JP6187350B2 - Method for producing layered silicate, method for producing catalyst component for olefin polymerization, and method for producing catalyst for olefin polymerization - Google Patents

Description

  The present invention relates to a method for producing a layered silicate, a catalyst component for olefin polymerization containing a layered silicate, and a catalyst for olefin polymerization. More specifically, the present invention promotes an ion exchange reaction between a proton and a metal cation of an ion-exchangeable layered silicate. Furthermore, the present invention relates to a method for producing a layered silicate capable of improving the efficiency of the subsequent treatment, a catalyst component for olefin polymerization and a catalyst for olefin polymerization containing the layered silicate obtained by the production method.

Ion exchange layered silicate is used as a catalyst carrier, a catalyst component for olefin polymerization, and the like.
Techniques for chemically treating ion-exchange layered silicates with acids, salts, bases, etc. are known (see, for example, Patent Documents 1 to 3). Further, a technique using an ion-exchange layered silicate in contact with a water-soluble salt or a salt soluble in an acidic aqueous solution as an olefin polymerization catalyst component is also known (see, for example, Patent Document 4). As a salt, a compound comprising a cation of a transition metal atom of Groups 4 to 6 of the periodic table and a anion of a halogen atom, an inorganic acid, or an organic acid is disclosed, and an acidic aqueous solution indicates a pH of 6 or less. Yes. Furthermore, it is also known to replace the exchangeable ions between the layers with other ions using the ion exchange properties of the ion-exchange layered silicate (see, for example, Patent Documents 5 and 6). About the ion-exchange layered silicate which is not yet processed, ion exchange is performed using a compound composed of a cation containing a group 1 to 14 atom of the periodic table and a halogen atom, an anion derived from an inorganic acid or an organic acid. Technology is disclosed.

In addition, as a technology related to chemical treatment of ion-exchange layered silicate, after treating ion-exchange layered silicate with acids, using a solvent and reducing the washing rate to 1/1000 or less, treatment with salts There is a method of ion exchange between exchangeable ions of ion-exchangeable layered silicate and ions of salts (for example, see Patent Document 7). According to this method, a cleaning process is required, and the cleaning rate must be 1/1000 or less, and a large amount of cleaning waste liquid is generated, which is an environmental burden. Further, this cleaning process takes time, production efficiency is reduced, and cost is also increased. Furthermore, the ion exchange rate (%, 100 × amount of exchanged metal cation mol × the valence of ion ÷ amount of layer charge mol) is high, but the ion conversion rate (%, 100 × of exchanged metal cation) The amount mol ÷ the amount of metal cation used mol) is a very low and inefficient method.
As described above, many methods for producing chemically treated ion-exchanged layered silicates that exhibit high activity when used as a catalyst component for olefin polymerization have been studied so far. In the future, many issues still remain regarding environmental impact and production efficiency.

Japanese Patent Laid-Open No. 7-309907 JP-A-8-127613 JP 2002-060412 A JP-A-9-194517 Japanese Patent Laid-Open No. 10-226712 JP-A-10-265518 JP 2003-020304 A

The object of the present invention is to save energy and achieve high production efficiency in light of the situation and problems of the prior art described above, and to reduce the environmental load. High ion conversion rate (%, 100 × amount of exchanged metal cations mol ÷ An object of the present invention is to provide a method for producing a chemically treated layered silicate having an amount of metal cation (mol) used, a catalyst component for olefin polymerization and a catalyst for olefin polymerization containing the layered silicate obtained by the method.
In the present specification, as described in paragraph [0041], which will be described later, hereinafter, both the ion conversion rate and the ion exchange rate are expressed as percentages and are defined as the following equations.
Ion conversion rate (%): 100 x amount of exchanged metal cation mol ÷ amount of metal cation used mol
Ion exchange rate (%): 100 x amount of exchanged metal cation mol x valence of ion ÷ amount of layer charge mol)

There are still unclear points regarding the reaction conditions for exchanging protons of ion-exchanged layered silicates with protons in the interlayer ions into metal cations, and the ion conversion rate (%) of the layered silicates produced therefrom. There was much room for study on the development of a method for producing a layered silicate that is more efficient and environmentally friendly.
Therefore, as a result of intensive studies to achieve the above object, the present inventors have obtained a layered silicate with a high ion conversion rate (%) by a specific production method. Also, it can be produced cleanly with respect to the environment, and when the layered silicate thus produced is used as a catalyst component for olefin polymerization, it has been found that polymerization proceeds with high activity. More specifically, the present inventors have obtained a layered silicate obtained by adding a base to an ion-exchangeable layered silicate having a proton in an interlayer ion and exchanging in a specific pH range. It has been found that the ion conversion rate (%) of the is significantly improved. The present invention has been completed based on these findings.

That is, according to the first invention of the present invention, a step (step C) of bringing an ion-exchange layered silicate having protons (H ⁺ ) as interlayer ions into contact with a base (step C), an ion-exchange layered silicate A method for producing a layered silicate comprising a step of ion-exchanging protons and metal cations (step D),
The ion exchange step (step D) is performed under an ion-exchange layered silicate slurry whose pH does not exceed 7.32 throughout the process, and at the end of the step, the pH of the slurry is 4. The manufacturing method of the layered silicate characterized by being 5-7.32 is provided.

According to a second aspect of the present invention, there is provided a method for producing a layered silicate characterized in that, in the first aspect, the step C is performed simultaneously with the step D or before the step D.
According to the third invention of the present invention, the layered silicate according to the first or second invention further comprises a step (step A) of bringing the ion-exchange layered silicate into contact with an acid. A manufacturing method is provided.
Furthermore, according to the fourth invention of the present invention, there is provided a method for producing a layered silicate characterized in that, in the third invention, step A is performed prior to step C.

According to a fifth aspect of the present invention, in the third or fourth aspect, the method further includes a step (step B) of washing the ion-exchange layered silicate with a solvent, wherein the washing has a washing magnification of 1/1000. The manufacturing method of the layered silicate characterized by performing above is provided.
Moreover, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the ion-exchangeable layered silicate in the step C constitutes an octahedral sheet of ion-exchangeable layered silicate. There is provided a method for producing a layered silicate, wherein 10 to 80 mol% of a metal is eluted.
Furthermore, according to a seventh invention of the present invention, in any one of the first to sixth inventions, the bases are selected from the group consisting of alkali metals, alkaline earth metals and metals of Groups 3 to 14 of the periodic table. Provided is a method for producing a layered silicate, which is an oxide, hydroxide, carbonate or hydrogen carbonate, amine, phenol, or ammonia of a selected metal.

According to an eighth invention of the present invention, in any one of the first to seventh inventions, the base is selected from the group consisting of alkali metals, alkaline earth metals, and metals of Groups 3 to 14 of the periodic table. Provided is a method for producing a layered silicate, which is a hydroxide of a selected metal.
Furthermore, according to the ninth invention of the present invention, in any one of the first to eighth inventions, the metal cation of step D is an alkali metal, an alkaline earth metal and a metal of Groups 3 to 14 of the periodic table. There is provided a method for producing a layered silicate, which is a metal cation selected from the group consisting of:

According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the metal cation in step D is the same kind as the metal cation generated from the bases. A method for producing a layered silicate is provided.
Furthermore, according to the eleventh aspect of the present invention, in any one of the first to tenth aspects, the layered silicic acid is characterized in that the metal cation in step D is a metal cation generated from the bases. A method for producing a salt is provided.

  According to the twelfth aspect of the present invention, in any one of the first to eleventh aspects, in the ion-exchange layered silicate of step C, the main metal element constituting the octahedral sheet is aluminum. A method for producing a layered silicate is provided.

According to a thirteenth aspect of the present invention, there is provided the production of a catalyst component for olefin polymerization characterized by using a layered silicate obtained by the method for producing a layered silicate according to any one of the first to twelfth aspects. A method is provided.
Furthermore, according to the fourteenth aspect of the present invention, for olefin polymerization, the following component (a), component (b), and component (c) and / or component (d) used as necessary are brought into contact with each other . A method for producing a catalyst is provided.
Component (a): Metallocene compound Component (b): Catalyst component for olefin polymerization obtained by the production method of the thirteenth invention Component (c): Organoaluminum compound Component (d): C2-C20 olefin

  According to the method for producing a layered silicate of the present invention, the amount of a treating agent such as bases to be used can be reduced, and further, the amount of waste liquid discharged can be reduced, and by-products and reaction residues contained in the waste liquid can be reduced. Since the concentration can be increased, the load on the environment can be reduced. When the layered silicate produced in this way is used as a catalyst component for olefin polymerization, olefin polymerization proceeds with high activity, and as a result, an olefin (co) polymer can be produced with high activity.

FIG. 1 is a graph in which the ion conversion rate (%) of the obtained layered silicate is plotted against the pH of the slurry at the end of Step D in Examples (Examples / Comparative Examples).

Hereinafter, the present invention will be described in detail.
I. Method for producing layered silicate About ion exchange layered silicate In this invention, the ion exchange layered silicate which has a proton (H ^<+> ) as an interlayer ion is used as an ion exchange layered silicate of a raw material.
The ion-exchange layered silicate having protons in the interlayer ions may be natural or produced by subjecting the ion-exchange layered silicate to chemical treatment. As a natural thing, as is well-known, there is what is called acid clay or simply clay. On the other hand, as a product produced by chemical treatment, the white clay described above, activated white clay activated by sulfuric acid, and ion-exchanged layered silicate that has not been whitened with acids such as inorganic acids and organic acids are used. Treated ion exchange layered silicates.
In this invention, it is preferable that it is an ion exchange layered silicate manufactured by the chemical process which processes an ion exchange layered silicate with acids.

