JP2012206910A - Method for producing layered silicate particle, and method for producing olefin polymerization catalyst using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing layered silicate particles with which a polymer with excellent properties is obtained with high activity, and to provide a method for producing an olefin polymerization catalyst using the same.SOLUTION: The method for producing the layered silicate particles is characterized in that in treating a layered silicate with acids, treatment is conducted by keeping maximum elimination speed of a cation to be eliminated with an acid at 0.0005 minor less, and further in that the layered silicate has a 2:1 type structure, etc. The method for producing an olefin polymerization catalyst using the layered silicate particles, etc. are also disclosed.

Description

  The present invention relates to a method for producing layered silicate particles and a method for producing a catalyst for olefin polymerization using the same, and more specifically, by using the catalyst for olefin polymerization using the layered silicate particles, polymerization is highly active. A method for producing specific layered silicate particles, which is a catalyst component that allows the production of polyolefins that are advanced and have a high bulk density and a good particle shape, and a catalyst for olefin polymerization using the same Regarding the method.

Ingredients classified as clay or clay mineral are used in the cosmetics and food fields in addition to decoloring agents and extenders such as fats and oils, and their uses are diverse. Among them, it is known to produce an olefin polymer by polymerizing an olefin in the presence of a catalyst using clay or clay mineral as a catalyst component for olefin polymerization (see, for example, Patent Documents 1 to 3). .
Moreover, the catalyst for olefin polymerization which contains the ion exchange layered compound which performed the acid treatment and salt treatment as a catalyst component is also known (for example, refer patent documents 4-6).

When clay or clay minerals are used as the catalyst component for olefin polymerization, chemical treatments with sulfuric acid, hydrochloric acid, acetic acid, and other acids are extremely effective in improving the performance of olefin polymerization catalysts such as polymerization activity and polymer particle shape. Many technologies have been developed so far.
For example, Patent Document 7 discloses a technique that achieves improved activity and improved polymer shape by performing acid treatment at a certain concentration or higher. Further, Patent Document 8 discloses an olefin polymerization catalyst capable of polymerizing a polyolefin having a high bulk density by changing the concentration of the treatment agent during the chemical treatment.
However, as described above, the conventional technology alone is still insufficient for the production of a highly active polymerization catalyst while maintaining good properties of the polymer of the olefin polymerization catalyst component. However, further technical improvement is desired.

Japanese Patent Laid-Open No. 5-301917 JP 2000-103807 A JP 2000-103808 A Japanese Patent Laid-Open No. 7-309907 JP-A-8-127613 JP-A-10-168109 Japanese Patent No. 4491117 JP 2001-31720 A

  An object of the present invention is to provide a method for producing layered silicate particles capable of obtaining a polymer having good properties with high activity in view of the situation and problems of the prior art, and production of an olefin polymerization catalyst using the same. It is to provide a method.

  As a result of intensive research to achieve the above object, the present inventors have used the layered silicate particles treated under specific acid treatment conditions as a catalyst component for olefin polymerization, thereby significantly improving the catalytic activity. We obtained the knowledge that Specifically, it has been found that when the layered silicate is treated with acids, if the maximum desorption rate of cations desorbed by the acid is set to a certain value or less, the catalytic activity effect is remarkably improved. The present invention has been completed based on these findings.

That is, according to the first invention of the present invention, when the layered silicate is treated with acids, the maximum desorption rate of cations desorbed by the acid is 0.0005 min- ¹ or less. A method for producing the featured layered silicate particles is provided.

According to a second aspect of the present invention, there is provided the method for producing layered silicate particles according to the first aspect, wherein the layered silicate has a 2: 1 type structure.
Furthermore, according to the third invention of the present invention, in the first invention, the layered silicate is a smectite group, and the cation desorbed by the acid is an aluminum ion. A method for producing salt particles is provided.

  According to the fourth invention of the present invention, the transition metal compound, the compound that activates the transition metal compound, and the layered form obtained from the method for producing layered silicate particles according to any one of the first to fourth inventions Provided is a method for producing a catalyst for olefin polymerization, characterized by using silicate particles.

As described above, the present invention relates to a method for producing layered silicate particles, and preferred embodiments include the following.
(1) The method for producing layered silicate particles according to the first or third invention, wherein the layered silicate subjected to the acid treatment is montmorillonite.
(2) The method for producing layered silicate particles according to the first invention, wherein after the acid treatment, salt treatment or intercalation is further performed.
(3) The layered silicate particles according to the first invention, wherein the maximum desorption rate of the cations desorbed by the acid is in the range of 0.00001 min- ^{1 to} 0.0005 min- ^1. Manufacturing method.
(4) A method for producing an olefin polymerization catalyst according to the fourth invention, wherein the transition metal compound is a metallocene compound of a Group 4 transition metal.
(5) In the fourth invention, the compound that activates the transition metal compound is an organic metal compound, an ionic compound capable of reacting with the transition metal compound to convert the transition metal compound into a cation, or a Lewis acid. A method for producing an olefin polymerization catalyst.

According to the method for producing layered silicate particles of the present invention, when the layered silicate is treated with acids, the maximum desorption rate of cations desorbed by the acid is 0.0005 min- ¹ or less. Thus, a remarkable effect is obtained that a layered silicate particle capable of obtaining a polymer having a good property with high activity or an olefin polymerization catalyst using the layered silicate particle is obtained.

The effects of the present invention will be discussed below.
That is, when the layered silicate is treated with an acid such as hydrochloric acid or sulfuric acid, impurities on the surface are removed and cations such as Al, Fe, Mg, etc. in the crystal structure are eluted and the surface area is generally increased. It is said. Also in the present invention, the cation in the crystal structure of the octahedral layer portion of the layered silicate is eluted by the acid treatment.
However, in the conventional technology, treatment with a high concentration of acid, that is, by increasing the cation desorption rate, large-sized pores can be formed, and mass transfer inside and outside the particle is facilitated. It has been considered that the points are uniformly dispersed and the particle shape is improved (see Patent Document 7).
On the other hand, in the present invention, the swellability or expansibility of the layered silicate can be controlled by reducing the cation desorption rate, contrary to the conventional case, and as a result, the catalytic activity is improved. Was found to be important. This is because during the acid treatment, the layered silicate particles are swollen or expanded to such an extent that the layered silicate particles do not collapse, so that the entire silicate particles are uniformly treated, and the portions that have not been treated so far are also treated. The present inventors consider that the reaction point increases by the treatment, resulting in high activation. Furthermore, this technical idea is supported by the fact that the surface area of the silicate particles is increased by reducing the desorption rate. In addition, the present inventors consider that highly active particles can be produced without deteriorating the particle shape because the reaction points increase and the particles are dispersed by increasing the surface area.

FIG. 1 is a graph plotting the Al removal rate versus the carrier composition (Al / Si) for Example 1 and Comparative Example 1. FIG. 2 is a graph plotting the carrier composition (Al / Si) against the acid treatment time (min) for Example 1 and Comparative Example 1.

