JP7092002B2 - A method for producing a catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same. - Google Patents

Description

The present invention relates to a method for producing a catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same. More specifically, it is a method for producing a catalyst component for olefin polymerization in which the acid treatment concentration and the elution rate of aluminum eluted by the acid treatment are controlled, and has high polymerization activity and few bright spots (fish eyes) in the product. The present invention relates to a method for producing a catalyst for olefin polymerization, which has good fluidity and can obtain a polymerized powder having good particle properties.

It is known to polymerize an olefin in the presence of a catalyst using clay or a clay mineral as a catalyst component for olefin polymerization to produce an olefin polymer (see, for example, Patent Document 1).
Further, a catalyst for olefin polymerization containing an ion-exchangeable layered compound subjected to acid treatment or salt treatment as a component is also known (see, for example, Patent Document 2).
Further, since these ion-exchange layered compounds act not only as a co-catalyst but also as a carrier, the control of the particle structure greatly affects the morphology of the powder particles of the polymer to be produced, which is the productivity of the polymer. It is an important factor that influences.
Conventionally, as a method for controlling the particle structure of an ion-exchangeable layered compound, chemical treatments such as acid treatment, salt treatment, and alkali treatment have been often used.
However, these techniques alone have not always been able to produce ion-exchangeable layered compound particles having a good particle structure.

In recent years, a technique for producing a soft material by a vapor phase process using a metallocene catalyst has been developed (see, for example, Patent Document 3). In order to produce such a soft polymer, a polymer powder having a larger particle size, and thus a catalyst having a larger particle size, is required. The reason is that in soft materials, sticky components tend to bleed out on the surface at the polymerization temperature, and powder particles tend to aggregate with each other, but when the particle size of the powder is increased, the outer surface surface of the particle surface per mass becomes smaller. Therefore, agglomeration of particles on the surface is less likely to occur.
On the other hand, spherical particles are required as the shape of the catalyst particles. The reason is that in a consumption type catalyst such as an olefin polymerization catalyst, the shape of the catalyst particles is almost the same as the shape of the powder particles (so-called replica effect), and the spherical powder has a larger bulk density and is more productive. At the same time, the fluidity and flowability of the powder are excellent, and the powder can be easily transported by force or by gravity in the plant.
Further, high particle strength is required as a catalyst carrier. The reason is that when the particle strength is strong, even if the particles are rubbed or hit the wall during stirring or flow in the polymerization tank, the particles are broken and fine powder is generated, or irregular powder is generated. This is because there is no problem of shaving.

Patent Document 4 discloses a method for producing large particle size particles by once granulating, performing acid treatment, and then further granulating. However, since the surface of the particles is extremely uneven and the gaps between the particles are large, when a block copolymer is polymerized using a carrier having such a surface shape, the rubber component bleeds out from the surface to form an aggregate. It is easily inferred to do.

Patent Document 5 discloses a method for producing smectite particles having a substantially spherical particle shape and high particle strength by producing granulated bodies using pulverized montmorillonite.

Further, in Patent Document 6, by crushing acid-treated clay and granulating it again, the particle surface is smooth without unevenness, and is spherical and has a large particle size at the same time with a high balance that has never existed in the past. The method for producing the clay mineral particles is disclosed. However, since these particles have a high acid concentration during acid treatment, there is a problem that the polymerization activity is lowered when they are used as a catalyst for olefin polymerization.

In Patent Document 7, the catalytic activity is increased by using an ion-exchangeable layered silicate in which the amount of specific minute pores occupies 60 to 100% of the total pore amount as a catalyst component for olefin polymerization. It is stated that there is a significant improvement.

Further, Patent Document 8 describes that an ion-exchangeable layered silicate treated with an acid having an acid concentration (N) satisfying the following formula is highly active and the polymerization proceeds in a state where dispersed particles are maintained. Has been done.
N ≧ 6.0
[The acid concentration N shown here indicates the number of moles of acid x the valence of acid / the volume of the aqueous acid solution (unit: liter)]

Further, in Patent Document 9, residual catalyst nuclei (usually called bright spots or fish eyes) that deteriorate the appearance of the product when a prepolymerization catalyst having a prepolymerization homogenization index (H value) of 60% or less is used. It is stated that there will be less. However, the particle size of the ion-exchange layered silicate used in these catalysts is small, and when a block copolymer is polymerized, the rubber component bleeds out from the surface and easily forms an aggregate. It is inferred. In addition, the amount of fine powder generated during polymerization also increases.

Japanese Unexamined Patent Publication No. 5-295022 Japanese Unexamined Patent Publication No. 7-228621 Japanese Unexamined Patent Publication No. 2005-132979 Japanese Unexamined Patent Publication No. 2005-335981 Japanese Unexamined Patent Publication No. 2008-156395 Japanese Unexamined Patent Publication No. 2012-126084 Japanese Unexamined Patent Publication No. 2015-108138 Japanese Unexamined Patent Publication No. 2002-037812 Japanese Unexamined Patent Publication No. 2006-274277

As described above, in the conventional technology, ion-exchangeable layered silicate particles and the ion-exchangeable layered silicate particles that simultaneously realize the three required performances of the number of bright spots in the product, the polymerization activity, and the powder properties of the polymer at a high level that has never been seen before. The catalyst for olefin polymerization using the above has not been manufactured.

In view of the situation of the prior art, the present application conventionally controls the acid treatment concentration in producing ion-exchangeable layered silicate particles which is a co-catalyst and carrier and the elution rate of aluminum eluted by the acid treatment. It is an object of the present invention to provide a method for producing an olefin polymerization catalyst containing a catalyst component for olefin polymerization, which has realized polymer physical properties and polymerization performance at a high level at the same time, which could not be produced.
Specifically, an olefin polymerization catalyst containing a catalyst component for olefin polymerization, which exhibits high polymerization activity, has few bright spots (fish eyes) in the product that deteriorates the appearance of the product, and can produce polymer particles having good particle properties. It is intended to be provided.

As a result of diligent research to achieve the above objectives, the present researchers have found that the ion-exchangeable layered silicate particles acid-treated with an acid concentration of less than 20% by mass satisfy the desired properties, and the ion-exchangeable layered silicate particles satisfy the desired properties. By using salt particles as a catalyst component for olefin polymerization, it is possible to produce a catalyst for olefin polymerization that can produce polymer particles having good particle properties with few bright spots (fish eyes) in the product while exhibiting high polymerization activity. I found a way.

The method for producing a catalyst component for olefin polymerization of the present invention is a method for producing a catalyst component for olefin polymerization composed of an ion-exchangeable layered silicate.
The step (1) of acid-treating the ion-exchangeable layered silicate particles with an acid concentration of less than 20% by mass is included.
The catalyst component for olefin polymerization is characterized by satisfying the following characteristics (i) to (iii).
(I) The average particle size is 26.0 μm to 200.0 μm.
(Ii) The elution rate of aluminum before the acid treatment is 26% to 64%.
(Iii) The crushing strength is 5.0 MPa to 100.0 MPa.

The method for producing a catalyst component for olefin polymerization of the present invention may further include a step (2) of treating the ion-exchangeable layered silicate particles with a base after the step (1).

In the method for producing a catalyst component for olefin polymerization of the present invention, the catalyst component for olefin polymerization may satisfy the following property (iv).
(Iv) The total pore volume of pores having a diameter in the range of 2 to 6 nm measured by the nitrogen adsorption method shall be 0.170 cm ³ / g or more and 0.500 cm ³ / g or less.

The method for producing a catalyst for olefin polymerization of the present invention is characterized in that the following components [A], component [B], and component [C] are brought into contact with an olefin.
Component [A]: Catalyst component for olefin polymerization obtained by the above-mentioned production method Component [B]: Transition metal compound component of Group 4 of the periodic table [C]: Organoaluminum compound

The method for producing an olefin polymer of the present invention is characterized in that olefin polymerization is carried out using a catalyst for olefin polymerization obtained by the above-mentioned production method.

The ion-exchangeable layered silicate particles acid-treated with an acid concentration of less than 20% by mass satisfy the desired properties, and high polymerization activity is achieved by using the ion-exchangeable layered silicate particles as a catalyst component for olefin polymerization. It is possible to obtain a catalyst for olefin polymerization capable of producing polymer particles having good particle properties with few bright spots (fish eyes) in the product while exhibiting.

