JP2024003376A - Method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer which can suppress the generation of a lumpy polymer and a deposited material to a reactor during the polymerization reaction without inhibiting the catalytic activity in the production of an olefin polymer using a catalyst having a specific clay mineral as a component.

SOLUTION: There is provided a method for producing an olefin polymer in the presence of an olefin polymerization catalyst containing the following components [A] and [B] in which the component [A] is ion-exchangeable layered silicate particles having a specific surface area of 150 m²/g or more and 700 m²/g or less, including montmorillonite and/or beidellite and the component [B] is a transition metal compound, wherein a polyoxyethylene compound having a number average molecular weight of 500 or more and 8000 or less is added.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a method for producing an olefin polymer.

BACKGROUND ART As a technique for producing polyolefins such as polyethylene and polypropylene, a technique using a solid catalyst in which an organometallic compound typified by a metallocene compound is supported on a solid carrier is widely known.
When polyolefins are produced using such solid catalysts, lumps, sheet-like polymers and fine powders are generated in the polymerization system, which increases the load on the heat removal and stirring capabilities of the polymerization reactor and can clog piping. It may cause problems such as
As a solution to such problems, it is known to use additives such as surfactants.

For example, in Patent Document 1, when producing an ethylene-hexene copolymer under specific polymerization conditions in the presence of a metallocene compound having a biscyclopentadienyl ligand, methylaluminoxane, and a catalyst consisting of a silica carrier, hydroxyl It is disclosed that adhesion to the reactor can be prevented by adding a compound having an ethyl group, ethyleneoxy group, or propyleneoxy group. However, there are few examples in which catalyst activity and bulk density equivalent to those without addition can be maintained.

In Patent Document 2, relatively low molecular weight polyethylene glycol monostearate, etc. is produced using a catalyst consisting of a metallocene compound having a crosslinked bisindenyl ligand, a boron compound which is a non-coordinating ion-containing compound, and a silica carrier. An example of its use is disclosed.
In Patent Document 3, ethylene is produced under specific polymerization conditions using a catalyst consisting of a metallocene compound having a biscyclopentadienyl ligand and a crosslinked cyclopentadienylfluorenyl ligand, methylaluminoxane, and a silica carrier. - Techniques for producing hexene copolymers and polypropylene have been disclosed, but polyethylene lauryl ether, which has a relatively low molecular weight, is not sufficiently effective in preventing adhesion to the reactor, and catalytic activity decreases. Therefore, polyalkylene oxide block copolymers with a specific composition and viscosity range are preferred. However, there are cases in which even the compound described as effective in Patent Document 1 is said to be insufficiently effective.

In Patent Document 4, stable operability is obtained by using a catalyst consisting of a metallocene compound having a crosslinked biscyclopentadienyl ligand, methylaluminoxane, and a silica carrier, and a carboxylic acid salt such as aluminum stearate. It is disclosed that
As described above, techniques for improving the operability of polymerization reactions using additives when using a supported metallocene catalyst containing an aluminoxane compound or a boron compound as a cocatalyst are widely known.

On the other hand, olefin polymerization techniques using clay minerals as promoters and supports are also known. Unlike aluminoxane compounds, clay minerals do not react violently with water or oxygen, are highly safe, and are relatively inexpensive, making olefin polymerization technology that uses them as a catalyst component an industrially superior technology. be. However, like other catalyst systems, the operability of the polymerization reaction may be impaired due to the formation of lumps, fine powder, adhesion to the reactor, etc. during polymerization.

For example, Patent Document 5 discloses an example in which a catalyst consisting of a carrier prepared by treating organically modified clay with polyethylene oxide sorbitan monooleate or polyoxyethylene and a crosslinked cyclopentadienylfluorenyl ligand metallocene compound is used. There is. However, in Patent Document 5, when polyethylene oxide, which is highly effective in Patent Document 1, is used, the catalyst activity is only about half that of the catalyst prepared using polyethylene oxide sorbitan monooleate. In addition, the clay mineral used as a promoter and support is synthetic hectorite, and depending on the structure of the metallocene compound and the type of olefin monomer, such clay minerals may not exhibit substantial catalytic activity. There is a problem (for example, Non-Patent Document 1).

On the other hand, in Patent Document 6, a metallocene compound having a biscyclopentadienyl ligand, a catalyst having a clay mineral activated by an acid as a carrier, and a nonionic surfactant reacted with an organic aluminum are used. It is disclosed that the adhesion of the catalyst to the catalyst container and the inside of the catalyst introduction pipe is reduced. However, the process of reacting organoaluminium and nonionic surfactant in advance is necessary, which causes an increase in cost, and is not as effective as when no additives are used. It's not something I can say. Furthermore, it was not possible to suppress adhesion during the polymerization reaction, adhesion of lumps and fine powder derived from the produced polymer, etc. Furthermore, it is stated that polypropylene glycol, which was considered to be effective in Patent Document 1, is not effective in preventing catalyst adhesion unless it undergoes a prior reaction with an organoaluminum compound.

Japanese Patent Application Publication No. 2000-327707 Japanese Patent Application Publication No. 2004-018785 Japanese Patent Application Publication No. 2004-262992 Special Publication No. 2002-520427 Japanese Patent Application Publication No. 2003-201309 JP2004-059828A Clay Science 20, 49-58 (2016)

As mentioned above, in conventional technology, the production process involves controlling the formation of adhesion, fine powder, and lumps without impairing the catalyst's original properties such as activity, by adjusting the cocatalyst and carrier, which are the components of the catalyst, and the polymerization conditions. The types, concentrations, and methods of addition of additives that can achieve this stability vary, and no additives are known to be effective in producing polyolefins using catalysts containing specific activated clay minerals. Ta.

As a result of intensive studies on the above-mentioned problems, it has been found that the above-mentioned problems can be solved by using a catalyst containing a specific ion-exchangeable layered silicate as a component and a compound having a specific structure.

In view of the situation of the prior art, the present invention aims to produce an olefin polymer using a catalyst containing a specific activated clay mineral as a component, without inhibiting the catalyst activity. The object of the present invention is to provide a method for producing an olefin polymer that can suppress the occurrence of deposits on containers.

By combining a catalyst containing specific ion-exchanged layered silicate particles with a polyether compound having a specific partial structure, the present inventor has succeeded in producing a block polymer during polymerization without impairing the catalyst activity or the quality of the polymer. It has been found that the generation of deposits on the reactor can be suppressed.
That is, the present invention relates to the following [1] to [3].

[1] A method for producing an olefin polymer in the presence of an olefin polymerization catalyst containing the following component [A] and component [B],
Component [A]: Ion-exchange layered silicate particles containing montmorillonite and/or beidellite and having a specific surface area of 150 m ² /g or more and 700 m ² /g or less Component [B]: Transition metal compound General formula (I) below A method for producing an olefin polymer, which comprises adding a polyoxyethylene compound represented by the following formula and having a number average molecular weight of 500 or more and 8000 or less.
Formula (I): R ^a -((CH ₂ CH ₂ O) _n -R ^b ) _m
[In formula (I),
R ^a is an m-valent substituent composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom,
R ^b is each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, an alkali metal atom, and an alkaline earth metal atom. is a monovalent substituent,
m is an integer from 1 to 6,
n is an integer of 2 or more,
When m is 2 or more, a plurality of R ^b's and n's may be the same or different. ]
[2] The method for producing an olefin polymer according to [1] above, wherein the ion-exchange layered silicate particles have an average particle diameter of 2 μm or more and 500 μm or less.
[3] The method for producing an olefin polymer according to [1] or [2] above, wherein the olefin polymerization catalyst further contains the following component [C].
Component [C]: Organic aluminum compound

According to the present invention, it is possible to provide a method for producing a stable olefin polymer that can suppress the generation of bulk polymers and deposits on a reactor during the polymerization reaction without impairing catalyst activity or polymer quality. .

FIG. 1 is a graph plotting catalyst activity against MFR for Examples P1 and P2 and Comparative Examples P1 and P2. FIG. 2 is a graph plotting the amount of lumps against MFR for Examples P1 and P2 and Comparative Examples P1 and P2. FIG. 3 is a graph plotting bulk density (BD) against MFR for Examples P1 and P2 and Comparative Examples P1 and P2. FIG. 4 is a graph plotting MFR=1 conversion catalyst activity against the amount of additive added for two polymerization activities under the same conditions except for different hydrogen concentrations in Examples P3 to P22 and Comparative Examples P1 to P12. It is.

The method for producing an olefin polymer of the present invention is a method for producing an olefin polymer in the presence of an olefin polymerization catalyst containing the following component [A] and component [B],
Component [A]: Ion exchange layered silicate particles containing montmorillonite and/or beidellite and having a specific surface area of 150 m ² /g or more and 700 m ² /g or less Component [B]: Transition metal compound General formula (I) below It is characterized by adding a polyoxyethylene compound represented by the following formula and having a number average molecular weight of 500 or more and 8000 or less.
Formula (I): R ^a -((CH ₂ CH ₂ O) _n -R ^b ) _m
[In formula (I),
R ^a is an m-valent substituent composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom,
R ^b is each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, an alkali metal atom, and an alkaline earth metal atom. is a monovalent substituent,
m is an integer from 1 to 6,
n is an integer of 2 or more,
When m is 2 or more, a plurality of R ^b's and n's may be the same or different. ]

In the method for producing an olefin polymer of the present invention, the olefin is polymerized in the presence of the specific polyoxyethylene compound added to the olefin polymerization catalyst containing the specific ion exchange layered silicate particles. It is possible to suppress the generation of bulk polymers and deposits on the reactor during the polymerization reaction without inhibiting the catalyst activity.

Hereinafter, the method for producing an olefin polymer of the present invention will be explained in detail for each item.
In this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as the lower limit and upper limit.
Further, the characteristics of the ion-exchangeable layered silicate particles described below are the characteristics as an aggregate of the ion-exchangeable layered silicate particles.
Further, in the present invention, "n" accompanying the alkyl group name is a symbol representing normal, "s" is a symbol representing secondary, and "t" is a symbol representing a tertiary isomer structure. Note that if an alkyl group is not accompanied by a symbol indicating an isomer structure, it indicates a normal structure.

I. Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention contains the following component [A] and component [B]. It is preferable that the olefin polymerization catalyst used in the present invention further contains the following component [C].
Component [A]: Ion-exchangeable layered silicate particles containing montmorillonite and/or beidellite and having a specific surface area of 150 m ² /g or more and 700 m ² /g or less Component [B]: Transition metal compound component [C]: Organic aluminum compound

1. Component [A]
Component [A] of the olefin polymerization catalyst used in the present invention is ion-exchangeable layered silicate particles containing montmorillonite and/or beidellite and having a specific surface area of 150 m ² /g to 700 m ² /g.