Hereinafter, the present invention will be described in detail for each item.
1. Method for Producing Layered Silicate Particles (1) Layered Silicate The layered silicate used in the present invention is a layer formed from silicon or a mixture of silicon and aluminum and oxygen atoms, and a mixture of aluminum or aluminum and magnesium. A mixture of iron and a layer formed of oxygen atoms or hydroxyl groups having a crystal structure in which they are stacked one by one or in parallel at a ratio of 2: 1, and a mixture thereof, and They may have a structure in which lamination is repeated with an exchangeable cation interposed therebetween.
The layered silicate is not limited to natural ones but may be artificial ones, and may contain impurities such as quartz and cristobalite.

  Specific examples of the layered silicate include (i) 1: 1 type structure and (ii) 2: 1 type structure described in, for example, “Clay Mineralogy” (Haruo Shiramizu, Asakura Shoten, 1995). A layered silicate having (I) The 1: 1 type structure is a stack of 1: 1 layer structures in which a single-layer tetrahedral sheet and a single-layer octahedral sheet are combined as described in the above “clay mineralogy” etc. And (ii) 2: 1 type structure is a structure based on a stack of 2: 1 layer structures in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets. Indicates.

(I) Crystal structures stacked one by one in parallel are called 1: 1 type structures, and specific examples of layered silicates having this structure as a main constituent layer are kaolinite, dickerite, halosite, chrysotile. Kaolinite-serpentine family such as lizardite and amesite.

(Ii) A crystal structure stacked in parallel at a ratio of 2: 1 is called a 2: 1 type structure, and specific examples of layered silicates having this structure as a main constituent layer include pyrophyllite, talc, and the like. Pyrophyllite-talc, muscovite, paragonite, illite, phlogopite, biotite, leoprite, and other micas, margarite, clintonite, anandite, and other british micas, donbasite, kukeite, sudite, clinochlore, chamo Chlorite groups such as sites and nimite, vermiculites such as vermiculite, smectites such as montmorillonite, beidellite, saponite, hectorite, and saconite.

  The layered silicate used in the present invention may be one in which the mixed layers (i) and (ii) above are formed. Among them, a layered silicate having a 2: 1 type structure is preferable, and a smectite group is more preferable. Particularly preferred is montmorillonite.

The layered silicate is preferably granulated and used.
The granulation method is not particularly limited, but preferred granulation methods include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method, submerged granulation method, compression molding granulation method and the like. Particularly preferred are spray-drying granulation, spray-cooled granulation, fluidized bed granulation, spouted bed granulation, submerged granulation, emulsification granulation, etc., particularly preferably spray-drying granulation and spray-cooled granulation. Can be mentioned.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as a dispersion medium. The concentration of the layered silicate in the raw material slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 70 wt%, preferably 5 to 50 wt%, particularly preferably 7 to 45 wt%, and most preferably 10 to 10 wt%. 40 wt%. If the upper limit of the above concentration is exceeded, spherical particles cannot be obtained, and if the lower limit of the above concentration is not reached, the average particle size of the granulated product becomes too small. The temperature at the inlet of hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but when water is taken as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, Examples thereof include latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate.
The shape of the layered silicate before granulation is not particularly limited, and may be a naturally produced shape or an artificially synthesized shape, or may be shaped by operations such as grinding, granulation, and classification. You may use the processed layered silicate.
The granulated layered silicate preferably has a spherical ion exchange layered silicate granulated product having an average particle size of 5 μm or more and 200 μm or less. If there are many fine particles of less than 5 μm, aggregation of the polymers, adhesion to the reactor, etc. are likely to occur, and depending on the polymerization process, it may cause a short path or long-term residence, which is not preferable. On the other hand, coarse particles exceeding 200 μm are not preferable because problems such as clogging (for example, during catalyst feeding) are likely to occur. In order to obtain an average particle size satisfying these, or when fine particles having an extremely small particle size are present, the particle size may be controlled by classification, classification, etc. .
The spherical particles obtained as described above preferably have a compressive fracture strength of 0.2 MPa or more in order to crush or suppress fine powder.

(2) Acid treatment method for layered silicate In the present invention, when layered silicate is treated with acids (hereinafter, this operation is referred to as acid treatment), the maximum desorption rate of cations desorbed by the acid is 0.0005 min- ¹ or less.
Examples of the cation desorbed from the layered silicate by the acid include Al ³⁺ , Mg ²⁺ , Fe ^2+, etc. Among them, it is particularly preferable to indicate Al ³⁺ .
The maximum cation desorption rate here refers to the molar ratio of cation to silicon in the layered silicate after acid treatment from the molar ratio of cation to silicon in the layered silicate before acid treatment. By dividing the desorption amount of the cation calculated by subtracting by the acid treatment time (minutes), the desorption rate obtained is the one that becomes the largest during acid treatment. If this maximum desorption rate is 0.0005 min- ¹ or less, the acid treatment condition can be any condition. The lower the maximum desorption rate, the more effective. However, taking the lower limit in consideration of industrial production efficiency as an example, it becomes 0.00001 min- ¹ .
At this time, the total amount of cations to be desorbed is preferably 5 to 70%, more preferably 7 to 60%, and still more preferably 10 to 50% with respect to the amount of cation (mol) before treatment. It is.

(3) Acid treatment Acids used in the acid treatment include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, fumaric acid, maleic acid, and phthalic acid, and organic acids. Examples are acids. Among these, inorganic acids are preferable, and hydrochloric acid, nitric acid, and sulfuric acid are preferable. More preferred are hydrochloric acid and sulfuric acid, and particularly preferred is sulfuric acid.
As an example of the conditions for the acid treatment, the temperature is preferably 40 to 100 ° C., and preferably 50 to 90 ° C. If the temperature is lowered too much, the elution rate of the cation is extremely lowered, and the production efficiency is reduced. descend. When the concentration of the acid is expressed in weight percent (percentage of the weight of the acid divided by the total weight of the reaction system), the concentration may be 3 to 20 wt%, preferably 5 to 15 wt%, more preferably depending on the reaction temperature. 7 to 12 wt%. As a combination of these acid treatment conditions, for example, when treating at a temperature of 90 ° C., the acid concentration may be about 10 wt%. In addition, when the treatment is performed at a temperature of 80 ° C., the acid treatment conditions may be such that the acid concentration is about 15 wt%, and the treatment at a temperature of 70 ° C. is about 20 wt%.
Examples of the concentration of the layered silicate at this time include 3 to 50 wt%, preferably 5 to 40 wt%, and more preferably 7 to 35 wt%.

  After carrying out the acid treatment, it is possible to remove excess acid treatment agent and ions eluted by the treatment, which is preferable. That is, it is preferable to wash. At this time, generally, a liquid such as water or an organic solvent is used. After washing and dehydration, drying is carried out. Generally, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C, and particularly preferably 150 to 300 ° C. If it exceeds 800 ° C., the structure of the layered silicate may be destroyed, which is not preferable.

  Even if these layered silicates are not structurally destroyed, the characteristics change depending on the drying temperature. Therefore, 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, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.