The ion-exchangeable layered silicate used in the present invention before chemical treatment may be a natural product or an artificially synthesized product. The ion exchange layered silicate before chemical treatment is preferably one having exchangeable ions between layers. Specific examples of the ion-exchange layered silicate include, for example, the following ones described in “Clay Handbook 3rd Edition” (written by the Japan Clay Society, Technical Hall Publishing Co., Ltd., 2009). .
2: 1 layer is the main constituent layer, smectite silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculite silicate such as vermiculite, mica, illite, sericite, sea Mica silicates such as chlorite, attapulgite, sepiolite, palygorskite, chlorite group, etc.

These may form a mixed layer. Many ion-exchange layered silicates are naturally produced as the main component of clay minerals, and therefore often contain impurities (such as quartz and cristobalite). You can leave.
The ion-exchange layered silicate according to the present invention is preferably an ion-exchange layered silicate having a 2: 1 type structure as described above. More preferred is a smectite silicate, and still more preferred is montmorillonite.

Next, each process of the manufacturing method of the layered silicate of this invention is demonstrated in detail.
2. Process A
In the method for producing a layered silicate of the present invention, as step A, a step of bringing an ion-exchangeable layered silicate into contact with an acid may be included. By performing this step A, the ion-exchange layered silicate can be converted into an ion-exchange layered silicate having protons in interlayer ions. In addition, contacting the ion-exchange layered silicate with the acid may be treating the ion-exchange layered silicate with an acid (sometimes referred to as chemical treatment).
The ion-exchange layered silicate having protons in the interlayer ions may be a natural product or a product obtained by chemical treatment.
As a method of producing a product obtained by chemical treatment, there is a method of treating with an acid such as an inorganic acid or an organic acid. A phenomenon and processing conditions will be described in detail with respect to a method of treating an ion-exchange layered silicate with acids.

When an ion-exchangeable layered silicate having exchangeable ions as interlayer ions is treated with acids, not only impurities on the surface are removed, but also exchangeable cations (interlayer ions) are eluted and protons are removed. Exchange with (H ⁺ ) occurs, and then the metal constituting the octahedral sheet elutes. By such chemical treatment, an ion-exchange layered silicate having protons in interlayer ions is generated.
In this elution process, characteristics such as acid point, pore structure, specific surface area and the like change (reference: “Clay Handbook 3rd Edition”, page 236, issued April 30, 2009, refer to Gihodo Publishing Co., Ltd.) . At this time, the amount of protons exchanged with the interlayer ions is equal to the amount of layer charges derived from the isomorphous substitution of the chemically treated ion-exchange layered silicate because of the formation of interlayer ions described later.

  The degree of elution of the metal constituting the octahedral sheet varies depending on the type of acid, the concentration of acids, the treatment time, etc., but the main metal of the octahedral sheet is generally large in magnesium and then in iron. In order of the most aluminium. In addition, the higher the degree of crystallinity and the larger the particle, the lower the degree of elution, which is considered to be related to the intrusion of acids into the crystal layer or crystal structure.

Next, the contact method etc. are demonstrated.
The contact between the ion-exchange layered silicate and the acid is preferably performed under an ion-exchange layered silicate slurry. Examples of the solvent for slurrying include organic solvents such as water and alcohol.
If the acid itself is liquid, the acid itself may be a solvent.
As the acid concentration, the acid concentration of the slurry is expressed in weight% [weight of acid used / (total of the weight of ion-exchange layered silicate used and the weight of the solvent, acid, other reagents used, etc.) ,%], The lower limit is preferably 3 wt%, more preferably 5 wt%, and even more preferably 7 wt%. On the other hand, the upper limit of the concentration is preferably 45 wt%, more preferably 40 wt%, still more preferably 35 wt%, still more preferably 30 wt%, and particularly preferably 25 wt%.
Further, the lower limit of the treatment temperature is preferably 40 ° C, more preferably 50 ° C, and further preferably 60 ° C. The upper limit of the treatment temperature is preferably 102 ° C, more preferably 100 ° C, and still more preferably 95 ° C. When the temperature is lowered too much, the elution rate of the cation is extremely lowered, and the production efficiency may be lowered. On the other hand, if the temperature is raised too much, operational safety may be reduced.
In addition, the lower limit of the concentration of the ion-exchange layered silicate [weight of ion-exchange layered silicate / (weight of ion-exchange layered silicate + total amount of reagents, solvents, etc.),%] is preferably Is 3 wt%, more preferably 5 wt%. On the other hand, the upper limit of the concentration of the ion-exchange layered silicate is preferably 30 wt%, more preferably 25 wt%, still more preferably 20 wt%. If the concentration is low, a large facility may be required for industrial production. On the other hand, when the concentration is high, the viscosity of the slurry increases, and uniform stirring and mixing becomes difficult, and the production efficiency may also decrease.
Furthermore, the treatment time is not particularly limited, but is determined by the above-described metal elution amount and treatment conditions (the above-mentioned acid concentration, treatment temperature, ion-exchange layered silicate slurry concentration). It is preferable to set the time for a preferable elution amount.

The chemical treatment with acids can be performed in multiple steps.
Examples of acids to be used include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propionic acid, fumaric acid, maleic acid, and phthalic acid. Among these, inorganic acids are preferable, and hydrochloric acid, nitric acid, and sulfuric acid are more preferable. More preferred are hydrochloric acid and sulfuric acid, and particularly preferred is sulfuric acid.

The ion-exchangeable layered silicate having protons in the interlayer ions used in the present invention is preferably an ion-exchangeable layered silicate in which the metal of the octahedral sheet is eluted by such chemical treatment.
In the chemical treatment, particularly the treatment with the above-described acids, the lower limit of the elution amount of the main metal constituting the octahedral sheet is preferably 10%, more preferably 15% with respect to the content before the chemical treatment, More preferably, it is 20%, More preferably, it is 25%. On the other hand, the upper limit of the main metal elution amount is preferably 80%, more preferably 75%, still more preferably 65%, still more preferably 60%, particularly preferably 55%, most preferably 50%. It is. The main metal constituting the octahedron eluting here includes aluminum, magnesium, iron and the like, preferably aluminum.
The elution amount of the main metal is calculated from the molar ratio as follows. For example, when the main metal is aluminum, it is expressed by the following formula.
[Aluminum / Si (Molar ratio) before chemical treatment−Aluminum / Si (Molar ratio) after chemical treatment] ÷ Aluminum / Si (Molar ratio) before chemical treatment × 100%
The treatment time with acids is determined by the settings of the acid concentration, treatment temperature and main metal elution amount, and any time is selected.

3. Process B
In the method for producing a layered silicate of the present invention, the cleaning step B may be performed while the step A to the step C are performed.
In the conventional technique, after the chemical treatment with the above-described acids, the reactants or unreacted substances remain in the slurry. Therefore, it is preferable to wash with a solvent such as water. Is not essential and may or may not be cleaned.
Cleaning with a cleaning magnification of 1/1000 or less may be performed, and cleaning exceeding 1/1000 may be performed. The washing magnification means “(amount of acids before dilution + amount of diluent−amount of diluent removed) ÷ (amount of acids before dilution + amount of diluent)”, for example, before dilution. The amount of the acid is 1, and as a washing operation, 99 diluent (solvent) is added and diluted uniformly, and then the diluted solution of 99 is removed, so that the washing magnification is 1/100. .

  In the cleaning from the chemical treatment with acids in step A to the next step, the upper limit of the amount of the cleaning solvent used is preferably 20 mL / g with respect to 1 g of ion-exchangeable layered silicate, for example. Preferably it is 17.5 mL / g, More preferably, it is 10 mL / g, More preferably, it is 7.5 mL / g. On the other hand, the lower limit is preferably 1 mL / g.

  In the case of performing ion exchange in Step D, which will be described later, without washing in Step B, the amount of bases added to bring the pH of the slurry to a predetermined range increases, resulting in an ion conversion rate (% The lower limit of the pH of the ion-exchanged layered silicate slurry chemically treated with acids is preferably pH 0.7 when the slurry concentration is adjusted to 17 wt%, More preferably, it is pH 0.9, More preferably, it is pH 1. On the other hand, the upper limit is preferably pH 3, more preferably pH 2.5, and still more preferably pH 2.

  There are a method of removing the supernatant by decantation after standing for a certain period of time, a method of forced filtration with an aspirator or a vacuum pump using a Nutsche or a filter bottle, and the latter is preferred.

Further, after step A or step B, drying may be performed. Drying is preferably performed so as not to cause structural destruction of the ion-exchange layered silicate, and even if the structure is not destroyed, the characteristics change depending on the drying temperature. It is preferable.
Generally, drying temperature can be implemented at 100-800 degreeC, Preferably it is 150-600 degreeC, More preferably, it is 150-300 degreeC. The drying temperature is preferably 800 ° C. or lower so that the structural breakdown of the ion-exchange layered silicate does not occur.
The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours. The drying 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). Process C
In the method for producing a layered silicate of the present invention, step C is a step of bringing an ion-exchangeable layered silicate having protons as interlayer ions into contact with a base.
First, the interlayer ion of ions in the ion-exchange layered silicate (ion incorporated between the layers) originates from the following silicate structure (Reference: “Clay Mineralogy” Asakura (See Bookstore, February 1, 2003, 8th edition, Chapter 2, 2 and Chapter 1.)
Broad silicate mineral containing also ion-exchange layered silicate, metal cations O ^2- or OH ^- octahedral sheets can be coordinated, and silicon ions (Si ⁴⁺⁾ to O ^2- or OH It is composed of a tetrahedral sheet formed by coordination of ⁻ . Among the ion-exchange layered silicates, in the case of the 2: 1 type structure, the unit silicate layer is constituted by a structure in which two tetrahedral sheets sandwich both sides of one octahedral sheet.

