JP2014177543A - Olefin polymerization solid catalyst storing method and method for producing olefin polymer using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low cost and simple olefin polymerization solid catalyst storing method in which, when storing a high activity olefin polymerization solid catalyst suitable as olefin polymerization catalyst, even if the catalyst aggregates it can be easily loosed in a short period of time, and in addition when such catalyst is used it exhibits only a small deterioration in performance such as catalytic activity, and to provide a method for producing olefin polymer using the catalyst.SOLUTION: The olefin polymerization solid catalyst storing method is characterized in that, when storing an olefin polymerization solid catalyst having average particle diameter of 1.0 to 100 μm slurried in a hydrocarbon solvent, a particular inorganic oxide particle is coexisted in the slurry at a weight ratio of 0.001 or more to the olefin polymerization solid catalyst.

Description

  The present invention relates to a method for storing a solid catalyst for olefin polymerization and a method for producing an olefin polymer using the catalyst, and more particularly, when a highly active solid catalyst for olefin polymerization suitable as an olefin polymerization catalyst is stored. In addition, a method for preserving a solid catalyst for olefin polymerization, which can be easily unraveled in a short time even when the catalyst is aggregated, and has low performance degradation such as catalytic activity when the catalyst is used, and its catalyst. The present invention relates to a method for producing an olefin polymer.

When an olefin polymer is produced industrially by polymerizing olefin in the presence of a catalyst, especially when an olefin polymer is produced industrially using a solid catalyst, usually a plurality of catalysts are used properly. The olefin polymerization catalyst is often stored for a long time. In addition, the plant may be stopped for periodic inspection or repair, and in such a case, the catalyst must be stored for a long time. That is, it is indispensable from the economical viewpoint to carry out the production of polyolefin using a catalyst stored for a long time.
However, when the solid catalyst for olefin polymerization is stored in a slurry state for a long time, there is often a problem that the precipitated solid catalyst is agglomerated tightly and it is difficult to re-disperse it.

As a method for preserving the catalyst, a method for preserving a specific transition metal catalyst for olefin polymerization as a slurry dispersed in a hydrocarbon medium, wherein the slurry is preserved at 10 ° C. to 120 ° C. A method for storing a catalyst slurry is disclosed (see, for example, Patent Document 1). However, although it has been shown that the storage method can suppress a decrease in the performance of the catalyst after storage for about 40 hours under stirring, there is no description regarding the agglomerated catalyst after storage for a long period of time.
In addition, the solid state catalyst for olefin polymerization containing a specific transition metal compound and a specific co-catalyst carrier is considered as having improved particle properties and the like of the catalyst powder and suppressing adhesion to the polymerization reactor wall and the like. An olefin polymerization catalyst composition obtained by mixing inorganic oxide fine particles having a specific degree of hydrophobicity in a specific weight range is disclosed (for example, Patent Document 2). However, the catalyst composition is a catalyst composition excellent in powder properties such as fluidity and adhesion, but has improved powder properties after storage or once aggregated. It is not always clear whether it is.

  As described above, a practical technique relating to a storage method that can be easily reused even when the solid catalyst for olefin polymerization is stored and aggregated has not been disclosed. Therefore, when a highly active solid catalyst for olefin polymerization suitable as an olefin polymerization catalyst is stored, it can be easily unraveled even if the catalyst is aggregated, and performance such as catalytic activity when the catalyst is used. There has been a demand for a method for preserving a solid catalyst for olefin polymerization that is low in cost and easy to reduce, and a method for producing an olefin polymer using the catalyst.

JP-A-61-188401 JP 2007-039603 A

  In view of the above-mentioned problems of the prior art, the object of the present invention is to easily unravel a short time even if the catalyst aggregates when storing a highly active olefin polymerization solid catalyst suitable as an olefin polymerization catalyst. In addition, the present invention provides an inexpensive and easy storage method for a solid catalyst for olefin polymerization, and a method for producing an olefin polymer using the catalyst, in which performance degradation such as catalytic activity is small when the catalyst is used. .

As a result of intensive studies to solve the above problems, the present inventor, when storing a solid catalyst for olefin polymerization slurried in a hydrocarbon solvent, in the slurry, specific inorganic oxide particles, By coexisting at a specific ratio with the solid catalyst for olefin polymerization, even if the catalyst is agglomerated, it can be easily unraveled in a short time, and when the catalyst is used, performance such as catalytic activity is reduced. It has been found that a low, inexpensive and easy solid catalyst for olefin polymerization can be obtained.
In addition, when the polymerization is performed using the solid catalyst for olefin polymerization stored by the above method, even if the catalyst is aggregated, it can be easily unraveled in a short time, and when the catalyst is used, The inventors have found that an advantageous olefin polymer can be produced with little performance degradation, and have completed the present invention.

That is, according to the first invention of the present invention, when storing a solid catalyst for olefin polymerization having an average particle diameter of 1.0 to 100 μm slurried in a hydrocarbon solvent, the following characteristics are contained in the slurry: The inorganic oxide particles satisfying (1) to (3) are 0.001 or more by weight ratio (weight of inorganic oxide particles / weight of solid catalyst for olefin polymerization) with respect to the solid catalyst for olefin polymerization. Provided is a method for preserving a solid catalyst for olefin polymerization, characterized by coexistence in a proportion.
Characteristic (1): The average particle diameter is 1 nm or more and less than 1000 nm.
Property (2): The surface has at least one group selected from the group consisting of a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, and an oxygen-containing group.
Characteristic (3): Carbon atoms are contained in a proportion of 1.0% by weight or more.

  According to a second aspect of the present invention, in the first aspect, the inorganic oxide particles are uniformly stirred and mixed with the solid catalyst for olefin polymerization, and then allowed to stand for olefin polymerization. A method for storing a solid catalyst is provided.

  According to a third invention of the present invention, in the first or second invention, the inorganic oxide particles have a surface comprising a hydrocarbon group having 3 or more carbon atoms, a silicon-containing group, and a nitrogen-containing group. There is provided a method for preserving a solid catalyst for olefin polymerization, which has at least one group selected from the group consisting of:

  According to a fourth aspect of the present invention, there is provided the solid catalyst for olefin polymerization according to any one of the first to third aspects, wherein the inorganic oxide particles have an organosilicon group on the surface. A storage method is provided.

  According to a fifth aspect of the present invention, in the fourth aspect, the organic silicon group is an organic silicon group having 2 to 30 carbon atoms. Is provided.

  According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the inorganic oxide particles are in a weight ratio (weight of inorganic oxide particles) to the solid catalyst for olefin polymerization. The weight ratio of the solid catalyst for olefin polymerization) is a coexistence at a ratio of 0.002 or more.

  According to a seventh invention of the present invention, in any one of the first to sixth inventions, the solid catalyst for olefin polymerization has an average particle diameter of 1.0 to 20 μm. A method for preserving a solid catalyst is provided.

  According to an eighth invention of the present invention, in any one of the first to seventh inventions, the solid catalyst for olefin polymerization contains silica as a carrier, and the storage of the solid catalyst for olefin polymerization is characterized in that A method is provided.

  According to a ninth invention of the present invention, in any one of the first to eighth inventions, the solid catalyst for olefin polymerization has silica, an organoaluminum oxy compound, and an element of Groups 3 to 11 of the periodic table. A method for preserving a solid catalyst for olefin polymerization, comprising an organometallic complex is provided.

  According to a tenth aspect of the present invention, there is provided the method for storing a solid catalyst for olefin polymerization according to any one of the first to ninth aspects, wherein the hydrocarbon solvent is an aliphatic hydrocarbon. Provided.

  According to an eleventh aspect of the present invention, an olefin polymer is obtained by performing polymerization using the solid catalyst for olefin polymerization stored by the method according to any one of claims 1 to 10. A manufacturing method is provided.