(Specific surface area)
The ion exchange layered silicate particles used in the present invention have a specific surface area of 150 m ² /g or more and 700 m ² /g or less.
The specific surface area of the ion exchange layered silicate particles used in the present invention has a lower limit of preferably 180 m ² /g or more, more preferably 200 m ² /g or more, and even more preferably 210 m ² /g or more, and an upper limit of is preferably 600 m ² /g or less, more preferably 500 m ² /g or less. The upper limit may be 400 m ² /g or less, or 300 m ² /g or less. Any combination of the upper limit and lower limit can be adopted.
Generally, as the specific surface area increases, the amount of active components of the catalyst or the amount of active components that can be supported increases, resulting in higher activity. On the other hand, if the specific surface area is too large, the pore diameter may become small. This may cause a decrease in the diffusion rate of the reaction substrate, leading to a decrease in the activity of the catalyst.
The specific surface area in the present invention refers to a value calculated by BET multipoint analysis (Rouquerol transformation) from adsorption isotherm data measured using nitrogen gas in a gas adsorption method. The method for measuring the specific surface area by gas adsorption method is explained in JIS Z8830, for example. Specifically, the measuring method described in Examples below can be adopted.

(Particle size)
There is no particular restriction on the particle size of the ion exchange layered silicate particles used in the present invention. Preferably, the average particle diameter is 2 μm or more and 500 μm or less.
The lower limit of the average particle diameter is more preferably 3 μm or more, still more preferably 8 μm or more, particularly preferably 10 μm or more, and even if it is 30 μm or more, from the viewpoint of preventing adhesion and clogging in the reactor and dispersibility. The thickness may be 40 μm or more. The upper limit is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 70 μm or less, even more preferably 60 μm or less, particularly preferably 55 μm or less. Any combination of the upper limit value and lower limit value can be adopted.
In general, if the particle size is too small, it may adhere to the inside of the reactor or cause clogging of pipes and filters. On the other hand, if it is too large, it may cause poor dispersion in liquid (slurry state) or during gas phase reactions.
Here, the average particle diameter of the present invention refers to the volume-based median diameter determined from the spherical equivalent particle diameter distribution. As a method for measuring the average particle diameter of the ion-exchangeable layered silicate particles of the present invention, specifically, the measuring method described in the Examples below can be adopted.

(composition)
The ion-exchanged layered silicate particles used in the present invention have at least a montmorillonite or beidellite structure, and also have a structure in which a portion of the octahedral sheet is missing due to weathering, acid treatment, salt treatment, etc. It is preferable that there be. Clays with this structure are also known as acid clays and activated clays.

The ion exchange layered silicate particles used in the present invention are preferably montmorillonite and/or beidellite type layered silicate particles. The octahedral sheets of montmorillonite are composed of metallic elements such as aluminum and magnesium. The metal elements (metal cations) constituting these octahedral sheets are eluted in an elution amount as described in the acid treatment of the method for producing ion-exchanged layered silicate particles described below, compared to the content before acid treatment. It is preferable that the

Further, when the main constituent metallic element of the octahedral sheet is aluminum and the main constituent metallic element of the tetrahedral sheet is silicon, the molar ratio of aluminum to silicon is preferably 0.05 to 0.05 from the viewpoint of catalytic activity and product quality. 0.40, more preferably 0.08 to 0.30, even more preferably 0.10 to 0.25, even more preferably 0.12 to 0.20. The molar ratio of aluminum to silicon may be between 0.15 and 0.20, and between 0.17 and 0.19.
If the amount of aluminum is too large relative to silicon, the pore volume and specific surface area tend to decrease. On the other hand, if the amount of aluminum is too small relative to silicon, the amount of active sites tends to decrease. Therefore, the activity as a catalyst or catalyst carrier may be reduced, and the quality of the product may be adversely affected.

In addition, the molar ratio of iron to silicon is preferably 0 to 0.20, more preferably 0.0005 to 0.10, still more preferably 0.001 to 0.08, and even more preferably is 0.005 to 0.05.
In addition, the molar ratio of magnesium to silicon is preferably 0 to 0.30, more preferably 0.001 to 0.30, still more preferably 0.01 to 0.20, and even more preferably is 0.02 to 0.10.

In the present invention, compositional analysis of the ion-exchanged layered silicate and ion-exchanged layered silicate particles described below is performed by creating a calibration curve in accordance with JIS R2212 and quantifying the composition by fluorescent X-ray measurement. As a method for measuring fluorescent X-rays, specifically, the method described in Examples below can be adopted.

(Method for producing ion exchange layered silicate particles)
The method for producing the ion-exchangeable layered silicate particles used in the present invention is not particularly limited as long as the ion-exchangeable layered silicate particles having the above characteristics can be obtained.

(1) Ion-exchanged phyllosilicate The ion-exchanged phyllosilicate particles used in the present invention are composed of ion-exchanged phyllosilicate containing montmorillonite and/or beidellite.
The above-mentioned ion-exchange layered silicate is a type of silicate compound that has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with weak bonding force. The above-mentioned ion-exchange layered silicate is not limited to natural products, and may be artificially synthesized, but it includes montmorillonite and/or beidellite structures. Since these are naturally produced as a mixture of clay minerals, they often contain impurities (including quartz, cristobalite, opal, carbonate, etc.), but they may also contain them. Examples of this include bentonite, which is a clay containing montmorillonite as a main component, and acid clay.
These ion exchange layered silicates may be used alone or in combination of two or more.

Moreover, it is more preferable to purify these natural products by elutriation or elutriation. By performing water elutriation or elutriation, not only impurities such as quartz and feldspar with high specific gravity are removed, but also silicates that do not swell can be removed, and a preferable ion-exchangeable layered silicate can be obtained. As the elutriation or elutriation method, commonly used methods can be used. Drying or pulverization may be performed before purification. Examples of the pulverization method include dry pulverization and wet pulverization. Examples of the crusher include a jaw crusher, gyratory crusher, roll crusher, edge runner, hammer mill, ball mill, bead mill, jet mill, and the like.

Further, for example, ion exchange treatment using a very small amount of soda carbonate or the like may be performed in advance.
An example of this is a product in which Ca-type bentonite is converted to Na-type activated bentonite (Central Customs Laboratory Report No. 56, p. 85, Clay Science Vol. 21, No. 1, 1-13 (1981)). )) Review). This makes it easier for smectite to disperse during elutriation, allowing coarse quartz and the like to be quickly separated by sedimentation due to the difference in particle size. Also, known substances may be added as dispersants, such as sodium silicate and sodium pyrophosphate.

The ion-exchanged layered silicate is preferably subjected to granulation and chemical treatment as described below.
In addition, in the present invention, if the silicate has ion exchange properties before being subjected to chemical treatment, the physical and chemical properties will change due to the treatment, and silicates that have lost their ion exchange properties and layer structure will also have ion exchange properties. Treated as an exchangeable layered silicate.

The type of interlayer cation (cation contained between the layers of the ion-exchanged layered silicate) of the ion-exchanged layered silicate is not particularly limited. The interlayer cation is selected as a main component from the group consisting of alkali metals in Group 1 of the periodic table such as lithium and sodium, alkaline earth metals in Group 2 of the periodic table such as calcium and magnesium, aluminum, and silicon. It may contain at least one kind. Alternatively, the interlayer cation may include transition metal atoms such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold. Such ion-exchangeable phyllosilicates or raw materials required for ion-exchange treatment are preferable because they are relatively easily available as industrial raw materials.

The above-mentioned ion-exchanged layered silicate may have a naturally occurring shape or an artificially synthesized shape, but it is preferable to adjust the shape and particle size by granulating or pulverizing it.
The shape of the ion-exchanged layered silicate before granulation is not particularly limited, and may be a naturally occurring shape or an artificially synthesized shape. An ion-exchangeable layered silicate whose shape has been processed by operations such as pulverization, granulation, and classification may also be used. Furthermore, a slurry obtained by a purification operation such as elutriation may be used as it is. It may also contain impurities (including quartz, cristobalite, opal, carbonate, etc.).

Preferred granulation methods include stirring granulation, spray granulation, rolling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, spouted bed granulation, and emulsion granulation. Examples include granulation method, submerged granulation method, compression molding granulation method, and the like. More preferred methods include spray drying granulation method, spray cooling granulation method, fluidized bed granulation method, spouted bed granulation method, submerged granulation method, emulsion granulation method, etc. Spray drying granulation method is particularly preferred. method and spray cooling granulation method.

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

The particle size distribution of the ion-exchanged layered silicate particles produced by granulation can also be adjusted by adjusting production conditions such as the atomizer, drying medium temperature, and flow rate. Further, the adjustment may be performed using a known classification technique such as a sieve or air classification.
The average particle diameter of the ion-exchange layered silicate particles may be 2 μm or more and 500 μm or less, as described above, even if granulation is performed.

(2) Acid treatment In the method for producing ion-exchanged phyllosilicate particles used in the present invention, acid treatment is performed in which the granulated ion-exchanged phyllosilicate particles or ion-exchanged phyllosilicate are brought into contact with an acid. , preferably ion exchange layered silicate particles.
The acid treatment dissolves impurities and exchanges cations present between the layers of the ion-exchangeable layered silicate. In addition, acid treatment can change the characteristics of the pore structure by eluting some or all of the cations such as aluminum, iron, and magnesium that constitute the crystal structure of the ion-exchanged layered silicate. Surface area can be increased. This contributes to increasing the acid strength of the ion-exchange layered silicate particles and increasing the amount of acid sites per unit mass.

It is preferable that the metal cations constituting the octahedral sheet be eluted by the acid treatment in an amount of 15% to 75%, more preferably 15% to 70%, even more preferably 17%, relative to the content before the acid treatment. ~65%, particularly preferably 20% to 60%. For example, when the metal cation is aluminum, the ratio (%) of the metal cation to be eluted is expressed by the following formula.
[Aluminum/Silicon (molar ratio) before chemical treatment - Aluminum/Silicon (molar ratio) after chemical treatment] ÷ Aluminum/Silicon (molar ratio) before chemical treatment x 100
When the elution rate is within the above range, the specific surface area is improved and the catalytic activity is improved.

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

The contact between the ion-exchanged layered silicate particles or the ion-exchanged layered silicate and the acid should be carried out under a slurry of the ion-exchanged layered silicate particles or the ion-exchanged layered silicate in order to react efficiently and uniformly. is preferred.
There are no particular limitations on the solvent for slurry formation. A solvent that does not cause a reaction during acid treatment is preferred, and water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, etc. is preferred. More preferred is water. Further, these solvents may be used alone or in combination of two or more.

There are no particular limitations on the acid concentration (mass percentage of acid with respect to the total mass of the reaction system) during acid treatment. The acid concentration is preferably 3% to 50% by weight, more preferably 4% to 40% by weight, even more preferably 5% to 20% by weight.
Furthermore, there is no limit to the temperature during acid treatment. The temperature is preferably 30°C to 102°C, more preferably 40°C to 100°C, even more preferably 50°C to 95°C.
There is also no particular restriction on the solid content concentration in the solvent during acid treatment. The concentration is preferably 3% to 50% by weight, more preferably 5% to 30% by weight, even more preferably 8% to 20% by weight.
There is also no limit to the time of acid treatment. The time is preferably 5 minutes to 3000 minutes, more preferably 10 minutes to 1500 minutes, and even more preferably 30 minutes to 750 minutes.
The degree to which impurities, cations, etc. are eluted can be adjusted by appropriately selecting the type of acid, the concentration of acid, treatment temperature, treatment time, etc.
Moreover, it is also possible to perform the acid treatment in multiple steps.