(4) Other chemical treatments The layered silicate according to the present invention is subjected to acid treatment under mild conditions in a state where the layered silicate swells, and treatment of the end face with acid while swelling causes the treatment to be uniform. Therefore, it is indispensable to perform acid treatment, and it is preferable to perform chemical treatment such as salt treatment after the acid treatment.
In the present invention, since acid treatment is performed while controlling the swelling property, the acid treatment is preferably the first treatment. This is because a highly active catalyst can be obtained.

Chemical treatment such as salt treatment causes metal ions or organic cations to enter between the layers of the layered silicate, thereby changing the charge and interlayer distance of the layered silicate layer to form polymerization active sites. The present inventors consider that a layered silicate structure that is easy to do is obtained.
Further, intercalation may be performed either before or after the chemical treatment such as the salt treatment.
Intercalation means that when clay minerals such as layered silicate are layered substances, another substance is introduced between the layers by bringing the treating agent containing the compound to be introduced into contact with the clay mineral. The substance to be introduced is called a guest compound.
In salt treatment or intercalation, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed. By intercalating the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material with the layers expanded. That is, the bulky ions play a role of supporting pillars and support the layered structure, and are called pillars.

  Below, the specific example of a processing agent is shown. In addition, in this invention, you may use what combined 2 or more types chosen from the compound which can intercalate between the layers of the following salts and layered silicate as a processing agent. Moreover, the compound which can intercalate between the layers of these salts and layered silicate may be a combination of two or more. Furthermore, these combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment.

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

Specific examples of such salts include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, Na ₂ SO ₄ , and Na ₃ (PO ₄ ). , NaNO ₃ , Na (OOCCH ₃ ), KCl, KBr, K ₂ SO ₄ , K ₃ (PO ₄ ), KNO ₃ , K (OOCCH ₃ ), CaCl ₂ , CaSO ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , La (OOCH ₃ ) ₃ , La (CH ₃ COCHCOCH ₃ ) ₃ , La ₂ (CO ₃ ) ₃ , La (NO ₃ ) ₃ , La (ClO ₄ ) ₃ , La ₂ (C ₂ O ₄ ) ₃ , LaPO ₄ , La ₂ (SO ₄ ) ₃ , LaF ₃ , LaCl ₃ , LaBr ₃ , LaI ₃ etc.
NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _2, etc.
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 ) _{4), Hf (OOCCH 3)} 4, Hf (CO 3) 2, Hf (NO 3) 4, Hf (SO 4) 2, HfOCl 2, HfF 4, HfCl 4, HfBr 4, HfI 4, V (CH 3 _{COCHCOCH 3) 3, VOSO 4,} VOCl 3, VCl 3, VCl 4, VBr 3, Nb (CH 3 COCHCOCH 3) 5, Nb 2 (CO 3 ) ₅ , Nb (NO ₃ ) ₅ , Nb ₂ (SO ₄ ) ₅ , ZrF ₅ , ZrCl ₅ , NbBr ₅ , NbI ₅ , Ta (OOCCH ₃ ) 5, Ta ₂ (CO ₃ ) ₅ , Ta (NO ₃ ) ₅ , Ta ₂ (SO ₄ ) ₅ , TaF ₅ , TaCl ₅ , TaBr ₅ , TaI ₅ etc.
CuCl ₂ , CuBr ₂ , Cu (NO ₃ ) ₂ , CuC ₂ O ₄ , Cu (ClO ₄ ) ₂ , CuSO ₄ , Cu (OOCCH ₃ ) ₂ , Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , nBr ₂ , ZnI ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , Sn (OOCCH ₃ ) ₄ , _{sn (SO 4) 2, SnF} 4, SnCl 4 and the like.

  Examples of organic cations include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5- Pentamethylanilinium, N, N-dimethyloctadecylammonium, octadodecylammonium, N, N-2,4,5-pentamethylanilinium, N, N-dimethyl-pn-butylanilinium, N, N- Ammonium compounds such as dimethyl-p-trimethylsilylanilinium, N, N-dimethyl-1-naphthylanilinium, N, N, 2-trimethylanilinium, 2,6-dimethylanilinium, pyridinium, quinolinium, N-methylpi Peridinium, 2,6-dimethyl Nitrogen-containing aromatic compounds such as pyridinium, 2,2,6,6-tetramethylpiperidinium, oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, oxolanium, triphenylphosphonium, tri-o Examples include phosphonium compounds such as -tolylphosphonium, tri-p-tolylphosphonium, and trimesitylphosphonium, and phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium.

  Although there is no restriction | limiting in particular about the quantity of the cation to exist, It is preferable to process by making 0.001 mol or more exist per 1g of layered silicates preferably. One kind of these cations may be used alone, or two or more kinds may be used in combination. When used in combination, it is preferable that the total amount to be present is 0.001 mol or more per 1 g of layered silicate.

  Examples of the anion include, in addition to the anions exemplified above, anions composed of boron compounds and phosphorus compounds such as hexafluorophosphate, tetrafluoroborate, tetraphenylborate and the like.

(B) Compound for intercalation Guest compounds used for intercalation between layers of layered silicate include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR ) ₄ , PO (OR) ₃ , B (OR) ₃ [R is an alkyl group, aryl group, etc.] and the like, [Al1 ₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and the} like, organic compounds such as ethylene glycol, glycerol, urea and hydrazine, and organic cations such as alkylammonium ions.

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

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

  Further, in general, the layered silicate includes adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water before use. A heat treatment is usually used to remove water. The method is not particularly limited, but it is necessary to select conditions so that adhering water and interlayer water do not remain and structural destruction does not occur. The heating time is 0.1 hour or longer, preferably 0.2 hour or longer. At that time, the moisture content after removal is 3% by weight or less, preferably 1% by weight or less when the moisture content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. It is preferable that

2. Olefin Polymerization Catalyst The layered silicate particles according to the present invention are suitably used as a carrier for an olefin polymerization catalyst.
Examples of the olefin polymerization catalyst generally include a Ziegler-Natta catalyst and a metallocene catalyst. Specifically, it is a catalyst prepared using (1) a transition metal compound, (2) a compound that activates a transition metal compound, and (3) the above-mentioned layered silicate particles.

  Details of (1) the transition metal compound, (2) the compound for activating the transition metal compound, the preparation method of the olefin polymerization catalyst, prepolymerization, etc. will be described below.

(1) Transition metal compound The transition metal compound used in the olefin polymerization catalyst of the present invention is a transition metal compound of Groups 3 to 12 of the periodic table. Specifically, a Group 3-10 transition metal halide, a Group 4-6 transition metal metallocene compound, a Group 4 transition metal bisamide or bisalkoxide compound, a Group 8-10 transition metal bisimide compound, Examples thereof include phenoxyimine compounds of Group 3-11 transition metals.
Examples of the Group 3-10 transition metal halides include TiCl ₃ , TiCl ₄ , VCl ₃ , VOCl ₃ , PdCl ₃ , FeCl _{3 and the} like.
Moreover, as a metallocene compound of a Group 4-6 transition metal, the compound represented by following General formula (1)-(4) can be mentioned.