According to the present invention, when the solid catalyst for olefin polymerization slurried in a hydrocarbon solvent is stored, the specific inorganic oxide particles are contained in the slurry in a specific ratio with respect to the solid catalyst for olefin polymerization. By coexisting with the catalyst, even if the catalyst is agglomerated, it can be easily redispersed in a short time with a normal stirring device, etc., and the effect of reducing the performance such as catalytic activity when using the catalyst is small. There is.
Further, when the polymerization is carried out using the solid catalyst for olefin polymerization stored by the above method, it is possible to avoid the blockage of the feed line or the formation of a bulk polymer by the agglomerated catalyst, and a stable continuous operation is possible. In addition, there is an effect that when the catalyst is used, an advantageous olefin polymer can be produced with little decrease in performance such as catalytic activity.
Therefore, when the solid catalyst for olefin polymerization is stored in a slurry state for a long period of time and then used again for the olefin polymerization reaction, the workability is improved, the catalytic activity is hardly decreased, and the product is not adversely affected. Therefore, there is an effect that it is particularly useful.

FIG. 1 is a schematic diagram illustrating a method for measuring a loosening time in the embodiment.

The method for preserving the solid catalyst for olefin polymerization according to the present invention comprises the step of preserving the solid catalyst for olefin polymerization having a mean particle size of 1.0 to 100 μm slurried in a hydrocarbon solvent with a specific inorganic substance in the slurry. The oxide particles coexist with the solid catalyst for olefin polymerization at a ratio of 0.001 or more by weight ratio (weight of inorganic oxide particles / weight of solid catalyst for olefin polymerization).
The method for producing an olefin polymer of the present invention is characterized in that polymerization is carried out using the solid catalyst for olefin polymerization stored by the above method.
The method for preserving the solid catalyst for olefin polymerization and the method for producing the olefin polymer of the present invention will be described in detail for each item of inorganic oxide particles, solid catalyst for olefin polymerization, hydrocarbon solvent, and the like.

1. Inorganic oxide particles The inorganic oxide particles used in the present invention satisfy the following characteristics (1) to (3), and can be used in any form as long as the effects of the present invention are recognized. For example, both spherical and indeterminate shapes can be used.
Characteristic (1): The average particle diameter is 1 nm or more and less than 1000 nm.
Property (2): The surface has at least one group selected from the group consisting of a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, and an oxygen-containing group.
Characteristic (3): Carbon atoms are contained in a proportion of 1.0% by weight or more.

  The inorganic oxide particles of the present invention must have an average particle size in the range of 1 nm or more and less than 1000 nm, preferably 100 nm or less, more preferably 50 μm or less, on the other hand, preferably 3 nm or more, more preferably 5 nm. That's it. Those having an average particle size of less than 1 nm are difficult to handle and are not practical. On the other hand, if the average particle size is larger than 1000 nm, the contact area between the inorganic oxide particles and the solid catalyst particles for olefin polymerization becomes small, so that the effect of redispersing the catalyst may be insufficient.

As a method for measuring the particle size of the inorganic oxide particles, a dynamic light scattering method, a laser diffraction / scattering method, an image imaging method, and the like are generally used. Among these methods, the image imaging method is applied to the particle size measurement of the inorganic oxide particles having the above-mentioned characteristics (1) to (3). The image imaging method is a method in which an image of a particle is directly acquired with an optical microscope or an electron microscope, and the size of the particle is measured from the image. Since particles having an average particle diameter of 1 nm or more and less than 1000 nm are likely to be loosely connected to each other due to particle surface interaction, an image imaging method is suitable for measuring the particle diameter.
The average particle size defined by the characteristic (1) uses a value measured by the following procedure.
The target inorganic oxide fine particles are observed with a transmission electron microscope (TEM) to obtain an image in which one particle can be identified. From the obtained image, the average of the horizontal and vertical lengths of the particles is taken as the particle size of one particle. The horizontal direction and the vertical direction are constant, the particle diameter is obtained for 50 particles arbitrarily selected, and the average value is defined as the average particle diameter.
On the other hand, as will be described later, the average particle diameter of the solid catalyst for olefin polymerization is measured using a laser diffraction / scattering method.

The average particle size of the inorganic oxide particles is preferably smaller than the average particle size of the solid catalyst for olefin polymerization used in the present invention. Furthermore, the ratio of the average particle diameter of the solid catalyst for olefin polymerization to the average particle diameter of the inorganic oxide particles (average particle diameter of the solid catalyst for olefin polymerization / average particle diameter of the inorganic oxide particles) is preferably 100 to 10,000. More preferably, it exists in the range of 200-5000. The reason has not been clarified so far, but the present inventor presumes that the number of inorganic oxide particles that can act on the particle surface of the solid catalyst for olefin polymerization is important.
In addition, it is estimated that the inorganic oxide particles have excellent operational effects by adhering to the particle surface of the solid catalyst for olefin polymerization to neutralize the surface charge of the catalyst or to bring it into an appropriate charge state. .

As the inorganic oxide particles, those having a hydrocarbon group, a silicon-containing group, a nitrogen-containing group and an oxygen-containing group on the surface thereof are used. These groups are usually introduced by substituting hydrogen atoms of surface hydroxyl groups present on the surface of the inorganic oxide particles.
As the hydrocarbon group, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, decyl group and other saturated hydrocarbon groups, vinyl group, allyl group, butenyl group, ethynyl group, etc. And an aromatic hydrocarbon group such as an unsaturated hydrocarbon group, phenyl group, tolyl group, mesityl group, benzyl group, phenethyl group, trityl group and naphthyl group. Among these, those having 3 or more carbon atoms are preferred. Furthermore, a saturated hydrocarbon group and an aromatic hydrocarbon group are preferable, and a saturated hydrocarbon group is most preferable.

  The silicon-containing group is preferably an organic silicon group, for example, a trimethylsilyl group, a triethylsilyl group, a tri-n-butylsilyl group, a tri-n-octylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, or a tribenzylsilyl group. , T-butyldimethylsilyl group, cyclohexyldimethylsilyl group, octylsilyl group, octyldimethylsilyl group, and the like. At this time, it is preferable that the number of carbon atoms contained in the silicon-containing group is 2 to 30.

  Examples of the nitrogen-containing group include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, an octylamino group, a dodecylamino group, an anilino group, a toluidino group, an acetamide group, a benzamino group, a succinimide group, and a phenylazo group. And naphthylazo group, amidino group and the like.

  Examples of oxygen-containing groups include ether groups such as methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, and benzyloxy group, carboxylic acid and ester groups such as carboxy group, methoxycarbonyl group, acetoxy group, and benzoyloxy group, Examples thereof include acyl groups such as acetyl group, propionyl group, butyryl group, octanoyl group, lauroyl group, acryloyl group, methacryloyl group and benzoyl group.

  A part of each hydrocarbon group, silicon-containing group, nitrogen-containing group and oxygen-containing group may be substituted with a hydrocarbon group, a silicon-containing group, a nitrogen-containing group and an oxygen-containing group.

  Among these, a preferable substituent is at least one group selected from the group consisting of a hydrocarbon group having 3 or more carbon atoms, a silicon-containing group, and a nitrogen-containing group, more preferably an organosilicon group, and preferably 2 carbon atoms. ˜30 organosilicon groups. Specific examples of the silicon-containing group include a trimethylsilyl group and an octylsilyl group.

  The amount of hydrocarbon group, silicon-containing group, nitrogen-containing group and oxygen-containing group contained in the inorganic oxide particles is 1.0% by weight or more, preferably 1.5% by weight as carbon atoms in the inorganic oxide particles. That's it. The upper limit of the carbon atom content is not particularly set, but from the viewpoint of being chemically bonded to the surface of the inorganic oxide particles, it is 10% by weight or less as carbon atoms.

The amount of carbon atoms contained in the inorganic oxide particles is considered to affect the affinity with the solvent when storing the solid catalyst for olefin polymerization in a slurry state. The higher the carbon atom content, the better the affinity for the solvent. As a result, it is presumed that strong aggregation of the solid catalyst for olefin polymerization due to long-term storage can be suppressed.
In addition, it is presumed that the same effect as described above is also a reason why a hydrocarbon group as a substituent is preferably a group having 3 or more carbon atoms and a silicon-containing group is preferable as a substituent.