(3) Base treatment The ion-exchanged layered silicate particles used in the present invention are obtained by subjecting the ion-exchanged layered silicate particles or ion-exchanged layered silicate to a base treatment in which they are brought into contact with a base. It's okay.
After the ion-exchange layered silicate particles or the ion-exchange layered silicate are subjected to the acid treatment, they may be further subjected to a base treatment by contacting them with a base.
The base treatment dissolves impurities and exchanges cations present between the layers of the ion-exchangeable layered silicate. In addition, the base treatment changes the characteristics of the pore structure by eluting some or all of the cations such as aluminum, iron, magnesium, and even silicon that constitute the crystal structure of the ion-exchanged layered silicate. , and the specific surface area can be increased.

The bases used in base treatment are substances that act as Brønsted bases. Bases are substances that have the property of reacting with protons to generate water (neutralization reaction). Preferred examples include hydroxides of metals selected from the group consisting of alkali metals, alkaline earth metals, and metals of groups 3 to 14 of the periodic table. More preferred are hydroxides of alkali metals, alkaline earth metals, Mn, Fe, Ni, Cu, Zn, Al, Sn, and Pb. More preferred are hydroxides of alkali metals, alkaline earth metals, Mg, Zn, and Al.
The bases are 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 , _Cs2CO3 , _Rb2CO3 , _BeCO3 , _MgCO3 , _{CaCO3 , MnCO3 ,} CuCO3, _Al2 (CO) ₃ , ZnCO3 _{, PbCO3} , LiHCO3, _{NaHCO3 , RpHCO3 ,} C sHCO ₃ , Ca(HCO ₃ ) ₂ , Mg(HCO ₃ ) ₂ and the like.
The bases may be used alone or in combination. There are no particular restrictions on how to use it.
When brought into contact with the ion-exchange layered silicate particles, the base may be dissolved in a solvent or may remain solid. When it is dissolved in a solvent and brought into contact, there is no restriction on its concentration, and the upper limit is preferably a saturation concentration or less.

The base treatment is preferably carried out under a slurry of ion-exchangeable layered silicate particles or under a slurry of ion-exchangeable layered silicate in order to react efficiently and uniformly.
Examples of the solvent for slurrying include water and organic solvents such as alcohol. Preferably ethanol, methanol, ethylene glycol, glycerin, or water, more preferably water. Further, these solvents may be used alone or in combination of two or more.

The amount of the base used varies depending on the amount of acid contained in the ion-exchange layered silicate particle slurry or the ion-exchange layered silicate slurry before contact with the base, and the purpose of the treatment.
When using an ion-exchanged layered silicate particle slurry or an ion-exchanged layered silicate slurry after acid treatment using water as a solvent, the amount of bases used is such that the pH during the base treatment step is 8 or less, and The amount is preferably such that the pH is 4.5 to 8 upon completion of the base treatment step.

Furthermore, there is no restriction on the temperature during the base treatment. The temperature is preferably -20°C to 120°C, more preferably 0°C to 105°C, even more preferably 10°C to 80°C.
There is no particular limit to the solid content concentration in the solvent during base treatment. The concentration is preferably 1% to 50% by weight, more preferably 2% to 30% by weight, even more preferably 3% to 20% by weight.
There is also no limit to the time of base treatment. The time is preferably 1 minute to 600 minutes, more preferably 5 minutes to 300 minutes, even more preferably 10 minutes to 120 minutes.
The degree to which impurities, cations, etc. are eluted can be adjusted by appropriately selecting the type of base, concentration of base, treatment temperature, treatment time, etc.
Moreover, it is also possible to perform the base treatment in multiple steps.

(4) Other chemical treatments In the present invention, the ion-exchange layered silicate particles or the ion-exchange layered silicate may be subjected to other chemical treatments in addition to acid treatment and base treatment.
After the ion-exchange layered silicate particles or the ion-exchange layered silicate are subjected to the acid treatment or the base treatment, they may be further subjected to other chemical treatments.

Other chemical treatments include contact with a treatment agent containing salts, oxidizing agents, reducing agents, or compounds that can intercalate between layers of the ion-exchanged layered silicate, and washing with a solvent.
Intercalation refers to introducing another substance between layers of a layered material. The introduced substance is called a guest compound.
In addition, intercalation, salt treatment, acid treatment, or base treatment can form ionic complexes, molecular complexes, organic derivatives, etc., and change the surface area and interlayer distance.
By utilizing ion exchange properties and replacing exchangeable ions between layers with other large bulky ions, it is also possible to obtain a layered material in which the interlayers are expanded. In other words, bulky ions play the role of pillars that support the layered structure, and are called pillars. Specific examples of the processing agent are shown below.

The salts include cations selected from the group consisting of organic cations and inorganic cations including metal ions, and anions selected from the group consisting of organic anions and inorganic anions including halide ions. Examples include salts composed of For example, a cation containing at least one atom selected from Groups 1 to 14 of the periodic table, and at least one member selected from the group consisting of a halogen anion, an inorganic Brønsted acid, and an organic Brønsted acid anion. A preferred example is a compound consisting of an anion of Particularly preferred are compounds in which the anion is an inorganic Brønsted acid or a halogen.

Specific examples of such salts include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, Na ₂ SO ₄ , Na ₃ (PO ₄ ). , _NaNO3 , Na( _OOCCH3 ), KCl, KBr _{, K2SO4} , K3( _PO4 ), _{KNO3 ,} K( _OOCCH3 ), _CaCl2 , _CaSO4 , Ca( _NO3 ) ₂ , _Ca3 ( _{C6H5O7 ) 2} , Ti( _OOCCH3 ) ₄ , Ti( _CO3 ) ₂ , Ti( _{NO3 ) 4} , Ti( _SO4 ) ₂ , _TiF4 , _TiCl4 , _TiBr4 , _TiI4 , Zr(OOCCH ₃ ) ₄ , Zr(CO ₃ ) ₂ , Zr(NO ₃ ) ₄ , Zr(SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrBr ₄ , ZrI ₄ , ZrOCl ₂ , ZrO(NO ₃ ) ₂ , ZrO( _ClO4 ) ₂ , ZrO( _SO4 ), Hf( _OOCCH3 ) ₄ , Hf( _CO3 ) ₂ , Hf( _NO3 ) ₄ , Hf( _SO4 ) ₂ , _HfOCl2 , _HfF4 , _HfCl4 , HfBr4 _{, HfI4 , CuCl2} , _CuBr2 , Cu _{( NO3} ) ₂ , CuC2O4, Cu( _ClO4 ) ₂ , _CuSO4 , Cu( _OOCCH3 ) ₂ , Zn( _OOCH3 ) ₂ , Zn( _{CH3COCHCOCH3 ) 2} , _ZnCO3 , Zn( _NO3 ) ₂ , Zn( _ClO4 ) ₂ , _Zn3 ( _PO4 ) ₂ , _ZnSO4 , ZnF2 _, ZnCl2 _{, nBr2} , _ZnI2 , AlF3 _{, AlCl3} , _AlBr3 , _AlI3 , _Al2 ( _SO4 ) ₃ , _Al2 ( _{C2O4 ) 3} , Al _{( CH3COCHCOCH3} ) ₃ , Al( _NO3 ) ₃ , _AlPO4 , _GeCl4 , Sn Examples include (OOCCH ₃ ) ₄ , Sn(SO ₄ ) ₂ , SnF ₄ , SnCl ₄ and the like, but are not limited thereto.

Examples of organic cations include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,5- Pentamethylanilinium, N,N-dimethyloctadecyl ammonium, octadodecyl ammonium, N,N-2,4,5-pentamethylanilinium, N,N-dimethyl-pn-butylanilinium, N,N- Ammonium compounds such as dimethyl-p-trimethylsilylanilinium, N,N-dimethyl-1-naphthylanilinium, N,N,2-trimethylanilinium, 2,6-dimethylanilinium, pyridinium, quinolinium, N-methylpyranilinium Nitrogen-containing aromatic compounds such as peridinium, 2,6-dimethylpyridinium, 2,2,6,6-tetramethylpiperidinium, oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, oxolanium, etc. , phosphonium compounds such as triphenylphosphonium, tri-o-tolylphosphonium, tri-p-tolylphosphonium, trimesitylphosphonium, and phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium. It is not limited to these.
Examples of anions include, in addition to the anions listed above, anions made of boron compounds and phosphorus compounds, such as hexafluorophosphate, tetrafluoroborate, and tetraphenylborate, but are limited to these. It is not something that will be done.
Moreover, these salts may be used alone or in combination of two or more types.

The salts may be further used in combination with acids, bases, oxidizing agents, reducing agents, or compounds that intercalate between layers of the ion-exchanged layered silicate.
These combinations may be used in combination with the processing agents added at the start of the treatment. Further, processing agents added during the processing may be used in combination.

In the above-mentioned salt treatment, a suitable solvent may be used, and a processing agent may be dissolved therein to be used as a processing agent solution. Furthermore, the processing agent itself may be used as a solvent.
Examples of solvents that can be used include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethyl formamide. Preferred are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers, more preferred are water, alcohols, aliphatic hydrocarbons, and ethers, and particularly preferred are water and alcohols.
Further, the concentration of the processing agent in the processing agent solution is preferably about 0.1% by mass to 100% by mass, more preferably about 5% by mass to 50% by mass. If the concentration of the processing agent is within this range, there is an advantage that the time required for processing is shortened and production can be carried out efficiently.

Further, as the chemical treatment, it is preferable to perform cleaning with a solvent. Washing dissolves impurities and exchanges cations present between the layers of the ion-exchangeable layered silicate. Furthermore, washing can remove acids, bases, salts, and solvents remaining during the treatment with the above-mentioned acids, bases, and salts.

Examples of the solvent used for cleaning include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethyl formamide. These may be used in combination of two or more types. Preferred are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers, more preferred are water, alcohols, aliphatic hydrocarbons, and ethers, and more preferred are water and alcohol. and mixed solvents thereof, particularly preferably water.
Furthermore, there is no restriction on the temperature during cleaning. The temperature is preferably 0°C to 100°C, more preferably 50°C to 95°C, even more preferably 10°C to 60°C.
There is no particular restriction on the solid content concentration in the solvent during washing. The concentration is preferably 3% to 50% by weight, more preferably 5% to 40% by weight, even more preferably 8% to 30% by weight.
There is also no limit to the cleaning time. The time is preferably 1 minute to 3000 minutes, more preferably 3 minutes to 1500 minutes, and even more preferably 5 minutes to 750 minutes.

