JPH08283327A - Catalyst and method for polymerizing olefin - Google Patents

Abstract

PURPOSE: To obtain an olefin polymer excellent in particle properties while producing only a small amt. of fine polymer particles. CONSTITUTION: This olefin polymn. catalyst contains a finely particulate carrier, a transition metal compd. of the group IVB contg. a ligand having a cyclopentadienyl backbone. and an organoaluminumoxy compd. having a molar ratio of alkyl group to aluminum atom of 1.3-1.7.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for olefin polymerization. More specifically, the present invention relates to an olefin polymerization catalyst containing a transition metal compound and a specific organoaluminumoxy compound, and an olefin polymerization catalyst using the catalyst. It relates to a polymerization method.

[0002]

BACKGROUND OF THE INVENTION As a catalyst for producing an olefin polymer or an olefin copolymer, an olefin polymerization catalyst composed of a transition metal compound and an organometallic compound has been known. Among them, a transition metal compound such as zirconocene and an organoaluminumoxy compound (aluminoxane) are used as a catalyst capable of producing an olefin polymer or an olefin copolymer with high polymerization activity.
An olefin polymerization catalyst composed of and is known, and a method for producing an olefin (co) polymer using such a catalyst is disclosed, for example, in JP-A-58-19309 and JP-A-6-30909.
0-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35.
It is proposed in Japanese Patent Publication No. 008.

Further, a suspension polymerization system or a gas phase is prepared by using a catalyst in which at least one component of a transition metal compound and an organoaluminum oxy compound is supported on a porous inorganic oxide carrier such as silica, alumina or silica-alumina. A method of polymerizing an olefin in a polymerization system is disclosed, for example, in the above-mentioned JP-A-60-35006 and JP-A-60-3500.
7 and JP-A-60-35008. JP-A-61-108610 and JP-A-61-296008 disclose a method of polymerizing an olefin in the presence of a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide. Has been described.

Further, a method of prepolymerizing an olefin in the presence of a carrier such as a zirconocene compound, an aluminoxane, an organoaluminum compound, and silica is disclosed in JP-A-63.
No. 280703.

By the way, when an olefin (co) polymer is produced by using an olefin polymerization catalyst comprising a transition metal compound, an organoaluminum oxy compound and a carrier as described above, a polymer having a particle diameter of 100 μm or less (fine powder) There are cases in which problems such as a large amount of polymer) being produced and a polymer having good particle properties cannot be obtained. Further, when an olefin is prepolymerized in the presence of a transition metal compound, an organoaluminum oxy compound and a carrier to prepare a prepolymerized catalyst, a prepolymerized catalyst having a good particle shape may not be obtained.

As a result of intensive investigations under such circumstances, the present inventors have found that when the molar ratio of the alkyl group and the aluminum atom in the organoaluminum oxy compound is within a specific range, An olefin polymerization catalyst containing a particulate support and a transition metal compound,
To complete the present invention by finding that the generation of finely divided polymer during the polymerization is small, and a polymer having excellent particle properties can be obtained, and further prepolymerization can prepare a prepolymerized catalyst having an excellent particle shape. I arrived.

[0007]

An object of the present invention is to provide a catalyst for olefin polymerization in which a fine powder polymer is less likely to be generated during the polymerization and a polymer having excellent particle properties can be obtained. It is an object of the present invention to provide a method for polymerizing an olefin using a catalyst for use.

[0008]

SUMMARY OF THE INVENTION A first olefin polymerization catalyst according to the present invention is a transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton in a particulate carrier. (B) An organic aluminum oxy compound having a molar ratio of an alkyl group to an aluminum atom in the range of 1.3 or more and less than 1.7 is supported.

A second catalyst for olefin polymerization according to the present invention is a transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton in a particulate carrier, and (B) ) A solid catalyst component carrying an organoaluminum oxy compound having a molar ratio of an alkyl group to an aluminum atom in the range of 1.3 or more and less than 1.7,
(C) An organoaluminum compound.

A third olefin polymerization catalyst according to the present invention comprises a fine particle carrier, (A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (B) ) It is characterized by comprising an organoaluminum oxy compound having a molar ratio of an alkyl group to an aluminum atom in a range of 1.3 or more and less than 1.7 and an olefin polymer produced by prepolymerization.