  In the above general formulas (1) to (4), A and A ′ are conjugated five-membered ring ligands which may have a substituent (in the same compound, A and A ′ may be the same or different. Q represents a bonding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom. Q ′ represents a bonding group that bridges Z with an arbitrary position of the conjugated five-membered ring ligand, M represents a metal atom selected from Groups 4 to 6 in the periodic table, and X and Y Is a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group (in the same compound, X and X ′ may be the same or different). Show.

Examples of A and A ′ include a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms [C ₅ H _5- ], or a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with substituents. May be.
Examples of this substituent are hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when there are a plurality of these, two of them are bonded to the other end (ω-end) to form a cyclo A ring may be formed together with a part of pentadienyl. Examples of the latter include those in which two substituents are each bonded at the ω-end to 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 those forming a condensed seven-membered ring, that is, an azulenyl group and a tetrahydroazurenyl group can be mentioned.

Preferable specific examples of the conjugated five-membered ring ligand represented by A and A ′ include a substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group. Of these, a substituted or unsubstituted indenyl group or an azulenyl group is particularly preferable.
As the substituent on the cyclopentadienyl group, in addition to the hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, a halogen atom group such as fluorine, chlorine or bromine, or 1 to 12 carbon atoms. An alkoxy group, for example, a silicon-containing hydrocarbon group represented by -Si (R ¹ ) (R ² ) (R ³ ), a phosphorus-containing hydrocarbon group represented by -P (R ¹ ) (R ² ), or -B And a boron-containing hydrocarbon group represented by (R ¹ ) (R ² ). When there are a plurality of these substituents, each substituent may be the same or different. R ¹ , R ² and R ³ described above may be the same or different and each represents an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.
Furthermore, you may have an at least 1 group 15-16 element (namely, hetero element) as a substituent on a cyclopentadienyl group. In this case, from the idea of improving the properties of the active site by allowing the hetero element itself to be present in the vicinity of the active site without bonding or coordination with the metal, a group 15-15 element and a conjugated five-membered ring are formed. A metallocene complex having 1 or less atoms bonding to the ligand is more preferable.
Although there is no restriction | limiting in particular in the position on the ligand of a 15-15 group element, It is preferable to have on the substituent of 2nd-position. More preferably, the 2-position substituent is monocyclic or polycyclic 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. Preferably there is. Further, it is preferably a heteroaromatic group having 4 to 20 carbon atoms which may contain silicon or halogen, and 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 more preferable.

Q is a bonding 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 with a group represented by Z. Represents a sex group.
Specific examples of Q and Q ′ include the following groups.
(I) Methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group and other alkylene groups (b) dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, Silylene groups such as methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group, etc. (C) hydrocarbon groups containing germanium, phosphorus, nitrogen, boron or aluminum 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, is a _{(C 4 H 9) B,} (C 6 H 5) B, (C 6 H 5) Al (C 6 H 5 O) groups represented by Al or the like Preference is given to alkylene groups and silylene groups.

  M represents a metal atom transition metal selected from Groups 4 to 6 of the periodic table, preferably a Group 4 metal atom of the periodic table, and specifically titanium, zirconium, hafnium, and the like. In particular, zirconium and hafnium are preferable.

  Z represents a ligand, a hydrogen atom, a halogen atom or a hydrocarbon group containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. Preferable specific examples include an oxygen atom, a sulfur atom, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, C1-C40, preferably C1-C18 nitrogen-containing hydrocarbon group, C1-C40, preferably C1-C18 phosphorus-containing hydrocarbon group, hydrogen atom, chlorine, bromine, C1 ˜20 hydrocarbon groups.

  X and Y are each a hydrogen atom, a halogen atom, a C1-C20, preferably a C1-C10 hydrocarbon group, a C1-C20, preferably a C1-C10 alkoxy group, an amino group, 1 to 20 carbon atoms such as a diphenylphosphino group, preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, or 1 to 20 carbon atoms such as a trimethylsilyl group or a bis (trimethylsilyl) methyl group, preferably 1 to 1 carbon atom. 12 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.

As the compound represented by the general formula (1), 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,
Etc.

Examples of the compound represented by the general formula (2) include:
(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-azulenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride,
(5) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(6) Diphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(8) ethylenebis {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-azulenyl]} 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-azulenyl)} {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-indolyl-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylene bis {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) Dimethylgermylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(28) Dimethylgermylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(29) phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,

(30) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(31) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(32) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(33) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(34) Dimethylsilylenebis [2- (2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl) zirconium dichloride,
(35) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(36) Dimethylsilylene [2- (2- (5-methyl) furyl) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(37) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(38) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(39) Dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride,
Etc.

Examples of the compound represented by the general formula (3) include:
(1) (tetramethylcyclopentadienyl) titanium (bis t-butylamide) dichloride,
(2) (tetramethylcyclopentadienyl) titanium (bisisopropylamide) dichloride,
(3) (tetramethylcyclopentadienyl) titanium (biscyclododecylamide) dichloride,
(4) (Tetramethylcyclopentadienyl) titanium {bis (trimethylsilyl) amide)} dichloride,
(5) (2-Methyl-4-phenyl-4H-azurenyl) titanium {bis (trimethylsilyl) amide} dichloride,
(6) (2-methylindenyl) titanium (bis t-butylamide) dichloride,
(7) (fluorenyl) titanium (bis t-butylamide) dichloride,
(8) (3,6-diisopropylfluorenyl) titanium (bis t-butylamide) dichloride,
(9) (Tetramethylcyclopentadienyl) titanium (phenoxide) dichloride,
(10) (tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride,
Etc.

Examples of the compound represented by the general formula (4) include:
(1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride,
(2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(3) Dimethylsilanediyl (2-methylindenyl) (t-butylamido) titanium dichloride,
(4) Dimethylsilanediyl (fluorenyl) (t-butylamido) titanium dichloride, and the like.

As the transition metal compound used in the present invention, a compound represented by the general formula (2) is preferable, and a compound having a condensed seven-membered ring as a substituent, that is, a compound having an azulenyl group or a tetrahydroazurenyl group. Is particularly preferred. The transition metal compounds represented by the general formulas (1) to (4) can be used as a mixture of two or more compounds represented by the same general formula and / or compounds represented by different general formulas.
Examples of the dichloride of these exemplified compounds include compounds in which dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide and the like are substituted. Furthermore, compounds in which zirconium and titanium in the exemplified compounds are replaced with hafnium are also exemplified.

  In the present invention, the amount of the transition metal compound used is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol per 1 g of the layered silicate.

(2) Compound that activates transition metal compound In the present invention, activation refers to a reaction that cationizes a transition metal compound and generates an active species for the coordination polymerization of olefin to proceed. The compound that activates the compound may be one kind, or a plurality of kinds may be mixed or used together.
As an example of a compound that activates a transition metal compound, it is possible to react with an organometallic compound such as an organoaluminum compound or an organoaluminum oxy compound, or a transition metal compound to convert the transition metal compound into a cation. Ionic compounds or compounds exhibiting Lewis acidity.