In the 2: 1 type structure, when the tetrahedral sheet is only Si and the metal of the octahedral sheet is only Al (trivalent) or Mg (divalent), it is electrically neutral. However, while the number of coordinated O ²⁻ or OH ⁻ is not changed, the tetrahedral sheet Si and the octahedral sheet metal are generally replaced with metals having different valences of ions. This is referred to as isomorphous substitution (see: Reference: Gihodo Publishing Co., Ltd. “Clay Handbook (Third Edition)” P124).
By this isomorphous replacement, excess or deficiency of charge occurs in the sheet, and the entire layer in which the octahedron sheet is sandwiched by the tetrahedron sheet is charged with plus or minus charge (layer charge). In order to electrically neutralize this layer charge, ions (interlayer ions) having a charge opposite to the layer charge exist. That is, the interlayer ion refers to a cation or an anion that exists between the layers corresponding to the layer charge. The amount of charge of interlayer ions per unit weight is equal to the amount of layer charge per unit weight, and the amount of layer charge per unit weight is the valence of ions of the metal that is isomorphously substituted with the main metal constituting the sheet. It can be obtained by multiplying the difference in number by the amount of substitution per unit weight. For example, when isomorphous substitution occurs only in an octahedral sheet, the main metal constituting the sheet is aluminum, and magnesium is isomorphously substituted with 0.3 mmol for 1 g of ion-exchanged layered silicate. The amount of the layer charge is determined as (difference of valence of ions 1 (aluminum trivalent-magnesium divalent)) × 0.3 mmol = 0.3 mmol (relative to 1 g of ion-exchangeable layered silicate).

It is preferable that the interlayer ion of the ion-exchange layered silicate according to the present invention is a cation generated by isomorphous substitution of the octahedral sheet. The amount of interlayer ions depends on the raw material when untreated, but a chemical treatment that changes the structure of the ion-exchange silicate, for example, an operation to elute the isomorphous substituted metal together with the metal of the octahedral sheet. In some cases, it may be less than the raw material. For example, in the chemical treatment with acids, the metal that is isomorphously substituted with the metal of the octahedral sheet is also eluted. Therefore, the amount of interlayer ions of the ion-exchange layered silicate after being treated with acids is also affected by the degree of cation elution by the acid treatment.
However, the amount of interlayer ions (amount of layer charge) can be obtained from the above calculation by quantifying isomorphous substituted atoms by chemical analysis described later, regardless of whether or not the metal is eluted by treatment with acids. It is.
As the isomorphous substituted metal for generating the layer charge, when the main metal is aluminum, magnesium and iron are preferable, and magnesium is particularly preferable.
Moreover, when isomorphous substitution is carried out by a plurality of cations, the isomorphous substitution amount is the sum of them.

The ion-exchangeable layered silicate used in the present invention is preferably an ion-exchangeable layered silicate in which isomorphous substitution occurs in the octahedral sheet, and the main metal constituting the octahedral sheet is preferably aluminum. More preferably, aluminum is isomorphously substituted with magnesium.
As the isomorphous substitution rate, the lower limit of the abundance ratio relative to the main metal (for example, the abundance ratio when the main metal is aluminum and the isomorphous substitution metal is magnesium is determined by magnesium mol / aluminum mol) is preferably 0. .05, 0.07 is more preferable, 0.09 is more preferable, 0.10 is still more preferable, and 0.13 is particularly preferable. On the other hand, the upper limit of the isomorphous substitution rate is 1.00, preferably 0.90, more preferably 0.80, still more preferably 0.70, still more preferably 0.60, and particularly preferably 0.50.
Further, the lower limit of the amount of isomorphous substitution is preferably 0.05 mmol, more preferably 0.10 mmol, still more preferably 0.20 mmol, still more preferably 0.30 mmol, with respect to 1 g of ion-exchangeable layered silicate. .40 mmol is particularly preferred. On the other hand, the upper limit of the amount of isomorphous substitution is preferably 5.0 mmol, more preferably 4.0 mmol, still more preferably 3.0 mmol, even more preferably 2.5 mmol, with respect to 1 g of ion-exchangeable layered silicate. 0.0 mmol is particularly preferred and 1.5 mmol is most preferred.

Next, the contact between the ion-exchange layered silicate and the base is preferably performed under an ion-exchange layered silicate slurry. Examples of the solvent for slurrying include water, organic solvents such as alcohol, and the like, preferably alcohol and water, and more preferably water.
The bases are substances that show basicity or alkalinity, and are substances that function as Bronsted bases. Bases are substances having the property of generating water by reacting with protons (neutralization reaction), preferably selected from the group consisting of alkali metals, alkaline earth metals, and metals of Groups 3-14 of the periodic table Metal hydroxides, oxides, carbonates, hydrogen carbonates, salts of organic polymer ions and inorganic polymer ions, amines, phenols or ammonia. More preferred are metal hydroxides, oxides, carbonates, and hydrogen carbonates selected from alkali metals, alkaline earth metals, and metals of Groups 3 to 14 of the periodic table. More preferred are metal hydroxides and carbonates selected from alkali metals, alkaline earth metals, and metals of Groups 3 to 14 of the periodic table. Even more preferred is a metal hydroxide selected from alkali metals, alkaline earth metals, and metals of Groups 3 to 14 of the periodic table. Particularly preferred are alkali metals, alkaline earth metals, hydroxides or carbonates of Mn, Fe, Ni, Cu, Zn, Al, Sn, and Pb. Particularly preferred are hydroxides of alkali metals, alkaline earth metals, Mn, Fe, Ni, Cu, Zn, Al, Sn, and Pb. Most preferred are alkali metal, alkaline earth metal, Mg, Zn, and Al hydroxides.

Although not limited to the following, specific examples include LiOH, NaOH, KOH, CsOH, RbOH, Be (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) _2. , Mn (OH) ₂ , Cu (OH) ₂ , Cu (OH) ₃ , Zn (OH) ₂ , Al (OH) ₃ , Sn (OH) ₄ , Pb (OH) ₂ , Ni (OH) ₂ , 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 , NaHCO ₃ , RpHCO ₃ , CsHCO ₃ , Ca (HCO ₃ ) ₂ , Mg (HCO ₃ ) _2, and the like.

Further, the base to be used is preferably a base of the same kind of metal as the metal cation exchanged with the proton of the ion-exchangeable layered silicate in step D described later. Or it is more preferable that the metal cation exchanged with the proton of the ion-exchange layered silicate in step D described later is a metal cation generated from a base.
The bases may be used alone or in combination. There are no particular restrictions on the method of use.
The state of the bases when contacting with the ion-exchange layered silicate may be dissolved in a solvent or may be a solid. When dissolved in a solvent and brought into contact, the concentration is not limited, and the upper limit is not more than a saturated concentration, while the lower limit is not lower than the lower limit of the slurry concentration of the ion-exchange layered silicate slurry. The prepared concentration.
Moreover, the usage-amount of bases also depends on the pH of the ion-exchange layered silicate slurry before contact with the bases, and these bases are added. The amount of the pH is 4.5 to 8 when the pH is 8 or less and Step D is completed. For example, the lower limit is 0.1 mmol, preferably 0.25 mmol, more preferably 0.40 mmol, and more preferably relative to the amount of layer charge in 1 g of ion-exchange layered silicate. Is 0.50 mmol. On the other hand, as an upper limit, it is 2.5 mmol of the amount of layer charges of the ion-exchange layered silicate similarly to 1 g of ion-exchange layered silicate, preferably 2.0 mmol, more preferably 1. 9 mmol.

As a method of adding bases, a method of adding bases to an ion-exchangeable layered silicate slurry in a solid state, a method of adding bases to an ion-exchangeable layered silicate slurry after dissolving the bases in a solvent, powder or There is a method of adding a base solution to a solid ion-exchange layered silicate such as a cake. A method of adding the bases to the ion-exchangeable layered silicate slurry in a solid state and a method of adding the bases to the ion-exchangeable layered silicate slurry after dissolving the bases in a solvent are preferable.
The solvent for dissolving the bases is preferably the same as the ion-exchange layered silicate slurry, or water or alcohol, and particularly preferably water. The upper limit of the bases (OH) concentration is a saturated solution, and the lower limit is preferably 0.01 mol / L.

The step C is preferably performed simultaneously with the step D, which will be described later, or before the step D. When the step C is performed simultaneously with the step D, a base to be contacted during the step may be added. Further, when the process is performed before the process D, it may be performed simultaneously with the process D or in the middle of the process D.
However, in any case, the process D needs to be performed under an ion-exchange layered silicate slurry having a pH of 8 or less throughout the process and a pH of 4.5 to 8 at the end of the process.
In the step D described later, when the metal cation generated from the base is the same or the same, the amount of the base used is the sum of the metal cation, and the upper limit is 2 with respect to the amount of the interlayer ion. The amount is preferably 5 times or less, more preferably 2 times or less. On the other hand, the lower limit depends on the pH of the ion-exchange layered silicate slurry, but is preferably 0.1 times or more, more preferably 0.3 times or more, relative to the amount of interlayer ions. More preferably, it is 0.5 times or more, and particularly preferably 1 time or more.