1. 1. Method for Producing Catalyst Component for Olefin Polymerization The method for producing the catalyst component for olefin polymerization of the present invention is a method for producing a catalyst component for olefin polymerization composed of an ion-exchangeable layered silicate.
The step (1) of acid-treating the ion-exchangeable layered silicate particles with an acid concentration of less than 20% by mass is included.
The catalyst component for olefin polymerization is characterized by satisfying the following characteristics (i) to (iii).
(I) The average particle size is 26.0 μm to 200.0 μm.
(Ii) The elution rate of aluminum before the acid treatment is 26% to 64%.
(Iii) The crushing strength is 5.0 MPa to 100.0 MPa.

In paragraphs 0026 to 0030 of Patent Document 8 (Japanese Unexamined Patent Publication No. 2002-037812), the ion-exchangeable layered silicate is treated with an acid having an acid concentration (N) satisfying the formula: N ≧ 6.0 (this operation is referred to as “this operation”. It is described that the polymerization can be promoted while maintaining high activity and dispersed particles by performing (referred to as "concentrated acid treatment").
Therefore, in a known technique, a carrier in which a specific amount of aluminum is eluted with a low concentration acid polymerizes an excellent powdery polymer while exhibiting high catalytic activity, and reduces bright spots in the product. It is not known what can be done.
The present application cannot be conventionally produced by controlling the average particle size of ion-exchangeable layered silicate particles, which is a co-catalyst and carrier, the acid treatment concentration at the time of production, and the elution rate of aluminum eluted by the acid treatment. We have completed a technique for producing a catalyst for olefin polymerization that simultaneously realizes polymer properties and polymerization performance at a high level.

Hereinafter, the method for producing the catalyst component for olefin polymerization of the present invention and the like will be described in detail for each item. In addition, in this specification, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

1. 1. (1) Ion-exchangeable layered silicate The catalyst component for olefin polymerization of the present invention comprises an ion-exchangeable layered silicate.
The ion-exchangeable layered silicate in the present invention is a kind of silicate compound having a crystal structure in which planes composed of ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and is not limited to naturally produced ones. It may be an artificial compound.
Specific examples include smectites such as montmorillonite, byderite, nontronite, saponite, hectorite, and stevensite, as described in "Clay Minerals" by Haruo Shiramizu, Asakura Shoten (1995). Be done. These may form a mixed layer. Since many smectites are naturally produced as a mixture of clay minerals, they often contain impurities (such as quartz and cristobalite), but they may be included. Preferably, the main component is montmorillonite.
Further, it is more preferable to purify these natural products by elutriation. By performing elutriation, impurities such as quartz and feldspar having a large specific density can be removed, and silicates that do not swell can also be removed, so that a preferable ion-exchangeable layered silicate can be obtained. As the elutriation method, a commonly used elutriation method can be used. The smectite used in the present invention can be obtained by removing impurities with elutriation.
Further, these ion-exchangeable layered silicates may be subjected to a chemical treatment described later. Further, in the present invention, if the silicate has an ion exchange property before the chemical treatment is applied, the physical and chemical properties are changed by the treatment, and the silicate having no ion exchange property and layer structure is also an ion. Treat as an exchangeable layered silicate.

The type of the interlayer cation (cation contained between the layers of the ion-exchangeable layered silicate) of the ion-exchangeable layered silicate of the present invention is not particularly limited, but the periodic table of lithium, sodium or the like as the main component. Periodic table of group 1 alkali metals, calcium, magnesium, etc. Group 2 alkaline earth metals, or iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, gold, etc. Transitional metals and the like are preferable because they are relatively easily available as industrial raw materials.

The ion-exchangeable layered silicate used in the present invention is a 2: 1 type ion-exchangeable layered silicate, and the octahedron sheet is a diocteohedral, and is represented by the following formula (a).
(M ⁺ , M 2 ⁺ _0.5 ) _{x + y} (Y ^{3 +} _2-y , Y 2 ⁺ _y ) (Si _4-x , Al _x ) O ₁₀ (OH) ₂ ... Equation (a)
[In the above formula (a), M ⁺ represents Na and / or K ion, M ²⁺ represents Ca ion, and Y ³⁺ represents one or more trivalent metal ions of Al, Fe, Mn, and Cr. , And Y ²⁺ represents any one or more divalent metal ions of Mg, Fe, Mn, Ni, and Zn. ]

Here, in the formula (a), (M ⁺ , M 2 ⁺ _0.5 ) is an interlayer ion, (Y ^{3 +} _2-y , Y 2 ⁺ _y ) is an octahedral sheet, and (Si _4-x , Al _x ). Represents a tetrahedral sheet, which is described on page 65 of the Clay Handbook, 3rd Edition (Japan Clay Society, Gihodo Publishing, April 30, 2009).

The 2: 1 type ion-exchangeable layered silicate means an ion-exchangeable layered silicate in which one octahedral sheet is sandwiched between two tetrahedral sheets and combined.
Further, the ion-exchangeable layered silicate may be shown by adding water molecules contained in the layers to the formula (a), but it is omitted here.
The amount of water molecules contained between layers varies depending on the type of metal between layers, and is constantly changing due to the influence of the external environment. Therefore, it is described as nH ₂ O, which is rarely shown as a qualitative quantity, and the range of n is also uncertain.
However, the value of n can be considered to be in the range in which the ion-exchangeable layered silicate can be handled as a powder, and is 20 at the maximum, preferably about 10.

For the composition analysis of the ion-exchangeable layered silicate, a calibration curve is prepared by chemical analysis by the JIS method and quantified by fluorescent X-ray measurement.
As the apparatus, ZSX-100e of Rigaku Denki Kogyo Co., Ltd. is used.
After baking the sample at 700 ° C. for 1 hour, 0.5 g is separated and mixed with 4.5 g of a flux (Li ₂ B ₄ O ₇ ) and 0.03 g of a release agent (KBr) to prepare a glass bead. Prepare with.
The calibration curve range for each atom is as follows.
Si: 19.8 to 44.22%, Al: 2.01 to 19.4%, Mg: 0.22 to 8.0%, Na: 0.21 to 3.62%, Fe: 0.53 to 5.83%.

The average particle size of the raw material clay measured by dispersing the ion-exchangeable layered silicate used in the present invention in an aqueous solvent may be 2 μm or less, preferably 1 μm or less.
The water dispersion diameter indicates the median diameter measured by the following method.
As a measuring method, first, 0.05 g of raw clay (smectite) is weighed and slowly added to 9.95 g of distilled water while stirring with a stirrer to prepare a uniform 0.5% by mass smectite / water slurry. ..
This is left to stand in a liquid temperature range of 20 to 60 ° C. for 12 hours or more, then ultrasonically treated for 10 minutes, and a laser diffraction scattering type particle size measuring device (for example, laser diffraction manufactured by Horiba Seisakusho) is used as a sample of this clay / water slurry. -Using a scattering type particle measuring device LA-920), the dispersion medium is measured under the conditions of water, a refractive index of 1.3, and a shape coefficient of 1.0.

1. 1. (2) Spray-dry granulation of ion-exchangeable layered silicate The ion-exchangeable layered silicate used in the present invention may be spray-dried and granulated. When spray-drying granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene or xylene is used as the dispersion medium of the raw material slurry. Water is preferably used as the dispersion medium.

The mechanical properties of the ion-exchangeable layered silicate significantly change depending on the water content, and a certain correlation can be seen between the ion-exchangeable layered silicate concentration and the slurry viscosity in the raw material slurry liquid for spray-dry granulation. Therefore, the clay / water slurry viscosity of spray-dried granulation from which spherical particles can be obtained is preferably 0.1 to 200 cp (≈0.0001 to 0.2 Pa · s), and more preferably 1 to 200 cp (≈0). .001 to 0.2 Pa · s). In particular, 1 to 200 cp (≈0.001 to 0.2 Pa · s) is preferable in an aqueous solvent.

The slurry concentration of the clay / water slurry (solid content concentration of clay) is not particularly limited, but is preferably 0.1 to 70% by mass, more preferably 1 to 50% by mass, and particularly preferably 4 to 40% by mass. be.
The temperature of the inlet of the hot air for spray-drying granulation varies depending on the dispersion medium, but in the case of water as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.
Further, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used for granulation.
Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethyl celluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols, starch, casein, and the like. Examples thereof include latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate.
The shape of the ion-exchangeable layered silicate before granulation is not particularly limited, and may be a naturally produced shape or a shape at the time of artificial synthesis.
Further, an ion-exchangeable layered silicate whose shape has been processed by operations such as pulverization, granulation, and classification may be used.
On the other hand, it is preferable that the ion-exchangeable layered silicate before granulation is not subjected to chemical treatment such as acid treatment and salt treatment. When these treatments are applied, the crushing strength of the granulated body is lowered, which has an adverse effect.
Further, it is preferable that the ion-exchangeable layered silicate is swellable before granulation. The swellability can be determined by whether or not the interlayer distance changes when water is added. The unfavorable pre-granulation chemical treatment does not include the solid salt treatment for purification of smectite.