Specific examples include the following (i) to (iii).
(I) Organoaluminumoxy compound (ii) Organoaluminum compound (iii) An ionic compound or Lewis acid capable of reacting with a transition metal compound to convert the transition metal compound into a cation These components are each independently You may use it, and you may use multiple, such as mixing or mixing. Among these components, it is preferable to use (ii) an organoaluminum compound.

  It is well known that the aluminumoxy compound (i) can activate a metallocene complex, and specific examples of such a compound include compounds represented by the following general formulas.

In each of the above general formulas, R ¹ represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms. Moreover, several R < ¹ > may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.
Among the general formulas, the compounds represented by the first and second formulas are compounds also referred to as aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
The compound represented by the third general formula is 10: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula: R ² B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio).
In the general formula, R ¹ and R ² represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

(Ii) The organoaluminum compound is preferably a compound represented by the general formula: AlR ³ _p X _3-p . In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of plural kinds or in combination. Moreover, this use is possible not only at the time of catalyst preparation but also at the time of preliminary polymerization or polymerization. In this formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p is in the range of 1 to 3. R ³ is preferably an alkyl group, and X is a chlorine atom when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 carbon atom when it is an amino group. An amino group of ˜8 is preferred.
Accordingly, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, linnormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl Examples include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, p = 3 trialkylaluminum and dialkylaluminum hydride are preferable. More preferably, R ³ is a trialkylaluminum having 1 to 8 carbon atoms.

The compound of (iii) is an ionic compound or Lewis acid that can react with the transition metal compound to convert the transition metal compound into a cation, and examples of such ionic compound include a carbonium cation and an ammonium cation. And a complex of a cation such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron.
Examples of the Lewis acid as described above include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halides such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a transition metal compound and can convert a transition metal compound into a cation.
Here, as the particulate carrier carrying the components (i), (ii), (iii), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, aluminum chloride Inorganic halides such as lanthanum chloride, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrenedivinylbenzene copolymer, and acrylic acid copolymer can be used.

(3) Preparation of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention comprises (1) a transition metal compound, (2) a compound that activates a transition metal compound, and (3) layered silicate particles. A catalyst prepared by contact.
Although the contact method is not specifically limited, Contact 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 preliminary polymerization with olefin or at the time of polymerization of olefin. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers.

(I) The three components are contacted simultaneously.
(Ii) After bringing the transition metal compound into contact with the layered silicate particles, a compound that activates the transition metal compound is added.
(Iii) After bringing the transition metal compound into contact with the compound that activates the transition metal compound, the layered silicate particles are added.
(Iv) After bringing the layered silicate particles into contact with the compound that activates the transition metal compound, the transition metal compound is added.

Among the above catalyst components, the amount of the transition metal compound and the compound that activates the transition metal compound is used in an optimum ratio among the combinations.
When the compound that activates the transition metal compound is an organometallic compound, the molar ratio of Al / transition metal is usually 1 or more and 100,000 or less, more preferably 2 or more and 20,000 or less, and particularly 2 or more and 10,000 or less. Is suitable. On the other hand, when an ionic compound or a Lewis acid is used as the compound that activates the transition metal compound, the molar ratio of the transition metal to the transition metal is 0.1 to 1,000, preferably 1 to 100, more preferably 2 to 2. The range is 10.
The three components are preferably brought into contact with each other in a solvent for uniform contact, and examples of the solvent include aliphatic saturated hydrocarbons, aromatic saturated hydrocarbons, aliphatic unsaturated hydrocarbons and prepolymerized monomers. Illustrated. As temperature at that time, 0-100 degreeC is preferable, More preferably, it is 20-80 degreeC, Most preferably, it is 30-60 degreeC. When it is lower than this range, the reaction is slow, and when it is high, there is a drawback that the decomposition reaction of the transition metal compound proceeds. Furthermore, as reaction time at that time, 15 minutes-24 hours, Preferably it is 30 minutes-12 hours, More preferably, 30 minutes-2 hours are mentioned. Moreover, as a density | concentration at that time, it is 20-300 g / L about layered silicate particle, Preferably it is 40-250 g / L.

(4) Prepolymerization The catalyst used in the present invention is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance in order to improve particle properties.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use it, and it is particularly preferable to use propylene.
The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 1 part by mass of the compound in which the amount of prepolymerization polymer activates the transition metal compound. After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.

The prepolymerization temperature is not particularly limited, but is usually 0 ° C to 100 ° C, preferably 10 to 70 ° C, more preferably 20 to 60 ° C, and particularly preferably 30 to 50 ° C. Below this range, the reaction rate may decrease or the activation reaction may not proceed, and if it exceeds this range, the prepolymerized polymer may be dissolved, or the prepolymerization rate may be too high and the particle properties may deteriorate. There is a possibility that the active point may be deactivated due to a side reaction.
The preliminary polymerization can be carried out in a liquid such as an organic solvent, but it is preferable to do so.
The concentration of the solid catalyst during the prepolymerization is not particularly limited, but is preferably 30 g / L or more, more preferably 40 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst. On the other hand, if the concentration is too high, performance deteriorates due to the influence of fluidity reduction, poor heat removal of reaction heat, progress of side reactions, and the like.

3. Method for Producing Olefin Polymer An α-olefin can be polymerized or copolymerized using the olefin polymerization catalyst of the present invention.
Preferred α-olefins that can be polymerized are those having about 2 to 20 carbon atoms, and specific examples include ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like. In the case of copolymerization, the type of comonomer used can be selected from α-olefins other than the main component among those listed as the α-olefin.
The amount of comonomer can be implemented under any conditions to produce a polymer having desired physical properties (melting point, molecular weight, rigidity, etc.), but the catalyst of the present invention is usually difficult to produce due to the deterioration of particle properties. For example, it is suitable for the production of random polymers, and is particularly suitable for the production of low melting point propylene random copolymers and high rubber content so-called ethylene / propylene block copolymers.
By using the catalyst of the present invention, a polymer having a uniform powder property can be produced. Also, a polymer having a large pore volume and relatively large pores can be obtained. There is an effect of remarkably improving adhesion between polymers and fouling to the polymerization reaction layer.

  As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a solution polymerization method, a bulk method using propylene as a solvent that does not substantially use an inert solvent, or gasifying each monomer substantially without using a liquid solvent. A gas phase method can be used. Further, it is applied to continuous polymerization and batch polymerization.

  In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 ° C. to 200 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 200 MPa.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.
The analytical instruments and measurement methods used for measuring physical properties are as follows.