5. Process D
Next, in the method for producing a layered silicate of the present invention, a step (Step D) of exchanging protons of an ion-exchangeable layered silicate having protons in interlayer ions with metal cations will be described.
The amount of interlayer ions corresponds to the amount of layer charge, and the amount of layer charge can be determined from the type of isomorphous substitution metal, the difference in valence of ions, and the amount thereof.
The type of metal substituted is the composition analysis by fluorescent X-rays, etc., and the type of ion-exchanged layered silicate (for example, vermiculite, smectite montmorillonite, saponite, and beidellite are the main metals that make up the sheet. And a metal having a different valence other than the main metal is an isomorphous substituted metal).
Further, the difference in valence of ions is the difference in valence with the main metal constituting the sheet (from the above type, silicon or aluminum), and the amount is the amount of isomorphous substitution and is determined by chemical analysis. be able to.

The analysis of the ion-exchange layered silicate is specifically shown in Part II Chapter 1 1-3 of “Clay Handbook 3rd edition” (issued on April 1, 2009) of the above reference. However, in the present invention, wet analysis or fluorescent X-ray analysis is used.
In addition, the structural formula can be determined by the method shown in P272-4 of the same book. From such a method, it is preferable to determine the amount of isomorphous substitution and the amount of layer charge to determine the amount of interlayer ions. . Furthermore, as another method for estimating the amount of interlayer ions, there is a method for obtaining by measuring a general ion exchange capacity (reference: “Clay Mineralogy” Asakura Shoten, February 1, 2003, 8th edition, (See Chapter 4, 9).

In the present invention, the ion exchange rate (%) represents the ratio of the exchanged metal cation to the charge necessary for neutralizing the layer charge, that is, the amount of interlayer ions (layer charge). Specifically, it refers to the percentage obtained by multiplying the amount (mol) of the exchanged metal cation by the valence of the ion and dividing by the amount (mol) of the layer charge.
Ion exchange rate (%): 100 x amount of exchanged metal cation mol x valence of ion ÷ amount of layer charge mol)
The step D is preferably a step of exchanging protons of 10 to 100% of interlayer ions with metal cations. More preferably, it is 20-100%, More preferably, it is 30-100%, Most preferably, it is 40-100%.
In the present invention, the ion conversion rate (%) indicates how much of the metal cation used is taken into the ion-exchange layered silicate, and the exchanged metal. It refers to the percentage obtained by dividing the amount of cation (mol) by the amount of metal cation used.
Ion conversion rate (%): 100 x amount of exchanged metal cation mol ÷ amount of metal cation used mol

Interlayer ions of untreated ion-exchange layered silicate have single or multiple alkali metal or alkaline earth metal cations such as sodium, magnesium, potassium, calcium, etc., but contacted with acids In the later ion-exchange layered silicate, the interlayer ions are replaced with protons of acids to form an ion-exchange layered silicate having protons between layers as described above.
Similarly, white clay and activated clay are ion-exchange layered silicates having protons between layers, and white clay is naturally occurring. Although it is known that the interlayer ions of such an ion-exchange layered silicate are exchanged with metal cations, in order to achieve a high ion exchange rate (%), the metal cations to be exchanged are made large excess. The ion conversion rate (%) was less than 10%.
Furthermore, in the known technique, when an ion exchange reaction is performed after treatment with acids, a washing operation with a solvent is performed in order to remove protons derived from the remaining acids and acid components generated by side reactions. This method requires a large amount of solvent and time for washing, and is not desirable in terms of economy and production efficiency. Also, protons chemically bonded such as hydrogen bonds are difficult to remove by these methods, and a large excess of metal cations is required to increase the ion exchange rate (%) even after washing. There was no change, and the ion conversion rate (%) could not be increased.

  In the present invention, at the time of ion exchange, a base is added to the slurry of the ion-exchangeable layered silicate as the above-mentioned Step C, and the ion-exchangeable layered silicate and the base are brought into contact with each other. By neutralizing protons in the layered silicate and making the concentration of protons in the slurry appropriate, the need to use excess exchange ions is reduced. As a result, it is considered that the ion conversion rate (%) can be greatly improved.

In the present invention, in the step D, it is preferable that the ion exchange layered silicate slurry does not exceed pH 8 throughout the step. In the present invention, the pH range is preferably pH 8 or less. When the pH exceeds 8, the ion-exchange layered silicate may undergo structural change due to progress of elution of silicon (Si) from silicic acid. Further, when the upper limit of pH 8 or higher, in addition to the ion exchange reaction with the interlayer, adsorption to the silicate surface also occurs, and when the ion exchange rate is calculated from the metal content, a phenomenon exceeding 100% occurs, which is not preferable. . Furthermore, when the upper limit pH is 8 or more, the sedimentation property is lowered, the filtration rate is slow, or the handling is worsened, so that the production time may be prolonged and the production efficiency may be lowered, which is not preferable. . For the above reasons, it is not preferable to exceed pH 8 at any point in the reaction. As a preferred range, the upper limit of the pH is 8, more preferably pH 7.5 or less, still more preferably pH 7.3 or less.
The pH of the slurry at this time is preferably 4.5-8.

Moreover, it is preferable that the pH of the ion exchange layered silicate slurry at the end of Step D is 4.5 or more. When it becomes lower than this, the ion conversion rate (%) is not improved. More preferably, the pH is 4.8 or more. On the other hand, the upper limit of the pH of the ion-exchange layered silicate slurry at the end of Step D is preferably pH 8.0 or less, more preferably pH 7.5 or less, and further preferably pH 7.3 or less.
Further, in the process D, the pH may be 4.5 or less during the process, and when the process is completed, the process D is performed under an ion-exchange silicate slurry having a pH of 4.5 to 8. It is more preferable to carry out the process from 5 minutes before the process is completed to the process is completed under an ion-exchange silicate slurry having a pH of 4.5 to 8, and the process is performed from 10 minutes before the process is completed. It is more preferable to carry out until completion of the treatment under an ion-exchangeable silicate slurry having a pH of 4.5 to 8, and from 30 minutes before the completion of the process to the completion of the process, the ion exchangeability of pH 4.5 to 8. It is more preferable to carry out under a silicate slurry, and it is even more preferred to carry out under an ion-exchange silicate slurry having a pH of 4.5 to 8 from 60 minutes before the completion of the process until the completion of the process. Further, the pH of the silicate slurry may be 4.5 to 8 throughout the process D. On the other hand, the pH of the ion-exchange silicate slurry at the end of the process needs to be 4.5-8.

  Here, the end of the step D refers to the end of the ion exchange reaction, and the silicate slurry is made into a cake or powder by separating the solvent and silicate from the slurry state. This is the time when the solid state is reached. The slurry state is a state in which silicate is suspended in a solvent and has fluidity, and the cake state is a state in which the silicate contains a solvent but does not have fluidity. Say. As an example, if the difference between the state of the slurry and the cake or powder is shown as the silicate concentration, the state in which the silicate concentration is 35 wt% or more is shown.

  The type of metal cation exchanged with proton is a metal cation selected from the group consisting of alkali metals and alkaline earth metals, metals of Groups 3 to 14 of the periodic table, and alkali metals and alkaline earth metals, manganese, Iron, nickel, copper, aluminum, zinc, tin and lead are preferred, more preferably alkali metal and alkaline earth metal, aluminum, zinc and tin, and further preferably lithium, sodium, potassium, magnesium, calcium and strontium , Zinc and tin, particularly preferably lithium, sodium, magnesium, calcium and zinc, and most preferably lithium, magnesium and zinc.

As specific treatment agents showing these, for example, LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, 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 ), MgCl ₂ , MgSO ₄ , Mg (NO ₃ ) ² , Mg ₃ (C ₆ H ₅ O ₇ ) ₂ , CaCl ₂ , CaSO ⁴ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , SrCl ₂ , SrSO ₄ , Sr (NO _{3) ) 2, Sr 3 (C 6} H 5 O 7) 2, NiCO 3, Ni (NO 3) 2, NiC 2 O 4, Ni (ClO 4) 2, NiSO 4, NiCl 2, NiB _{2, FeCl 3, Fe 2 (} SO 4) 3, Fe (NO 3) 3, Fe (C 6 H 5 O 7), CuCl 2, CuBr 2, Cu (NO 3) 2, CuC 2 O 4, Cu ( _{ClO 4) 2, CuSO 4,} Cu (OOCCH 3) 2, Zn (OOCH 3) 2, Zn (CH 3 COCHCOCH 3) 2, ZnCO 3, Zn (NO 3) 2, Zn (ClO 4) 2, Zn 3 (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , MgCl 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 , Sn (OOCCH ₃ ) ₄ , Sn (SO ₄ ) ₂ , SnF ₄ , SnCl _{4 and the} like.
These various treatment agents 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.

It is preferable to implement the process D in the slurry state which disperse | distributed the ion exchange layered silicate in the solvent. The solvent to be used is not particularly limited, such as water or an organic solvent, but is preferably alcohol or water, more preferably water.
Moreover, it is preferable that the density | concentration of an ion exchange layered silicate slurry is 3-30 wt%, 5-25 wt% is more preferable, 7-20 wt% is further more preferable.
Step D is preferably carried out at a temperature from 0 ° C. until the solvent is refluxed. The upper limit is preferably 100 ° C., more preferably 90 ° C., still more preferably 80 ° C., and even more preferably 70 ° C. is there. On the other hand, the lower limit of the preferable temperature is 5 ° C, more preferably 10 ° C, still more preferably 20 ° C, and still more preferably 30 ° C. If the temperature is low, energy consumption for temperature control may increase during industrial production, and conversely, if the temperature is raised too much, operational safety may decrease. It is preferable to carry out at an appropriate temperature as in the exemplified range.

  The reaction time is not particularly limited, but for example, it is preferably 5 minutes or longer, more preferably 10 minutes or longer, still more preferably 30 minutes or longer, particularly preferably 60 minutes or longer. On the other hand, the upper limit is not particularly limited, but in consideration of productivity, it is preferably within 48 hours, more preferably 24 hours or less, further preferably 12 hours or less, and particularly preferably 6 hours or less.