1. 1. (3) Step (1): Acid treatment of ion-exchangeable layered silicate particles The ion-exchangeable layered silicate particles used in the present invention are characterized by being acid-treated with acids.
The acid treatment is performed on the ion-exchangeable layered silicate particles obtained by processing the shape of the ion-exchangeable layered silicate by granulation or the like.
The acid treatment removes impurities on the surface or exchanges cations existing between layers, and elutes some or all of the cations such as Al, Fe, and Mg incorporated in the crystal structure. Can increase the surface area. This contributes to increasing the acid strength of the ion-exchangeable layered silicate particles and increasing the amount of acid points per unit mass.
Examples of the acids used in the acid treatment include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propyrionic acid, fumaric acid, maleic acid and phthalic acid. Among them, inorganic acids are preferable, and hydrochloric acid, nitric acid, and sulfuric acid are preferable. Hydrochloric acid and sulfuric acid are more preferable, and sulfuric acid is particularly preferable.

Acid concentration during acid treatment of the present invention (mass percentage of acid to total mass of reaction system = [mass of acid used (g) / (mass of clay (g) + mass of water (g) + mass of acid used (G))] × 100) is less than 20% by mass, the lower limit is preferably 5% by mass or more, more preferably 9% by mass or more, and the upper limit is preferably 15% by mass or less, more preferably. It is 12% by mass or less. When the acid concentration is low, the elution rate of cations is lowered and the production efficiency is lowered. On the other hand, if the acid concentration is high, the treatment proceeds non-uniformly, so that there are sites where cation elution progresses excessively, and the structure is not optimal, so the active sites decrease and the polymerization activity decreases. There is.
As the acid treatment conditions, the lower limit of the temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, and the upper limit value is preferably 102 ° C. or lower, more preferably 100 ° C. or lower. More preferably, it is 95 ° C. or lower. If the temperature is lowered too much, the elution rate of cations is extremely lowered, and the production efficiency is lowered. On the other hand, if the temperature is raised too high, the operational safety will decrease.
The concentration of the ion-exchangeable layered silicate particles in the solvent can be adjusted to 3 to 50% by mass. The lower limit of the concentration is preferably 5% by mass or more, and the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. When the concentration is low, large equipment is required for industrial production. On the other hand, when the concentration is high, the viscosity of the slurry increases, it becomes difficult to perform uniform stirring and mixing, and the production efficiency also decreases.
As the acid treatment condition, the lower limit value of the acid treatment time may be 500 minutes or more, preferably 540 minutes or more, and the upper limit value may be 1600 minutes or less, preferably 1000 minutes or less. It may be, more preferably 960 minutes or less. Within the above range, the optimum structure as a co-catalyst can be maintained.

After performing the above acid treatment, the reaction product or the unreacted product remaining in the reaction solution may cause a decrease in activity, and therefore washing is preferable.
As the solvent used for washing, it is preferable to use the same type as the solvent used for the reaction, and it is more preferable to use water or alcohols.

1. 1. (4). Characteristics of Catalyst Component for Olefin Polymerization The catalyst component for olefin polymerization obtained in the present invention satisfies the following characteristics (i) to (iii).

(I) Average particle size The average particle size of the catalyst component for olefin polymerization in the present invention is 26.0 μm to 200.0 μm.
The lower limit of the average particle size is preferably 30.0 μm or more, more preferably 34.3 μm or more, and the upper limit is preferably 100.0 μm or less, more preferably 90.0 μm or less, still more preferably 80.0 μm or less. Particularly preferably, it is 46.9 μm or less. It is considered that the amount of fine powder generated increases when the average particle size is less than 26.0 μm. In addition, it is considered that the fluidity of the particles is poor and static electricity is likely to adhere.
Furthermore, when an ethylene-propylene block copolymer or the like is produced as a catalyst component for olefin polymerization, the rubber component elutes on the surface and the powder becomes sticky, which not only causes a decrease in polymer bulk density and deterioration of fluidity. , May cause localization of rubber components.
On the other hand, even if the average particle size exceeds 200.0 μm, it may cause deterioration of fluidity and blockage of piping.
Here, the average particle size in the present invention is determined by using a laser diffraction / scattering type particle size distribution measuring device LA-920 manufactured by Horiba Seisakusho Co., Ltd. under the conditions that the dispersion solvent is ethanol, the refractive index is 1.0, and the shape coefficient is 1.0. The value of the measured medium diameter based on the volume is taken as the average particle diameter.

(Ii) Elution rate of aluminum In the catalyst component for olefin polymerization in the present invention, the aluminum ions constituting the octahedral sheet are subjected to acid treatment of ion-exchangeable layered silicate particles before chemical treatment such as acid treatment and base treatment. It is characterized by eluting 26 to 64% with respect to the content. The lower limit of the elution rate of aluminum is preferably 40% or more, more preferably 44% or more, and the upper limit is preferably 60% or less.
Here, the elution rate (%) of aluminum is expressed by the following formula.
{[(Aluminum / silicon (molar ratio) before chemical treatment)-(Aluminum / silicon (molar ratio) after chemical treatment)] ÷ (Aluminum / silicon (molar ratio) before chemical treatment)} × 100
It is considered that when the elution rate is small, the particle strength is high because the number of adhesion points between the constituent particles constituting the ion-exchangeable layered silicate particles is large.
As a result, poor dispersibility of the ion-exchangeable layered silicate particles occurs during polymerization, so that particle growth proceeds non-uniformly, and problems such as a decrease in polymer bulk density and generation of fine powder due to deformation of the shape of the obtained polymer are problems. I think that may occur.
Furthermore, when producing ethylene-propylene block copolymers, etc., the rubber components (high ethylene content, high molecular weight polymer) produced in the second stage are localized because the particle growth in the first stage is non-uniform. It is conceivable that the number of bright spots will increase.
Further, it is considered that the active site of the catalyst for olefin polymerization reacts with the transition metal complex and is formed by the elution of metal ions mainly composed of aluminum. If the elution rate is small, the active site decreases and the activity decreases. Is possible.
On the other hand, it is considered that if the elution rate is large, the number of adhesion points between the constituent particles constituting the ion-exchangeable layered silicate particles is reduced, so that the particle strength is lowered. In that case, it is conceivable that the decrease in particle strength may generate fine powder during polymerization or cause deterioration of powder properties.
It is also considered that if the elution rate is large, the active site decreases due to excessive elution of metal ions, and the activity decreases.

(Iii) Crushing strength The crushing strength of the catalyst component for olefin polymerization in the present invention is 5.0 MPa or more and 100.0 MPa or less. The lower limit of the crushing strength is preferably 8.0 MPa or more, more preferably 10.0 MPa or more, and the upper limit is preferably 50.0 MPa or less, more preferably 25.0 MPa or less. If the crushing strength is less than 5.0 MPa, there arises a problem that the ion-exchangeable layered silicate particles, which are catalyst components for olefin polymerization, are broken during the polymerization to generate fine powder. It is considered that if the crushing strength exceeds 100.0 MPa, the particles do not grow due to the replica effect during the polymerization, and there arises a problem that strained powder particles are generated, fine powder is generated, and the initial activity is lowered.
Here, for the crushing strength, the crushing strength of 10 or more particles arbitrarily selected can be measured using a crushing tester "MCT-210" manufactured by Shimadzu Corporation, and the average value thereof can be adopted. can.