Introduction of a substituent to the surface of the inorganic oxide particle is also referred to as surface treatment, and can be performed, for example, by a reaction between various compounds as shown below and a hydroxyl group on the surface of the inorganic oxide particle.
・ Dehydration condensation reaction with alcohol ・ Dehydrohalogenation condensation reaction with organic silyl halide ・ Dealcoholization condensation reaction with alkoxysilyl compound ・ Desilanol condensation reaction with siloxane compound ・ Deammonia condensation reaction with silazane compound

As the inorganic oxide particles of the present invention, specifically, for example, those exemplified below can be used. TiO ₂ , SiO ₂ , Al (OH) ₃ , Al ₂ O ₃ , CaCO ₃ , MgCO ₃ , Al ₂ O ₃ · 4SiO ₂ · H ₂ O, Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O, Al ₂ O _{3 · 2SiO 2, 3MgO · 4SiO} 2 · H 2 O, 3CaO · Al 2 O 3 · 3CaSO 4 · 31H 2 O, SiO 2 · nH 2 O, BaSO 4, Al 2 SiO 5, 3CaO · SiO 2, Ba 2 _{SiO 4, Al 2 O 3 ·} Na 2 O · 6SiO 2, Al 2 O 3 · CaO · 2SiO 2, ZrO 2, there are zeolite, preferably _{zeolite, Al 2 O 3, TiO 2} , SiO 2 and ZrO ₂ More preferred are TiO ₂ , Al ₂ O ₃ and SiO ₂ , and particularly preferred are TiO ₂ and SiO ₂ .

  In addition, the manufacturing method of the inorganic oxide particle before surface treatment generally includes the following method described in “Particle Engineering Basic Volume I Basic Technology” (637-764, Fuji Techno System). Chemical flame method, electric furnace heating method, thermal plasma method, laser heating method, laser excitation reaction method, resistance heating method, electron beam heating method, thermal plasma heating method, coprecipitation method, uniform precipitation method, compound precipitation method, metal alkoxide Method, hydrothermal synthesis method, sol-gel method, spray method, freeze-drying method, emulsion method, nitrate decomposition method, solution combustion method, crystallization method, thermal decomposition method, mechanical pulverization and the like.

  The inorganic oxide fine particles of the present invention may be used as they are, but it is preferable to remove the adsorbed water contained therein. Adsorbed water is water adsorbed on the surface or crystal fracture surface of the inorganic oxide. If the amount of adsorbed water is excessively large, the catalyst performance may be degraded.

The method for removing adsorbed water may be any suitable method. In the present invention, it is desirable to use a method in which these adsorbed water is removed by heat drying treatment, reduced pressure drying treatment, gas circulation drying treatment or the like. The heat treatment method of adsorbed water is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used.
The temperature at the time of heating is preferably 100 ° C. or higher, and more preferably 200 ° C. or higher so that adsorbed water does not remain. The upper limit is about 800 ° C.
The heating time is 0.05 hours or longer, preferably 0.5 hours or longer, more preferably 1 hour or longer.

At that time, when the moisture content of the inorganic oxide particles after removal is dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 760 mmHg, 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less, and the lower limit is preferably 0% by weight.
In the present invention, the inorganic oxide particles that have been dehydrated and adjusted to a water content of 3% by weight or less may be handled so as to maintain the same water content when coexisting with the solid catalyst for olefin polymerization. preferable.

2. Solid catalyst for olefin polymerization (1) Particle size The method for storing the solid catalyst for olefin polymerization of the present invention is preferably applied to a solid catalyst for olefin polymerization having an average particle size of 1.0 to 100 µm. More preferably, the average particle size is 5 μm or more. On the other hand, it is more preferably 70 μm or less, and particularly preferably applied to a solid catalyst for olefin polymerization of 20 μm or less.
The particle size of the solid catalyst for olefin polymerization can be determined by a laser diffraction / scattering method. The laser diffraction / scattering method uses the property that when a particle is irradiated with a laser beam (monochromatic light), the intensity distribution of the diffracted light and scattered light emitted in various directions varies depending on the particle size. Thus, the particle size of the particles is measured. Using this principle, various laser diffraction / scattering particle size distribution measuring devices are commercially available and can be used.
In this specification, the average particle diameter of the solid catalyst for olefin polymerization is a median diameter (central cumulative value) obtained by measurement using a laser diffraction scattering type particle size distribution analyzer (for example, LA-920, manufactured by HORIBA). , 50% particle size). The average particle diameter of the solid catalyst for olefin polymerization is set according to the particle diameter of the obtained polyolefin and the requirements of the catalyst feed process.

(2) Component The solid catalyst for olefin polymerization of the present invention is not particularly limited as long as it has olefin polymerization ability. For example, the solid catalyst for olefin polymerization includes those containing a transition metal compound.
Examples of the transition metal compound component include all transition metal compounds of Groups 3 to 11 of the periodic table. Preferably, a metallocene compound of a Group 3-6 metal, a bisamide of a Group 4 metal, a biimino compound of a Group 8-10 metal, or a salicylaldiminato compound of a Group 4-10 metal is used. That is, as the solid catalyst for olefin polymerization in the present invention, various catalysts such as a single site catalyst such as a Ziegler catalyst, a Phillips catalyst, and a metallocene catalyst are used.
In the present invention, preferably, a polymerization active species formed from atoms selected from Group 4 to 6 elements of the periodic table and a metallocene catalyst are preferable from the viewpoint of balance of catalyst performance. More preferably, a metallocene catalyst containing Ti, Zr or Hf is applied.

  Examples of the metallocene catalyst include a combination of a co-catalyst and a complex called a metallocene complex in which a ligand having a cyclopentadiene skeleton is coordinated to a transition metal. Specific examples of the metallocene catalyst include a complex catalyst in which a ligand having a cyclopentadiene skeleton such as methylcyclopentadiene, dimethylcyclopentadiene, and indene is coordinated to a transition metal containing Ti, Zr, Hf, and the like. Examples of the catalyst include a combination of organic metal compounds of Group 1 to Group 3 elements such as aluminoxane, and a supported type in which these complex catalysts are supported on a carrier such as silica.

The metallocene catalyst preferably used in the present invention includes the following components (a) and (b), and is a catalyst combined with the component (c) as necessary.
Component (a): Metallocene complex Component (b): Compound that reacts with component (a) to form a cationic metallocene compound Component (c): Fine particle carrier

(I) Component (a)
As the component (a), a metallocene compound of a Group 4 transition metal is used.
Specifically, compounds represented by the following general formulas (I) to (VII) are used.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY (I)
^{_{Q 1 (C 5 H 4-}} c R 1 c) (C 5 H 4-d R 2 d) MXY (II)
^{_{Q 2 (C 5 H 4-}} e R 3 e) ZMXY (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW (V)
^{_{Q 3 (C 5 H 5-}} g R 4 g) (C 5 H 5-h R 5 h) MXY (VI)
^{_{Q 4 Q 5 (C 5 H}} 3-i R 6 i) (C 5 H 3-j R 7 j) MXY (VII)

Here, Q ¹ , Q ⁴ and Q ⁵ are binding groups that bridge two conjugated five-membered ring ligands, Q ² is a binding group that bridges conjugated five-membered ring ligands and Z groups, Q ³ is a bonding group that bridges R ⁴ and R ⁵ , M is a transition metal of Group 3-12 of the periodic table, X, Y, and W are each independently hydrogen, halogen, C 1-20 Hydrocarbon group, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or silicon-containing hydrocarbon having 1 to 20 carbon atoms Z represents oxygen, a ligand containing sulfur, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. Show. M is a Group 4 transition metal such as Ti, Zr, or Hf.

R ^{1 to} R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an oxygen-containing hydrocarbon group, silicon A hydrocarbon-containing group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; Among these, it is preferable that at least one of R ^{1 to} R ⁵ is a heterocyclic aromatic group. Among the heterocyclic aromatic groups, a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group are preferable, and a furyl group and a benzofuryl group are more preferable. These heterocyclic aromatic groups include hydrocarbon groups having 1 to 20 carbon atoms, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, silicon-containing hydrocarbon groups, and phosphorus-containing carbon groups. Although it may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. Also, two adjacent R ¹ , 2 R ² , 2 R ³ , 2 R ⁴ , 2 R ⁵ , 2 R ⁶ , or 2 R ⁷ are bonded to each other. Thus, a ring having 4 to 10 carbon atoms may be formed. a, b, c, d, e, f, g, h, i, and j are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 0 ≦ e ≦, respectively. 4, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h ≦ 5, 0 ≦ i ≦ 3, 0 ≦ j ≦ 3.