A fourth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, (A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (B) ) An organoaluminum oxy compound and a (C) organoaluminum compound in which the molar ratio of the alkyl group to the aluminum atom is 1.3 or more and less than 1.7.
It is characterized by comprising an olefin polymer produced by prepolymerization.

A fifth olefin polymerization catalyst according to the present invention is a particulate carrier, (A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (B) ) An organoaluminum oxy compound and a (C) organoaluminum compound in which the molar ratio of the alkyl group to the aluminum atom is 1.3 or more and less than 1.7.
It is characterized by comprising a prepolymerization catalyst component composed of an olefin polymer produced by the prepolymerization and (C) an organoaluminum compound.

In the present invention, the organoaluminum oxy compound (B) has a molar ratio (R / Al) of an alkyl group (R) and an aluminum atom (Al) obtained by bringing the organoaluminum oxy compound into contact with water. 1.3 or more and 1.
The organoaluminum oxy compound is preferably less than 7, and the water is preferably adsorbed water adsorbed by an inorganic compound.

In the organoaluminum oxy compound (B), the organoaluminum oxy compound is brought into contact with an inorganic compound containing substantially no water to give a molar ratio of the alkyl group (R) and the aluminum atom (Al). (R / A
It is preferably an organoaluminum oxy compound in which l) is in the range of 1.3 or more and less than 1.7.

The organoaluminum oxy compound (B) usually contains an organoaluminum compound. The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst according to the present invention and the olefin polymerization method using the olefin polymerization catalyst will be specifically described below.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymers. In some cases, it is used in the sense of including a copolymer.

The olefin polymerization catalyst according to the present invention comprises a particulate carrier as described below, a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, an alkyl group and aluminum. It is formed from an organoaluminum oxy compound having a molar ratio with the atom within a specific range and, if necessary, an organoaluminum compound. FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.

First, each component forming such an olefin polymerization catalyst of the present invention will be described. The fine particle carrier that forms the olefin polymerization catalyst of the present invention is an inorganic or organic compound and has a particle size of 10 to 300 μm.
m, preferably 20 to 200 μm, in the form of granular or fine particles.

Of these, porous oxides are preferable as the inorganic compound, specifically, SiO ₂ , Al ₂ O ₃ , MgO,
ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO,
ThO _{2 and the} like, or mixtures thereof, such as SiO _{2
-MgO, SiO 2 -Al 2 O 3} , SiO 2 -TiO 2, SiO
_2- V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO
And the like. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The above inorganic oxide is a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It may contain carbonate, sulfate, nitrate, and oxide components such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O.

The properties of such a fine particle carrier vary depending on the type and production method, but the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² /
g, preferably 100 to 700 m ² / g, and the pore volume is 0.3 to 2.5 cm ³ / g.
This fine particle-like carrier is 100 to 1000 as needed.
It is used after firing at a temperature of 150 ° C, preferably 150 to 700 ° C.

In such a particulate carrier, it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably 1.5%. ~ 4.0% by weight, particularly preferably 2.0 ~
It is preferably 3.5% by weight.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the particulate carrier are determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss when dried for a period of time is determined and shown as a percentage with respect to the sample weight before drying. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Amount of surface hydroxyl groups (% by weight) = {(X−Y) / X} × 100 (A) A periodic table containing a ligand having a cyclopentadienyl skeleton which forms the catalyst for olefin polymerization of the present invention. IV
The group B transition metal compound (hereinafter sometimes referred to as “component (A)”) is a transition metal compound represented by the following general formula (I).

ML _x (I) (In the formula, M represents a transition metal atom selected from Group IVB of the periodic table, L represents a ligand coordinated to the transition metal, and at least one L represents L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R
¹ group (provided that R ¹ is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom, and x represents the valence of the transition metal. In the above general formula (I), M is a transition metal atom selected from Group IVB of the periodic table, specifically a zirconium atom, a titanium atom or a hafnium atom, and preferably a zirconium atom.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Of these ligands which coordinate to the transition metal atom, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (I) includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons are ethylene, Alkylene groups such as propylene, isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene groups,
It may be bonded via a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples of the ethoxy group, butoxy group and the like, examples of the aryloxy group include a phenoxy group and the like, examples of the trialkylsilyl group include a trimethylsilyl group, and examples of the ligand represented by SO ₃ R ¹ include: Examples thereof include p-toluenesulfonato group, methanesulfonato group, trifluoromethanesulfonato group and the like.