(Iv) Pore volume of 2 to 6 nm The catalyst component for olefin polymerization in the present invention may further satisfy the following property (iv).
In the catalyst component for olefin polymerization in the present invention, the total pore volume of pores having a diameter in the range of 2 to 6 nm measured by the nitrogen adsorption method is 0.170 cm ³ / g or more and 0.500 cm ³ / g or less. Is.
The total pore volume of the pores having a diameter in the range of 2 to 6 nm may be a lower limit of 0.170 cm ³ / g or more, preferably larger than 0.170 cm ³ / g, and 0.173 cm ³ It is more preferably more than / g, and the upper limit value may be 0.500 cm ³ / g or less, preferably less than 0.500 cm ³ / g, and more preferably smaller than 0.400 cm ³ / g. , 0.247 cm, particularly preferably smaller than ³ / g.
It is considered that many active sites of the catalyst for olefin polymerization react with the transition metal complex in the mesopore region, and the total pore volume of the pores in the range of 2 to 6 nm is 0. If the pore volume is less than 170 cm ³ / g, it is considered that the activity may decrease.
Further, if the number of pores in the range of 2 to 6 nm is small, poor dispersibility of the ion-exchangeable layered silicate particles occurs during polymerization, so that the particle growth proceeds non-uniformly and the shape of the obtained polymer is deformed. It is considered that problems such as a decrease in polymer bulk density and generation of fine particles may occur.
In addition, during two-stage polymerization to produce ethylene-propylene block copolymers, the rubber components produced in the second stage are localized and the number of bright spots increases because the particle growth in the first stage is non-uniform. It is conceivable to do.
On the other hand, when the total pore volume of the pores in the range of 2 to 6 nm exceeds 0.500 cm ³ / g, the particle strength is lowered and fine powder is generated during the polymerization or powder. It is possible that it may cause deterioration of the properties.

1. 1. (5) Step (2): Treatment of ion-exchangeable layered silicate particles with bases In the present invention, it is preferable to treat the ion-exchangeable layered silicate particles with bases after the step (1).
The contact between the ion-exchangeable layered silicate particles and the bases is preferably carried out with a slurry in which the ion-exchangeable layered silicate particles are dispersed in a solvent.
Examples of the solvent for slurrying include water and organic solvents such as alcohol, preferably alcohol and water, and more preferably water.
The amount of the base used depends on the pH of the ion-exchangeable layered silicate slurry before contact with the base, but the pH after the addition of the base is 8 or less throughout the process, and the pH is 8 or less. It is preferable to use an amount having a pH of 4.5 to 8 at the end of the step.
The above-mentioned bases are substances that act as Bronsted bases. Bases are substances having the property of generating water by reacting with protons (neutralization reaction), and are preferably selected from the group consisting of alkali metals, alkaline earth metals, and metals of Groups 3 to 14 of the Periodic Table. There is a metal hydroxide. More preferably, it is a hydroxide of an alkali metal, an alkaline earth metal, Mn, Fe, Ni, Cu, Zn, Al, Sn and Pb. Particularly preferred are alkali metals, alkaline earth metals, and hydroxides of Mg, Zn, and Al.

The bases are not limited to the following, but to give specific examples, LiOH, NaOH, KOH, CsOH, RbOH, Be (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ , Sr ( OH) ₂ , Mn (OH) ₂ , Cu (OH) ₂ , Cu (OH) ₃ , Zn (OH) ₂ , Al (OH) ₃ , Sn (OH) ₄ , Pb (OH) ₂ , Ni (OH) ₂ , Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , Rb ₂ CO ₃ , BeCO ₃ , MgCO ₃ , CaCO ₃ , MnCO ₃ , CuCO ₃ , Al ₂ (CO) ₃ , ZnCO ₃ , PbCO _{3, LiHCO 3, NaOH3 3, RpHCO 3 , CsHCO 3 ,} Ca (HCO ₃ ) ₂ , Mg (HCO ₃ ) ₂ , and the like.

The bases may be used alone or in combination of two or more. There are no particular restrictions on how to use it.
The state of the bases upon contact with the ion-exchangeable layered silicate particles may be dissolved in a solvent or may remain solid. When it is dissolved in a solvent and brought into contact with it, the concentration is not limited, and the upper limit is not more than the saturated concentration.

It is preferable to perform cleaning even after the chemical treatment with bases.
As the solvent used for washing, it is preferable to use the same type as the solvent used for the reaction, and it is more preferable to use water or alcohols.
The cleaning rate is preferably 1/5 to 1/1000 and 1/100 to 1/1000.

After washing and dehydration, it is preferable to perform drying.
Drying is preferably performed so as not to cause structural destruction of the ion-exchangeable layered silicate particles.
The drying temperature is generally 100 to 800 ° C., preferably 150 to 600 ° C., and particularly preferably 150 to 300 ° C.
Since the characteristics of these ion-exchangeable layered silicate particles change depending on the drying temperature even if the structure is not destroyed, it is preferable to change the drying temperature according to the application.
The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours.
The atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure.
The drying method is not particularly limited and can be carried out by various methods.

1. 1. (6) Other Chemical Treatments In the present invention, ion-exchangeable layered silicate particles may be subjected to other chemical treatments in addition to acid treatment and base treatment.
Other chemical treatments include contact with a treatment agent containing salts, oxidizing agents, reducing agents, compounds capable of intercalating between layers of ion-exchangeable layered silicate particles, and the like.
Intercalation refers to the introduction of another substance between layers of a layered substance, and the introduced substance is called a guest compound.
Further, the chemical treatment can be performed in a plurality of times, and the order of the treatment is not limited.
A common effect of chemical treatment is the exchange of interlayer cations.
Further, in intercalation and salt treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.
By utilizing the ion exchange property and substituting the exchangeable ions between the layers with another large bulky ion, it is possible to obtain a layered substance in a state where the layers are expanded. That is, bulky ions play a supporting role in supporting the layered structure, and are called pillars. Specific examples of the treatment agent are shown below.

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

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

Examples of organic cations are trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5- Pentamethylanilinium, N, N-dimethyloctadecylammonium, octadodecylammonium, N, N-2,4,5-pentamethylanilinium, N, N-dimethyl-pn-butylanilinium, N, N- Ammonium compounds such as dimethyl-p-trimethylsilylanilinium, N, N-dimethyl-1-naphthylanilinium, N, N,2-trimethylanilinium, 2,6-dimethylanilinium,
Nitrogen-containing aromatic compounds such as pyridinium, quinolinium, N-methylpiperidinium, 2,6-dimethylpyridinium, 2,2,6,6-tetramethylpiperidinium,
Oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, flanium, oxolanium, etc.
Phosphonium compounds such as triphenylphosphonium, tri-o-tolylphosphonium, tri-p-tolylphosphonium, and trimesitylphosphonium,
Phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium are exemplified, but the present invention is not limited thereto.

Examples of anions include, but are limited to, examples of anions composed of boron compounds and phosphorus compounds, such as hexafluorophosphate, tetrafluoroborate, and tetraphenylborate, in addition to the anions exemplified above. It is not something that will be done.

Further, these salts may be used alone or in combination of two or more.
Further, it may be used in combination with an acid, an alkali, an oxidizing agent, a reducing agent, a compound intercalating between layers of an ion-exchangeable 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 in the middle of the treatment.
In the above-mentioned chemical treatment with salts, an appropriate solvent may be used, and the treatment agent may be dissolved therein and used as a treatment agent solution, or the treatment agent itself may be used as a solvent.
Examples of the solvent that can be used include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide and the like. Water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters and ethers are preferable, water, alcohols, aliphatic hydrocarbons and ethers are more preferable, and water and alcohol are particularly preferable. It is a kind.
The concentration of the treatment agent in the treatment agent solution is preferably about 0.1 to 100% by mass, more preferably about 5 to 50% by mass. If the concentration of the treatment agent is within this range, there is an advantage that the time required for the treatment is shortened and efficient production becomes possible.

It is preferable to perform cleaning even after the chemical treatment with salts.
As the solvent used for washing, it is preferable to use the same type as the solvent used for the reaction, and it is more preferable to use water or alcohols.
The cleaning rate is preferably 1/5 to 1/1000 and 1/100 to 1/1000.

2. 2. Method for Producing Catalyst for Olefin Polymerization The method for producing a catalyst for olefin polymerization of the present invention is characterized in that the following components [A], [B], and [C] are brought into contact with an olefin.
Component [A]: Catalyst component for olefin polymerization obtained by the above-mentioned production method Component [B]: Transition metal compound component of Group 4 of the periodic table [C]: Organoaluminum compound

2. 2. (1) Olefin polymerization catalyst <Component [A]>
The component [A] is a catalyst component for olefin polymerization obtained by the above-mentioned method.