A binding group Q ¹ , Q ⁴ , Q ⁵ that bridges between two conjugated five-membered ring ligands, a binding group Q ² that bridges a conjugated five-membered ring ligand and a Z group, and R Specific examples of Q ³ that crosslinks ⁴ and R ⁵ include the following. Methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenyl Silicon-containing crosslinking groups such as silylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group, germanium-containing crosslinking group, alkylphosphine, amine, etc. . Among these, an alkylene group, an alkylidene group, a silicon-containing crosslinking group, and a germanium-containing crosslinking group are particularly preferably used.

  Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V), (VI) and (VII) are exemplified below. Alternatively, a compound substituted with Ti can be used in the same manner. Among group 4 transition metals, Ti, Zr, and Hf are preferable. In addition, the metallocene complexes represented by the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) are compounds represented by the same general formula or different general formulas. It can be used as a mixture of two or more compounds represented by the formula.

Compounds of general formula (I) Biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-methyl-4,5-benzoin Denyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azurenyl) zirconium dichloride, bis (2-methyl-4H-azurenyl) cyclopentadienylzirconium dichloride, bis (2-methylbiscyclopentadienylzirconium) Dichloride, bis (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H-azurenyl) zirconium dichloride, bis (2-furylcyclo) Pentadienyl) zirconium dichloride, bis (2-furylindenyl) zirconium dichloride, bis (2-furyl-4,5-benzoindenyl) zirconium dichloride.

Compounds of general formula (II) Dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis [1,1 ′-(2-methylindenyl)] zirconium dichloride, dimethylsilylene bis [1, 1 '-(2-methyl-4-phenyl-indenyl)] zirconium dichloride, ethylene bis [1,1'-(2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylene bis [1,1 '-(2-Methyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1,1'-(2-methyl-4-phenyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis {1,1'- [2-Methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium dic Lido, dimethylsilylene bis [1,1 '- (2-ethyl-4-phenyl -4H- azulenyl)] zirconium dichloride, ethylene bis [1,1' - (2-methyl -4H- azulenyl)] zirconium dichloride.
Dimethylsilylenebis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride, dimethylsilylenebis {1,1 ′-[2- (2-furyl) -4,5-dimethyl-cyclopentadienyl] ]} Zirconium dichloride, dimethylsilylenebis {1,1 ′-{2- [2- (5-trimethylsilyl) furyl] -4,5-dimethyl-cyclopentadienyl}} zirconium dichloride, dimethylsilylenebis {1,1 '-[2- (2-furyl) indenyl]} zirconium dichloride, dimethylsilylenebis {1,1'-[2- (2-furyl) -4-phenyl-indenyl]} zirconium dichloride, dimethylsilylenebis {1, 1 ′-[2- (2- (2- (5-methyl) furyl) -4-phenyl-indenyl]} zirconium dichloride, di Tylsilylenebis {1,1 ′-[2- (2- (5-methyl) furyl) -4- (4-isopropyl) phenyl-indenyl]} zirconium dichloride, dimethylsilylenebis {1,1 ′-[2- (2 -(5-methyl) furyl) -4- (4-t-butyl) phenyl-indenyl]} zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) (9-Fluorenyl) zirconium dichloride, diphenyl Methylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, dimethylsilylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) [9 -(2,7-t-butyl) fluorenyl] zirconium dichloride.

Compound of general formula (III) (t-Butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η5-cyclopentadienyl) -1 , 2-ethanediyl-zirconium dichloride, (ethylamide) (tetramethyl-η5-cyclopentadienyl) -methylenezirconium dichloride, (t-butylamido) dimethyl- (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride, ( t-butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanezirconium dichloride, (phenylphosphine) Id) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dibenzyl.

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

Compounds of general formula (V) (cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) Zirconium triisopropoxide, (pentamethylcyclopentadienyl) zirconium triisopropoxide.

Compound of general formula (VI) Ethylene bis (7,7'-indenyl) zirconium dichloride, dimethylsilylene bis {7,7 '-(1-methyl-3-phenylindenyl)} zirconium dichloride, dimethylsilylene bis {7, 7 ′-[1-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, dimethylsilylenebis [7,7 ′-(1-ethyl-3-phenylindenyl)] zirconium dichloride, dimethylsilylenebis {7 , 7 '-[1-Isopropyl-3- (4-chlorophenyl) indenyl]} zirconium dichloride.

Exemplary compounds of general formula (VII) i) complexes containing secondary carbons:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CHMe ₂ ) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CHMe ₂ ) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- (CHMe 2) 2} 2 Zr (n-C 4 H 9) 2, (Me 2 Si) 2 {η _{^{5 -C 5 H-3,5- (CHMe}} 2) 2} 2 Zr (CH 2 C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, rac- (Me 2 Si) 2 {η ^{_{5 -C 5 H-3- (CHMe}} 2) -5-Me} 2 Zr (n-C 4 H 9) 2, rac- (M ^{_{2 Si) 2 {η 5 -C}} 5 H-3- (CHMe 2) -5-Me} 2 Zr (CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H _{-3- (CHMe 2) -5-Me} } 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- (CHMe 2) -5-Me} 2 Zr (n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 _{H-3- (CHMe 2) -5} -Me} 2 Zr (CH 2 C 6 H 5) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- (2- _adamantyl) 2} _{2 ZrCl 2, (Me 2 Si} ) 2 {η 5 -C 5 H-3,5- (2- _adamantyl) 2} _{ZrMe 2, (Me 2 Si)} 2 {η 5 -C 5 H-3,5- (2- _{adamantyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 - C ₅ H-3,5- (2- _{adamantyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- adamantyl) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 { _{^{η 5 -C 5 H-3- (}} 2- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{2-adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2,

meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (2-adamantyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(2-adamantyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H _{9) 2, meso- (Me 2} Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) 2 {Η ⁵ -C ₅ H-3,5- (cyclohexyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (cyclohexyl) ₂ } ₂ ZrMe ₂ , (Me ^{_{2 Si) 2 {η 5 -C}} 5 H-3,5- ( _{cyclohexyl) 2 2 Zr (n-C 4 H} 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( _{cyclohexyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{cyclohexyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( cyclohexyl) -5 _{-Me} 2 ZrMe 2, rac- (} Me 2 Si) 2 {η 5 -C 5 H-3- ( _{cyclohexyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 ^{_{Si) 2 {η 5 -C 5}} H-3- ( _{cyclohexyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3 - _{(cyclohexyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 ^{_{i) 2 {η 5 -C 5}} H-3- ( _{cyclohexyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( cyclohexyl) -5-Me } ₂ Zr (n-C ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (cyclohexyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ .

ii) Exemplary compounds containing tertiary carbon:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CMe ₃ ) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CMe ₃ ) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- (CMe 3) 2} 2 Zr (n-C 4 H 9) 2, (Me 2 Si) 2 {η ^{_{5 -C 5 H-3,5- (CMe}} 3) 2} 2 Zr (CH 2 C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) -5-Me} 2 ZrMe 2, rac- (Me 2 Si) 2 {η ^{_{5 -C 5 H-3- (CMe}} 3) -5-Me} 2 Zr (n-C 4 H 9) 2, rac- (Me 2 Si) 2 ^{_{η 5 -C 5 H-3- (}} CMe 3) -5-Me} 2 Zr (CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe _{3) -5-Me} 2 ZrCl} 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (CMe ₃ ) -5-Me} ₂ Zr (nC ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- ( _{CMe 3) -5-Me} 2} Zr (CH 2 C 6 H 5) 2,
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1-adamantyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1- _{adamantyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- (1- _{adamantyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) ₂ {η ⁵ -C ₅ H-3,5- (1-adamantyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ^{_{2 Si) 2 {η 5 -C}} 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} n _{C 4 H 9) 2, rac-} (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- (1- _{adamantyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H 9) 2 , Meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1,1- _{dimethylpropyl) 2} 2 ZrCl 2, (} Me ^{_{Si) 2 {η 5 -C 5}} H-3,5- (1,1- _{dimethylpropyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- (1, _{1-dimethylpropyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- (1,1- _{dimethylpropyl) 2}} 2 Zr ( _{CH 2 C 6 H 5) 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (1,1- _{dimethylpropyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1, _{1-dimethylpropyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H 3- _{(1,1-dimethylpropyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1,1- dimethylpropyl) -5-Me } ₂ ZrMe ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (n—C ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ .

iii) Examples of compounds containing alkylsilyl groups:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (dimethylsilyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (dimethylsilyl) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- ( _{dimethylsilyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η _⁵ -C ⁵ H-3,5- _{(dimethylsilyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethylsilyl) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η _⁵ -C ⁵ H-3- _{(butyldimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , meso- (Me ₂ Si) ₂ { η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} _{2 ZrMe 2, meso- (Me 2 Si} ) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- ( _{trimethylsilyl) 2} 2 ZrCl 2, (} Me 2 Si) 2 {η 5 -C 5 H-3 5- _{(trimethylsilyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( _{trimethylsilyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3,5- (trimethylsilyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- ( _{trimethylsilyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 { η ⁵ -C ₅ H-3- (trimethylsilyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (trimethylsilyl) -5-Me} ₂ Zr ( _{n-C 4 H 9) 2} , rac- ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H 3- _{(trimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 ^{_{Si) 2 {η 5 -C 5}} H-3- ( _{trimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3 - _{(trimethylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( diphenyl _{silyl) 2}} 2 ZrCl 2, ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3,5 (Diphenyl _{silyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( diphenyl _{silyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3,5- (diphenylsilyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (Diphenylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si ) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ Zr (n-C ₄ H ₉ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3 - (diphenyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) _{, Meso- (Me 2 Si) 2} {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- _{(butyldiphenylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (phenylmethyl _{silyl) 2} 2 ZrCl 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( phenylmethyl _{silyl) 2}} 2 ZrMe 2, ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3,5- ( Fe _{Rumechirushiriru) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( phenylmethyl _{silyl) 2} 2 Zr (CH 2} C 6 H 5 ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (phenylmethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H 3- (phenylmethyl _{silyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 Zr (} n- _{C 4 H 9) 2, rac-} (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( Fenirumechi _{Silyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) ₂ {η ⁵ -C ₅ H-3- (phenylmethylsilyl) -5-Me} ₂ Zr (nC ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3 - (phenylmethyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, a.

Among these, a compound of a combination of secondary carbon and primary carbon is preferable, and rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (CHMe ₂ ) — is more preferable. _{5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {η 5 _{-C 5 H-3- (CHMe 2} ) -5-Me} 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2 Rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(dimethylsilyl) -5-Me} 2 ZrMe 2} , meso _{(Me 2 Si) 2 {η} 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethyl silyl ) -5-Me} ₂ ZrMe ₂ .
In addition, the compound which replaced the silylene group of the compound of these specific examples with the germylene group is illustrated as a suitable compound.
As a special example of a metallocene complex, an element other than carbon is added to a 5-membered ring or a 6-membered ring disclosed in Japanese Patent Application Laid-Open No. 7-188335 and “Jonal of American Chemical Society, 1996, Vol. 118, 2291”. Transition metal compounds having one or more ligands can also be used.
An example of a metallocene complex having a heterocyclic hydrocarbon group as a substituent is disclosed in Japanese Patent No. 3675509.

  In the present invention, a metallocene complex having a heterocyclic aromatic group as a substituent among metallocene complexes is preferable. If the said compound is used, the effect of this invention can be exhibited in the more outstanding form.

  Furthermore, these metallocene complexes can be used as a mixture of two or more. In addition, a plurality of types can be used in combination with the metallocene complex described above.

  Among the transition metal compound components (a) described above, a preferred metallocene complex for producing an olefin polymer is preferably a metallocene complex represented by general formula (I) or general formula (II). Furthermore, the metallocene complex represented by the general formula (II) is preferable from the viewpoint that a high molecular weight polymer can be produced and that the copolymerization with ethylene and other α-olefins is excellent in copolymerizability. The ability to produce a high molecular weight product has the advantage that polymers having various molecular weights can be designed by adjusting the molecular weight of various polymers.

(Ii) Component (b)
As a component of the metallocene catalyst preferably used in the present invention, in addition to the component (a), it reacts with a metallocene compound of component (a) (component (a), hereinafter may be simply referred to as (a)). A compound that forms a cationic metallocene compound (component (b), hereinafter may be simply referred to as (b)), and, if necessary, a fine particle carrier (component (c), hereinafter simply referred to as (c). There is also.

One of the compounds (b) that react with the metallocene compound (a) to form a cationic metallocene compound is an organoaluminum oxy compound.
The organoaluminum oxy compound has Al—O—Al bonds in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of the compounds represented by the following general formula (8) can be used, but trialkylaluminum is preferably used.
R ³¹ _t AlX ³¹ _3-t (8)
(In the formula (8), R ³¹ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ³¹ represents a hydrogen atom or a halogen atom. Represents an atom, and t represents an integer of 1 ≦ t ≦ 3.)

The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. It is particularly preferred that
Two or more of the above organoaluminum compounds can be mixed and used.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is -70-100 degreeC, Preferably it exists in the range of -20-20 degreeC. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds may be used in combination, and a solution obtained by dispersing or dispersing the organoaluminum oxy compound in the aforementioned inert hydrocarbon solvent. You may use.

Other specific examples of the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound include borane compounds and borate compounds.
More specifically, the borane compound is represented by triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris ( p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl), tris ( Perfluoroanthryl) borane, tris (perfluorobi) Fuchiru) such as borane and the like.

  Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, and tris (perfluorobinaphthyl) borane are more preferred, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula (9).
^{[L 1 -H] + [BR} 26 R 27 X 24 X 25] - (9)

In Formula (9), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium, or the like.
Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In formula (9), R ²⁶ and R ²⁷ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are linked to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.
Further, X ²⁴ and X ²⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

  Specific examples of the compound represented by the general formula (9) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) ) Borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5- Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyla Monium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

  Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylaniliniumtetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

Moreover, the 2nd example of a borate compound is represented by following General formula (10).
[L ² ] ⁺ [BR ²⁶ R ²⁷ X ²⁴ X ²⁵ ] ⁻ (10)

In the formula (10), L ² represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. A cation, a proton, etc. are mentioned. R ²⁶ , R ²⁷ , X ²⁴ and X ²⁵ are the same as defined in the general formula (9).

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na _{B (o-F-Ph)} 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , NaB (3,5- (CF ₃ ) ₂ -Ph) ₄ , NaB (C ₁₀ F ₇ ) ₄ , H ⁺ BPh ₄ · 2 diethyl _{^{ethers, H + B (3,5-F}} 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 6 F}} 5) 4 - · 2 diethyl _{^{ether, H + B (2,6- (CF}} 3) 2 _{-Ph) 4} · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^ether, can be exemplified _{H + B (C 10 H 7} ) 4 · 2 diethyl ether it can.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, ^{_{H + B (C 6 F 5}} ) 4 - · 2 diethyl _{^{Ether, H + B (2,6- (CF}} 3) 2 -Ph) 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{ether, H} + B ( C ₁₀ H _{7) 4} · 2 diethyl ether.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) methylphenyl) _{borate, NaB (C 6 F 5)} 4, NaB (2,6- (CF 3) 2 -Ph) 4, H + B (C 6 F 5) 4 - · 2 diethyl ^{ether, H} + B ( _{2,6- (CF 3) 2 -Ph)} 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 10 H}} 7) 4 -2 diethyl ether is mentioned.

  As the compound (b), an organoaluminum oxy compound is preferable, and methylalumoxane is more preferable.

(Iii) Component (c)
Examples of the fine particle carrier as the component (c) include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.