  For step D, the concentration of the metal cation is not particularly limited. For example, the lower limit is preferably 0.001 mmol / L or more, more preferably 0.01 mmol / g or more, and further 0.05 mmol / g or more. Preferably, 0.1 mmol / L or more is even more preferable. On the other hand, the upper limit is not particularly limited as long as the ion-exchange layered silicate can flow as a slurry.

As a known production method, an excessive amount of a metal cation is present in the reaction system, and there is a possibility that the economical efficiency is reduced and the generated waste liquid treatment may be a problem, and high exchange is achieved with a small amount. It is hoped that.
On the other hand, in the present invention, by setting the pH of the ion-exchangeable layered silicate slurry at the end of step D to 4.5 to 8, the amount of the treating agent can be greatly reduced as compared with the conventional method.
Moreover, as an upper limit of the quantity of the metal cation used for the process D, it is preferable that it is 2.5 times or less with respect to the quantity of interlayer ion (layer charge), More preferably, it is 2 times or less. It is. On the other hand, the lower limit depends on the pH of the ion-exchange layered silicate slurry, but is preferably 0.1 times or more with respect to the amount of interlayer ions (layer charge amount). Is 0.3 times or more, more preferably 0.5 times or more, and particularly preferably 1 time or more.

  Thus, the lower limit of the exchange rate (%) of the interlayer ions of the chemically treated layered silicate obtained through Step C and Step D or Steps A to D is 10%, preferably 20%, more preferably. Is 30%, more preferably 40%. On the other hand, the upper limit is preferably 100%. The lower limit of the ion conversion rate (%) is 40%, preferably 45%, more preferably 50%, and still more preferably 60%. On the other hand, the upper limit is preferably 100%.

Here, what kind of effect is produced by exchanging interlayer ions for different kinds of metal cations will be exemplified.
By substituting a cation having a lower cation than H ⁺ for an ion-exchange layered silicate having protons (H ⁺ ) as interlayer ions, for example, the layer charge balance of montmorillonite can be increased. Even if it is electrically neutralized and balanced, it gives subtle changes in properties due to ionic differences, and such a layered silicate is used as one of the catalyst components for olefin polymerization, for example, I think that it will improve the performance.

Moreover, it is preferable to wash | clean after completion | finish of the process D. There are no particular limitations on the cleaning method and conditions, but it is preferable to perform cleaning so that the cleaning magnification is 1/10 or less.
Solvents used for washing are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide, carbon disulfide, Examples thereof include nitrobenzene, pyridines and halides thereof. Preferably, the same type as that used as the solvent in Step B is preferable, and water, ethanol, and hydrocarbon are more preferable.

6). Drying In the method for producing a layered silicate of the present invention, washing and dehydration are performed after Step C and Step D, or Steps A to D, and thereafter, drying is preferably performed.
Drying is preferably performed so as not to cause structural destruction of the obtained layered silicate. In general, the drying temperature is 100 to 800 ° C., preferably 150 to 600 ° C., particularly preferably. Is preferably carried out at 150 to 300 ° C.
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 reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.

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. For the removal of water, heat treatment is usually used. The method is not particularly limited, but it is preferable to select conditions that do not cause adhesion water and interlayer water to remain and do not cause structural destruction.
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

7). Granulation The ion-exchangeable layered silicate or layered silicate can be granulated, and is preferably granulated and used in the granulated body.
The granulation method is not particularly limited, but preferred granulation production methods include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, flow Examples thereof include layer granulation method, emulsion granulation method, submerged granulation method, and compression molding granulation method. More preferably, spray drying granulation, spray cooling granulation, fluidized bed granulation, spouted bed granulation, submerged granulation, emulsification granulation, etc. are mentioned, and spray drying granulation and spray cooling granulation are particularly preferable. 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.
During spray granulation, the concentration of the ion-exchange layered silicate or layered silicate in the raw slurry liquid is 0.1 to 70% by weight, preferably 1 to 50% by weight, more preferably 4 to 45% by weight, More preferably, a spherical granule can be obtained by adjusting the content to 5 to 40% by weight. When the upper limit of the concentration is exceeded, spherical particles cannot be obtained, and when the concentration is lower than the lower limit of the concentration, the average particle size of the granule 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 various binders, such as organic substance and an inorganic salt, 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 and casein. , Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, sodium alginate and the like.
The shape of the ion-exchange layered silicate before granulation is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or by operations such as grinding, granulation, and classification. You may use what processed the shape.

  The granulated ion-exchange layered silicate or layered silicate has a particle size of 5 μm or more and 300 μm or less, and preferably spherical. More preferably, they are 5 micrometers or more and 250 micrometers or less, More preferably, they are 5 micrometers or more and 200 micrometers or less. If there are many fine particles of less than 5 μm, adhesion to the reactor is likely to occur, and depending on the aggregation of the polymers and the polymerization process, it may cause a short pass or a long-term residence, which is not preferable. Coarse particles having a size of 300 μm or more are not preferable because problems such as blockage tend to occur. In order to obtain an average particle diameter that satisfies these conditions, or when particles that are extremely small or large with respect to the average particle diameter are present, the particle diameter may be controlled by classification, classification, or the like.

II. Olefin Polymerization Catalyst The layered silicate obtained from the method for producing a layered silicate of the present invention is suitably used as an olefin polymerization catalyst component. Examples of the olefin polymerization catalyst generally include a Ziegler-Natta catalyst and a metallocene catalyst.
In the present invention, the catalyst for olefin polymerization can be preferably prepared by contacting the component (a), the component (b) and, if necessary, the component (c) and / or the component (d).
Component (a): Metallocene compound Component (b): Layered silicate produced by the above-described production method Component (c): Organoaluminum compound Component (d): C2-C20 olefin

1. Component (a): Metallocene Compound A preferred metallocene compound of Group 4 transition metal of the periodic table of component (a) used in the present invention is a metallocene compound having at least one conjugated five-membered ring ligand. Preferred as such 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 ′ 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 binding group that bridges Z with an arbitrary position of the conjugated five-membered ring ligand, M represents a metal atom selected from Group 4 of the periodic table, and X and Y are A hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group (in the same compound, X and X ′ may be the same or different).

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, and when there are a plurality of these, two of them are bonded at the other end (ω-end). A ring may be formed together with a part of cyclopentadienyl. As an example of the latter, two substituents are bonded to each other at the ω-end, and two adjacent carbon atoms in the cyclopentadienyl group are shared 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 azulenyl group or a tetrahydroazurenyl group.

  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. 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- Examples thereof include a boron-containing hydrocarbon group represented by B (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.
The position of the group 15 to 16 element on the ligand is not particularly limited, but is preferably on the 2-position substituent. 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

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. Preference is given to alkylene groups and silylene groups.

M represents a metal atom, and particularly represents a transition metal atom selected from Group 4 of the periodic table, and examples thereof include titanium, zirconium, hafnium, and the like. In particular, zirconium and hafnium are preferable.
Furthermore, 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, A nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a chlorine atom, a bromine atom, carbon It is a hydrocarbon group of number 1-20.

  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-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-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- (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 tert-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.

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

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.
In addition, a metallocene compound can 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 general formulas (1) to (4). It is also possible to select one or two or more selected from the group of compounds included in the above and one or two or more selected from the group of compounds included in other general formulas.
For example, it is a metallocene compound that forms a polymerization catalyst for producing an olefin macromer, and a metallocene compound that forms a polymerization catalyst for producing an olefin macromer is a terminal vinyl ratio when propylene homopolymerization is carried out at 70 ° C. A combined use of the metallocene compound (a-1) forming a propylene homopolymer satisfying 0.5 or more and the metallocene compound (a-2) represented by the general formula (4) can be given. The molar ratio (a-1) / (a-2) of the component (a-1) to the component (a-2) can be 1.0 to 99.0.

2. Component (c): Organoaluminum compound Component (c) is an organoaluminum compound.
As the organoaluminum compound used as the component (c) in the present invention, 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 atom, a hydrogen atom, an alkoxy group or an amino group, n represents an integer of 1 to 3, and m represents 1 or 2. Represent.
The organoaluminum compounds can be used alone or in combination.

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

3. Component (d): Olefin having 2 to 20 carbon atoms In the olefin polymerization catalyst according to the present invention, it is preferable that the olefin polymerization catalyst is preliminarily subjected to a prepolymerization treatment in which a small amount is polymerized by contacting the olefin.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use, and it is particularly preferable to use propylene.

As a method for supplying olefin during the prepolymerization, any method can be used, such as a method for supplying olefin to the reaction tank at a constant speed or a constant pressure, 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 g, more preferably 0.1 to 50 g, based on 1 g of the component (b).
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 further preferably 30 to 50 ° C. Below this range, there is a possibility that the reaction rate decreases or the activation reaction does not proceed. On the other hand, when it exceeds the above range, the prepolymerized polymer dissolves or the prepolymerization rate is too high, and the particle properties May be adversely affected or the active site may be deactivated due to side reactions.

The preliminary polymerization can be carried out in a liquid such as an organic solvent, and this is preferable. Although there is no restriction | limiting in particular in the density | concentration of the catalyst at the time of prepolymerization, Preferably it is 30 g / L or more, More preferably, it is 40 g / L or more, Most preferably, it is 45 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

  The catalyst after the prepolymerization may be used as it is or may be dried. The drying method is not particularly limited, and examples include drying under reduced pressure, drying by heating, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. It may be used. In the drying step, the catalyst may be stirred, vibrated or fluidized, or may be allowed to stand.