(Various physical property measurement methods)
(1) Measurement of moisture content of carrier:
The measurement was performed under the conditions of an electric furnace temperature of 400 ° C. and a droplet end point of 0.4 μg / s using Dia Instruments CA-07 and a moisture vaporizer Dia Instruments VA-21.
(2) Measurement of particle size distribution:
Using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by HORIBA, Ltd., the dispersion solvent was measured under the conditions of ethanol, refractive index 1.3, and shape factor 1.0.
(3) Composition analysis of layered silicate:
A calibration curve was prepared by chemical analysis by the JIS method and quantified by fluorescent X-ray.
(4) MFR (melt mass flow rate):
Using Takara's melt indexer, JIS K7210 "Plastics-Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics": compliant with 230 ° C, 2.16 kg load And measured.
(5) Measurement of ethylene content:
The peak height I in the range of 700-760 cm ⁻¹ in the infrared absorption spectrum based on the ethylene content of the standard sample calculated by the ethylene content measurement method by ¹³ C-NMR described in JP-A No. 2003-73426. The relational expression (the following formula [1]) between [absorbance] and ethylene content E [mass%] was calculated and calculated using this.
The sample was prepared by preparing a 0.5 mm sheet of about 5 g of sample polymer by press molding at 190 ° C., and measuring the infrared absorption spectrum.
D [mm] in the following formula [1] is a sheet thickness, and a numerical value accurately measured to a unit of 10 μm was used.
Formula [1]: E (A) = 5 × I / D + 0.0613
(6) Polymer bulk density:
The bulk density (BD) of the polymer (polymer) was measured using an apparatus according to ASTM D1895-69.

[Example 1]
1. Chemical Treatment of Layered Silicate 982 g of pure water was added to a 2 L separable flask equipped with a stirring blade and a reflux device, and 126 g of 96% sulfuric acid was added dropwise. When the target temperature was reached by heating with an oil bath until the internal temperature reached 90 ° C., a commercially available granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7 to After adding 150 g of 30 μm, composition (wt%): Al = 9.11, Si = 32.91), the mixture was stirred. At this time, the acid concentration was 10 wt%, and the acid concentration with respect to the clay was 8.2 mmol / g.
Thereafter, the reaction was continued for 480 minutes while maintaining 90 ° C. The reaction was stopped by emptying the reaction solution in 0.75 L of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed with 2 L of pure water three times.
The recovered cake was dried at 120 ° C. overnight, and 105 g was weighed and used in the next step. This clay was added to an aqueous solution in which 118 g of lithium sulfate hydrate was dissolved in 525 mL of pure water in a 1 L plastic beaker and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 1 L of pure water three times.

The collected cake was dried at 120 ° C. overnight. As a result, 73.9 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an opening of 53 μm, the sieve passage was 32.6 g, which was 44.1% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.8 μm.
The composition (wt%) of the obtained chemically treated montmorillonite contained 7.05 Al and 37.77 Si, and the molar ratio of Al to Si was 0.194. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000370 min− ¹ (see FIGS. 1 and 2).
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of the dried montmorillonite was measured, the moisture value was 0.98 wt%. The results are summarized in Table 1.

2. Preparation of catalyst Weighing 20.13 g of dry montmorillonite obtained from the chemical treatment of the above layered silicate into a 1 L internal volume flask, 131 mL of heptane, 69.0 mL (49.4 mmol, concentration of heptane solution of triisobutylaluminum (TiBA)) 141.9 mg / L) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the remaining liquid was washed to 1/100 with heptane, and finally the amount of slurry was adjusted to 100 mL.
Next, 181 mL of heptane and 3.1 mL of a heptane solution of TnOA (concentration 143.6 mg / mL, 1214 μmol) were added to the TiBA-treated montmorillonite heptane slurry.
In another flask (volume 200 mL), (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium dichloride (synthesis is It carried out according to the Example of Unexamined-Japanese-Patent No. 10-110136.) The slurry which added heptane (48 mL) to 254 mg (312.4 micromol) was added, and it stirred at 60 degreeC for 60 minutes.
The montmorillonite heptane slurry was introduced into a 1 L stirred autoclave that had been thoroughly dried and purged with nitrogen. When the temperature in the autoclave was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to keep the temperature constant. After 4 hours, the supply of propylene was stopped and maintained for another hour.
After completion of the prepolymerization, the remaining monomer was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered preliminary polymerization catalyst slurry was allowed to stand, and 215 mL of the supernatant was extracted. Subsequently, 8.6 mL (6.1 mmol) of a heptane solution of triisobutylaluminum (TiBA) was added at room temperature, and then dried under reduced pressure at 40 ° C. for 1 hour to recover 65.17 g of a solid catalyst.
The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.18 g / g. The amount of Hf complex supported per amount of solid catalyst of this catalyst was 14.3 μmol. The average particle size was 32.1 μm.

[Example 2]
1. Chemical treatment of layered silicate Into a 2 L separable flask equipped with a stirring blade and a reflux apparatus, 929 g of pure water was added, and 104 g of 96% sulfuric acid was added dropwise. When the target temperature was reached by heating with an oil bath until the internal temperature reached 90 ° C., a commercially available granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7 to 30 μm, composition (wt%): Al = 8.87, Si = 33.66) was added and stirred after adding 100 g. At this time, the acid concentration was 8.8 wt%, and the acid concentration relative to the clay was 10.1 mmol / g.
Thereafter, the reaction was continued for 660 minutes while maintaining 90 ° C. The reaction was stopped by emptying the reaction solution in 0.5 L of pure water. Further, the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed three times with 1 L of pure water.
The recovered cake was dried at 120 ° C. overnight, then weighed 70 g and used in the next step. This clay was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 480 mL of pure water in a 1 L plastic beaker and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed three times with 0.7 L of pure water.

The collected cake was dried at 120 ° C. overnight. As a result, 69.3 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an aperture of 53 μm, the amount passing through the sieve was 57.1 g, which was 82.4% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.2 μm.
The composition (wt%) of the obtained chemically treated montmorillonite contained 6.10 Al and 38.93 Si, and the molar ratio of Al to Si was 0.163. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000355 min- ¹ .
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of this dried montmorillonite was measured, the moisture value was 0.92 wt%. The results are summarized in Table 1.

2. Catalyst Preparation 20.05 g of dry montmorillonite obtained from the chemical treatment of the above layered silicate, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared similarly to the catalyst preparation of Example 1 except that 244 mg (300.1 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.18 g / g. The amount of Hf complex supported per amount of solid catalyst of this catalyst was 11.8 μmol. The average particle size was 29.9 μm.

[Example 3]
1. Chemical treatment of layered silicate Into a 2 L separable flask equipped with a stirring blade and a reflux apparatus, 1307.3 g of pure water was added, and 147.8 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 90 ° C., and when the target temperature was reached, further commercially available granulated montmorillonite (structural formula Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm) , Composition (wt%): Al = 8.87, Si = 33.66) was added, and then stirred. At this time, the acid concentration was 8.9 wt%, and the acid concentration with respect to the clay was 10.3 mmol / g. Thereafter, the reaction was continued for 540 minutes while maintaining 90 ° C. The reaction is stopped by emptying the reaction solution in 0.7 L of pure water, and the slurry is filtered through a device in which an aspirator is connected to Nutsche and a suction bottle, and then washed three times with 1.4 L of pure water. did.
The recovered cake was dried at 120 ° C. overnight and then weighed 95 g and used in the next step. This clay was added to an aqueous solution in which 151.2 g of lithium sulfate hydrate was dissolved in 683 mL of pure water in a 1 L plastic beaker and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 1 L of pure water three times.