There are no particular limitations on the solid-liquid separation method for separating the solvent and the ion-exchange layered silicate particles. Examples include sedimentation separation, filtration separation, centrifugal sedimentation separation and centrifugal filtration using centrifugal force. These may be performed multiple times, or multiple methods may be combined.
The cleaning rate is preferably 1/5 to 1/10000, more preferably 1/10 to 1/1000. Here, the cleaning rate represents the residual ratio of the solvent at the start of cleaning. For example, if cleaning is performed by bringing 100 L of solvent into contact with the ion exchange layered silicate particles and then removing 90 L of solvent, the cleaning rate will be (100-90)/100=1/10.
Further, washing is performed until the electrical conductivity of the supernatant liquid, which indicates the amount of remaining ions, is preferably 1000 mS/cm or less, more preferably 100 mS/cm or less, still more preferably 10 mS/cm or less, and most preferably 1 mS/cm or less. I can do it.

(5) Other steps After performing the above chemical treatment, it is preferable to dry the obtained ion-exchangeable layered silicate particles.
The drying method is not particularly limited, and various methods can be used for drying. Drying is preferably carried out so as not to cause structural destruction of the ion-exchange layered silicate particles.
The drying temperature can generally be 100°C to 800°C, preferably 120°C to 600°C, particularly preferably 150°C to 300°C.
The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours.
The atmosphere during drying is preferably dry air, dry nitrogen, dry argon, or under reduced pressure.

Since the characteristics of these ion-exchange layered silicate particles change depending on the drying temperature even if the structure is not destroyed, it is preferable to change the drying temperature depending on the application.
When used as a component of an olefin polymerization catalyst, the moisture content after removal is 3% by mass or less, when the moisture content when dehydrated for 2 hours at a temperature of 200°C and a pressure of 1mmHg is 0% by mass. , preferably 1% by mass or less.

2. Component [B]
Component [B] of the olefin polymerization catalyst used in the present invention is a transition metal compound.
Component [B] may be a transition metal compound of Group 4 of the periodic table. A preferred transition metal compound of Group 4 of the periodic table is a metallocene compound having at least one conjugated five-membered ring ligand. Preferred such transition metal compounds are compounds represented by the following general formulas (1) to (4).

［上記一般式（１）～（４）中、ＡおよびＡ’は、置換基を有してもよい共役五員環配位子（同一化合物内においてＡおよびＡ’は同一でも異なっていてもよい）を示し、
Ｑは、二つの共役五員環配位子を任意の位置で架橋する結合性基を示し、Ｚは、窒素原子、酸素原子、ケイ素原子、リン原子またはイオウ原子を含む配位子、水素原子、ハロゲン原子、又は炭化水素基を示し、Ｚ’は、窒素原子、酸素原子、ケイ素原子、リン原子またはイオウ原子を含む配位子、又は炭化水素基を示す。
Ｑ’は、共役五員環配位子の任意の位置とＺを架橋する結合性基を示し、Ｍは、周期表第４族から選ばれる金属原子を示し、ＸおよびＹは、水素原子、ハロゲン原子、炭化水素基、アルコキシ基、アミノ基、リン原子含有炭化水素基またはケイ素原子含有炭化水素基（同一化合物内においてＸ及びＹは、同一でも異なっていてもよい。）を示す。］

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

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

The substituent on the conjugated five-membered ring ligand includes a hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, and a 1-carbon group substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. -30 hydrocarbon groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, etc., alkoxy groups having 1 to 12 carbon atoms, for example, silicon atoms represented by -Si(R ¹ )(R ² )(R ³ ) Examples thereof include a phosphorus atom-containing hydrocarbon group represented by -P(R ¹ )(R ² ), or 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.
The above R ¹ , R ² and R ³ may be the same or different and represent an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.
Further, the substituent on the conjugated five-membered ring ligand may have at least one group 15 and 16 element of the periodic table (ie, a hetero element). Such a substituent is preferably a monocyclic or polycyclic group containing at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom in a 5- or 6-membered ring. Included are cyclic substituents. More preferred are substituents derived from optionally substituted heteroaromatic compounds, and particularly preferred are optionally substituted furyl groups and optionally substituted thienyl groups. In the case of a compound having a crosslinking group represented by general formula (2) or (4), these substituents are not particularly limited; (based on the body part) is preferable.

Q is a bonding group that bridges two conjugated five-membered ring ligands at any position, and Q' is a bond that bridges any position of the conjugated five-membered ring ligand and the group indicated by Z. Represents a sexual group.
Specific examples of Q and Q' include the following groups.
(a) Alkylene groups such as methylene group, ethylene group, isopropylene group, dimethylmethylene group, phenylmethylmethylene group, diphenylmethylene group, cyclobutylene group, cyclohexylene group (b) Dimethylsilylene group, diethylsilylene group, Silylene groups such as propylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisilylene group, silacyclobutylene group (c) Hydrocarbon group Substituted germylene group, substituted phosphorus group, substituted amino group, substituted boron group or substituted alumylene group substituted with

Furthermore, specifically, ( _{CH3 ) 2Ge} , _{( C6H5} ) _{2Ge ,} ( _CH3 )P, _{( C6H5} )P, ( _C4H9 )N, ( _C6H5 )N, (C ₄ H ₉ )B, (C ₆ H ₅ )B, (C ₆ H ₅ )Al, (C ₆ H ₅ O)Al, and the like. Preferred are alkylene groups or silylene groups.

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

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

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

Examples of the compound represented by general formula (2) include:
(1) dimethylsilylene bis{1-(2-methyl-4-isopropyl-4H-azulenyl)}zirconium dichloride,
(2) dimethylsilylene bis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium dichloride,
(3) dimethylsilylenebis[1-{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium dichloride,
(4) dimethylsilylene bis[1-{2-methyl-4-(2,6-dimethylphenyl)-4H-azulenyl}]zirconium dichloride,
(5) dimethylsilylene bis{1-(2-methyl-4,6-diisopropyl-4H-azulenyl)}zirconium dichloride,
(6) diphenylsilylene bis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium dichloride,
(7) dimethylsilylene bis{1-(2-ethyl-4-phenyl-4H-azulenyl)}zirconium dichloride,
(8) ethylenebis{1-[2-methyl-4-(4-biphenylyl)-4H-azulenyl]}zirconium dichloride,
(9) dimethylsilylene bis{1-[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]}zirconium dichloride,
(10) dimethylsilylene bis{1-[2-methyl-4-(2',6'-dimethyl-4-biphenylyl)-4H-azulenyl]}zirconium dichloride,
(11) Dimethylsilylene {1-[2-methyl-4-(4-biphenylyl)-4H-azulenyl]} {1-[2-methyl-4-(4-biphenylyl)indenyl]} zirconium dichloride,
(12) dimethylsilylene {1-(2-ethyl-4-phenyl-4H-azulenyl)} {1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(13) dimethylsilylene bis{1-(2-ethyl-4-phenyl-7-fluoro-4H-azulenyl)}zirconium dichloride,
(14) dimethylsilylene bis{1-(2-ethyl-4-indolyl-4H-azulenyl)}zirconium dichloride,
(15) dimethylsilylene bis[1-{2-ethyl-4-(3,5-bistrifluoromethylphenyl)-4H-azulenyl}]zirconium dichloride,
(16) dimethylsilylene bis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium bis(trifluoromethanesulfonic acid),
(17) dimethylsilylene bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,
(18) dimethylsilylene bis{1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride,
(19) dimethylsilylene bis[1-{2-methyl-4-(1-naphthyl)indenyl}]zirconium dichloride,
(20) dimethylsilylene bis{1-(2-methyl-4,6-diisopropylindenyl)}zirconium dichloride,

(21) dimethylsilylene bis{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) Isopropylidene bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,
(25) ethylene-1,2-bis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium dichloride,
(26) Isopropylidene bis{1-(2-methyl-4-phenyl-4H-azulenyl)}zirconium dichloride,
(27) dimethylgermylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,
(28) dimethylgermylenebis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
(29) phenylphosphinobis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
(30) dimethylsilylenebis[3-(2-furyl)-2,5-dimethyl-cyclopentadienyl]zirconium dichloride,
(31) dimethylsilylene bis[2-(2-furyl)-3,5-dimethyl-cyclopentadienyl]zirconium dichloride,
(32) dimethylsilylene bis[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) dimethylsilylene bis[2-(2-thienyl)-indenyl]zirconium dichloride,
(36) dimethylsilylene [2-(2-(5-methyl)furyl)-4-phenylindenyl][2-methyl-4-phenylindenyl]zirconium dichloride,
(37) dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)zirconium dichloride,
(38) dimethylsilylenebis(2,3-dimethyl-5-ethylcyclopentadienyl)zirconium dichloride,
(39) dimethylsilylenebis(2,5-dimethyl-3-phenylcyclopentadienyl)zirconium dichloride,
(40) silacyclobutylene bis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride,

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

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

(81) silacyclobutylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(82) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(83) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(84) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-1,5,6,7-tetrahydro-s-indacene-1- il] zirconium dichloride,
(85) silacyclobutylene bis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(86) silacyclobutylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(87) silacyclobutylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(88) Silacyclobutylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacen-1-yl]zirconium dichloride,
(89) Silacyclobutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacene-1 -yl] zirconium dichloride,
(90) silacyclobutylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2,5-dimethyl-4-phenyl-1-indenyl] zirconium dichloride,
(91) Silacyclobutylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(2-furyl)-4-phenyl-5-methyl-1- indenyl] zirconium dichloride,
(92) Silacyclobutylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-t-butyl-2-furyl)-4-phenyl- 5-methyl-1-indenyl]zirconium dichloride,
(93) Silacyclobutylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-1- indenyl] zirconium dichloride,
(94) silacyclobutylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-5, 6-dimethyl-1-indenyl]zirconium dichloride,
(95) silacyclobutylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-1, 5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(96) silacyclopentylene bis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride,
(97) silacyclopentylene bis[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride,
(98) silacyclopentylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
(99) Silacyclopentylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, etc. .

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

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

Compounds in which dichloride in these exemplified compounds is replaced with dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide, etc. are also exemplified. Furthermore, compounds in which zirconium in the exemplified compounds 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 general formula (2) is preferable.
Note that the 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 group of compounds included in any one of the above general formulas (1) to (4). Furthermore, one or more types selected from a group of compounds included in one general formula and one or more types selected from a group of compounds included in another general formula can also be selected.

3. Component [C]
Component [C] of the olefin polymerization catalyst used in the present invention is an organoaluminum compound.
The organoaluminum compound may be an organoaluminum compound represented by the general formula (AlR _n X _3-n ) _m . In the formula, R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen atom, a hydrogen atom, an alkoxy group, or an amino group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2. . The organoaluminum compounds can be used alone or in combination.

Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, trinarypropylaluminum, trinarybutylaluminum, triisobutylaluminum, trinahexylaluminum, trinaryoctylaluminum, trinormaldecylaluminum, diethylaluminium chloride, diethylaluminium. Examples include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride, and the like.
Among these, preferred are trialkylaluminum and alkylaluminum hydride where m=1 and n=3.
More preferably, R is trialkylaluminum having 1 to 8 carbon atoms.

