049, WO98 / 27124, a bridged transition metal bisimide compound having a bulky substituent on the nitrogen atom can be cited as a suitable example.

  Other suitable examples of the phenoxyimine compounds of Group 3 to 10 transition metals in the periodic table include compounds disclosed in JP-A-11-315109.

  Furthermore, these components [B] can be used as a mixture of two or more. Further, a plurality of types can be used in combination with the above-mentioned periodic table group 3-12 metallocene compound.

<Ingredient [C]>
The component [C], the general formula organoaluminum compound represented by _{(AlR n X 3-n)} m is used. In formula, R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents 1-3, m represents the integer of 1-2, respectively. The organoaluminum compounds can be used alone or in combination.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(2) Preparation of olefin polymerization catalyst and preliminary polymerization The olefin polymerization catalyst of the present invention is prepared by bringing component [B] into contact with component [A] and optionally component [C]. The contact method is not particularly limited, but can be contacted in the following order. Moreover, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers.

1) Contact component [B] and component [A] 2) Add component [C] after contacting component [B] and component [A] 3) Contact component [B] and component [C] 4) Add component [A] after contacting component [A] and component [C], and add component [B]. In addition, three components may be contacted simultaneously.

A preferred contact method is to contact the component [A] with the component [C], then remove the unreacted component [C] by washing or the like, and then contact the necessary minimum component [C] with the component [A] again. And then contacting the component [B]. In this case, the molar ratio of Al / transition metal is in the range of 0.1 to 1,000, preferably 2 to 10, and more preferably 4 to 6.
The temperature at which component [B] and component [C] are brought into contact (in which case component [A] may be present) is preferably from 0 ° C. to 100 ° C., more preferably from 20 to 80 ° C., particularly preferably from 30 to 30 ° C. 60 ° C. When it is lower than this range, the reaction is slow, and when it is high, the decomposition reaction of component [B] proceeds.
In addition, when the component [B] and the component [C] are brought into contact (in this case, the component [A] may be present), it is preferable that an organic solvent is present as a solvent. In this case, the concentration of component [B] in the organic solvent should be high, preferably 3 mM, more preferably 4 mM, and even more preferably 6 mM.

  The amount of the transition metal complex is 0.001 to 10 mmol, preferably 0.001 to 1 mmol, per 1 g of the component [A].

  Component [A] preferably has an acid point. The lower limit of the amount of the acid point is preferably 30 μmol, more preferably 50 μmol, still more preferably 100 μmol, and particularly preferably 150 μmol of the strong acid point of pKa <−8.2 or less per 1 g of the component [A]. The amount of acid points is measured according to the description in JP-A-2000-158707.

  These may be contacted in the polymerization tank or outside the polymerization tank and prepolymerization may be performed in the presence of olefin. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. An olefin having 3 or more carbon atoms is preferable.

  The catalyst of the invention of the present application is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance to improve the particle property. 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 and the like can be used. It is possible to use, and it is particularly preferable to use propylene. The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50, based on 1 part of the component [A]. After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.

The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10-70 ° C, particularly preferably 20-60 ° C, and further preferably 30-50 ° C. Below this range, the reaction rate may decrease or the activation reaction may not proceed, and if it exceeds this range, the prepolymerized polymer may dissolve, or the prepolymerization rate may be too high and the particle properties may deteriorate. There is a possibility that the active site may be deactivated due to a side reaction.
The preliminary polymerization can be carried out in a liquid such as an organic solvent, and this is preferable. The concentration of the solid catalyst during the prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.

  Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

  The catalyst may be dried after the prepolymerization. There are no particular restrictions on the drying method, but examples include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. Also good. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

3. Method for Producing Olefin Polymer Polymerization carried out using an olefin polymerization catalyst comprising component [A], component [B], and component [C] used as necessary is olefin alone or the olefin and another comonomer. Is mixed and contacted. In the case of copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change it. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

  As the olefin that can be polymerized, those having about 2 to 20 carbon atoms are preferred. Specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7 -Octadiene, cyclopentene, norbornene, ethylidene norbornene and the like. Preferred is an α-olefin having 2 to 8 carbon atoms. In the case of copolymerization, the type of comonomer used can be selected from olefins other than the main component from those mentioned as the olefin.