The metal as the oxide, alone oxide or composite oxide of a 1 to 14 elements of group can be mentioned the Periodic Table, for _{example, SiO 2, Al 2 O 3} , MgO, CaO, B 2 O 3, TiO 2, _{ZrO 2, Fe 2 O 3,} Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · SiO 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2, Al Examples include various natural or synthetic single oxides or composite oxides such as ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO.
In the solid catalyst for olefin polymerization, the carrier as the component (c) is SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO, SiO ₂ · TiO ₂ , SiO ₂ .MgO is preferable, and SiO ₂ (silica) is particularly preferable because of low reactivity of the support itself.
Here, the above formula represents not a molecular formula but only a composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited.

As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable.
As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon.
Any of the above inorganic carriers can be suitably used in the present invention, but a metal oxide is particularly preferable.

These inorganic carriers are usually used after drying at 150 to 800 ° C., preferably 200 to 700 ° C. in order to remove adsorbed water. After drying, it is usually handled under an inert gas atmosphere such as nitrogen.
Although there is no restriction | limiting in particular as the property of these inorganic substance support | carriers, the average particle diameter measured with the laser diffraction scattering type particle size distribution measuring apparatus is 1-200 micrometers normally, Preferably it is 1-100 micrometers, More preferably, it is 5-20 micrometers, BET It is preferable to use an inorganic carrier having a specific surface area of 150 to 1000 m ² / g, preferably 200 to 700 m ² / g, and an apparent specific gravity of 0.10 to 0.50 g / cm ³ .
Here, the average particle diameter of the inorganic carrier is a median diameter (central cumulative value, 50% particle diameter), and is a value measured by a laser diffraction / scattering method.

  Of course, the above-mentioned inorganic carriers can be used as they are, but as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, It can be used after contacting an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

  The metallocene catalyst according to the present invention is a catalyst comprising a metallocene compound (a), a compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound, and, if necessary, a particulate carrier (c). There are no particular limitations on the method of contacting each component in obtaining the above, and for example, the following methods can be arbitrarily employed.

(I) After contacting the metallocene compound (a) with the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound, the fine particle carrier (c) is contacted.
(II) After contacting the metallocene compound (a) and the fine particle carrier (c), the compound (b) that reacts with the metallocene compound (A) to form a cationic metallocene compound is contacted.
(III) The metallocene compound (a) is contacted with the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound and the fine particle carrier (c).

Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.
This contact is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, as described above, certain components are soluble when the metallocene compound (a), the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound and the fine particle carrier (c) are contacted. Either an aromatic hydrocarbon solvent that is hardly soluble or an aliphatic or alicyclic hydrocarbon solvent in which a certain component is insoluble or hardly soluble can be used.

  When the contact reaction between the components is carried out stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

  In the present invention, the use ratio of the metallocene compound (a), the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound and the fine particle carrier (c) is not particularly limited. A range is preferred.

When an organoaluminum oxy compound is used as the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound, the aluminum of the organoaluminum oxy compound relative to the transition metal (M) in the metallocene compound (a) is used. The atomic ratio (Al / M) is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 500, and when a borane compound or a borate compound is used, transition in the metallocene compound The atomic ratio (B / M) of boron to metal (M) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the compound (b) for generating a cationic metallocene compound, for each compound in the mixture, the transition metal (M) It is desirable to select at the same usage ratio as above.

  The amount of the fine particle carrier (c) used is preferably 0.0001 to 5 mmol, more preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 0.0001 to 5 mmol of the transition metal in the metallocene compound (b). It is 1g per hit.

  The metallocene compound (a), the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound, and the fine particle carrier (c) are any of the contact methods (I) to (III). Then, the catalyst for olefin polymerization can be obtained as a solid catalyst by removing the solvent. The removal of the solvent is desirably performed under normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

The metallocene catalyst can also be obtained by the following method.
(IV) The metallocene compound (a) and the fine particle carrier (c) are contacted to remove the solvent, which is used as a solid catalyst component, and an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions Make contact.
(V) The organoaluminum oxy compound, borane compound, borate compound or a mixture thereof and the fine particle carrier (c) are contacted to remove the solvent, using this as a solid catalyst component, and the metallocene compound (a) under polymerization conditions Make contact.
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

Moreover, a layered silicate can also be used as a component which serves as the compound (b) which reacts with the metallocene compound (a) used in the present invention to form a cationic metallocene compound and the fine particle carrier (c).
The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force.
Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized.

  Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.

In general, natural products are often non-ion-exchangeable (non-swellable). In that case, in order to have preferable ion-exchange (or swellable), ion exchange (or swellable) is provided. It is preferable to perform the process for providing. Among such treatments, particularly preferred are the following chemical treatments.
Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate can be used.
Specifically, (a) acid treatment performed using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment performed using NaOH, KOH, NH _3, etc., (c) selected from Groups 2 to 14 of the periodic table. Salt treatment with a salt comprising at least one anion selected from the group consisting of a cation containing at least one atom and a halogen atom or an anion derived from an inorganic acid, (d) alcohol, hydrocarbon Examples thereof include organic compounds such as compounds, formamide and aniline. These processes may be performed independently or two or more processes may be combined.

  The layered silicate can control the particle properties by pulverization, granulation, sizing, fractionation, etc. at any time before, during, or after all the steps. The method can be any purposeful. In particular, for granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method and submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

  Of course, the above-mentioned layered silicate can be used as it is, but these layered silicates are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, It can be used in combination with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

In the metallocene catalyst preferably used in the present invention, in order to support the metallocene compound (a) on the layered silicate, the metallocene compound (a) and the layered silicate are brought into contact with each other, or the metallocene compound (a), organic An aluminum compound and a layered silicate may be brought into contact with each other.
The contact method of each component is not specifically limited, For example, the following methods are arbitrarily employable.
(VI) The metallocene compound (a) and the organoaluminum compound are contacted, and then contacted with the layered silicate support.
(VII) The metallocene compound (a) and the layered silicate support are contacted and then contacted with the organoaluminum compound.
(VIII) The organoaluminum compound and the layered silicate support are contacted and then contacted with the metallocene compound (A).

  Of these contact methods, (VI) and (VIII) are preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.

The use ratio of the metallocene compound (a), the organoaluminum compound, and the layered silicate carrier is not particularly limited, but the following ranges are preferable.
The supported amount of the metallocene compound (a) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support.
In the case of using an organoaluminum compound, the amount of Al supported is preferably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.

For the method of supporting and removing the solvent, the same conditions as those for the inorganic carrier can be used.
When a layered silicate is used as a component that serves as both the catalyst component (b) and the component (c), the polymerization activity is high and the productivity of an ethylene polymer having a long chain branch is improved.
The olefin polymerization catalyst thus obtained may be used after prepolymerization of monomers as required.

Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.
The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

  As a solid catalyst for olefin polymerization used in the method for storing a solid catalyst for olefin polymerization of the present invention, as a suitable combination of components (a) to (c), the effect of maintaining catalyst performance and suppressing aggregation is sufficiently exhibited. From the viewpoint of combination, an organic metal complex having an element of Group 3-11 of the periodic table as a central metal as component (a), an organoaluminum oxy compound as component (b), and silica as component (c) Is preferred.

3. Hydrocarbon solvent The method for preserving the solid catalyst for olefin polymerization of the present invention is suitably used when preserving the solid catalyst for olefin polymerization having a mean particle size of 1.0 to 100 μm slurried in a hydrocarbon solvent.
Hydrocarbon solvents used for catalyst storage are generally nonpolar hydrocarbons, for example, aliphatic hydrocarbons such as isobutane, butane, pentane, hexane, heptane, and octane, and aromatics such as benzene, toluene, and xylene. It is selected from hydrocarbons, cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and the like. These solvents are used alone or in a mixture. Among these solvents, aliphatic hydrocarbons are preferable, and pentane, hexane, and heptane are more preferable from the viewpoint of being inert to various olefin polymerization catalyst components.