Halogen includes fluorine, chlorine, bromine,
Examples thereof include iodine. Such a transition metal compound containing a ligand having a cyclopentadienyl skeleton is more specifically represented by the following general formula (Ia) when the valence of the transition metal is 4.

R² _kR³ _lR^Four _mR^Five _nM (Ia) (In the formula, M represents a transition metal atom, R²Is cyclopenta
A group (ligand) having a dienyl skeleton is shown, and R³, R^Four
And R^FiveIs a group having a cyclopentadienyl skeleton (
Ligand), alkyl group, cycloalkyl group, aryl group,
Aralkyl group, alkoxy group, aryloxy group, thoria
Rukyril silyl group, SO₃R¹Group, halogen atom or water
Represents a elementary atom, k is an integer of 1 or more, and k + l + m +
n = 4. ) In the present invention, the transition metal compound represented by the above general formula (Ia) is used.
In the thing, R³, R ^FourAnd R^FiveAt least one of
Is a group (ligand) having a cyclopentadienyl skeleton
Certain compounds, such as R²And R³Is cyclopentadi
A compound that is a group (ligand) having an enyl skeleton is preferable.
Used well. Thus represented by the above general formula (Ia)
A compound having a cyclopentadienyl skeleton (coordination
If two or more children are included, two of them
The groups (ligands) having an interdienyl skeleton are
Propylene, alkylene groups such as propylene, isopropylidene
Substituted alkylene groups such as amine and diphenylmethylene
Len group or dimethylsilylene, diphenylsilylene,
Substitute silylene groups such as methylphenylsilylene groups
It may be connected via. Also, R²And R³But
It is a group (ligand) having a cyclopentadienyl skeleton
If R^FourAnd R^FiveHas a cyclopentadienyl skeleton
Groups, alkyl groups, cycloalkyl groups, aryl groups,
Aralkyl group, alkoxy group, aryloxy group, thoria
Rukyril silyl group, SO₃R¹, Halogen atom or hydrogen
Is an atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride , Dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silane Renbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4. -Includes substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert.
-Including isomers such as.

In the present invention, in the above zirconium compound, a compound in which a zirconium atom is replaced with a titanium atom or a hafnium atom can be used.
Next, the olefin polymerization catalyst of the present invention is formed (B).
The organoaluminum oxy compound (hereinafter sometimes referred to as “component (B)”) will be described.

The organoaluminum oxy compound (B) forming the olefin polymerization catalyst of the present invention has a molar ratio (R / Al ratio) of an alkyl group (R) and an aluminum atom (Al) in the organoaluminum oxy compound. Is 1.3 or more and less than 1.7, preferably 1.4 or more and less than 1.7.

It is considered that the organoaluminum oxy compound (B) has an alkylaluminum oxy compound represented by the following formula (i) as a main component and a small amount of an organoaluminum compound such as trialkylaluminum. Therefore, the alkyl group in the organoaluminum oxy compound in the present invention is the total of the alkyl group in the alkyl aluminum oxy compound and the alkyl group in the organo aluminum compound, and the aluminum atom in the organo aluminum oxy compound is alkyl. It is the total of the aluminum atoms in the aluminum oxy compound and the aluminum atoms in the organoaluminum compound.

[0038]

Embedded image

The olefin polymerization catalyst containing such an organoaluminum oxy compound has a particle size of 10 during polymerization.
The amount of polymer (fine polymer) of 0 μm or less is small,
An olefin polymer having excellent particle properties can be obtained. Also,
By preliminarily polymerizing the olefin polymerization catalyst containing the organoaluminum oxy compound, a prepolymerization catalyst excellent in particle formation can be prepared.