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

[In the above general formulas (1) to (4),
A and A'indicate a conjugated five-membered ring ligand that may have a substituent (A and A'may be the same or different within the same compound).
Q indicates a binding group that crosslinks two conjugated five-membered ring ligands at arbitrary positions.
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.
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'indicates a binding group that crosslinks Z with any position of the conjugated five-membered ring ligand.
M indicates a metal atom selected from Group 4 of the periodic table.
X and Y may be hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group (X and Y may be the same or different in the same compound. ) Is shown. ]

As A and A', for example, a cyclopentadienyl group can be mentioned.
The cyclopentadienyl group may be one having _five hydrogen atoms [C5 _H5- ], and a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with substituents. You may.
An example of this substituent is a hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms.
Even if this hydrocarbon group is bonded to a cyclopentadienyl group as a monovalent group, or when there are a plurality of these groups, two of them are bonded to each other at the other end (ω-end). It may form a ring with a part of cyclopentadienyl.
As an example of the latter, two substituents are bonded at the ω-end and share two adjacent carbon atoms in the cyclopentadienyl group to form a condensed six-membered ring. That is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and a group forming a condensed seven-membered ring, that is, an azrenyl group, a tetrahydroazulenyl group and the like can be mentioned.

Preferred specific examples of the conjugated five-membered ring ligand represented by A and A'include substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group, azurenyl group and the like. Of these, particularly preferred are substituted or unsubstituted indenyl groups or azulenyl groups.

As the substituent on the cyclopentadienyl group, in addition to the above-mentioned hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, halogen atomic groups such as fluorine, chlorine and bromine, and 1 to 12 carbon atoms. Alkoxy groups of, for example, -Si (R ¹ ) (R ² ) (R ³ ) silicon-containing hydrocarbon groups, -P (R ¹ ) (R ² ) phosphorus-containing hydrocarbon groups, or-. Examples thereof include the boron-containing hydrocarbon groups represented by B (R ¹ ) and (R ² ). When there are a plurality of these substituents, the respective substituents may be the same or different.
The above-mentioned R ¹ , R ² , and R ³ may be the same or different, and represent an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.
Further, as a substituent on the cyclopentadienyl group, at least one Group 15 to 16 element (that is, a hetero element) may be contained. In this case, the hetero element itself is present in the vicinity of the active point without being bonded or coordinated with a metal to improve the properties of the active point, so that the group 15 to 16 elements and the conjugated five-membered ring are arranged. A metallocene complex having 1 or less atoms to bond with a ligand is more preferable.
The position of the Group 15 to 16 elements on the ligand is not particularly limited, but it is preferably held on the substituent at the 2-position.
More preferably, the substituent at the 2-position is a monocyclic or polycyclic group containing a heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom in a 5-membered or 6-membered ring. It is preferable to have.
Further, it is preferably a heteroaromatic group having 4 to 20 carbon atoms which may contain silicon or halogen, the heteroaromatic group preferably has a 5-membered ring structure, and the heteroatom is an oxygen atom, a sulfur atom or a nitrogen atom. Preferably, an oxygen atom and a sulfur atom are more preferable, and an oxygen atom is further preferable.

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

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

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

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

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

Examples of the compound represented by the general formula (2) include, for example.
(1) Dimethylsilylenebis {1- (2-methyl-4-isopropyl-4H-azurenyl)} zirconium dichloride,
(2) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(3) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azurenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azurenyl}] zirconium dichloride,
(5) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(6) Diphenylcilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(8) Ethylene bis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(9) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(10) Dimethylsilylenebis {1- [2-methyl-4- (2', 6'-dimethyl-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(11) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(12) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azurenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(13) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azurenyl)} zirconium dichloride,
(14) Dimethylsilylenebis {1- (2-ethyl-4-indrill-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(17) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(18) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(19) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(20) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,
(21) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(22) Ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(23) Ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(24) Isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(25) Ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(26) Isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(27) Dimethylgelmilenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(28) Dimethylgelmilenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(29) Phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(30) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(31) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(32) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(33) Dimethylsilylenebis [2- (2- (5-methyl) frill) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(34) Dimethylsilylenebis [2- (2- (5-trimethylsilyl) frill) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(35) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(36) Dimethylsilylene [2- (2- (5-methyl) frill) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(37) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(38) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(39) Dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride,
(40) Dichlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride (41) Dichlorosilacyclobutylene bis [2- (4) , 5-Dimethyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride (42) dichlorosilacyclobutylene bis [2- (5-t-butyl-2-furyl) -4 -Phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride (43) dichlorosilacyclobutylene bis [2- (5-phenyl-2-furyl) -4-phenyl-5,6-dimethyl-1-indenyl] Zylzyl dichloride (44) dichlorosilacyclobutylene bis [2- (2-thienyl) -4-phenyl-5,6-dimethyl-1-indenyl] Zyrazine dichloride (45) dichlorosilacyclobutylene bis [2- (5-methyl) -2-Thienyl) -4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride (46) dichlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4- (4-fluorophenyl) ) -5,6-Dimethyl-1-indenyl] Zirconid dichloride (47) Dichlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -5,6-dimethyl-1 -Indenyl] zirconium dichloride (48) dichlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4- (4-methylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride (49) Dichlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride (50) dichlorosilacyclobutylene bis [ 2- (5-Methyl-2-furyl) -4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride (51) dichlorosilacyclobutylene bis [2- (5-methyl) -2-Frill) -4- (3,5-dit-butylphenyl) -5,6-dimethyl-1-indenyl] zirconium dichloride (52) dichlorosilacyclobutylene bis [2- (5-methyl-2-) Frill) -4- (1-naphthyl) -5,6-dimethyl-1-indenyl] zirconium dichloride (53) di Chlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4- (2-naphthyl) -5,6-dimethyl-1-indenyl] zirconium dichloride (54) dichlorosilacyclobutylene bis [2-( 5-Methyl-2-furyl) -4- (4-biphenylyl) -5,6-dimethyl-1-indenyl] zirconium dichloromethane and the like can be mentioned.

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

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

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

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

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

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

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

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

The preferred contact method is to bring the component [A] of the above 4) into contact with the component [C], remove the unreacted component [C] by washing or the like, and then add the minimum necessary component [C] again. This is a method of contacting with [A] and then with component [B]. In this case, the molar ratio of Al / transition metal is in the range of 0.1 to 1,000, preferably 1 to 100, and more preferably 4 to 50.
The temperature at which the component [B] and the component [C] are brought into contact (in which case, the component [A] may be present) is preferably 0 ° C to 100 ° C, more preferably 20 to 80 ° C, and particularly preferably 30 to 30. It is 60 ° C. If it is lower than this range, the reaction is slow, and if it is higher than this range, the decomposition reaction of the component [B] proceeds.
Further, when the component [B] and the component [C] are brought into contact with each other (in that case, the component [A] may be present), it is preferable to allow an organic solvent to be present as a solvent. In this case, the concentration of the component [B] in the organic solvent is preferably high, preferably 3 to 50 mM, more preferably 4 to 40 mM, still more preferably 6 to 30 mM.

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

The component [A] preferably has an acid point. The lower limit of the amount of the preferable acid point is 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 point is measured according to the description of JP-A-2000-158707.

These may be brought into contact with each other in the polymerization tank or outside the polymerization tank to carry out prepolymerization in the presence of an olefin.
In the present invention, the olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene. The type is not particularly limited, and a mixture of these and other olefins may be used. An olefin having 3 or more carbon atoms is preferable.

The catalyst for olefin polymerization of the present invention is preferably subjected to a prepolymerization treatment consisting of contacting olefins in advance and polymerizing in a small amount in order to improve the particle property.
The olefin 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 can be used, and it is particularly preferable to use propylene.
As the olefin supply method, any method can be used, such as a supply method for maintaining the olefin in the reaction vessel at a constant speed or a constant pressure state, a combination thereof, and a stepwise change.
The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours.
The amount of prepolymerized polymer is preferably 0.01 to 100, more preferably 0.1 to 50, with respect to one part of the component [A].
After the prepolymerization is completed, it can be used as it is depending on the usage mode of the catalyst, but it may be dried if necessary.

The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 to 70 ° C, particularly preferably 20 to 60 ° C, and even more preferably 30 to 50 ° C. If it falls below this range, the reaction rate may decrease or the activation reaction may not proceed. If it exceeds this range, the prepolymerized polymer may dissolve, or the prepolymerization rate may be too fast and the particle properties may deteriorate. There is a possibility that the active point will be deactivated due to a side reaction.
The prepolymerization can also be carried out in a liquid such as an organic solvent, which is preferable.
The concentration of the solid catalyst at the time of prepolymerization is not particularly limited, but is preferably 10 to 100 g / L, more preferably 20 to 80 g / L or more, and particularly preferably 25 to 70 g / L or more. The higher the concentration, the more the activation of metallocene progresses, and it becomes a highly active catalyst.