The collected cake was dried at 120 ° C. overnight. As a result, 93.4 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an aperture of 53 μm, the sieve passage was 86.3 g, which was 92.4% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.5 μm.
The composition (wt%) of the obtained chemically treated montmorillonite contained 6.67 Al and 38.34 Si, and the molar ratio of Al to Si was 0.181. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000362 min- ¹ .
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of the dried montmorillonite was measured, the moisture value was 0.95 wt%. The results are summarized in Table 1.

2. Catalyst preparation 20.04 g of dry montmorillonite obtained from the chemical treatment of the above layered silicate, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared similarly to the catalyst preparation of Example 1 except that 245 mg (301.4 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.16 g / g. The amount of Hf complex supported per solid catalyst amount of this catalyst was 11.5 μmol. The average particle size was 28.3 μm.

[Example 4]
1. Chemical treatment of layered silicate Into a 2 L separable flask equipped with a stirring blade and a reflux apparatus, 855 g of pure water was added and 253 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 75 ° C., and when the target temperature was reached, further commercially available granulated montmorillonite (structural formula Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm) , Composition (wt%): Al = 8.87, Si = 33.66) was added and stirred. At this time, the acid concentration was 19.3 wt%, and the acid concentration relative to the clay was 16.5 mmol / g. Thereafter, the mixture was reacted for 480 minutes while maintaining 75 ° C. The reaction was stopped by emptying the reaction solution in 0.7 L of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed three times with 1.5 L of pure water. did.
The recovered cake was dried at 120 ° C. overnight and then weighed 107 g and used in the next step. This clay was added to an aqueous solution in which 116 g of lithium sulfate hydrate was dissolved in 526 mL of pure water in a 1 L plastic beaker and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 1 L of pure water three times.

The collected cake was dried at 120 ° C. overnight. As a result, 105.3 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an opening of 53 μm, the amount passing through the sieve was 103 g, which was 97.8% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.8 μm.
The composition (wt%) of the obtained chemically treated montmorillonite contained 7.53 Al and 37.03 Si, and the molar ratio of Al to Si was 0.212. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000328 min- ¹ .
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of this dried montmorillonite was measured, the moisture value was 0.92 wt%. The results are summarized in Table 1.

2. Catalyst Preparation 20.05 g of dry montmorillonite obtained from the chemical treatment of the above layered silicate, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared similarly to the catalyst preparation of Example 1 except that 250 mg (307.5 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.16 g / g. The amount of Hf complex supported per amount of the solid catalyst of this catalyst was 14.3 μmol. The average particle size was 27.7 μm.

[Example 5]
1. Chemical treatment of layered silicate Into a 2 L separable flask equipped with a stirring blade and a reflux apparatus, 1132 g of pure water was added and 333 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 80 ° C., and when the target temperature was reached, further commercially available granulated montmorillonite (structural formula Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm) , Composition (wt%): Al = 9.11, Si = 32.91) was added and stirred. At this time, the acid concentration was 19.2 wt%, and the acid concentration with respect to the clay was 16.3 mmol / g. Then, it was made to react for 300 minutes, keeping 80 degreeC. The reaction was stopped by emptying the reaction solution in 1 L of pure water, and the slurry was filtered through a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed 3 times with 2 L of pure water.
The recovered cake was directly used in the next step. The recovered cake was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 481 mL of pure water in a 1 L plastic beaker, and reacted at room temperature for 2 hours. This slurry was filtered with a Nutsche and a suction bottle connected to an aspirator, and washed three times with 2 L of pure water.

The collected cake was dried at 120 ° C. overnight. As a result, 138.7 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an aperture of 53 μm, the sieve passage was 132.6 g, which was 96.8% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.6 μm.
The composition (wt%) of the obtained chemically treated montmorillonite contained 6.71 Al and 38.01 Si, and the molar ratio of Al to Si was 0.184. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000480 min- ¹ .
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of this dried montmorillonite was measured, the moisture value was 1.09 wt%. The results are summarized in Table 1.

2. Catalyst preparation Dry montmorillonite 20.03 g of dry montmorillonite obtained from chemical treatment of layered silicate, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared in the same manner as the catalyst preparation of Example 1 except that 242 mg (297.7 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.15 g / g. The amount of Hf complex supported per amount of the solid catalyst of this catalyst was 11.7 μmol. The average particle size was 27.5 μm.

[Comparative Example 1]
1. Chemical treatment of layered silicate Into a 3 L separable flask equipped with a stirring blade and a reflux apparatus, 2264 g of pure water was added and 670 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 90 ° C., and when the target temperature was reached, further commercially available granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm) , Composition (wt%): Al = 9.11, Si = 32.91) was added and stirred. At this time, the acid concentration was 19.7 wt%, and the acid concentration relative to the clay was 16.4 mmol / g. Then, it was made to react for 300 minutes, keeping 90 degreeC. The reaction was stopped by emptying the reaction solution in 2 L of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed with 4 L of pure water three times.
The recovered cake was dried at 120 ° C. overnight and then weighed 100 g and used in the next step. The recovered cake was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 481 mL of pure water in a 1 L plastic beaker, and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed three times with 3 L of pure water.

The collected cake was dried at 120 ° C. overnight. As a result, 73.3 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an aperture of 53 μm, the sieve passage was 72.3 g, which was 98.7% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.1 μm.
The composition (wt%) of the obtained chemically treated montmorillonite contained 6.16 Al and 39.15 Si, and the molar ratio of Al to Si was 0.164. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000707 min− ¹ (see FIGS. 1 and 2).
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of this dried montmorillonite was measured, the moisture value was 0.96 wt%. The results are summarized in Table 1.

2. Catalyst Preparation 19.99 g of dried montmorillonite obtained from the chemical treatment of the above layered silicate, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared similarly to the catalyst preparation of Example 1 except that 244 mg (300.1 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.16 g / g. The amount of Hf complex supported per amount of solid catalyst of this catalyst was 12.3 μmol. The average particle size was 29.1 μm.

[Comparative Example 2]
1. Chemical treatment of layered silicate Into a 3 L separable flask equipped with a stirring blade and a reflux apparatus, 2264 g of pure water was added and 667 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 90 ° C., and when the target temperature was reached, further commercially available granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm) , Composition (wt%): Al = 9.11, Si = 32.91) was added and stirred. At this time, the acid concentration was 19.6 wt%, and the acid concentration relative to the clay was 16.3 mmol / g. Thereafter, the reaction was carried out for 120 minutes while maintaining 90 ° C. The reaction was stopped by emptying the reaction solution in 2 L of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed with 4 L of pure water three times.
The recovered cake was dried at 120 ° C. overnight and then weighed 100 g and used in the next step. The recovered cake was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 481 mL of pure water in a 1 L plastic beaker, and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed three times with 3 L of pure water.