Next, the method for obtaining the R / Al ratio will be described by taking the case where R is a methyl group as an example. Into a flask sufficiently replaced with nitrogen, a solution of 2 mmol of organoaluminum oxy compound in terms of aluminum atom is charged. At this time, toluene is added and adjusted so that the total amount of the solution becomes 40 ml liter. After cooling the system to 10 ° C., 10 ml of 0.5 N sulfuric acid aqueous solution is added dropwise. The methane gas generated by this operation is collected by a gas buret. After confirming that the generation of methane gas has completely stopped, the amount of methane gas generated (a milliliter) and the temperature of the gas (t ° C.) are measured and determined by the following formula.

[0041]

[Equation 1]

The amount of aluminum atoms in the organoaluminum oxy compound is determined by plasma emission spectroscopy (I
It is measured as follows by CP). Collect 1 ml of the sample in a 50 ml Erlenmeyer flask. The inside of the pipette is washed several times with toluene, and the washing solution is
Put together in an Erlenmeyer flask. The 6N-H ₂ SO ₄ 20ml was added to the Erlenmeyer flask, and stirred over 15 minutes with a magnetic stirrer,
Extract aluminum into dilute sulfuric acid. Take 1ml with dilute sulfuric acid phase, 6N-H ₂ SO ₄ 10m
1 is added and the total amount is made up to 100 ml with distilled water. Aluminum is quantified by the ICP method. (Aluminum standard solution, 20 ppm) The organoaluminum oxy compound (B) used in the present invention can be prepared, for example, by the following method. (A) A conventionally known organoaluminum oxy compound, for example, a commercially available aluminoxane is brought into contact with water to obtain R / A.
How to adjust the l ratio. (B) A method of adjusting the R / Al ratio by bringing a conventionally known organoaluminum oxy compound, for example, a commercially available aluminoxane, into contact with an inorganic compound containing substantially no water.

Aluminoxane is usually commercially available as a solution, but in this case, this solution can be used as it is. Further, the aluminoxane solution may contain other components as long as it does not adversely affect the reaction.

Hereinafter, the organoaluminum oxy compound for adjusting the R / Al ratio may be referred to as a starting organoaluminum oxy compound. In the method (a), the R / Al ratio can be adjusted by bringing the starting organoaluminum oxy compound into contact with water and reacting the organoaluminum compound in the starting organoaluminum oxy compound with water. In this case, a raw material organoaluminum oxy compound having an R / Al ratio of more than 1.7 is brought into contact with water to prepare an organoaluminum oxy compound having an R / Al ratio of 1.3 or more and less than 1.7. The R / Al ratio was adjusted to 1.3 or more and less than 1.7, and the (raw material) organoaluminum oxy compound was brought into contact with water to bring the R / Al ratio to 1.3 or more and 1.7. It may be adjusted to a specific value within the range below.

Water to be brought into contact with the raw material organoaluminum oxy compound can be used in any state of liquid, vapor or solid. Specifically, for example, silica,
Adsorbed water adsorbed on inorganic compounds such as alumina and aluminum hydroxide, or polymers, benzene, toluene,
Hydrocarbon solvent such as hexane, ether solvent such as tetrahydrofuran, water dissolved or dispersed in amine solvent such as triethylamine, magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, ceric chloride, etc. The water of crystallization of the salt can be mentioned. Of these, it is desirable to use adsorbed water adsorbed on an inorganic compound.

In the present invention, the adsorbed water of the fine particle carrier may be used as the water to be brought into contact with the starting organic aluminum oxy compound. When adsorbed water or crystallization water is used as the water to be brought into contact with the raw material organic aluminum oxy compound, the contact between the raw material organic aluminum oxy compound and water is usually performed in an organic medium.

As the organic medium used at this time, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; Aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene, and light oil; or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons Halides of hydrogen, especially halogenated hydrocarbons such as chlorides and bromides; ethers such as ethyl ether and tetrahydrofuran.