Further, it is also possible to allow a polymer such as polyethylene, polypropylene or polystyrene or an inorganic oxide solid such as silica or titania to coexist at the time of or after the contact of each of the above components.

The catalyst may be dried after the prepolymerization.
The drying method is not particularly limited, and examples thereof 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. May be good.
In the drying step, the catalyst may be agitated, vibrated, flowed, or allowed to stand.

3. 3. Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention is characterized in that olefin polymerization is carried out using a catalyst for olefin polymerization obtained by the above-mentioned production method.

In the present invention, the polymerization carried out using the olefin polymerization catalyst composed of the component [A], the component [B], and the component [C] is carried out by olefin alone or by mixing and contacting the olefin with another comonomer. Will be done.
In the case of copolymerization, the amount ratio of each monomer in the reaction system does not have to be constant over time, it is convenient to supply each monomer at a constant mixing ratio, and the mixing ratio of the supplied monomers is changed over time. It is also possible to change the target. Further, any of the monomers may be added in portions in consideration of the copolymerization reaction ratio.

The olefin that can be polymerized is preferably one having about 2 to 20 carbon atoms, and specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7. -Octane, cyclopentene, norbornene, etilidennorbornene and the like can be mentioned. It is preferably an α-olefin having 2 to 8 carbon atoms.
In the case of copolymerization, as the type of comonomer used, an olefin other than the main component can be selected and used from those listed as the olefin.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer are in efficient contact with each other. Specifically, the slurry method using an inert solvent, the method using propylene as a solvent without substantially using the inert solvent, the solution polymerization method, or the vapor phase in which each monomer is kept in a gaseous state without using a liquid solvent substantially. The law can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.

In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the polymerization solvent.
The polymerization temperature is usually 0 to 150 ° C.
Further, hydrogen can be used as an auxiliary as a molecular weight adjusting agent.
The appropriate polymerization pressure is 0 to 2000 kg / cm ² G (≈0 to 196.14 MPaG), preferably 0 to 60 kg / cm ² G (≈0 to 5.88 MPaG).

The olefin polymer obtained by the production method of the present invention has few bright spots that deteriorate the appearance of the product.
The smaller the number of bright spots, the better the olefin polymer obtained by the production method of the present invention, and the number may be 0 to 100/900 mm ² , preferably 0 to 70/900 mm ² .

The olefin polymer obtained by the production method of the present invention may have a polymer bulk density of 0.39 to 0.60 g / cm ³ , preferably 0.40 to 0.50 g / cm ³ . , 0.40 to 0.47 g / cm ³ .

The olefin polymer obtained by the production method of the present invention may have a fine powder ratio (ratio of 212 μm or less) of 0 to 0.04% by mass, preferably 0 to 0.01% by mass.
The olefin polymer obtained by the production method of the present invention may have an average polymer particle size of 800 to 2000 μm, preferably 900 to 1500 μm.

Since the measurement method of each of the above characteristics will be described later, the description here is omitted.

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

(Various physical property measurement methods)
[Composition analysis of ion-exchangeable layered silicate]
A calibration curve was prepared by chemical analysis by the JIS method and quantified by fluorescent X-ray measurement.
As the apparatus, ZSX-100e of Rigaku Denki Kogyo Co., Ltd. was used.
After baking the sample at 700 ° C. for 1 hour, 0.5 g is separated and mixed with 4.5 g of a flux (Li ₂ B ₄ O ₇ ) and 0.03 g of a release agent (KBr) to prepare a glass bead. Prepared in.
The calibration curve range for each atom is as follows.
Si: 19.8% to 44.22%, Al: 2.01% to 19.4%

[Pore distribution measurement and specific surface area measurement]
The pore distribution and specific surface area were measured by the nitrogen adsorption method.
The adsorption isotherm was measured under the temperature of liquid nitrogen.
The BET multipoint method analysis was carried out using the obtained adsorption isotherm to determine the specific surface area.
In addition, the pore volume of pores having a diameter of 2 to 6 nm was determined by BJH (Barrett, Joiner, Hallender) method analysis using an adsorption isotherm.
Equipment: Canter Chrome Autosorb 3B
Measurement method: Nitrogen gas adsorption method Pretreatment conditions: Heat the sample under vacuum (1.3 MPa or less) at 200 ° C under reduced pressure for 2 hours Sample amount: Approximately 0.2 g
Gas liquefaction temperature: 77K

[Measurement of average particle size]
Using a laser diffraction / scattering type particle size distribution measuring device LA-920 manufactured by HORIBA, Ltd., the dispersion solvent was measured under the conditions of ethanol, a refractive index of 1.3, and a shape coefficient of 1.0. The average particle size refers to the median diameter on a volume basis.

[MFR (Melt Mass Flow Rate)]
Test conditions of JIS K7210 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics" using Takara's melt indexer: 230 ° C, 2.16 kg load compliant And measured.

[Polymer bulk density]
Measured according to ASTM D1895-69.

[Calculation of fine powder ratio]
For the fine powder ratio, the ratio of the particle size of 212 μm or less was calculated from the particle size distribution obtained in the above [Measurement of particle size].

[Measurement of bright spots]
After measuring 13 g of the polymer obtained in the following (e) production of the propylene-ethylene block copolymer and kneading it with Xplore (Xplore microcompounder manufactured by DSM) (conditions: 200 ° C., 50 rpm, 2 min) to form pellets. Weigh 5 g of the pellet and perform a 0.2 mm thick press (preheating: 190 ° C, 0 MPa, 2 minutes, heating: 190 ° C, 10 MPa, 1 minute, cooling: 30 ° C, 15 MPa, 2 minutes) to form a sheet. Got
The above sheet was captured as an image (600 dpi) with a scanner (canon canoscan9000F mark2), and the captured image was analyzed using ImageJ (30 mm × 30 mm square range (900 mm ² ) with a uniform matrix part and brightness. The points were binarized and the number of bright spots was calculated). This measurement was performed in three different fields of view, and the average value was taken as the number of bright spots.

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

[Calculation method of acid concentration]
Acid concentration (mass%) = [mass of acid used (g) / (mass of clay (g) + mass of water (g) + mass of acid used (g))] x 100
When the mass% concentration of the acid contained in the acid solution used is not 100% by mass, it means that the acid solution contains water. At this time, the mass (g) of the acid to be used is obtained by multiplying the mass (g) of the acid solution by the mass% concentration of the acid contained in the acid solution.

(Example 1)
[Manufacturing of catalyst components for olefin polymerization]
(A) Acid treatment and base treatment of ion-exchangeable layered silicate particles Ion-exchangeable layered silicate particles mainly composed of smectite group montmorillonite having a 2: 1 type layer structure (Benclay SL manufactured by Mizusawa Chemical Industry Co., Ltd.) , With an average particle size of 46.9 μm).
The chemical composition (% by mass) of this raw material was Al = 9.09, Si = 32.80, Fe = 2.63, Mg = 2.12, Na = 2.39, Al / Si = 0.289. rice field.

[Acid treatment]
1300 g of distilled water was put into a 2 L flask equipped with a stirring blade and a reflux device, and 168 g of 96% sulfuric acid was added dropwise.
The mixture was heated in an oil bath until the internal temperature reached 95 ° C., and when the target temperature was reached, 200 g of an ion-exchangeable layered silicate as a raw material was added and then stirred.
After that, the reaction was carried out for 840 minutes while maintaining 95 ° C.
The reaction was stopped by pouring this reaction solution into 2 L of pure water, and the slurry was further filtered by a device in which an aspirator was connected to a nutche and a suction bottle.
The cake-like ion-exchangeable layered silicate particles after filtration were rinsed with 1 L of distilled water.
902.1 g of distilled water was added to the cake to form a slurry.
The pH of the slurry at this time was 1.7.

[Base treatment]
The temperature was raised to 40 ° C., and the entire amount of the lithium hydroxide aqueous solution obtained by dissolving 3.54 g of lithium hydroxide / monohydrate in 42.11 g of distilled water was gradually added, and stirring was continued for 90 minutes to react. rice field.
The slurry pH after 90 minutes was 5.68.
The pH of the slurry did not exceed 8 during the process.
The reaction slurry was filtered through a device in which an aspirator was connected to a nutche and a suction bottle, and washed three times with 2 L of distilled water.