4. Preparation of Olefin Polymerization Catalyst, Prepolymerization The olefin polymerization catalyst used in the present invention is prepared by contacting the component [A], the component [B], and, if necessary, the component [C].
Although the contact method is not particularly limited, the contact can be performed in the following order.
Further, this contact may be carried out not only during catalyst preparation but also during prepolymerization with olefin or during olefin polymerization. A solvent may be used in these contacts to ensure sufficient contact. Furthermore, a polyoxyethylene compound may be added during the production of the olefin polymerization catalyst.
1) Bringing component [B] and component [A] into contact 2) Adding component [C] after bringing component [B] and component [A] into contact 3) Bringing component [B] and component [C] into contact 4) Add component [B] after contacting component [A] and component [C]. Alternatively, the three components may be brought into contact at the same time.
When adding the polyoxyethylene compound (referred to as component [D]) during the production of an olefin polymerization catalyst, it can be added as follows.
5) Add component [B] after contacting component [A] and component [D]. 6) Add component [C] after contacting component [B] and component [A], then add component [D]. 7) After bringing component [B] and component [A] into contact, add component [D] and then adding component [C]. 8) After bringing component [B] and component [C] into contact, add component [D]. ], then add component [A] 9) After contacting component [B] and component [C], add component [A] and then add component [D] 10) Component [A] and component [C] 11) After bringing component [A] and component [C] into contact, add component [D] and then add component [B] Other, 4 The components may be contacted simultaneously.
From the viewpoint of efficiently obtaining the effect with the minimum amount added, it is preferable to add the polyoxyethylene compound by the above method. At this time, the amount of component [D] added is based on the catalyst (ion exchange layered (the sum of the masses of the silicate particles and the transition metal compound), the upper limit may be 0.2% by mass or less.

A preferable contact method is the method 4) above, and among them, after bringing the component [A] and the component [C] in 4) into contact with each other, unreacted component [C] is removed by washing etc., and then the contact is carried out again. This is a method in which a necessary minimum amount of component [C] is brought into contact with component [A], and then component [B] is brought into contact with component [A].
When bringing a polyoxyethylene compound (referred to as component [D]) into contact with each other during the production of a catalyst component for olefin polymerization, a preferred method is the method described in 11) above, and in particular, the method described in 11) above, in which component [A] and component [ After contacting component [C], unreacted component [C] is removed by washing, etc., and then component [D] is brought into contact with component [C], and the necessary minimum amount of component [C] is brought into contact with component [A] again. , followed by contacting component [B].

The molar ratio of Al in component [C] to the transition metal in component [B] is in the range of 0.1 to 1000, preferably 1 to 100, more preferably 4 to 50.

The contact temperature is not particularly limited, but is preferably 0°C to 100°C, more preferably 10°C to 80°C, particularly preferably 20°C to 60°C.

As the solvent, organic solvents are preferred. More preferred are saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, and olefins described below. These may be used alone or in combination.
The concentration of component [B] in the solvent is also not limited, but is preferably 3 mmol/L to 50 mmol/L, more preferably 4 mmol/L to 40 mmol/L, and still more preferably 6 mmol/L to 30 mmol/L.
The amount of component [B] used is more preferably in the range of 0.001 mmol to 10 mmol, preferably 0.001 mmol to 1 mmol, per 1 g of component [A].

The olefin polymerization catalyst used in the present invention may be subjected to a preliminary polymerization treatment in which a small amount of olefin is polymerized by contacting the catalyst.
The olefin used is not particularly limited. It is possible to use ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, or styrene, in particular ethylene , or propylene is preferably used.
Any method can be used to supply the olefin. Examples include a method of supplying olefin to a reactor at a constant rate or a constant pressure state, a combination thereof, and a method of making 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 such that the mass of the prepolymerized polymer is preferably 0.01 to 100, more preferably 0.1 to 50, per 1 part of component [A].
The prepolymerization temperature is not particularly limited, but is preferably 0°C to 100°C, more preferably 10°C to 70°C, particularly preferably 20°C to 60°C, even more preferably 30°C to 50°C.
Prepolymerization can also be carried out in a liquid such as an organic solvent, and this is preferred.
The concentration of the solid catalyst during prepolymerization is not particularly limited, but is preferably 10 g/L to 300 g/L, more preferably 20 g/L to 200 g/L, particularly preferably 25 g/L to 150 g/L.

The catalyst may be dried after contacting each component.
There are no particular restrictions on the drying method. Examples include drying under reduced pressure, drying by heating, and drying by circulating dry gas. These methods may be used alone or in combination of two or more.
In the drying process, the catalyst may be stirred, vibrated, flowed, or allowed to stand still.

Furthermore, it is also possible to coexist a polymer such as polyethylene, polypropylene, polystyrene, or an inorganic oxide solid such as silica or titania during or after the contact of the above-mentioned components. Furthermore, alkoxysilanes, aminosilanes, ethers, phthalic esters, carboxylic esters, etc., which are known as donors in olefin polymerization catalysts, can also be added.

II. Polyoxyethylene compound The polyoxyethylene compound added in the method for producing an olefin polymer of the present invention is a polyoxyethylene compound represented by the following general formula (I) and having a number average molecular weight of 500 or more and 8000 or less. .
Formula (I): R ^a -((CH ₂ CH ₂ O) _n -R ^b ) _m
[In formula (I),
R ^a is an m-valent substituent composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom,
R ^b is each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, an alkali metal atom, and an alkaline earth metal atom. is a monovalent substituent,
m is an integer from 1 to 6,
n is an integer of 2 or more,
When m is 2 or more, a plurality of R ^b's and n's may be the same or different. ]

There is no particular restriction on n as long as it is 2 or more, but the upper limit is preferably 100 or less, more preferably 50 or less, particularly preferably 25 or less.

The reason why a sufficient effect can be obtained by using the polyoxyethylene compound in which n is 2 or more is not clear, but it can be considered as follows. That is, according to Davies' HLB (Hydrophilic-Lipophilic Balance) Group Number, the oxyethylene group is 0.33 and is a so-called hydrophilic group, so it forms a certain amount of aggregates in a hydrophobic environment such as an olefin polymerization environment. It is presumed that it is. On the other hand, in the olefin polymerization catalyst containing ion-exchanged layered silicate particles of the present application, polymerization active sites exist on the outer surface of the ion-exchanged layered silicate particles, but most of them are located on the inner surface (inside the pores). It is thought that it is distributed in When the polyoxyethylene compound aggregates, it is no longer able to diffuse into the pores of the ion-exchange layered silicate particles, and the overall activity is reduced by selectively deactivating only the polymerization active sites on the outer surface. It is thought that this method is effective in suppressing the formation of bulk polymers and deposits on the reactor without causing any damage. If n is small and aggregates cannot be formed, the polyoxyethylene compound will diffuse into the pores, and although the effect of suppressing the generation of lumpy polymers and deposits will be exerted, the catalyst deactivation effect will become large.
Alternatively, it is also possible that the aggregate acts as an antistatic agent and suppresses the formation of bulk polymers and deposits on the reactor. Therefore, it is presumed that a sufficient effect can be obtained when n is 2 or more. Furthermore, it is presumed that by setting n to an appropriate size, the aggregate of oxyethylene groups will have an appropriate size, maintaining dispersibility within the polymerization system, and exhibiting sufficient effects.

The lower limit of the number average molecular weight of the polyoxyethylene compound used in the present invention is 500 or more, more preferably 700 or more, even more preferably 900 or more, and may be 1200 or more, or 1500 or more. . On the other hand, the upper limit is 8000 or less, preferably 6000 or less, more preferably 5000 or less. Any combination of the upper limit and lower limit can be adopted.
It is not clear why there is an optimal range for the number average molecular weight, but as with n, if it is within the above range, catalyst deactivation due to diffusion into the pores of the ion-exchangeable layered silicate particles is suppressed. It is presumed that the effect is sufficiently exerted by maintaining dispersibility within the polymerization system and on the outer surface of the catalyst.

R ^a is an m-valent substituent that bonds to the carbon atom of the polyoxyethylene group. When R ^a is monovalent, examples thereof include the same groups as R ^c in general formula (II) and R ^c in general formula (III), which will be described later, to which a polyoxypropylene group is added. When R ^a is divalent, examples thereof include the same compounds as R ^e in general formula (IV) and -O(CH ₂ CHR ^f O) _h - in general formula (V), which will be described later. When R ^a is trivalent to hexavalent, for example, a trivalent or more alkoxy group or an aryloxy group derived by removing a hydrogen atom from three or more hydroxyl groups in a polyol, a phosphoric acid group ((O=)P( -O-) ₃ ), boric acid group (B(-O-) ₃ ), and the like. When R ^a is trivalent to hexavalent, one or more selected from the group consisting of an amino group, an amide group, a sulfonamide group, and a urethane group similar to R ^e in the general formula (IV) described below is further added. It may be a polyvalent substituent having a valence of 3 or more.
R ^b is a monovalent substituent that bonds with oxygen of the polyoxyethylene group, and examples thereof include the same substituents as R ^d in general formula (II) described below.

Examples of preferred structures include compounds represented by the following general formula (II), where m=1 in the above general formula (I).
Formula (II): R ^c -(CH ₂ CH ₂ O) _n - R ^d
[In formula (II), R ^c is a hydroxyl group, an alkoxy group (R ^c' O), an aryloxy group (R ^c'' O), an amino group ((R ^c' ) ₂ N), an amide group (R ^c' CONH), and a monovalent substituent selected from the group consisting of an acyloxy group (R ^c' COO) (where R ^c' is an alkyl group having 1 to 30 carbon atoms, and R ^c'' is an alkyl group having 6 to 30 carbon atoms); 30 aryl group or alkyl-substituted aryl group),
R ^d is a hydrogen atom, an acyl group (COR ^d' , COR ^d'' ), a sulfate ester (SO ₃ R ^d' ), a sulfate (SO ₃ M), a phosphate ester (P(=O) (OR ^d' ) ₂ ), phosphates (P(=O)(OH)(OM)), borate esters (B(OR ^d' ) ₂ ), and borates (B(OH)(OM)) ^A monovalent ^substituent selected from (SO ₃ M) is a substituted group, M is an alkali metal atom, triethanolamine, or ammonium),
n is an integer of 2 or more. ]

Examples of the alkyl group having 1 to 30 carbon atoms in R ^c' and R ^d' include methyl group, ethyl group, butyl group, dodecyl group (lauryl group), tetradecyl group (myristyl group), hexadecyl group (cetyl group) , octadecyl group (stearyl group), and the like.
Examples of the aryl group or alkyl-substituted aryl group having 6 to 30 carbon atoms in R ^c'' include phenyl group, tolyl group, tribenzylphenyl group, and the like.
Examples of the alkoxy group include ethoxy group, butoxy group, lauryloxy group, cetyloxy group, myristyloxy group, and stearyloxy group.
Examples of the aryloxy group include a phenoxy group and a tribenzylphenyloxy group.
Examples of the amino group include an amino group (NH ₂ ), a dimethylamino group, and a diethylamino group.
Examples of the amide group include laurylamide group, cetylamide group, myristylamide group, and stearylamide group.
In addition, examples of the acyloxy group include propanoyloxy group, dodecanoyloxy group, tetradecanoyloxy group, hexadecanoyloxy group, octadecanoyloxy group, etc. ) and/or sulfate (SO ₃ M).
n in formula (II) may be the same as n in formula (I).