Among these organic media, aromatic carbonization
Hydrogen is particularly preferred. Raw material Organic aluminum oxy compound
The water used to contact the product with water is the raw material organic aluminum.
0.01 with respect to the aluminum atom in the muoxy compound
~ 0.3 mol, preferably 0.02-0.2 mol, more
It is preferably used in an amount of 0.03 to 0.15 mol.
Concentration of raw material organoaluminum oxy compound in the reaction system
Is the aluminum in the raw organic aluminum oxy compound.
It is usually 1 x 10 ^-3~ 5 grams atom / liter
Bottle (solvent), preferably 1 × 10^-2~ 3 grams atom
/ Liter (solvent) range is desirable, and
The concentration of water in the reaction system is usually 0.01 to 1 mol / lit.
(Solvent), preferably 0.02 x 0.5 mol / lit
The concentration of the solvent (solvent) is desirable.

The contact between the starting organoaluminum oxy compound and water is usually -50 to 150 ° C, preferably 0 to 1
It is carried out at a temperature of 20 ° C, more preferably 20 to 100 ° C. The reaction time varies depending on the reaction temperature, but is usually 0.5 to 300 hours, preferably 1 to 150 hours.
It's about time.

In order to bring the starting organoaluminum oxy compound into contact with water, specifically, the following may be carried out. (1) A method of mixing a raw material organoaluminum oxy compound and a compound containing adsorbed water to bring the raw material organoaluminum oxy compound into contact with the adsorbed water. (Note that the compound containing adsorbed water includes the fine particle carrier) (2) A raw material organoaluminum oxy compound and a compound containing crystallization water are mixed to obtain a raw material organoaluminum oxy compound and crystallization water. How to contact. (3) A method of bringing the starting organoaluminum oxy compound into contact with a hydrocarbon solvent containing (dissolving or dispersing) water. (4) A method of bringing the raw material organic aluminum oxy compound and the steam into contact with each other, for example, by blowing steam into the solution of the raw material organic aluminum oxy compound. (5) A method of directly contacting the raw material organoaluminum oxy compound with water or ice.

In the method (b), the raw material organoaluminum oxy compound having an R / Al ratio of less than 1.3 or more than 1.7 is brought into contact with an inorganic compound containing substantially no water to obtain R / Al. An organoaluminum oxy compound having a ratio in the range of 1.3 or more and less than 1.7 can be prepared. In the present invention, "not containing substantially water" means that the amount of adsorbed water of the inorganic compound is 0.1% by weight or less.

By contacting the inorganic compound substantially free of water with the starting organic aluminum oxy compound, a specific component in the starting organic aluminum oxy compound, for example, an alkyl aluminum oxy compound having a specific R / Al ratio can be obtained. It is considered that the R / Al ratio changes due to the fact that the inorganic compound is adsorbed and separated. Therefore, as the inorganic compound, a substance which does not substantially contain water is used. Among such inorganic compounds, those having a surface hydroxyl group can also change the R / Al ratio by the action of the hydroxyl group. In this case, specific examples of the inorganic compound to be brought into contact with the raw material organic aluminum oxy compound include silica, alumina and aluminum hydroxide. The amount of surface hydroxyl groups of this inorganic compound is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight, and the amount of adsorbed water is 0.1. Weight% or less, preferably 0.01% by weight
The following is desirable.

The particle size of the inorganic compound is 10 to 300 μm.
m, preferably 20 to ²⁰⁰ μm, and a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g.

Here, the amount of water adsorbed by the inorganic compound (% by weight)
And the amount of surface hydroxyl groups (% by weight) is determined in the same manner as in the case of the fine particle carrier. The contact between the raw material organic aluminum oxy compound and the above-mentioned inorganic compound is usually carried out in an organic medium. Examples of the organic medium used at this time include the above-mentioned hydrocarbons, halogenated hydrocarbons, ethers and the like. Of these organic media, aromatic hydrocarbons are particularly preferred.

The inorganic compound used for the contact with the raw material organic aluminum oxy compound is 1 to 50 mol%, preferably 5 to 45 mol%, and more preferably 10 to the aluminum atom in the raw material organic aluminum oxy compound.
Used in an amount of 40 mol%. The concentration of the starting organoaluminum oxy compound in the reaction system is usually 1 in terms of aluminum atoms in the starting organoaluminum oxy compound.
It is desirable to be in the range of × 10 ^{-3 to} 5 gram atom / liter (solvent), preferably 1 × 10 ^{-2 to} 3 gram atom / liter (solvent).