4). Preparation of Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises a component (a), a component (b) and, if necessary, a component (c), and then a component (d) if necessary. Contact to make a catalyst.
Although the contact method of the components (a), (b), and (c) is not particularly limited, they can be contacted in the following order. This contact may be performed in the absence or presence of the olefin shown as component (d). 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 component (a) is contacted with the component (b).
(Ii) After contacting the component (a) and the component (b), the component (c) is contacted.
(Iii) After contacting the component (b) and the component (c), the component (a) is contacted.
(Iv) After contacting the component (a) and the component (c), the component (b) is contacted.
(V) contacting the three components simultaneously.

A preferred contact method is to contact the component (b) with the component (c), then remove the unreacted component (c) by washing or the like, and then convert the necessary minimum component (c) to the component (b) again. It is the method of making it contact, and making a component (a) contact after that. In this case, the Al / transition metal molar ratio is in the range of 0.1 to 1,000, preferably 2 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 30-60 ° C. When it is lower than this range, the reaction is slow, and when it is high, there is a disadvantage that a side reaction proceeds.
Moreover, when a component (a) and a component (c) are made to contact (in that case component (b) may exist), it is preferable to make an organic solvent exist as a solvent. In this case, the concentration of component (a) in the organic solvent is preferably higher. The lower limit of the concentration of the component (a) in the organic solvent is preferably 3 mmol / L, more preferably 4 mmol / L, still more preferably 6 mmol / L. If it is less than the lower limit, the reaction is slow and the reaction may not proceed sufficiently.
Component (a) is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol per 1 g of component (b).

III. Production method of olefin (co) polymer Polymerization carried out using the above-mentioned component (a), component (b), and optionally used component (c), component (d), an olefin polymerization catalyst is 1 It is carried out by polymerizing kinds of olefins or copolymerizing two or more kinds of olefins.
In the case of copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is possible to supply each monomer at a constant mixing ratio. It is also possible to change with time. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

  As the olefin that can be polymerized, those having about 2 to 20 carbon atoms are preferred, and specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl. -1,7-octadiene, cyclopentene, norbornene, ethylidene norbornene and the like. Preferably it is a C2-C8 alpha olefin, More preferably, they are ethylene and propylene. In the case of copolymerization, the type of comonomer used can be selected from one or two or more olefins other than the main component from those listed as the olefin. Preferably, the main component is propylene.

As the polymerization mode, any mode can be adopted as long as the catalyst and the monomer are in efficient contact. Specifically, a slurry method using an inert solvent, a method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas phase method for maintaining a monomer in a gaseous state without using a liquid solvent. Etc. can be adopted. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure is suitably 0 to 2000 kg / cm ² G, preferably 0 to 60 kg / cm ² G.

  Although it does not specifically limit as an olefin (co) polymer obtained by the manufacturing method of the olefin (co) polymer which concerns on this invention, If an example is given to the following, an ethylene homopolymer, a propylene homopolymer, propylene -Ethylene block copolymer, propylene-ethylene random copolymer, propylene / ethylene-α-olefin copolymer and the like.

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) Composition analysis of ion-exchange layered silicate:
For Al, Si and Mg, after baking the sample at 700 ° C. for 1 hour, 0.5 g of the sample was mixed with 4.5 g of a flux (Li ₂ B ₄ O ₇ ) and 0.03 g of a release agent (KBr), and glass A bead was prepared, and quantitative analysis was performed by a calibration curve method using an XRF analyzer (Rigaku Denki Kogyo Co., Ltd. ZSX-100e).
The calibration curve ranges are 19.48 to 44.22% for Si, 2.01 to 19.41% for Al, and 0.22 to 3.02% for Mg.
For Li, a sample was taken in a quartz beaker, placed in an electric furnace, and baked at 700 ° C. for 1 hour. After firing, a sample was taken in a platinum crucible, and sulfuric acid and hydrofluoric acid were added and heated to remove Si. The solution was fixed in a measuring flask, and Li was measured with an atomic absorption photometer (manufactured by Hitachi, Ltd., Z-5310 type).
Zn was heated and dissolved by adding sulfuric acid and hydrofluoric acid to a sample dried at 700 ° C. for 1 hour, and the solution was measured by ICP emission analysis ICP-OES (manufactured by Horiba, Ltd., ULTIMA2).

(2) Slurry pH measurement of ion-exchangeable layered silicate slurry The ion-exchangeable layered silicate slurry is dispersed at a uniform rotational speed (approximately 100-300 rpm) using a stirrer, and Horiba glass is used there. An electrode-type hydrogen ion concentration meter D-21 type was immersed and the read numerical value was adopted. In step D, the pH was constantly monitored (continuous monitoring).
“Metal cation amount, mmol / g-silicate” described in Table 1 below is the sum of the metal cations used when the same kind of metal cations generated from bases (Table) 1) The amount of metal cations described in 1 = metal cations generated from bases + metal cations).

[Example 1]
1. Process A: Acid treatment of ion-exchange layered silicate Add 82.6 g of 98% sulfuric acid to 645.1 g of distilled water in a 1 L three-necked flask equipped with a stirring blade and a reflux apparatus, and raise the temperature to 95 ° C. did. When the temperature was stabilized, commercially available montmorillonite (manufactured by Mizusawa Chemical Industry Co., Ltd., average particle size 14 μm, Al = 9.78 wt%, Si = 31.79 wt%, Mg = 3.18 wt%, Al / Si = 0.320, Mg / Al = 0.359, the main metal of the octahedron sheet is aluminum, the isomorphous substitution metal is magnesium, and the isomorphous substitution amount is 1.31 mmol / g). It was made to react for minutes. After 320 minutes, the above montmorillonite acid aqueous solution was poured into 0.5 L of distilled water to stop the reaction. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle.

2. Process B: Washing of ion-exchange layered silicate The cake-like montmorillonite after the filtration was rinsed with 0.25 L of distilled water. 4 g of the cake obtained from this was sampled and dried in an oven at 95 ° C. for 2 hours or longer to obtain a solid content in the cake.
The solid content in 1 g of the cake was 0.31 g. The chemical composition of this chemically treated montmorillonite is 7.68 wt% Al, 36.05 wt% Si (Al / Si = 0.222), 2.13 wt% Mg (the amount of isomorphous substitution after sulfuric acid treatment is 0.2%). 876 mmol / g), and Al eluted by this treatment was 30.6%. The washing magnification was 0.11.

3. Steps C and D: Contact and ion exchange of ion-exchangeable layered silicate and bases Distilled water was added to the cake so that the montmorillonite concentration was 16.5 wt%. The pH of the slurry at this time was 1.63. The temperature was raised to 40 ° C., and 3.414 g of lithium hydroxide hydrate (bases) was added as a solid to 1.03 mmol / g with respect to montmorillonite. The reaction was allowed to proceed.
At this time, the pH of the slurry at the end of the reaction was 6.74. During the process, the pH of the slurry did not exceed 8.
After 1 hour, the reaction slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 1 L of distilled water three times. The collected cake was dried at 110 ° C. overnight to obtain 79 g of chemically treated montmorillonite.
In this chemically treated montmorillonite, 0.72 mmol / g of lithium was exchanged, the lithium ion conversion rate (%) was 69.9%, and the lithium ion exchange rate (%) was 82.2%. Met.

[Example 2]
1. Step A: Acid treatment of ion-exchangeable layered silicate The same procedure as in Example 1 was performed.
2. Step B: Washing of ion-exchange layered silicate In Example 1, after the rinsing in Step B, the same operation as in Example 1 was performed except that 1 L of distilled water was used for further washing. The washing magnification was 0.047.

3. Steps C and D: Contact and ion exchange of ion-exchange layered silicate and bases The pH of the ion-exchange layered silicate slurry before contact with the bases was 2.48.
The chemically treated montmorillonite obtained through the above steps was used, and the amount of lithium hydroxide / hydrate used was 0.73 mmol / g with respect to montmorillonite so that the pH of the slurry did not exceed 8. Except for the above, the same operations as in Steps C and D of Example 1 were performed.
The slurry pH at the end of the reaction was 7.18. During the process, the pH of the slurry did not exceed 8.
The chemically treated montmorillonite obtained from this reaction was 78.3 g. In this chemically treated montmorillonite, 0.73 mmol / g of lithium was exchanged, the lithium ion conversion rate (%) was 100.0%, and the lithium ion exchange rate (%) was 83.3%. Met.

[Example 3]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same procedure as in Example 1 was performed.
2. Steps C and D: Contact and ion exchange of ion-exchange layered silicate and bases Using chemically treated montmorillonite obtained through the above steps, the amount of lithium hydroxide and hydrate used was 0 with respect to montmorillonite. The same operations as in Steps C and D of Example 1 were performed except that the amount was set to 0.85 mmol / g.
The slurry pH at the end of the reaction at this time was 5.02. During the process, the pH of the slurry did not exceed 8.
The chemically treated montmorillonite obtained from this reaction was 81 g. In this chemically treated montmorillonite, 0.53 mmol / g of lithium was exchanged, the lithium ion conversion rate (%) was 62.4%, and the lithium ion exchange rate (%) was 60.5%. there were.

[Example 4]
1. Process A: Acid treatment of ion exchange layered silicate The same operation as Example 1 was implemented.
2. Step B: Cleaning of ion-exchangeable layered silicate No rinsing operation was performed. The washing magnification was 0.21.