More specifically, the compound represented by the general formula (II) includes polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene myristyl ether, polyoxyethylene stearyl ether, polyoxyethylene phenyl ether, polyoxyethylene (tribenzyl) phenyl ether,
Polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, polyoxyalkylene lauryl ether sulfate ammonium, polyoxyethylene lauryl disodium sulfosuccinate,
Examples include polyethylene glycol distearate, polyethylene glycol monostearate, polyoxyethylene lauryl ether phosphate, polyoxyethylene phenyl ether phosphate, and the like.

A more preferable example where m=1 is a compound represented by the following general formula (III).
Formula (III): R ^c -(CH ₂ CH (CH ₃ ) O) _k - (CH ₂ CH ₂ O) _n - (CH ₂ CH (CH ₃ ) O) _l - R ^d
[In formula (III), R ^c and R ^d are as described in formula (II).
k and l are each independently an integer of 0 or more, k+l is 1 or more, and n is an integer of 2 or more. ]

k and l are each independently an integer of 0 or more, and there is no particular restriction as long as they do not become 0 at the same time, but since the effect of the polyoxyethylene group is likely to be obtained when k+l is an appropriate size, preferably k+l is 1 or more and 200 or less, more preferably 1 or more and 100 or less, even more preferably 1 or more and 80 or less.
n in formula (III) may be the same as n in formula (I).
When k and l are each 1 or more, what is known as a reverse type of pluronic surfactant (polyoxyethylene polyoxypropylene block copolymer) can be used. These are commercially available under the trade names Pluronic (BASF) and ADEKA Pluronic (ADEKA), and include structures such as 31R1, 25R1, 10R5, 10R8, 17R2, 17R4, 25R2, and 25R4. Here, the number before R indicates the molecular weight, and the number after R indicates the content of polyoxyethylene groups.

In the above general formula (I), particularly preferably as a compound where m=1, k and l are each 1 or more among polyethylene glycol, polyethylene glycol monoether, and a compound represented by general formula (III). compound (reverse type pluronic surfactant).

In the above general formula (I), a preferable example when m=2 is a compound represented by the following general formula (IV).
Formula (IV): R ^d -(OCH ₂ CH ₂ ) _i -R ^e -(CH ₂ CH ₂ O) _j -R ^d
[In formula (IV), R ^d is as described in formula (II).
R ^e is a divalent alkoxy group (-O-R ^e' -O-), an aryloxy group (-O-R ^e" -O-), an amino group (R ^e'" N=), an amide group (R ^e'" CON=), sulfonamide group (R ^e'" SO ₂ N=), urethane group (-OCONH-R ^e" -NHCOO-), phosphoric acid group (-O-P(=O) (OH) -O-), and a divalent substituent selected from the group consisting of a boric acid group (-O-B(OH)-O-) (where R ^e' is an alkylene group having 1 to 30 carbon atoms; , R ^e" is an arylene group having 6 to 30 carbon atoms or an alkyl- or alkylene-substituted arylene group; R ^e'" is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl-substituted arylene group) It may also be a group in which a polyoxypropylene group is added to these,
i and j are each independently an integer of 2 or more. ]

The upper limit of i+j is preferably 100 or less, more preferably 50 or less, particularly preferably 25 or less.

Examples of the alkylene group having 1 to 30 carbon atoms in R ^e' include a methylene group, an ethylene group, a propylene group, a butylene group, and the like.
Examples of the arylene group having 6 to 30 carbon atoms or the alkyl- or alkylene-substituted arylene group in "R ^e" include a phenylene group, a bisisopropylidenephenylene group, and the like.
Examples of the alkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, or alkyl-substituted aryl group in R ^e''' include the alkyl group having 1 to 30 carbon atoms in R ^c' explained in formula (II); It may be the same as the aryl group having 6 to 30 carbon atoms or the alkyl-substituted aryl group in "R ^c" .

Specific examples of the compound represented by the general formula (IV) include N,N-bis(polyoxyethylene)octadecylamine, N,N-bis(polyoxyethylene)p-toluenesulfonic acid amide, N, Examples include N-bis(polyoxyethylene)tolylamine, bisphenol A ethylene oxide adduct, and urethane compounds obtained by addition-reacting a compound having two isocyanate groups such as xylylene diisocyanate with a polyethylene glycol derivative.

In the above general formula (I), a particularly preferable example when m=2 includes a structure as shown in the following general formula (V).
Formula (V): R ^d -(OCH ₂ CH ₂ ) _i -O(CH ₂ CHR ^f O) _h -(CH ₂ CH ₂ O) _j -R ^d
[In formula (V), R ^d is as described in formula (II).
R ^f is a methyl group or an ethyl group.
i and j are each independently an integer of 2 or more, and h is an integer of 1 or more. ]

The upper limit value of i+j may be the same as that described in formula (IV) above.
The upper limit of h is preferably 100 or less, more preferably 85 or less, particularly preferably 70 or less.

In formula (V), when each R ^d is a hydrogen atom, a compound known as a pluronic surfactant (polyoxyethylene polyoxypropylene block copolymer or polyoxyethylene polyoxybutylene block copolymer) may be used. I can do it. The structure of such a compound can be represented by a Pluronic grid (for example, Journal of the Japan Oil Chemists' Society Vol. 49, No. 10 (2000), Current Opinion in Colloid & Interface Science Volume 2, Issue 5, 1997, 478, etc.). These are also commercially available under the trade names Pluronic (BASF) and ADEKA Pluronic (ADEKA), and in this application, L121, L122, L81, L82, L72, L71, L62, L61, etc. are liquids, It is particularly preferred because it has a relatively low viscosity, is easy to handle, and has excellent balance in anti-adhesion performance.
In the polyoxyethylene/polyoxypropylene block copolymer or the polyoxyethylene/polyoxybutylene block copolymer, the preferable range of the polyoxyethylene content is such that the upper limit is 30% by mass or less, more preferably 20% by mass or less, and the lower limit is 30% by mass or less. is 5% by mass or more, more preferably 10% by mass or more. Further, the preferable range of the number average molecular weight is such that the upper limit is 5,000 or less, more preferably 4,000 or less, and the lower limit is 900 or more.

When m is 3 or more, the structure of R ^a is a polyvalent substituent derived from a polyol represented by a sugar alcohol such as glycerin or pentaerythritol, or a polyvalent substituent derived from a synthetic polyol such as trimethylolpropane. , a polyvalent substituent derived from a polyol in which some hydroxyl groups of the polyol are condensed with a fatty acid or the like to have an ester structure.
Also included are polyvalent substituents derived from ethylenediamine and polyols obtained by adding polyoxypropylene groups to ethylenediamine.
Examples of the trivalent or higher polyvalent substituent derived from the polyol include trivalent or higher alkoxy groups or aryloxy groups derived by removing hydrogen atoms from three or more hydroxyl groups in the polyol.
Particularly preferred are polyvalent substituents derived from trimethylolpropane, pentaerythritol, sorbitan or sorbitan fatty acid esters. A compound having a substituent derived from a sorbitan fatty acid ester and a polyoxyethylene skeleton is known as a polysorbate, and examples thereof include polysorbate 20, 60, 65, and 80.
m is 6 or less, but may be 5 or less, or may be 4 or less.

In the method for producing the olefin polymer of the present invention, there is no particular restriction on the method of adding the polyoxyethylene compound, and it may be added when producing the olefin polymerization catalyst, or the polyoxyethylene compound may be added when producing the olefin polymerization catalyst and the olefin. It may be added to the reactor for the reaction, it may be added to both the reactor when producing the olefin polymerization catalyst and the reactor where the olefin polymerization catalyst and the olefin are reacted, or it may be added in multiple steps. Also good. Preferred is a method in which a polyoxyethylene compound is added when producing an olefin polymerization catalyst.
Moreover, a plurality of polyoxyethylene compounds may be used in combination, or may be added separately. In order to adjust the viscosity and the amount added, it may be used after being dissolved or dispersed in a solvent. As the solvent, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene can be used alone or in mixtures. Further, in order to adjust the solubility and viscosity in the solvent, the temperature may be adjusted by heating, cooling, etc.

In the method for producing an olefin polymer of the present invention, there is no particular restriction on the amount of polyoxyethylene compound added. Although addition can prevent lumps and adhesion, it is also possible to control catalyst activity at the same time. Control of the catalyst activity is sometimes carried out especially to adjust the composition of impact copolymers produced by multistage polymerization, and in this case, the amount added can be adjusted so as to obtain a desired polymer composition.
As for the specific amount added, when the reference is the catalyst (the sum of the masses of the ion exchange layered silicate particles and the transition metal compound), the lower limit is preferably 0.005% by mass, more preferably 0.01% by mass. %, more preferably 0.05% by mass, the upper limit is preferably 100% by mass or less, more preferably 50% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 1 It is preferably at most 0.5% by mass, even more preferably at most 0.2% by mass.

III. Method for producing an olefin polymer The method for producing an olefin polymer of the present invention involves adding the specific polyoxyethylene compound in the presence of the specific olefin polymerization catalyst to polymerize the olefin, thereby producing an olefin polymer. It is characterized by manufacturing.
In the method for producing an olefin polymer, olefins having 2 to 20 carbon atoms are homopolymerized or copolymerized in the presence of the olefin polymerization catalyst. That is, in this production method, one type of olefin is polymerized, or two or more types of olefins are copolymerized. In addition, in this specification, a polymer means at least one of a homopolymer and a copolymer.

In the case of copolymerization, the quantitative ratio of each monomer in the reaction system does not need to be constant over time, and it is also possible to supply each monomer at a constant mixing ratio. It is also possible to change the mixing ratio of monomers supplied over time. Further, any of the monomers can be added in portions taking into account the copolymerization reaction ratio.

The polymerizable olefin preferably has 2 to 20 carbon atoms, and specifically includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1, Examples include 7-octadiene, cyclopentene, norbornene, and ethylidene norbornene. Preferred are ethylene, propylene and α-olefins having 4 to 8 carbon atoms, and more preferred is ethylene or propylene.

In the case of copolymerization, the type of comonomer used can be one or more olefins other than the main component selected from those listed as the olefins. The preferred comonomer base is propylene.

Any polymerization mode may be adopted as long as the catalyst component and each monomer are brought into contact with each other efficiently. Specifically, the slurry method using an inert solvent, the method using a monomer such as propylene as a solvent without using an inert solvent, the solution polymerization method, or the method using each monomer without using a liquid solvent. A gas phase method that maintains it in a gaseous state can be used. Further, continuous polymerization, batch polymerization, or prepolymerization methods are also applicable.