4). In the storage method of the present invention, when the solid catalyst for olefin polymerization having an average particle size of 1.0 to 100 μm is slurried and stored in a hydrocarbon solvent, It is necessary that inorganic oxide particles having an average particle diameter of 1 nm or more and less than 1000 nm coexist in a weight ratio (inorganic oxide particles / olefin polymerization catalyst) of 0.001 or more with respect to the solid catalyst for olefin polymerization. Preferably, it is 0.002 or more. If the amount of inorganic oxide particles added is too small, the amount contacting the surface of the solid catalyst for olefin polymerization may be insufficient, and a sufficient effect may not be obtained. As long as it does not affect the performance of the olefin polymerization catalyst, it is possible to increase the amount of inorganic oxide particles added, but if it increases too much, it may affect the appearance of the polymer product to be produced. Usually, the weight ratio (inorganic oxide particles / solid catalyst for olefin polymerization) is used in the region of 0.1 or less. Preferably, the weight ratio is 0.05 or less.

The procedure for preserving the inorganic oxide particles in the slurry is not particularly limited,
(I) A method of adding and mixing inorganic oxide particles in powder form to a slurry of a solid catalyst for olefin polymerization in a hydrocarbon solvent, and storing it,
(Ii) a method of adding inorganic oxide particles to a slurry of a solid catalyst for olefin polymerization in a hydrocarbon solvent, adding the slurry in a hydrocarbon solvent, mixing, and storing;
(Iii) A method in which a solid catalyst for olefin polymerization is added as a solid to a slurry of inorganic oxide particles in a hydrocarbon solvent and mixed and stored. (Iv) A powdery olefin polymerization catalyst is used as a powder. After adding the inorganic oxide particles, a method of slurrying with a hydrocarbon solvent, mixing and storing can be mentioned, but the inorganic oxide particles are efficiently dispersed in a state where the solid catalyst for olefin polymerization is neatly dispersed. In view of the above, the methods (i) and (ii) are preferable. That is, a method in which the inorganic oxide particles are uniformly stirred and mixed with the slurry of the solid catalyst for olefin polymerization and then allowed to stand for storage is preferable.

5. Process for Producing Olefin Polymer The process for producing an olefin polymer of the present invention is characterized in that polymerization is carried out using the solid catalyst for olefin polymerization stored by the method for storing a solid catalyst for olefin polymerization of the present invention.
The solid catalyst for olefin polymerization stored by the method for storing a solid catalyst for olefin polymerization of the present invention is a special apparatus in a short time even if the solid catalyst for olefin polymerization settles and aggregates in the slurry. Work efficiency is improved because it can be easily unraveled. Further, since the risk that the aggregated catalyst is fed as it is is reduced, it is also effective for process problems such as clogging of the catalyst feed line.

  The polymerization reaction of olefin is carried out in the presence or absence of an inert solvent such as butane, pentane, hexane, heptane, toluene, cyclohexane, or a solvent such as liquefied α-olefin. The polymerization temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but is preferably in the range of normal pressure to 200 MPa. Also, hydrogen can be present as a molecular weight regulator in the polymerization system.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
The measurement methods used in the examples are as follows. The catalyst synthesis step and the polymerization step were all performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxygenated by nitrogen bubbling. The various inorganic oxide particles used were dried by heating to 200 ° C. under reduced pressure.

[Various measurement methods]
(1) Measurement of average particle diameter:
(I) Inorganic oxide particles:
The target inorganic oxide fine particles were observed with a transmission electron microscope (TEM) to obtain an image in which one particle could be identified. From the obtained image, the average of the horizontal and vertical lengths of the particles was taken as the particle size of one particle. The horizontal direction and the vertical direction were fixed, the particle diameter was determined for 50 particles arbitrarily selected, and the average value was defined as the average particle diameter.
(Ii) Solid catalyst for olefin polymerization:
The average particle size of the inorganic oxide and the solid particles was measured using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by HORIBA). The average particle diameter was determined by taking the median diameter (central cumulative value, 50% particle diameter) obtained by this measurement as the average particle diameter.

(2) Measurement of carbon content in inorganic oxide particles:
The carbon content in the inorganic oxide particles was determined by burning the organic groups of the inorganic oxide particles and quantifying the generated carbon dioxide.

(3) Measurement of loosening time:
In a nitrogen atmosphere, a 50 ml screw centrifuge tube (made of glass) was mixed with 2 g of catalyst, 30 ml of hexane, and a predetermined amount of inorganic oxide particles in advance, and then centrifuged at 2500 rpm using a centrifuge. For 10 minutes to allow the solid component to settle.
Next, as shown in FIG. 1, a screw centrifuge tube in which a solid component was settled was set and rotated in one direction at 60 rpm to redisperse the sedimented catalyst. The time from the start of rotation at 60 rpm to the time of redispersion uniformly was defined as the loosening time.

Example 1
1- (a) Preparation of Solid Catalyst for Olefin Polymerization A flask equipped with an induction stirrer sufficiently substituted with nitrogen was charged with 5 g of silica (GRACE, Sypolpol 2212) having an average particle diameter of 11 μm as component (c). And heated to 40 ° C. with an oil bath. Into another flask, 11.7 ml of a toluene solution of methylalumoxane (MAO) (manufactured by Albemarle, 3.0 mol Al / L) was collected as component (b). As a component (a), a toluene solution (50 ml) of n-butylcyclopentadienylzirconium dichloride (BCZ, 60.6 mg, 150 μmol) was added to a toluene solution of methylalumoxane at room temperature and stirred for 30 minutes. Next, this toluene solution was added to silica heated to 40 ° C. with stirring and held for 1 hour. Thereafter, the solvent was distilled off under reduced pressure while being heated at 40 ° C. After the degree of vacuum became 0.8 mmHg or less, drying under reduced pressure was further continued for 15 minutes to obtain a supported catalyst. The average particle size of the solid catalyst for olefin polymerization was 12 μm.

1- (b) Mixing of supported catalyst and inorganic oxide particles In a flask equipped with a stirrer, 2 g of the solid catalyst for olefin polymerization obtained in 1- (a) was fractionated, and 30 ml of hexane was added and stirred. Thereafter, 40 mg of inorganic oxide particles (manufactured by Nippon Aerosil Co., Ltd., R-812, average particle size of 7 nm, carbon content of 2.2 wt%) was added and stirred for 1 hour.
In addition, R-812 of the inorganic oxide particles was hydrophobic silica having a trimethylsilyl group on the surface.
A part of the catalyst slurry obtained here was fractionated, diluted with hexane so that the supported catalyst concentration was 10 mg / ml, and used for polymerization evaluation.

1- (c) Measurement of unraveling time Solid in olefin polymerization containing inorganic oxide particles adjusted to the same method as 1- (b) in a 50 ml screw centrifuge tube (made of glass) under nitrogen atmosphere The entire amount of catalyst hexane slurry was transferred. Then, using the centrifuge, it hold | maintained at 2500 rpm for 10 minutes, and settled the solid component.
As a result of measuring the loosening time by the method for measuring the loosening time, it was 80 seconds.

1- (d) Ethylene polymerization The inside of a 2 liter induction stirring stainless steel autoclave was replaced with purified nitrogen, and purified hexane (1000 mL) was introduced into the autoclave. After adding 1 ml of a hexane solution (0.1 mmol / ml) of triisobutylaluminum and 5 ml of 1-hexene, the temperature was raised to 80 ° C. After increasing the pressure to 0.7 MPa with ethylene, 2.1 ml (21 mg catalyst) of the hexane slurry of the solid catalyst for olefin polymerization containing the inorganic oxide particles obtained in 1- (b) is injected into the autoclave reactor. The polymerization was started.
After 1 hour, ethanol was injected to stop the polymerization reaction, and the polymer was recovered by filtration. The obtained polymer was 118 g (polymerization activity 5630 g PE / g catalyst).
The evaluation results are shown in Table 1.

(Examples 2 to 4)
It implemented like Example 1 except having changed the kind or addition amount of the inorganic oxide particle as shown in Table 1.
The inorganic oxide particles T-805 (manufactured by Nippon Aerosil Co., Ltd., T-805, average particle size 21 nm, carbon content 3.2 wt%) were hydrophobic TiO ₂ having octylsilyl groups on the surface. .
The evaluation results are shown in Table 1.

(Comparative Example 1)
It carried out like Example 1 except not adding an inorganic oxide particle like Table 1.
The evaluation results are shown in Table 1.