3. Process C, D: Contact and ion exchange of ion-exchange layered silicate and bases The pH of the ion-exchange layered silicate slurry before contact with the bases was 1.15.
Similar to steps C and D of Example 1 except that chemically treated montmorillonite obtained through the above steps was used and the amount of lithium hydroxide and hydrate used was 1.73 mmol / g with respect to montmorillonite. Was performed.
The pH of the slurry at the end of Step D was 5.87. During the process, the pH of the slurry did not exceed 8.
The chemically treated montmorillonite obtained from this reaction was 80 g. In this chemically treated montmorillonite, 0.76 mmol / g of lithium was exchanged, the lithium ion conversion rate (%) was 43.9%, and the lithium ion exchange rate (%) was 86.8%. Met.

[Example 5]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same operation as in Example 1 was performed.
2. Steps C and D: Contact and ion exchange of ion-exchangeable layered silicate and bases Using chemically treated montmorillonite obtained through the above steps, zinc hydroxide is converted into montmorillonite instead of lithium hydroxide / hydrate. On the other hand, the same operation as in Example 1 was performed except that 0.60 mmol / g was used.
At this time, the slurry pH at the end of the reaction was 7.21. During the process, the pH of the slurry did not exceed 8.
The chemically treated montmorillonite obtained from this reaction was 79 g. This chemically treated montmorillonite is exchanged with 0.38 mmol / g of zinc ions, the conversion rate (%) of zinc ions is 63.3%, and the exchange rate (%) of zinc ions is 86.8. %Met.

[Example 6]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same operation as in Example 1 was performed.
2. Steps C and D: Contact and ion exchange of ion-exchangeable layered silicate and bases 40 g of chemically treated montmorillonite obtained through the above steps was used (as powder) and slurried with 176 g of distilled water (pH 1. 62, 18.5 wt%). At 40 ° C., an aqueous lithium hydroxide solution (lithium hydroxide concentration: 3.0 mol / L) in which 2.03 g (0.048 mol) of lithium hydroxide hydrate was dissolved in 16 mL of distilled water was applied over 3 minutes. The mixture was gradually added, and stirring was continued for 117 minutes after the addition of the entire amount, thereby causing the reaction.
During the process, the pH of the slurry did not exceed 8. The slurry pH at the end of the reaction after 117 minutes was 6.34.
Washing and drying were performed in the same manner as in Example 1 to obtain 39.3 g of chemically treated montmorillonite.
In this chemically treated montmorillonite, 0.72 mmol / g of lithium was exchanged, the amount of lithium used was 1.2 mmol / g with respect to 1 g of clay, and the lithium ion conversion rate (%) was 60.0. %, The exchange rate (%) of lithium ions was 82.2%.

[Example 7]
1. Steps C and D: Contact and ion exchange of ion-exchangeable layered silicate and base Commercially available activated clay (the main metal of the octahedral sheet is aluminum, isomorphous substitution is due to magnesium, and the isomorphous substitution amount is 0.677 mmol. / G) 50 g was slurried with 268 g of distilled water (pH 2.48, 15.7 wt%) and heated to 40 ° C.
To this, 1.343 g (0.032 mol) of solid lithium hydroxide hydrate was gradually added. After the entire amount was added, stirring was continued for 95 minutes to allow reaction.
The slurry pH after 95 minutes was 6.72. During the process, the pH of the slurry did not exceed 8.
Washing and drying were performed in the same manner as in Example 1 to obtain 49.5 g of chemically treated montmorillonite.
In this chemically treated montmorillonite, 0.63 mmol / g of lithium was exchanged, the amount of lithium used was 0.64 mmol / g with respect to 1 g of clay, and the lithium ion conversion rate (%) was 98.4. %, The lithium ion exchange rate (%) was 93.1%.

[Example 8]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same operation as in Example 2 was performed.
2. Step C: Contact between ion-exchange layered silicate and base 40 g of chemically treated montmorillonite obtained through the above steps was used (as powder) and slurried with 176 g of distilled water (pH 2.12, 18.5 wt. %). To the temperature of 40 ° C., an aqueous lithium hydroxide solution (lithium hydroxide concentration 1.9 mol / L) obtained by dissolving 1.225 g (0.029 mol) of lithium hydroxide hydrate in 15 mL of distilled water was gradually added. When the whole amount was added, the pH of the slurry of the reaction solution was 7.25.

3. Step D: Ion Exchange of Ion-Exchangeable Layered Silicate 2.432 g (0.019 mol) of solid lithium sulfate hydrate was added to the above reaction slurry, and stirring was continued for 100 minutes after the addition of the total amount to react. .
The slurry pH after 100 minutes was 6.23. During the process, the pH of the slurry did not exceed 8.
Washing and drying were performed in the same manner as in Example 1 to obtain 39.3 g of chemically treated montmorillonite.
In this chemically treated montmorillonite, 0.80 mmol / g of lithium was exchanged, the amount of lithium used was 1.68 mmol / g with respect to 1 g of clay, and the lithium ion conversion rate (%) was 47.6. %, The exchange rate (%) of lithium ions was 91.3%.

[Example 9]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same operation as in Example 1 was performed.
2. Steps C and D: Contact and ion exchange of ion-exchange layered silicate with bases 40 g of chemically treated montmorillonite obtained through the above steps was used (as powder) and slurried with 174 g of distilled water (pH 1. 61, 18.7 wt%). At 40 ° C., a lithium hydroxide aqueous solution (concentration 1.7 mol / L) in which 1.430 g (0.034 mol) of lithium hydroxide hydrate was dissolved in 20 mL of distilled water was gradually added. When 10 mL was added, the operation was completed.
The slurry pH at this time was 4.8. When 2.560 g (0.020 mol) of solid (powder) lithium sulfate hydrate was added thereto, the slurry pH gradually decreased due to proton release from the interlayer accompanying ion exchange. After the lapse of time, the pH of the silicate slurry became 4.2. Therefore, the remaining 10 mL of the previous lithium hydroxide aqueous solution was gradually added to this slurry, and after adding the entire amount, stirring was continued for 95 minutes to cause reaction.
After 95 minutes, the pH of the silicate slurry at the end of the reaction was 5.87. During the process, the pH of the slurry did not exceed 8.
Washing and drying were performed in the same manner as in Example 1 to obtain 39.2 g of chemically treated montmorillonite.
In this chemically treated montmorillonite, 0.76 mmol / g of lithium was exchanged, the amount of lithium used was 1.85 mmol / g with respect to 1 g of clay, and the lithium ion conversion rate (%) was 41.1. %, The lithium ion exchange rate (%) was 86.8%.

[Example 10]
1. Step A: Acid treatment of ion-exchangeable layered silicate To a 1 L three-necked flask equipped with a stirring blade and a reflux apparatus, 669 g of 98% sulfuric acid was added to 2264 distilled water, and the temperature was raised to 90 ° C. When the temperature was stabilized, a commercially available montmorillonite (manufactured by Mizusawa Chemical Co., Ltd., average particle size 18 μm, Al = 9.44 wt%, Si = 35.81 wt%, Mg = 1.45 wt%, Al / Si = 0.274, The main metal of the octahedral sheet was aluminum, and the isomorphic substituted metal was magnesium (400 g). The mixture was reacted for 215 minutes while maintaining 90 ° C. After 215 minutes, the above montmorillonite acid aqueous solution was poured into 2 L of distilled water to stop the reaction.

2. Step B: Washing The slurry was filtered with a Nutsche and a suction bottle connected to an aspirator, and rinsed with 1 L of distilled water. After filtration, the cake in Nutsche was collected in a 5 L plastic beaker, and 4 L of distilled water was added thereto for washing.
This slurry was filtered, and the resulting cake was dried in an oven at 95 ° C. overnight to obtain 275 g of chemically treated montmorillonite.
The chemical composition of this chemically treated montmorillonite is as follows: Al is 6.71 wt%, Si is 38.27 wt% (Al / Si = 0.183), Mg is 1.14 wt% (the isomorphous substitution amount after sulfuric acid treatment is 0.469 mmol) / G, Mg / Al = 0.189), and Al eluted by this treatment was 33.2%. The washing magnification was 0.047.

3. Steps C and D: Contact and ion exchange of ion-exchange layered silicate and bases Using 73 g of chemically treated montmorillonite obtained through the above steps, in steps C and D of Example 1, lithium hydroxide / hydrate The same operation was performed except that was 0.73 mmol / g.
The pH of the ion-exchangeable layered silicate slurry before contact with the bases was 2.58. The slurry pH at the end of the reaction was 7.32. During the process, the pH of the slurry did not exceed 8.
The chemically treated montmorillonite obtained from this reaction is exchanged with 0.46 mmol / g of lithium, the lithium ion conversion rate (%) is 63.0%, and the lithium ion exchange rate (%) is , 98.1%.

[Comparative Example 1]
1. Step A: Acid treatment of ion-exchangeable layered silicate The same procedure as in Example 1 was performed.
2. Step B: Washing In Example 1, the same procedure as in Example 1 was performed, except that after rinsing and washing with 1 L of distilled water four times. The cleaning rate was 0.0004.

3. Step D: Ion Exchange of Ion Exchangeable Layered Silicate 84.736 g (0.662 mol) of lithium sulfate hydrate was taken in a 1 L flask, and 480 ml of distilled water was added thereto to prepare an aqueous lithium sulfate solution.
To this aqueous solution, 78.3 g of chemically treated montmorillonite obtained through the above steps was added and reacted at 40 ° C. for 2 hours.
At this time, the pH of the slurry at the end of the reaction was 3.0.
The slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, washed with 0.7 L of pure water three times, and the recovered cake was dried at 120 ° C. overnight.
As a result, 78.3 g of chemically treated montmorillonite was obtained. In this chemically treated montmorillonite, 0.74 mmol / g of lithium was exchanged, the amount of lithium used was 16.9 mmol / g with respect to 1 g of clay, and the conversion rate (%) of lithium ions was 4 The exchange rate (%) of lithium ions was 84.5% at 0.4%.