In the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures as the polymerization solvent.
The polymerization temperature is usually 0°C to 150°C.

Additionally, hydrogen can be used as a molecular weight regulator. Further, in order to adjust the amount of reaction, a compound having an effect of deactivating the catalyst, such as oxygen or alcohol, may be supplied. Known additives such as oxygen, alcohol, and alkoxysilane may be added for the purpose of improving drivability.
The appropriate polymerization pressure is 0 kg/cm ² to 2000 kg/cm ² G (≈0 MPaG to 196.14 MPaG), preferably 0 kg/cm ² to 60 kg/cm ² G (≈0 MPaG to 5.88 MPaG).

The olefin polymer obtained by the above method for producing an olefin polymer is not particularly limited. For example, suitable examples include ethylene homopolymer, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, propylene/ethylene-olefin copolymer, and the like.

In the production method of the present invention, when adding a polyoxyethylene compound during polymerization, there are no particular restrictions on the method, place, or timing of addition. It may be added to the reactor at the same time as the catalyst or separately from the catalyst. Moreover, when performing multistage polymerization using a plurality of reactors, it may be added to all the reactors or only to a specific reactor. Further, it may be added to pipes through which solvents and monomers flow, or may be added to parts where adhesion or clogging is particularly likely to occur, such as pipes for instruments such as heat exchangers, filters, and pressure gauges. Further, it may be supplied continuously or may be added intermittently.
Among them, from the viewpoint of efficiently obtaining effects with respect to the amount added, there is a method in which the catalyst and the polyoxyethylene compound are added as a mixture, or a method in which the catalyst and the polyoxyethylene compound are added simultaneously or separately in the same reactor to which the catalyst is added. A method of adding is preferred.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by these Examples unless it departs from the gist thereof. Note that the measurement method in this example is as follows.

[Various physical property measurement methods]
1. Composition analysis of ion exchange layered silicate particles A calibration curve was created in accordance with JIS R2212, and the composition of the ion exchange layered silicate particles was determined by fluorescent X-ray measurement.
The device used was ZSX Primus IV manufactured by Rigaku Corporation.
After baking the sample at 1050°C for 1 hour, take 0.4g of the sample and mix it with 4g of flux (Li ₂ B ₄ O ₇ ) and 15 μL of 50% LiBr aqueous solution (mold release agent) to create glass beads. Prepared with

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

3. Specific Surface Area Measurement The adsorption and desorption isotherms of the ion-exchange layered silicate particles were measured by the nitrogen adsorption method.
BET multipoint analysis (Rouquerol transformation) was performed using the obtained adsorption isotherm to determine the specific surface area of the ion-exchange layered silicate particles.
The specific measurement conditions were as follows.
Equipment: Gas adsorption amount measuring device Autosorb-iQ3 manufactured by Anton-Paar
Measurement method: Nitrogen gas adsorption method Pretreatment conditions: Sample heated at 200°C under reduced pressure (1.3 Pa or less) for 2 hours Sample amount: Approx. 0.2 g
Gas liquefaction temperature: 77K

4. Measurement of average particle diameter of ion-exchange layered silicate particles The average particle diameter was measured using Horiba's laser diffraction/scattering particle size distribution analyzer LA-960, using ethanol as the dispersion solvent and a refractive index real number term of 1.490. , the imaginary term is 0.000, and the dispersion solvent refractive index real term is 1.360. The average particle diameter refers to the volume-based median diameter.

5. MFR (melt mass flow rate)
Using a melt indexer manufactured by Takara Corporation, the test conditions are 230°C and 2.16 kg load according to JIS K7210 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics and thermoplastics". It was measured by

6. Mass amount The polymer obtained by polymerization was placed on a sieve having a diameter of 300 mm and conforming to JIS Z 8801-1:2000, thoroughly shaken, the weight of the polymer remaining on the sieve was measured, and the weight was calculated using the following formula.
Amount of lumps (wt%) = Amount of polymer remaining on the sieve ÷ Amount of polymer introduced into the sieve x 100
The opening of the sieve was 2360 μm in the propylene homopolymerization experiment, and 2800 μm in the propylene-ethylene random copolymerization experiment.

7. BD (bulk density)
Using the polymer that passed through the sieve, bulk density was measured in accordance with ASTM 1895-96 TEST METHOD A.

8. Tm (melting point)
The melting point of the polymer was measured using a Seiko Instruments DSC6200 differential scanning calorimeter. A 5 mg sample piece made into a sheet using the polymer that passed through the sieve was packed in an aluminum pan, heated from room temperature to 200°C at a rate of 100°C/min, held at 200°C for 5 minutes, and then heated to 10°C. After crystallizing by lowering the temperature to 20°C at a rate of 10°C/min, a melting curve was obtained by increasing the temperature to 200°C at a rate of 10°C/min. The peak top temperature of the main endothermic peak in the heating stage of the melting curve was taken as the melting point.

9. Evaluation of deposits After polymer recovery, the interior of the polymerization reactor and the surface of the stirring blade were visually observed to confirm the presence or absence of deposits.

[Polyoxyethylene compounds and other reagents]
Commercially available reagents were obtained from the listed vendor and diluted with toluene to a concentration of 5 g/l. Note that aluminum distearate (DSA) was dried at 80° C. under reduced pressure before use, and since it was not completely dissolved in toluene, it was used as a toluene slurry.
The number average molecular weight etc. of each are shown in the table. In addition, PPG represents polypropylene glycol and PEG represents polyethylene glycol.
・31R1: Pluronic 31R1 (PPG-block-PEG-block-PPG) Sigma Aldrich Japan LLC ・L121: Pluronic L121 (PEG-block-PPG-block-PEG) Sigma Aldrich Japan LLC ・L81: Pluronic L81 (PEG- block-PPG-block-PEG ) Sigma Aldrich Japan LLC・L31: Pluronic L31 (PEG-block-PPG-block-PEG) Sigma Aldrich Japan LLC・PEG (23) L: Polyoxyethylene (23) Lauryl Ether Fuji Film Wako Pure Chemical Industries, Ltd.・PEG1000: Polyethylene glycol 1000 Tokyo Chemical Industry Co., Ltd.・Tween80: Polyoxyethylene sorbitan monooleate Tokyo Chemical Industry Co., Ltd.・Brij4: Polyoxyethylene (4) lauryl ether Sigma-Aldrich Japan LLC・LEA :N-lauryl diethanolamine Tokyo Chemical Industry Co., Ltd. DSA: Aluminum distearate Fujifilm Wako Pure Chemical Industries, Ltd.

[Synthesis Example 1: Production of catalyst for olefin polymerization]
(a) Chemical treatment of ion-exchanged layered silicate particles As a raw material, ion-exchanged layered silicate particles (“Benclay SL” manufactured by Mizusawa Chemical Industry Co., Ltd.) whose main component is smectite group montmorillonite with a 2:1 layer structure are used as raw materials. used.
The chemical composition of this raw material was Al/Si=0.289.

[Acid treatment]
1,300 g of distilled water was placed in a 2 L flask equipped with a stirring blade and a reflux device, and 168 g of 96% sulfuric acid was added dropwise.
The mixture was heated in an oil bath until the internal temperature reached 95°C, and when the target temperature was reached, 200 g of ion-exchanged phyllosilicate as a raw material was added and stirred.
Thereafter, the reaction was carried out for 540 minutes while maintaining the temperature at 95°C.
The reaction was stopped by pouring this reaction solution into 2 L of pure water, and further, this slurry was filtered using a device in which an aspirator was connected to a Nutsche and suction bottle.
The cake-like ion exchange layered silicate particles after filtration were rinsed with 1 L of distilled water.
902.1 g of distilled water was added to the above cake to form a slurry.
The pH of the slurry at this time was 1.7.

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

[Drying process]
The collected cake was dried at 110° C. overnight to obtain 140.8 g of chemically treated ion-exchanged layered silicate particles.
The chemically treated ion-exchanged layered silicate particles were placed in a flask having a volume of 1 L, and dried under reduced pressure at 200° C., and after gas generation had ceased, the particles were further dried under reduced pressure for 2 hours.
The Al and Si molar ratio (Al/Si) of the obtained ion-exchange layered silicate particles was 0.176, the elution rate of aluminum (Al) was 39%, and the specific surface area measured by the BET method was 298 m ² /g. The average particle diameter was 48.1 μm.

(b) Organoaluminum treatment of ion-exchanged layered silicate particles 10 g of the chemically treated ion-exchanged layered silicate particles obtained in (a) above were weighed into a flask with an internal volume of 1000 mL, and 36 ml of heptane was added to the ion-exchanged layered silicate particles as component [C]. 64 ml (25 mmol) of a heptane solution of normal octyl aluminum (TnOA) was added, and the mixture was stirred at room temperature for 1 hour.
Thereafter, the slurry was washed with heptane to a residual liquid ratio of 1/100, and finally the slurry volume was adjusted to 50 mL.

(c) Prepolymerization with propylene To the heptane slurry of the TnOA-treated ion-exchange layered silicate particles prepared in (b) above, 31 mL (12.2 mmol) of a TnOA heptane solution was added.
Here, in another flask (volume 200 mL), as component [B] (r)-silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)- A slurry of 184 mg (196 μmol) of 5,6-dimethyl-1-indenyl]zirconium dichloride and toluene (30 mL) was added and stirred at 40° C. for 60 minutes.
Next, 189 mL of heptane was further added to the heptane slurry of the ion-exchange layered silicate particles to make the total volume 300 mL, and the slurry was introduced into a stirring autoclave with an internal volume of 1 L that had been sufficiently purged with nitrogen.
When the temperature inside the autoclave stabilized at 40° C., propylene was supplied at a rate of 10 g/hour to maintain the temperature.
After 120 minutes, the supply of propylene was stopped, and the temperature was maintained at 40°C for an additional 60 minutes.
Thereafter, the remaining monomer was purged and the prepolymerized catalyst slurry was recovered from the autoclave.
The recovered prepolymerized catalyst slurry was allowed to stand still, and the supernatant liquid was extracted.
Subsequently, 8.3 mL (6 mmol) of a heptane solution of triisobutylaluminum (TiBA) was added as component [C] at room temperature, and then dried under reduced pressure to obtain 33.15 g of a solid catalyst for olefin polymerization (prepolymerized catalyst). Recovered.
The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.25.

[Synthesis Example 2: Production of catalyst for olefin polymerization]
(a) Chemical treatment of ion exchange layered silicate particles [acid treatment]
2250 g of pure water was put into a 3L separable flask equipped with a stirring blade and a reflux device, and 665 g of 98% sulfuric acid was added dropwise to bring the internal temperature to 90°C. Thereto, 400 g of commercially available granulated montmorillonite (manufactured by Mizusawa Chemical Co., Ltd., Benclay SL) was added and stirred. Thereafter, the mixture was reacted at 90°C for 3 hours. This slurry was filtered using a device in which an aspirator was connected to a suction bottle and washed five times with 2 L of pure water.
[Salt treatment]
The thus recovered cake was added to an aqueous solution in which 423 g of zinc sulfate heptahydrate was dissolved in 1523 ml of pure water in a 5 L beaker, and reacted at room temperature for 2 hours. The slurry was filtered using a Nutsche filter and an aspirator connected to a suction bottle, washed five times with 2 L of pure water to collect a cake, which was dried overnight at 120°C to produce 295 g of chemically treated ion-exchange layered material. Silicate particles were obtained. When this was sieved through a sieve with an opening of 74 μm, the amount that passed through the sieve was 90% of the total weight.