(Comparative Examples 2 to 5)
It implemented like Example 1 except having changed the kind or addition amount of the inorganic oxide particle as shown in Table 1.
The inorganic oxide particles RA200H (manufactured by Nippon Aerosil Co., Ltd., RA200H, average particle size 12 nm, carbon content 0 wt%) were hydrophilic silica that had not been surface-treated.
Further, R972 of inorganic oxide particles (manufactured by Nippon Aerosil Co., Ltd., R972, average particle size 16 nm, carbon content 0.8 wt%) was hydrophobic SiO ₂ having a methyl group on the surface.
In addition, Sylpol 2212 (manufactured by GRACE, Sypolol 2212, average particle size 11 μm, carbon content 0 wt%) of inorganic oxide particles was hydrophilic silica that was not surface-treated.
The evaluation results are shown in Table 1.

(Example 5)
A part of the hexane slurry of the solid catalyst for olefin polymerization containing the inorganic oxide particles redispersed after settling obtained in 1- (c) of Example 1 was collected, and the supported catalyst concentration was 10 mg / After diluting with hexane to a volume of 1.5 ml, polymerization was started in the same manner as in Example 1 1- (d) by injecting 2.1 ml (21 mg catalyst) of the supported catalyst slurry.
After 1 hour, ethanol was injected to stop the polymerization reaction, and the polymer was recovered by filtration. The obtained polymer was 115 g (polymerization activity 5480 g PE / g catalyst).
The evaluation results are shown in Table 1.
From the above, it was confirmed that the polymerization activity did not decrease even with the solid catalyst for olefin polymerization redispersed after settling.

(Example 6)
In a nitrogen atmosphere, an inorganic oxide particle (manufactured by Nippon Aerosil Co., Ltd., R-812, average particle diameter) prepared in a 50 ml screw centrifuge tube (made of glass) by the same method as 1- (b) of Example 1 All the hexane slurry of the solid catalyst for olefin polymerization containing 7 nm and carbon content of 2.2 wt% was transferred. Then, it was left still for 1 month under nitrogen atmosphere, and the solid component was settled. When the solid component was settled, the loosening time was measured and found to be 65 seconds.
A part of the hexane slurry of the solid catalyst for olefin polymerization was collected and diluted with hexane so that the supported catalyst concentration was 10 mg / ml, and then 2.1 ml (21 mg catalyst) of the supported catalyst slurry was transferred to the autoclave reactor. Polymerization was started by press-fitting.
After 1 hour, ethanol was injected to stop the polymerization reaction, and the polymer was recovered by filtration. The obtained polymer was 120 g (polymerization activity 5710 g PE / g catalyst).
The evaluation results are shown in Table 1.
From this, it was confirmed that the polymerization activity did not decrease even with the solid catalyst for olefin polymerization that was redispersed after long-term storage.

[Evaluation]
As is clear from Table 1, when Examples 1 to 4 and Comparative Example 1 are compared, “the average particle size is 1 nm or more and less than 1000 nm, and the surface has hydrocarbon groups, silicon-containing groups, nitrogen-containing groups and oxygen-containing groups. In the presence of inorganic oxide particles having a carbon atom content of 1.0 wt% or more in the inorganic oxide particles, the polymerization activity is hardly reduced and the loosening time is greatly shortened. I understand that.
From the comparison between Example 1 and Comparative Example 2 and Comparative Example 3, when inorganic oxide particles containing no carbon atom or having a low carbon atom content were used, the loosening time was not added. It turns out that it gets worse. This is presumably because the inorganic oxide particles added in Comparative Example 2 and Comparative Example 3 improved the cohesive strength of the solid catalyst for olefin polymerization.
From the comparison between Example 3 and Comparative Example 4, it can be seen that if the amount added is too small, the effect of improving the loosening time cannot be obtained.
From comparison between Example 1, Comparative Example 1 and Comparative Example 5, it can be seen that when silica having a large particle size is used, the loosening time is longer than that when no silica is added (Comparative Example 1).
From the comparison between Examples 5 and 6 and Example 1 and Comparative Example 1, when polymerization was performed using the solid catalyst for olefin polymerization stored by the storage method of the present invention, the catalyst after re-dispersion after aggregation was obtained. Even (Example 5), it was confirmed that there was no decrease in the loosening time and polymerization activity even in the case of the catalyst after standing and redispersing for a long time (Example 6).
From the above, the present invention is an inexpensive and easy solid catalyst for olefin polymerization that can be easily unraveled in a short time even when the catalyst is agglomerated, and has little performance degradation such as catalytic activity when the catalyst is used. This was proved to be a method for producing the olefin polymer using the storage method and the catalyst.

In the present invention, when a highly active solid catalyst for olefin polymerization suitable as an olefin polymerization catalyst is stored, it can be easily unraveled in a short time even when the catalyst is agglomerated, and when the catalyst is used, Low cost and easy storage method of solid catalyst for olefin polymerization, and production of olefin polymer using the catalyst, in which performance degradation such as catalyst activity is small and there is no adverse effect on the product even if the catalyst after storage is used Since it is a method, even if the solid catalyst for olefin polymerization settles and aggregates during storage in a slurry state, for example, it can be easily unraveled in a short time, so that the working efficiency is improved. Further, since the risk that the aggregated catalyst is fed as it is is reduced, it is also effective for process problems such as clogging of the catalyst feed line. Moreover, since there is no adverse effect on the product, it is particularly useful, and the applicability in the field of olefin polymerization is extremely high.

Claims (11)

Inorganic oxide satisfying the following characteristics (1) to (3) when storing a solid catalyst for olefin polymerization having an average particle size of 1.0 to 100 μm slurried in a hydrocarbon solvent A solid for olefin polymerization, wherein particles are allowed to coexist in a ratio of 0.001 or more in a weight ratio (weight of inorganic oxide particles / weight of solid catalyst for olefin polymerization) with respect to the solid catalyst for olefin polymerization. Storage method of catalyst.
Characteristic (1): The average particle diameter is 1 nm or more and less than 1000 nm.
Property (2): The surface has at least one group selected from the group consisting of a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, and an oxygen-containing group.
Characteristic (3): Carbon atoms are contained in a proportion of 1.0% by weight or more.   The method for preserving the solid catalyst for olefin polymerization according to claim 1, wherein the inorganic oxide particles are allowed to stand after being uniformly stirred and mixed with the solid catalyst for olefin polymerization.   The inorganic oxide particle has at least one group selected from the group consisting of a hydrocarbon group having 3 or more carbon atoms, a silicon-containing group, and a nitrogen-containing group on the surface. A method for preserving a solid catalyst for olefin polymerization.   The method for preserving a solid catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the inorganic oxide particles have an organosilicon group on the surface.   The method for preserving a solid catalyst for olefin polymerization according to claim 4, wherein the organosilicon group is an organosilicon group having 2 to 30 carbon atoms.   The inorganic oxide particles coexist with the solid catalyst for olefin polymerization at a ratio of 0.002 or more by weight ratio (weight of inorganic oxide particles / weight of solid catalyst for olefin polymerization). The storage method of the solid catalyst for olefin polymerization of any one of Claims 1-5.   The method for preserving the solid catalyst for olefin polymerization according to any one of claims 1 to 6, wherein the solid catalyst for olefin polymerization has an average particle diameter of 1.0 to 20 µm.   The said solid catalyst for olefin polymerization contains a silica as a support | carrier, The preservation | save method of the solid catalyst for olefin polymerization of any one of Claims 1-7 characterized by the above-mentioned.   The said solid catalyst for olefin polymerization contains the organometallic complex which has a silica, an organoaluminum oxy compound, and an element of the periodic table group 3-11, The one of Claims 1-8 characterized by the above-mentioned. A method for storing a solid catalyst for olefin polymerization.   The method for preserving a solid catalyst for olefin polymerization according to any one of claims 1 to 9, wherein the hydrocarbon solvent is an aliphatic hydrocarbon.   The manufacturing method of the olefin polymer characterized by performing superposition | polymerization using the solid catalyst for olefin polymerization preserve | saved by the method of any one of Claims 1-10.