  As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas phase in which each monomer is kept in a gaseous state without substantially using a liquid solvent. Laws can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure is 0 to 2000 kg / cm ² G, preferably 0 to 60 kg / cm ² G.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention will not be restrict | limited by these Examples, unless it deviates from the summary. In the following examples, montmorillonite used as an ion-exchange layered silicate as a starting material is spray-dried granulated clay “Benclay SL” manufactured by Mizusawa Chemical Industry Co., Ltd., and has an average particle size of 19.3 μm by classification. Was used.
In addition, the measuring method in a present Example is as follows.

(Various physical property measurement methods)
(1) MFR: Melt index with a load of 2.16 kg at 230 ° C. according to JIS-K-6758.
(2) Measurement of particle size distribution of ion-exchange layered silicate: Laser diffraction / scattering type particle size distribution measuring device LA-920 manufactured by Horiba, Ltd., ethanol as dispersion solvent, refractive index 1.0, shape factor 1 0.0, and the median diameter value was defined as the average particle diameter.
(3) Measurement of average particle diameter of powder: 20 g of sample powder manufactured by Lecce Technology Co., Ltd. using a particle size distribution measuring device camsizer, DIN 66141 Q3 (0.5) (mass-based cumulative distribution Q3 (x) X = 0. The particle size of 5) was defined as the average particle size.
(4) Polymer bulk density: Measured according to ASTM D1895-69.

(5) Measurement of compressive fracture strength: Using a crushing tester “MCTM-500” manufactured by Shimadzu Corporation, the crushing strength of 10 or more arbitrarily selected particles was measured, and the average value was adopted.
(6) Measurement of surface area: Measured by the BET multipoint method using Autosorb 3B manufactured by Canterchrome. An adsorption isotherm of a sample pretreated for 2 hours at 200 ° C. under vacuum was measured using nitrogen gas as an adsorbate. A BET plot was prepared from the adsorption isotherm, the monomolecular adsorption amount was determined from the gradient and the intercept, and the specific surface area was calculated.
(7) Measuring method of slurry viscosity: Measured at 100 rpm using a B-type viscometer manufactured by BROOKFIELD.
(8) Particle shape (powder properties): Observed using a real microscope and a scanning electron microscope.

(Example 1)
(A) “Ben clay SL” (manufactured by Mizusawa Industries Co., Ltd.), which is a spray granulation (surface area 74 m ² / g) of ion exchange layered silicate (montmorillonite); A φ25 screw feeder was supplied to a counter jet mill 100AFG manufactured by Hosokawa Micron Co., Ltd. under the following operating conditions: 0.57 kg of ion-exchange layered silicate granules were supplied over 94 minutes, and 0.36 kg of pulverized product was supplied. The remaining amount of the reactor was 0.21 kg.
Supply condition: φ25SF feeder transmission scale 0.1
Compressed air amount: 0.5 [Nm ³ / min]
Air pressure: 0.39 MPa
Nozzle diameter: φ1.9
Classifier format: 50 ATP
Rotation speed: 22000rpm
Rotor rinsing air volume: 0.31 [Nm ³ / min]
Rotor rinsing air pressure: 0.098 [MPa]
Bearing rinsing air amount: 0.15 [Nm ³ / min]
Bearing rinsing air pressure: 0.098 [MPa]

(B) Spray granulation of pulverized ion-exchange layered silicate 100 g of the pulverized montmorillonite was added to 1900 g of distilled water, stirred for 2 hours, and left as a slurry for one day. The viscosity of the slurry was 2.0 cP. Spray granulation of the above montmorillonite slurry was carried out under the following conditions using a spray granulator (Okawara Chemical Industries "L-8").
Atomizer speed: 10000rpm
Cyclone differential pressure: 0.60 KPa
Slurry supply speed: 900 mL / h
Entrance temperature: 170 ° C
Outlet temperature: 124 ° C

As a result of spray granulation, 84.3 g of a granulated product having an average particle size of 26.2 μm and a surface area of 124 m ² / g was recovered.
When the particle shape was observed with a scanning electron microscope, the particles were almost spherical.