[Drying process]
The chemically treated ion-exchanged layered silicate particles obtained above were placed in a 1 L flask and dried under reduced pressure at 200° C. for 3 hours, and gas generation stopped. Thereafter, it was further dried under reduced pressure for 2 hours. When the moisture content was measured, the moisture value was 1.11% by mass.
The Al and Si molar ratio (Al/Si) of the obtained ion-exchange layered silicate particles was 0.183, the elution rate of aluminum (Al) was 35%, and the specific surface area measured by the BET method was 219 m ² /g. The average particle diameter was 50.9 μm.

(b) Organoaluminum treatment of ion-exchanged layered silicate particles 19.9 g of the ion-exchanged layered silicate particles obtained above were weighed into a flask with an internal volume of 1 L, and 72 ml of heptane and tri-normal octyl aluminum (TnOA) were added. 128.0 ml (50.1 mmol) of heptane solution was added and stirred at room temperature for 1 hour. Thereafter, the slurry was washed with heptane to a residual liquid ratio of 1/100, and a slurry adjusted to a volume of 100 ml was obtained.

(c) Prepolymerization with propylene To the heptane slurry of the TnOA-treated ion-exchanged layered silicate particles prepared in (b) above, 6.13 ml (2400 μmol) of a heptane solution of tri-n-octyl aluminum was added. Here, in another flask (volume 200 ml), heptane (60 ml) was added to 439 mg (600.7 μmol) of dimethylsilylene bis[1-{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium dichloride. The slurry containing the above was added and stirred at 60°C for 60 minutes.
To the slurry thus obtained, 340 ml of heptane was further added to adjust the total volume to 500 ml, and the slurry was introduced into a stirring autoclave with an internal volume of 1 L that was sufficiently purged with nitrogen. When the temperature inside the autoclave stabilized at 40° C., propylene was supplied at a rate of 10 g/hour to maintain the temperature. After 4 hours, the supply of propylene was stopped, and the temperature was maintained at 40°C for an additional 2 hours.
Thereafter, the remaining monomer was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and 400 ml of supernatant liquid was extracted. Subsequently, 16.72 ml (12.01 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, and then dried under reduced pressure to recover 63.46 g of a solid catalyst.
The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.12.

[Example C1: Production of catalyst for olefin polymerization]
In Synthesis Example 1, before step (c) (prepolymerization with propylene), a toluene solution of 31R1 (10 mg as 31R1) was added to the heptane slurry of TnOA-treated ion-exchanged layered silicate particles prepared in step (b). An olefin polymerization catalyst was produced in the same manner as in Synthesis Example 1 except that the above components were added.

[Example P1: Propylene homopolymerization]
The inside of a stirring autoclave with an internal volume of 3 L was sufficiently replaced with propylene. Then, 5.6 mL (4.04 mmol) of a heptane solution of triisobutylaluminum (TiBA) was added. Next, 38 mL of hydrogen and 750 mL of liquid propylene were introduced, and the temperature was raised to 80°C.
The olefin polymerization catalyst obtained in Example C1 was slurried in heptane. 17.7 mg of this slurry as a solid catalyst (the sum of the amount of ion exchange layered silicate particles and the amount of metallocene complex) was injected to initiate polymerization.
After polymerizing at 80° C. for 1 hour, 5 mL of ethanol was added to stop the polymerization reaction.
After purging the remaining propylene, the polymer was recovered and dried at 90° C. for 1 hour. The obtained polymer was passed through a sieve, and the amount remaining on the sieve was measured. Moreover, MFR and BD were measured using the polymer that passed through the sieve. In addition, the interior of the polymerization reactor and the surface of the stirring blade after polymer recovery were visually observed to confirm the presence or absence of deposits. The results are shown in Table 4.

[Example P2: Propylene homopolymerization]
Polymerization was carried out in the same manner as in Example P1, except that the amount of catalyst (the sum of the amount of ion exchange layered silicate particles and the amount of metallocene complex) and the amount of hydrogenation were set to the conditions listed in Table 3. The results are shown in Table 4.

[Examples P3 to P22: Propylene homopolymerization]
In Example P1, the catalyst was changed to the olefin polymerization catalyst synthesized in Synthesis Example 1, the amount of catalyst and the amount of hydrogenation were set to the conditions listed in Table 3, and the autoclave was replaced with propylene. Polymerization was carried out in the same manner as in Example P1, except that the oxyethylene compound was used as a toluene solution, and the amounts listed in Table 3 were added in the manner described in Table 3. The results are shown in Table 4.

[Comparative Examples P1 to P12: Propylene homopolymerization]
The same method as Example P3 except that the type of catalyst for olefin polymerization, the amount of catalyst, the amount of hydrogenation, and whether or not a polyoxyethylene compound was used, the amount used, and the addition method if used were set to the conditions listed in Table 3. Polymerization was carried out using The results are shown in Table 4.

＊添加方法 Ａ：触媒と添加剤を重合反応器とは別の反応器で接触
添加方法 Ｂ：触媒と添加剤を重合反応器へ別々に供給

*Addition method A: Catalyst and additives are brought into contact in a reactor separate from the polymerization reactor Addition method B: Catalyst and additives are supplied separately to the polymerization reactor

[Example P23: Propylene-ethylene random copolymerization]
The inside of a stirring autoclave with an internal volume of 3 L was sufficiently replaced with propylene. Thereafter, 0.75 ml of a toluene solution of 31R1 (3.75 mg as 31R1) and 5.6 mL (4.04 mmol) of a heptane solution of triisobutylaluminum (TiBA) were added. Next, 69 mL of hydrogen, 23 g of ethylene, and 750 mL of liquid propylene were introduced, and the temperature was raised to 70°C.
The olefin polymerization catalyst obtained in Synthesis Example 2 was slurried in heptane. 6.82 mg of this slurry as a solid catalyst (the sum of the amount of ion exchange layered silicate particles and the amount of metallocene complex) was injected to initiate polymerization.
After polymerizing at 70° C. for 1 hour, 5 mL of ethanol was added to stop the polymerization reaction.
After purging the remaining propylene, the polymer was recovered and dried at 90° C. for 1 hour. The obtained polymer was passed through a sieve, and the amount remaining on the sieve was measured. Moreover, MFR and BD were measured using the polymer that passed through the sieve. The results are shown in Table 6.

[Comparative Examples P13 to P15: Propylene-ethylene random copolymerization]
In the same manner as in Example P23, except that the catalyst amount (the sum of the amount of ion exchange layered silicate particles and the amount of metallocene complex) and the amount of hydrogenation were set as shown in Table 5, and the toluene solution of 31R1 was not added. Polymerization was performed. The results are shown in Table 6.

＊添加方法 Ｂ：触媒と添加剤を重合反応器へ別々に供給

*Addition method B: Catalyst and additives are supplied separately to the polymerization reactor

[Comparison of Examples and Comparative Examples]
In Examples P1 and P2, a catalyst containing specific ion exchange layered silicate particles as a component and the specific polyoxyethylene compound of the present application were brought into contact in a reactor different from the polymerization reactor, and then the catalyst was used. This is an example in which propylene homopolymerization was carried out. Comparative Examples P1 and P2 are examples in which propylene homopolymerization was carried out using a catalyst containing specific ion-exchangeable layered silicate particles as a component without using the polyoxyethylene compound specified in the present application. Graphs comparing catalyst activity, lump amount, and bulk density (BD) for Examples P1 and P2 and Comparative Examples P1 and P2 are shown in FIGS. 1, 2, and 3, respectively.
When a catalyst containing specific ion-exchanged layered silicate particles as a component is used in combination with the specific polyoxyethylene compound of the present application, the amount of agglomerates can be reduced, BD can be increased, and adhesion can be reduced without impairing the catalytic activity. It can be seen that it has disappeared.

Examples P3 to 22 in which a catalyst containing ion exchange layered silicate particles as a component and the polyoxyethylene compound specified in the present application were separately supplied to a polymerization reactor to carry out propylene homopolymerization; In Comparative Examples P1 to 12, propylene homopolymerization was carried out using a catalyst containing ion-exchangeable layered silicate particles as a component without using an ethylene compound or using a known additive other than the polyoxyethylene compound specified in the present application. Regarding the results of two points polymerized with different amounts (for example, the two points of Example 3 and Example 4 in Table 4), assuming that there is a linear correlation with respect to Log(MFR), the catalytic activity at MFR = 1 is calculated. Calculated. FIG. 4 shows the results of plotting the obtained catalyst activity in terms of MFR=1 against the amount of the polyoxyethylene compound specified in the present application or a known additive other than the polyoxyethylene compound specified in the present application.
From the results shown in Figure 4 and Table 3, it is clear that by combining the specific polyoxyethylene compound of the present application with a catalyst containing specific ion-exchangeable layered silicate particles as a component, it is possible to transfer bulk polymers and reactors without impairing catalytic activity. It can be seen that the generation of deposits can be suppressed.

Further, a comparison of Example P23 and Comparative Examples P13 to P15 shows that even in propylene-ethylene random copolymerization, lumps can be suppressed without impairing the catalyst activity.

According to the present invention, an olefin polymerization catalyst containing ion-exchanged layered silicate particles as a component, which is safe and economical, is used to stably produce olefins without impairing catalyst activity or polymer quality. It can provide a method for producing a polymer and has high industrial applicability.

Claims (3)

A method for producing an olefin polymer in the presence of an olefin polymerization catalyst containing the following component [A] and component [B],
Component [A]: Ion-exchange layered silicate particles containing montmorillonite and/or beidellite and having a specific surface area of 150 m ² /g or more and 700 m ² /g or less Component [B]: Transition metal compound General formula (I) below A method for producing an olefin polymer, which comprises adding a polyoxyethylene compound represented by the following formula and having a number average molecular weight of 500 or more and 8000 or less.
Formula (I): R ^a -((CH ₂ CH ₂ O) _n -R ^b ) _m
[In formula (I),
R ^a is an m-valent substituent composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom,
R ^b is each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, an alkali metal atom, and an alkaline earth metal atom. is a monovalent substituent,
m is an integer from 1 to 6,
n is an integer of 2 or more,
When m is 2 or more, a plurality of R ^b's and n's may be the same or different. ] The method for producing an olefin polymer according to claim 1, wherein the ion-exchange layered silicate particles have an average particle diameter of 2 μm or more and 500 μm or less. The method for producing an olefin polymer according to claim 1 or 2, wherein the olefin polymerization catalyst further contains the following component [C].
Component [C]: Organic aluminum compound