[Other chemical treatment]
The recovered cake was dried at 110 ° C. overnight to obtain 140.8 g of chemically treated ion-exchangeable layered silicate particles.
The chemically treated ion-exchangeable layered silicate particles were placed in a flask having a volume of 1 L, dried under reduced pressure at 200 ° C., and dried under reduced pressure for another 2 hours after the gas generation had subsided to obtain the catalyst component for olefin polymerization of the present invention. .. The results are shown in Table 1.

[Manufacturing of catalyst for olefin polymerization]
(B) Organic Aluminum Treatment of Catalyst Component for Olefin Polymerization Weigh 10 g of the chemically treated ion-exchangeable layered silicate particles (catalyst component for olefin polymerization) obtained in (a) above into a flask with an internal volume of 1000 mL, and weigh 36 ml of heptane, the component. As [C], 64 ml (25 mmol) of a heptane solution of trinormal octyl aluminum (TnOA) was added, and the mixture was stirred at room temperature for 1 hour.
Then, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the slurry amount was adjusted to 50 mL.

(C) Prepolymerization with Propylene 31 mL (12.2 mmol) of a heptane solution of TnOA was added to the heptane slurry of the ion-exchangeable layered silicate particles prepared in (b) above.
Here, in another flask (volume 200 mL), as component [B], (r) -dichlorosilacyclobutylene bis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) A slurry obtained by adding toluene (30 mL) to 283 mg (300 μmol) of zirconium dichloride [-5,6-dimethyl-1-indenyl] was added, and the mixture was stirred at 40 ° C. for 60 minutes.
Next, 189 mL of heptane was further added to the heptane slurry of the ion-exchangeable layered silicate particles to prepare a total volume of 300 mL, which was introduced into a stirring autoclave having an internal volume of 1 L and sufficiently nitrogen-substituted.
When the temperature in the autoclave became stable at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature.
After 120 minutes, the supply of propylene was stopped, and the temperature was maintained at 40 ° C. for another 60 minutes.
Then, the residual monomer was purged and the prepolymerization catalyst slurry was recovered from the autoclave.
The recovered prepolymerization catalyst slurry was allowed to stand, and the supernatant liquid was withdrawn.
Subsequently, 8.3 mL (6 mmol) of a heptane solution of triisobutylaluminum (TiBA) as a component [C] was added at room temperature, and then dried under reduced pressure to add 35.83 g of a solid catalyst (prepolymerization catalyst) for olefin polymerization. Collected.
The prepolymerization ratio (value obtained by dividing the amount of prepolymer by the amount of solid catalyst) was 2.42.

(Example 2)
As a raw material, ion-exchangeable layered silicate particles (“Benclay SL” manufactured by Mizusawa Industrial Chemicals Co., Ltd.) containing the Smectite group montmorillonite of the 2: 1 type layer structure described in Example 1 as a main component were classified to have an average particle size of 38. .Prepared to 1 μm. The ion-exchangeable layered silicate particles were chemically treated in the same manner as in Example 1 except that the ion-exchangeable layered silicate particles having an average particle size of 38.1 μm were used, and then a solid catalyst for olefin polymerization (preliminary polymerization catalyst) was used. ) Was obtained. The results are shown in Table 1.

(Example 3)
Chemical treatment was carried out in the same manner as in Example 1 except that the acid treatment time was set to 540 minutes, and then a solid catalyst (preliminary polymerization catalyst) for olefin polymerization was obtained. The results are shown in Table 1.

(Example 4)
The acid treatment time was 960 minutes, and the chemical treatment was carried out in the same manner as in Example 1 except that the ion-exchangeable layered silicate particles of Example 2 were used as the raw material, and then a solid catalyst for olefin polymerization (preliminary polymerization catalyst) was performed. ) Was obtained. The results are shown in Table 1.

(Comparative Examples 1 to 5)
The ion-exchangeable layered silicate particles were chemically treated in the same manner as in Example 1 except that the treatment was performed under the acid treatment conditions shown in Table 1, and then a solid catalyst (preliminary polymerization catalyst) for olefin polymerization was obtained. The results are shown in Table 1.

(Comparative Example 6)
As a catalyst component for olefin polymerization, chemically treated montmorillonite was prepared according to Example 1 described in Patent Document 5 (Japanese Patent Laid-Open No. 2008-156395).
The average particle size of this chemically treated montmorillonite was 46.0 μm, the amount of ΔAl (elution rate of Al) was 46%, the crushing strength was 17.0 MPa, and the pore volume at 2 to 6 nm was 0.125 cm ³ / g. ..
Subsequent preparation of the solid catalyst (prepolymerization catalyst) for olefin polymerization was prepared in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 7)
As the catalyst component for olefin polymerization, chemically treated montmorillonite particles were prepared according to Example 1 described in Patent Document 6 (Japanese Unexamined Patent Publication No. 2012-126084).
The average particle size of this chemically treated montmorillonite was 70.5 μm, the amount of ΔAl was 40%, the crushing strength was 4.0 MPa, and the pore volume of 2 to 6 nm was 0.150 cm ³ / g.
Subsequent preparation of the solid catalyst (prepolymerization catalyst) for olefin polymerization was prepared in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 8)
As a catalyst component for olefin polymerization, chemically treated montmorillonite was prepared according to Example 4 described in Patent Document 7 (Japanese Patent Laid-Open No. 2015-108138).
The average particle size of this chemically treated montmorillonite was 13.0 μm, the amount of ΔAl was 46%, the crushing strength was 25.0 MPa, and the pore volume at 2 to 6 nm was 0.247 cm ³ / g.
Subsequent preparation of the solid catalyst (prepolymerization catalyst) for olefin polymerization was prepared in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 9)
As a catalyst component for olefin polymerization, chemically treated montmorillonite was prepared according to the method for producing chemically treated silicate-B described in Patent Document 8 (Japanese Unexamined Patent Publication No. 2002-037812).
The average particle size of this chemically treated montmorillonite was 25.0 μm, the amount of ΔAl was 49%, the crushing strength was 15.1 MPa, and the pore volume of 2 to 6 nm was 0.146 cm ³ / g.
Subsequent preparation of the solid catalyst (prepolymerization catalyst) for olefin polymerization was prepared in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 10)
As a catalyst component for olefin polymerization, chemically treated montmorillonite was prepared according to Example 1 described in Patent Document 9 (Japanese Unexamined Patent Publication No. 2006-274277).
The average particle size of this chemically treated montmorillonite was 25.0 μm, the amount of ΔAl was 57%, the crushing strength was 13.0 MPa, and the pore volume at 2 to 6 nm was 0.119 cm ³ / g.
Subsequent preparation of the solid catalyst (prepolymerization catalyst) for olefin polymerization was prepared in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
(D) Polymerization of propylene After sufficiently replacing the inside of a stirring autoclave having an internal volume of 3 L with propylene, 5.6 mL (4.04 mmol) of a heptane solution of TiBA was added as a component [C], and 675 mL of hydrogen and 750 mL of liquid propylene were introduced. Then, the temperature was raised to 65 ° C. and the temperature was maintained.
The prepolymerization catalyst obtained in (c) of Example 1 was slurryed into heptane, and 15.0 mg (excluding the mass of the prepolymerized polymer) was press-fitted as a solid catalyst to initiate polymerization.
Polymerization was continued for 1 hour while maintaining the internal temperature at 65 ° C.
Then, 5 mL of ethanol was added to stop the polymerization reaction.
The residual gas was purged to obtain a polymer.
The obtained polymer was dried at 90 ° C. for 1 hour.
As a result, 216 g of polymer was obtained.
The catalytic activity was 14,400 g-PP / g-catalyst.
The MFR was 87 g / 10 min and the bulk density of the polymer was 0.44 g / cm ³ .
The results are shown in Table 2.

(Examples 6 to 8)
Using the prepolymerization catalysts obtained in Examples 2 to 4, an olefin polymer was obtained in the same manner as in Example 5 except that the amount of catalyst and the amount of hydrogen were different according to the conditions shown in Table 2. The results are shown in Table 2.

(Comparative Examples 11 to 19)
According to the conditions shown in Table 2, an olefin polymer was obtained by the same method as in Example 5 except that at least one of the conditions of the prepolymerization catalyst, the amount of catalyst, and the amount of hydrogen was different. The results are shown in Table 2.