(C) Chemical treatment of spray-granulated product of ion-exchange layered silicate Into a 500 mL round three-necked flask equipped with a stirring blade and a reflux device, 168.6 g of distilled water was added and 49.9 g of 98% sulfuric acid was added. It was dripped and internal temperature was 90 degreeC. Thereto, 30 g of the above spray granulated product was added and stirred. Thereafter, the reaction was carried out at 90 ° C. for 3.5 hours. The slurry was poured into 150 mL of distilled water to stop the reaction, filtered through a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 75 mL of distilled water. The obtained cake was dispersed in 300 mL of distilled water, filtered after stirring. This operation was repeated three times.
The recovered cake was added to an aqueous solution in which 36.7 g of zinc sulfate heptahydrate was dissolved in 135 mL of pure water in a 1 L beaker and reacted at room temperature for 2 hours. This slurry was filtered through a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 75 mL of distilled water. The obtained cake was dispersed in 300 mL of distilled water, filtered after stirring. This operation was repeated three times.
The collected cake was dried at 120 ° C. overnight. As a result, 20 g of a chemically treated product was obtained.
This chemically treated montmorillonite was put into a 200 mL volumetric flask and dried under reduced pressure at 200 ° C., and further dried under reduced pressure for 2 hours after the generation of gas was stopped. When the moisture content of this dried montmorillonite was measured, the moisture value was 1.40 wt%.

(D) Chemically treated montmorillonite treated with organoaluminum 5.0 g of the dried montmorillonite obtained in (c) above was weighed into a 200 mL flask, and 18 mL of heptane and 32 mL (12.5 mmol) of heptane solution of tri-normal octylaluminum were added. And stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 25 mL.

(E) Prepolymerization with propylene To a heptane slurry of montmorillonite treated with tri-normal octyl aluminum prepared in (d) of (1) above, 1.25 mL (600 μmol) of a heptane solution of tri-normal octyl aluminum was added. In another flask (volume 200 mL), (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride 111 mg (127 μmol) ) And a slurry of heptane (15 mL) added thereto was added and stirred at 60 ° C. for 60 minutes.
Next, 210 mL of heptane was further added to the montmorillonite heptane slurry to adjust the total amount to 250 mL, and the mixture was introduced into a stirring autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen. When the temperature in the autoclave was stabilized at 40 ° C., propylene was supplied at a rate of 5 g / hour to maintain the temperature. After 2 hours, the supply of propylene was stopped and maintained at 40 ° C. for another 2 hours.
Thereafter, the residual monomer was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. Subsequently, 4.18 mL (3.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, and then dried under reduced pressure to recover 13.89 g of a solid catalyst.
The prepolymerization ratio (a value obtained by dividing the prepolymerized polymer amount by the solid catalyst amount) was 1.65.

(F) Propylene-ethylene random copolymer After the inside of the autoclave with a stirrer with a volume of 3 L is sufficiently substituted with propylene, 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) is added, and hydrogen in a standard state volume is added. 90 mL, 12 g of ethylene, and then 750 g of liquid propylene were introduced, and the temperature was raised to 70 ° C. Slurry the prepolymerized catalyst obtained in (e) above into heptane, and press-fit 10 mg (amount of net solid catalyst excluding prepolymerized polymer; the same applies hereinafter) with 1 mL of heptane as a solid catalyst, and further feed the catalyst with 5 mL of heptane The line was washed to initiate the polymerization.
The temperature inside the tank was maintained at 70 ° C. for 60 minutes after the catalyst was charged. Thereafter, 5 mL of ethanol was injected to stop the polymerization. The polymerization results are summarized in Table 1. The obtained polymer powder particles were spherical.

(Examples 2 to 8)
Polymerization was conducted in the same manner as in Example 1 except that the polymerization conditions were different. The results of Examples 2 to 4 are shown in Table 1, and the results of Examples 5 to 8 are shown in Table 2.

(Comparative Example 1)
Spray granulation was carried out in the same manner as in Example 1 except that the operation of (a) in Example 1 was not carried out and a 5 wt% water slurry of Benclay SL (slurry viscosity: 8.3 cP) was used. 62.1 g of a granulated product having an average particle diameter of 27.6 μm was recovered.
When the particle shape was observed with a scanning electron microscope, it was a flat particle.
The other operations were carried out in the same manner as in Example 1 for polymerization. The results are summarized in Table 1. The obtained polymer powder particles were flat and spherical.

(Comparative Examples 2-6)
Polymerization was conducted in the same manner as in Comparative Example 1 except that the polymerization conditions were different. The results of Comparative Examples 2 to 4 are shown in Table 1, and the results of Comparative Examples 5 and 6 are shown in Table 2.

(Comparative Examples 7-8)
8 kg of commercially available montmorillonite (“Kunipia F” manufactured by Kunimine Kogyo Co., Ltd .: surface area of 26 m ² / g) was pulverized with a vibration ball mill. Polymerization was conducted in the same manner as in Example 1 except that this was used and the polymerization conditions were different. The results are shown in Table 2.