The collected cake was dried at 120 ° C. overnight. As a result, 79.9 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an aperture of 53 μm, the sieve passage was 79.6 g, which was 99.6% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.7 μm.
As for the composition (wt%) of the obtained chemically treated montmorillonite, Al was 7.63 and Si was 37.38, and the molar ratio of Al to Si was 0.213. The maximum desorption rate of aluminum during the acid treatment step of the layered silicate was 0.000712 min- ¹ .
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of the dried montmorillonite was measured, the moisture value was 1.10 wt%. The results are summarized in Table 1.

2. Catalyst preparation Dry montmorillonite 20.02 g obtained from chemical treatment of layered silicate, (r)-[1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared similarly to the catalyst preparation of Example 1 except that 245 mg (301.7 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.13 g / g. The amount of Hf complex supported per amount of the solid catalyst of this catalyst was 11.3 μmol. The average particle size was 27.5 μm.

[Comparative Example 3]
1. Chemical treatment of layered silicate Into a 3 L separable flask equipped with a stirring blade and a reflux apparatus, 2264 g of pure water was added and 667 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 90 ° C., and when the target temperature was reached, further commercially available granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm) , Composition (wt%): Al = 9.11, Si = 32.91) was added and stirred. At this time, the acid concentration was 19.6 wt%, and the acid concentration relative to the clay was 16.3 mmol / g. Thereafter, the reaction was carried out for 120 minutes while maintaining 90 ° C. The reaction was stopped by emptying the reaction solution in 2 L of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed with 4 L of pure water three times.
The recovered cake was dried at 120 ° C. overnight and then weighed 100 g and used in the next step. The recovered cake was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 483 mL of pure water in a 1 L plastic beaker, and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed three times with 3 L of pure water.

The collected cake was dried at 120 ° C. overnight. As a result, 75 g of chemically treated montmorillonite was obtained. When this was sieved with a sieve having an aperture of 53 μm, the sieve passage was 73.9 g, which was 98.5% of the total weight. When these average particle diameters were measured by a laser diffraction / scattering method, the average particle diameter was 17.6 μm.
As for the composition (wt%) of the obtained chemically treated montmorillonite, Al was 7.14, Si was 38.12, and the molar ratio of Al to Si was 0.195. The maximum aluminum desorption rate during the acid treatment step of the layered silicate was 0.000663 min- ¹ .
The total amount of the chemically treated montmorillonite thus obtained was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after the bumping had subsided). When the moisture content of this dried montmorillonite was measured, the moisture value was 1.02 wt%. The results are summarized in Table 1.

2. Catalyst Preparation 20.05 g of dry montmorillonite obtained from the chemical treatment of the above layered silicate, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -Azulenyl}] Prepared similarly to the catalyst preparation of Example 1 except that 244 mg (300.1 μmol) of hafnium dichloride was used.
The prepolymerization rate was 2.18 g / g. The amount of Hf complex supported per amount of solid catalyst of this catalyst was 12.5 μmol. The average particle size was 29.6 μm.

[Production Example 1]
(Ethylene-propylene polymerization)
After fully replacing the inside of the autoclave with a stirrer with a volume of 3 L with propylene, 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) is added, 50 mL of hydrogen in a standard state, 12 g of ethylene, and then liquid propylene 750 g was introduced and the temperature was raised to 70 ° C.
The prepolymerized catalyst obtained from Example 1 was slurried in heptane, and 15 mg (the amount of the net solid catalyst excluding the prepolymerized polymer; the same applies hereinafter) as a solid catalyst was injected together with 1 mL of heptane, and the catalyst feed line was further added with 5 mL of heptane. And the polymerization was started.
The temperature inside the tank was maintained at 70 ° C. for 60 minutes after the catalyst was charged. Thereafter, 5 mL of ethanol was injected to stop the polymerization. The polymerization results are summarized in Table 2.

[Production Example 2]
(Ethylene-propylene polymerization)
Polymerization was carried out in the same manner as in the ethylene-propylene polymerization in Production Example 1 except that the catalyst used was 10 mg and hydrogen was 100 mL. The polymerization results are summarized in Table 2.

[Production Example 3]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Example 2 was used. The polymerization results are summarized in Table 2.

[Production Example 4]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as in the ethylene-propylene polymerization of Production Example 3 except that the catalyst used was 10 mg and hydrogen was 100 mL. The polymerization results are summarized in Table 2.

[Production Example 5]
1. Ethylene-propylene polymerization The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Example 3 was used. The polymerization results are summarized in Table 2.

[Production Example 6]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as in the ethylene-propylene polymerization of Production Example 5 except that the catalyst used was 10 mg and hydrogen was 100 mL. The polymerization results are summarized in Table 2.

[Production Example 7]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Example 4 was used. The polymerization results are summarized in Table 2.

[Production Example 8]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 7 except that the catalyst used was 10 mg and hydrogen was 100 mL. The polymerization results are summarized in Table 2.

[Production Example 9]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Example 5 was used. The polymerization results are summarized in Table 2.

[Production Example 10]
(Ethylene-propylene polymerization)
Polymerization was carried out in the same manner as in the ethylene-propylene polymerization of Production Example 9, except that the catalyst used was 10 mg and hydrogen was 100 mL. The polymerization results are summarized in Table 2.

[Production Example 11]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Comparative Example 1 was used. The polymerization results are summarized in Table 2.

[Production Example 12]
1. Ethylene-propylene polymerization Polymerization was carried out in the same manner as ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Comparative Example 2 was used. The polymerization results are summarized in Table 2.

[Production Example 13]
(Ethylene-propylene polymerization)
The polymerization was carried out in the same manner as the ethylene-propylene polymerization in Production Example 1 except that the catalyst prepared in Comparative Example 3 was used. The polymerization results are summarized in Table 2.

  As apparent from Tables 1 and 2, when Examples 1 to 5 and Comparative Examples 1 to 3 and Production Examples 1 to 10 and Production Examples 11 to 13 using these catalysts are compared, the present invention (Example 1) It can be seen that the catalyst using the layered silicate particles obtained by the method for producing the layered silicate particles of (5) to (5) is superior in catalytic activity as compared with the catalyst of the comparative example.

  The layered silicate particles obtained by the method for producing layered silicate particles of the present invention, and the olefin polymerization catalyst using the same, the polymerization proceeds with high activity, and the resulting polymer powder has a high bulk density, Polyolefins with good particle shape can be produced, and the industrial applicability is high.

Claims (4)

A method for producing layered silicate particles, wherein when a layered silicate is treated with acids, the maximum desorption rate of cations desorbed by an acid is 0.0005 min- ¹ or less.   The method for producing layered silicate particles according to claim 1, wherein the layered silicate has a 2: 1 type structure.   The method for producing layered silicate particles according to claim 1, wherein the layered silicate is a smectite group, and the cation desorbed by an acid is an aluminum ion.   Olefin polymerization characterized by using a transition metal compound, a compound that activates the transition metal compound, and layered silicate particles obtained from the method for producing layered silicate particles according to any one of claims 1 to 4 For producing a catalyst for use.

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