(Example 9)
(E) Production of propylene-ethylene block copolymer (ei) First-stage polymerization: Production of propylene polymer by bulk polymerization method After sufficiently replacing the inside of an autoclave with a stirrer with an internal volume of 3 L with propylene, the component [ As C], 5.6 mL (4.04 mmol) of a heptane solution of TiBA was added, 702 ml of hydrogen and then 750 g of liquid propylene were introduced, and the temperature was raised to 65 ° C.
The prepolymerization catalyst obtained in (c) of Example 1 is slurryed into heptane, and 14.0 mg (the amount of the net solid catalyst excluding the prepolymerized polymer) as a solid catalyst is press-fitted together with 5 ml of heptane to initiate polymerization. did.
After the catalyst was charged, the temperature inside the tank was maintained at 65 ° C. for 60 minutes, the remaining monomer was purged, the argon was pressurized to 0.5 MPa, and then the purge was performed 5 times to replace the inside of the tank with argon.
A Teflon (registered trademark) tube was inserted into the tank while stirring was stopped and argon was allowed to flow, and a small amount of polypropylene was extracted.
The extraction amount was 15.6 g.
(E-ii) Second-stage polymerization: Production of propylene-ethylene random copolymer by vapor phase polymerization method After resuming stirring in the polymerization tank and setting the internal temperature to 60 ° C., ethylene and propylene have a molar ratio of 50:50. The pressure was supplied up to 1.8 MPa.
After that, the internal temperature was raised to 80 ° C., maintained at 80 ° C. for 46 minutes, and ethylene and propylene were supplied at a molar ratio of 45:55 so as to keep the pressure at 2.0 MPa, and vapor phase copolymerization was carried out. did.
After completion of the polymerization, the recovered polymer was dried at 90 ° C. for 1 hour.
As a result, 193 g of polymer was obtained.
The MFR was 20 g / 10 min and the bulk density of the polymer was 0.40 g / cm ³ .
The results are shown in Tables 3-4.

(Examples 10 to 12)
Using the prepolymerization catalysts obtained in Examples 2 to 4, at least one of the catalyst amount, the first stage hydrogen amount and the extraction amount, and the second stage polymerization time according to the conditions shown in Tables 3 to 4. An olefin polymer was obtained in the same manner as in Example 9 except that the two conditions were different. The results are shown in Tables 3-4.

(Comparative Examples 20 to 27)
According to the conditions shown in Tables 3 to 4, the procedure was carried out except that at least one of the conditions of the prepolymerization catalyst, the amount of catalyst, the amount of hydrogen in the first stage, the amount of extraction in the first stage, and the polymerization time in the second stage were different. An olefin polymer was obtained in the same manner as in Example 9. The results are shown in Tables 3-4.

[Comparison between Examples and Comparative Examples]
In the comparison of Examples 5 to 8 and Examples 9 to 12 with Comparative Example 11 and Comparative Example 20, the ion-exchangeable layered silicates of Examples 1 to 4 used in Examples 5 to 8 and Examples 9 to 12 were used. Since the particles satisfy the range of the elution rate of aluminum with respect to the property (ii) of the present application before the acid treatment, the elution rate of aluminum in Examples 5 to 8 and 9 to 12 is 65%, respectively, which is the characteristic ( It can be seen that the catalytic activity is higher and the performance is improved as compared with Comparative Example 11 and Comparative Example 20 using Comparative Example 1 which exceeds the range of ii).
In the comparison between Example 9 and Comparative Example 21, the ion-exchangeable layered silicate particles of Example 1 used in Example 9 satisfy the range of the elution rate of aluminum with respect to the characteristic (ii) of the present application before the acid treatment. Therefore, Example 9 is inferior in catalytic activity to Comparative Example 21 using Comparative Example 2 in which the elution rate of aluminum is 25% and is below the range of the characteristic (ii), but the number of bright spots is reduced. It can be seen that the overall performance has improved.
In comparison of Examples 5 to 6 and Examples 9 to 12 with Comparative Examples 12 to 19 and Comparative Examples 22 to 26, ion exchange of Examples 1 to 4 used in Examples 5 to 6 and Examples 9 to 12 Since the production conditions of the layered silicate particles satisfy the range of the acid concentration of the present application and the range of the average particle size of the characteristic (i), Examples 5 to 6 and Examples 9 to 12 are the same. The catalytic activity is higher and the performance is improved as compared with Comparative Examples 12 to 19 and Comparative Examples 22 to 26 using Comparative Examples 3 to 10 which do not satisfy at least one of the conditions of the acid concentration and the characteristic (i), respectively. You can see that.
In the comparison between Examples 5 to 8 and Comparative Examples 17 to 19, the ion-exchangeable layered silicate particles of Examples 1 to 4 used in Examples 5 to 8 are in the range of the average particle size of the characteristic (i) of the present application. In Examples 5 to 8, the fine powder ratio is smaller than that of Comparative Examples 17 to 19 using Comparative Examples 8 to 10 which are below the range of the average particle size of the characteristic (i) of the present application. , It can be seen that the performance is improved.
In the comparison between Examples 9 to 12 and Comparative Examples 22 to 26, the production conditions of the ion-exchangeable layered silicate particles of Examples 1 to 4 used in Examples 9 to 12 satisfy the range of the acid concentration of the present application. Therefore, it can be seen that the number of bright spots is smaller than that of Comparative Examples 22 to 26 using Comparative Examples 3 to 7 produced under conditions exceeding the acid concentration range.
In comparison between Examples 9 to 12 and Comparative Example 27, Examples 1 to 4 used in Examples 9 to 12 satisfy the range of the average particle size of the ion-exchangeable layered silicate particles of the characteristic (i) of the present application. Therefore, in Examples 9 to 12, the number of bright spots is smaller than that in Comparative Example 27 using Comparative Example 8 which is below the range of the average particle size of the characteristic (i) of the present application, and the performance is improved. You can see that.
Further, in the comparison between Examples 10 to 12 and Comparative Examples 20 to 27, it can be seen that the number of bright spots in Examples 10 to 12 is smaller than that in Comparative Examples 20 to 27.

The catalyst component for olefin polymerization composed of the ion-exchangeable layered silicate obtained by the production method of the present invention is eluted by the acid treatment concentration and acid treatment when producing the ion-exchangeable layered silicate particles which are co-catalysts and carriers. By controlling the elution rate of aluminum, polymer physical properties and polymerization performance, which could not be produced in the past, are simultaneously realized at a high level.
When the catalyst component for olefin polymerization of the present invention is used as a catalyst for olefin polymerization, it is possible to reduce bright spots (fish eyes) in the product while exhibiting high polymerization activity, and to obtain a polyolefin powder having good particle properties. Therefore, production efficiency and production stability are improved, and it has an excellent industrial effect.

Claims (5)

A method for producing a catalyst component for olefin polymerization composed of an ion-exchangeable layered silicate.
The step (1) of acid-treating the ion-exchangeable layered silicate particles with an acid concentration of less than 20% by mass is included.
A method for producing an olefin polymerization catalyst component, wherein the olefin polymerization catalyst component satisfies the following characteristics (i) to (iii).
(I) The average particle size is 26.0 μm to 200.0 μm.
(Ii) The elution rate of aluminum before the acid treatment is 26% to 64%.
(Iii) The crushing strength is 5.0 MPa to 100.0 MPa. The method for producing a catalyst component for olefin polymerization according to claim 1, further comprising a step (2) of treating the ion-exchangeable layered silicate particles with a base after the step (1). The method for producing an olefin polymerization catalyst component according to claim 1 or 2, wherein the olefin polymerization catalyst component satisfies the following characteristic (iv).
(Iv) The total pore volume of the pores having a diameter in the range of 2 to 6 nm measured by the nitrogen adsorption method shall be 0.170 cm ³ / g or more and 0.500 cm ³ / g or less. A method for producing a catalyst for olefin polymerization, which comprises contacting the following component [A], component [B], and component [C] with an olefin.
Component [A]: Catalyst component for olefin polymerization obtained by the production method according to any one of claims 1 to 3 Component [B]: Transition metal compound component of Group 4 of the periodic table [C]: Organoaluminum Compound A method for producing an olefin polymer, which comprises performing olefin polymerization using the catalyst for olefin polymerization obtained by the production method according to claim 4.