As is clear from Table 1, Examples 1 and ² do not satisfy the requirement of “surface area of 40 m ² / g or more”, which is a specific matter of the production method of the present invention, as compared with Comparative Examples 7 and 8. Is the method. It can be seen that the products obtained in the comparative examples are olefin polymerization catalysts having good polymerization activity as compared with the low polymerization activity of Examples 1 and 2 of the production method of the present invention. Specifically, in the comparison between Example 1 and Comparative Example 7, Example 1 is highly active while having the same MFR, and the same is true in the comparison between Example 2 and Comparative Example 8.
Moreover, what was obtained in Comparative Examples 1 to 4 which is a specific matter of the production method of the present invention, which is a method that does not satisfy the requirement of “performing the pulverization step after the first granulation step”, is the same amount of hydrogen. In comparison, the yield of the polypropylene polymer is not good, and the powder properties of the obtained polymer are flat, as compared with Examples 1-4 according to the examples of the production method of the present invention. The obtained polymer has a good spherical powder property. Therefore, it can be seen that the olefin polymerization catalyst of Examples satisfying the specific matters of the production method of the present invention is an excellent olefin polymerization catalyst having high activity.
Therefore, it can be said that the Examples obtained excellent results in terms of polymerization activity and polymer particle properties.

  FIG. 1 is a diagram summarizing the relationship between MFR and activity based on the results of Examples 1-4 and Comparative Examples 1-4. It is clear that the catalyst according to the invention is highly active.

By the method of the present invention, ion-exchangeable layered silicate particles having a good particle structure can be produced by reducing the size of the basic particles (particles before the granulation step), and the ion-exchangeable layered compound is a promoter and carrier. It is possible to produce ion-exchange layered silicate particles with controlled particle structure and size.
Further, by using this adjusted ion-exchangeable layered compound, it is possible to obtain an olefin polymerization catalyst that gives polymer particles having high activity and good particle properties.
In addition, by using this olefin polymerization catalyst, it is possible to produce a polymer with high activity, and to obtain an excellent performance such that the obtained polymer has good particle properties and can be obtained as a high bulk density powder. The olefin polymer which has can be manufactured.
Therefore, according to the present invention, an olefin polymerization catalyst that gives polymer particles with high activity and good particle properties and an olefin polymer having excellent performance using the same can be produced. Very big.

FIG. 1 is a diagram summarizing the relationship between MFR and activity based on the results of Examples 1 to 4 and Comparative Examples 1 to 4.

Claims (11)

A first granulation step of granulating an ion-exchange layered silicate to produce a granule having a surface area of 40 m ² / g or more, and pulverizing the granule obtained in the first granulation step A method for producing ion-exchangeable layered silicate particles, comprising a second granulation step of producing a granulated product by granulation again.   The method for producing ion-exchangeable layered silicate particles according to claim 1, wherein the first granulating step includes an operation of evaporating a liquid from the slurry of the ion-exchangeable layered silicate.   The method for producing ion-exchangeable layered silicate particles according to claim 2, wherein the operation is a spray granulation method.   The method for producing ion-exchange layered silicate particles according to any one of claims 1 to 3, wherein the second granulation step includes a spray granulation method.   Furthermore, a chemical treatment process is included, The manufacturing method of the ion exchange layered silicate particle | grains of any one of Claims 1-4 characterized by the above-mentioned.   Ion-exchange layered silicate particles obtained by the production method according to claim 1.   The ion-exchangeable layered silicate particles according to claim 6, having a compressive fracture strength of 2 MPa or more.   The ion-exchange layered silicate particles according to claim 6 or 7, wherein the ion-exchange layered silicate is mainly composed of montmorillonite. A catalyst for olefin polymerization, comprising contacting the following component [A] and component [B] with an olefin.
Component [A]: Ion-exchange layered silicate particles according to any one of claims 6 to 8 Component [B]: Transition metal compound of Groups 3-12 of the periodic table An olefin polymerization catalyst comprising the following component [A], component [B] and component [C] in contact with an olefin.
Component [A]: Ion-exchange layered silicate particles according to any one of claims 6 to 8 Component [B]: Transition metal compound of Groups 3-12 of the periodic table Component [C]: Organoaluminum compound A method for producing an olefin polymer, wherein the olefin polymerization catalyst according to claim 9 or 10 is used.