[Comparative Example 2]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same procedure as in Example 1 was performed.
2. Step D: Ion exchange of ion-exchange layered silicate Using chemically treated montmorillonite obtained through the above steps, lithium sulfate hydrate was used instead of lithium hydroxide, and the amount of lithium was 0.52 mmol relative to montmorillonite. The same operations as in Steps C and D of Example 1 were performed except that an amount of / g was used.
The slurry pH at the end of the reaction at this time was 1.6. The chemically treated montmorillonite obtained from this reaction was 80 g.
In this chemically treated montmorillonite, 0.07 mmol / g of lithium was exchanged, the lithium ion conversion rate (%) was 6.7%, and the lithium ion exchange rate (%) was 8.0%. Met

[Comparative Example 3]
1. Step A: Acid treatment of ion-exchangeable layered silicate The same procedure as in Example 10 was performed.
2. Step B: Washing The same procedure as in Example 10 was performed.

3. Step D: Ion exchange of ion-exchanged layered silicate Implementation was performed except that 3.411 g (0.027 mol) of lithium sulfate hydrate was used instead of lithium hydroxide hydrate and 71 g of chemically treated montmorillonite was used. The same operation as in Example 10 was performed.
The slurry pH at the end of the reaction at this time was 2.21. The chemically treated montmorillonite obtained from this reaction has 0.21 mmol / g of lithium exchanged, the lithium ion conversion rate (%) is 27.6%, and the lithium ion exchange rate (%) is 44.8%.

[Comparative Example 4]
1. Steps A and B: Acid treatment and washing of ion-exchangeable layered silicate The same procedure as in Example 1 was performed.
2. Steps C and D: Contact and ion exchange of ion-exchange layered silicate and bases Using chemically treated montmorillonite obtained through the above steps, the amount of lithium hydroxide / hydrate is 1.03 mmol / g instead In addition, the same operations as in Steps C and D of Example 1 were performed except that 1.27 mmol / g was used with respect to montmorillonite.
At this time, the slurry pH at the end of the reaction was 8.57. In addition, filtration under reduced pressure by washing after completion of the process required a filtration time three times as long as that required for Example 1.
The chemically treated montmorillonite obtained from this reaction was 80 g. In this chemically treated montmorillonite, 0.92 mmol / g of lithium was exchanged, the lithium ion conversion rate (%) was 72.4%, and the lithium ion exchange rate (%) was 105.0%. Met.

Table 1 shows the summary of each process and the evaluation results for Examples 1 to 10 and Comparative Examples 1 to 4. Moreover, in FIG. 1, the result of having plotted the ion conversion rate (%) of the obtained layered silicate with respect to the pH of the slurry at the time of completion | finish of the process D is shown.
Moreover, in the evaluation of the ease of filtration in Table 1, it evaluated by the following evaluation criteria.
A: Cleaning operation at the end of the process D, the filtration time is short, and it is very good.
○: It is a washing operation at the end of the process D, and the filtration time is short to medium time, which is good.
X: It is a washing operation at the end of the process D, and the filtration time is long and is impossible.

[Polymerization Example 1]
1. Catalyst preparation The following operations were carried out under inert gas using deoxygenated and dehydrated solvents and monomers.
The chemically treated montmorillonite prepared in Example 1 was placed in a 200 ml flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after bumping had subsided).
Next, 10.01 g of this dry montmorillonite was weighed into a 1 L flask, and 65 ml of heptane and 35 ml of heptane solution (25.5 mmol, concentration 144.3 g / l) of triisobutylaluminum (TiBA) were added at room temperature. Stir for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. To this, 85 ml of heptane and 1.53 ml (concentration 143.6 mg / ml, 599.2 μmol) of a heptane solution of trinormal octylaluminum (TnOA) were added and stirred at room temperature for 15 minutes.
Here, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride (synthesis) prepared in another flask (volume: 200 ml) Was carried out according to the example of JP-A-10-110136.) A solution of 125 mg (153.8 μmol) of heptane (30 mL) was added and stirred at 60 ° C. for 60 minutes. After completion of the reaction, heptane was added to prepare 333 ml.
The montmorillonite / metallocene complex prepared above was introduced into a stirring autoclave having an internal volume of 1 L subjected to nitrogen substitution. When the temperature in the autoclave was stabilized at 40 ° C., propylene was supplied at a rate of 5 g / hour to maintain the temperature at 40 ° C. After 4 hours, the supply of propylene was stopped and maintained for another 1 hour for prepolymerization.
After the prepolymerization, the remaining propylene was purged, and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and 160 ml of the supernatant was extracted. Subsequently, 4.14 ml (2.96 mmol) of a heptane solution of TiBA was added at room temperature, and then dried under reduced pressure at 40 ° C. for 1 hour.
As a result, 30.67 g of a prepolymerized catalyst containing 2.03 g of polypropylene per 1 g of catalyst was obtained.

2. Propylene Polymerization After the inside of the stirred autoclave with an internal volume of 3 L is sufficiently substituted with propylene, 5.6 ml (4.04 mmol) of a heptane solution of TiBA is added, 45 ml of hydrogen and 750 g of liquid propylene are introduced, and the temperature is raised to 70 ° C. The temperature was maintained. The prepolymerized catalyst was slurried with heptane, and 20.8 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to start polymerization. While maintaining the internal temperature at 70 ° C., polymerization was continued for 1 hour. Thereafter, 5 ml of ethanol was added to stop the polymerization reaction. The residual gas was purged to obtain a polymer. The resulting polymer was dried at 90 ° C. for 1 hour.
As a result, 225.8 g of polymer was obtained. The catalytic activity was 10,856 g-PP / g-catalyst / hr. The MFR was 2.0 g / 10 minutes. The obtained polymer powder had a powder BD of 0.45 g / cc.

  From Table 1 and FIG. 1, the process C in which montmorillonite having protons in interlayer ions is brought into contact with bases, the pH does not exceed 8 throughout the process, and at the end of the process, the pH is 4.5-8. By performing the step D of performing ion exchange under a certain ion-exchange layered silicate slurry simultaneously or sequentially, a layered silicate having a high ion exchange rate (%) is obtained with a high ion conversion rate (%). You can see that it is possible.

  In the method for producing the layered silicate of the present invention, for example, in the production process of chemically treated montmorillonite, a large amount of water and time used for a known washing operation and the metal ion content in the waste liquid can be greatly reduced. , Greatly contribute to energy saving and productivity improvement. In addition, when the layered silicate obtained from the method for producing a layered silicate of the present invention is used as a catalyst component for olefin polymerization, olefin polymerization proceeds with high activity, and as a result, olefin (co) heavy is highly active. A coalescence can be manufactured, and industrial applicability is high.

Claims (14)

A step of contacting an ion-exchange layered silicate having protons (H ⁺ ) as interlayer ions with a base (step C), and a step of ion-exchanging a proton and a metal cation of the ion-exchange layered silicate (step) D) and a method for producing a layered silicate,
The ion exchange step (step D) is performed under an ion-exchange layered silicate slurry whose pH does not exceed 7.32 throughout the process, and at the end of the step, the pH of the slurry is 4. It is 5-7.32 , The manufacturing method of the layered silicate characterized by the above-mentioned.   The method for producing a layered silicate according to claim 1, wherein the step C is performed simultaneously with the step D or before the step D.   Furthermore, the manufacturing method of the layered silicate of Claim 1 or 2 including the process (process A) which makes an ion exchange layered silicate and acids contact.   The process A is performed before the process C, The manufacturing method of the layered silicate of Claim 3 characterized by the above-mentioned.   The layered silicic acid according to claim 3 or 4, further comprising a step of washing the ion-exchange layered silicate with a solvent (step B), wherein the washing is performed at a washing magnification of 1/1000 or more. Method for producing salt.   The ion-exchange layered silicate of the step C is obtained by eluting 10 to 80 mol% of a main metal constituting the octahedral sheet of the ion-exchange layered silicate. The manufacturing method of the layered silicate of any one of Claims 1.   The base is an oxide, hydroxide, carbonate or bicarbonate, amines, phenols or a metal selected from the group consisting of alkali metals, alkaline earth metals and metals of Groups 3-14 of the periodic table It is ammonia, The manufacturing method of the layered silicate of any one of Claims 1-6 characterized by the above-mentioned.   The base is a hydroxide of a metal selected from the group consisting of alkali metals, alkaline earth metals and metals of Groups 3 to 14 of the periodic table. The manufacturing method of layered silicate as described in 2.   9. The metal cation of step D is a metal cation selected from the group consisting of alkali metals, alkaline earth metals, and metals of Groups 3 to 14 of the periodic table. The manufacturing method of the layered silicate as described in a term.   The method for producing a layered silicate according to any one of claims 1 to 9, wherein the metal cation in Step D is the same kind as the metal cation generated from the bases.   The method for producing a layered silicate according to any one of claims 1 to 10, wherein the metal cation in Step D is a metal cation generated from the bases.   The method for producing a layered silicate according to any one of claims 1 to 11, wherein in the ion-exchangeable layered silicate in the step C, a main metal element constituting the octahedral sheet is aluminum. Method for producing a catalyst component for olefin polymerization which comprises using the layered silicate obtained by the manufacturing method of the layered silicate according to any one of claims 1 to 12. The manufacturing method of the catalyst for olefin polymerization which makes the following component (a), component (b), and the component (c) and / or component (d) used as needed contact.
Component (a): Metallocene compound Component (b): Catalyst component for olefin polymerization obtained by the production method according to claim 13 Component (c): Organoaluminum compound Component (d): Olefin having 2 to 20 carbon atoms

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