The contact between the starting organoaluminum oxy compound and the inorganic compound containing substantially no water is usually from -50 to
150 ° C, preferably 0 to 120 ° C, more preferably 2
It is carried out at a temperature of 0 to 100 ° C. The contact time varies depending on the contact temperature, but is usually 0.5 to 300.
The time is preferably about 1 to 150 hours.

Further, in the present invention, the method of (a) and the method of (b) are combined to prepare an organoaluminum oxy compound having an R / Al ratio of 1.3 or more and less than 1.7. Good. For example, by the method (a), R
The ratio of the R / Al ratio of the (raw material) organoaluminum oxy compound having the / Al ratio adjusted to 1.3 or more and less than 1.7 is 1.3 or more and less than 1.7 by the method (b). Of the organoaluminum oxy compound (raw material) whose R / Al ratio is adjusted to 1.3 or more and less than 1.7 by the method (b).
The / Al ratio may be adjusted to a specific value within the range of 1.3 or more and less than 1.7 by the method (a).

The olefin polymerization catalyst of the present invention contains, as essential components, the fine particle carrier, the transition metal compound, and the organoaluminum oxy compound.
You may contain the (C) organoaluminum compound which is mentioned later.

Examples of the (C) organoaluminum compound (hereinafter sometimes referred to as “component (C)”) which is optionally used include organoaluminum compounds represented by the following general formula (III). can do.

R ⁶ _n AlX _3-n (III) (In the formula, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, and X 6
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ) In the above general formula (III), R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl Group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group, heptyl group, nonyl group, alkyl group such as octyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, phenyl group, tolyl group An aryl group such as a group.

Such an organoaluminum compound (C)
Specifically, the following compounds may be mentioned.
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum;
Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc. Alkyl aluminum sesquihalides; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum Arm, diisopropyl aluminum hydride, di -n- butyl aluminum hydride,
Diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-
Alkyl aluminum hydride such as sec-nonyl aluminum hydride.

Further, as an organoaluminum compound (C)
It is also possible to use a compound represented by the following general formula (IV)
it can. R⁶ _nAlY_3-n (IV) (In the formula, R⁶Is the same as above, and Y is -OR⁷Group,-
OSiR⁸ ₃Group, -OAlR⁹ ₂Group, -NR^Ten ₂Group, -S
iR¹¹ ₃Group or -N (R¹²) AlR¹³ ₂A group, n
Is 1 to 2 and R⁷, R⁸, R⁹And R¹³Is methyl
Group, ethyl group, isopropyl group, isobutyl group, cyclo
Hexyl group, phenyl group, etc., R ^TenIs a hydrogen atom,
Methyl group, ethyl group, isopropyl group, phenyl group,
R is a methylsilyl group, etc.¹¹And R¹²Is methyl
Group, ethyl group and the like. ) As such an organoaluminum compound,
The following compounds may be mentioned. (1) R⁶ _nAl (OR⁷)_3-nThe compound represented by
For example, dimethyl aluminum methoxide, diethyl aluminum
Aluminum ethoxide, diisobutylaluminum methoxy
(2) R⁶ _nAl (OSiR⁸ ₃)_3-nCompound represented by
Thing, eg Et₂Al (OSiMe₃), (Iso-B
u)₂Al (OSiMe₃), (Iso-Bu)₂Al (OS
iEt₃) Etc .; (3) R⁶ _nAl (OAlR⁹ ₂)_3-nCompound represented by
Thing, eg Et₂AlOAlEt₂, (Iso-Bu)
₂AlOAl (iso-Bu)₂Etc. (4) R⁶ _nAl (NR^Ten ₂)_3-nThe compound represented by
For example, Me₂AlNEt₂, Et₂AlNHMe, Me
₂AlNHEt, Et₂AlN (SiMe₃)₂, (Iso
-Bu)₂AlN (SiMe₃)₂Etc. (5) R⁶ _nAl (SiR¹¹ ₃)_3-nA compound represented by
For example (iso-Bu)₂AlSiMe₃Etc .; (6) R⁶ _nAl (N (R¹²) AlR¹³ ₂)_3-nRepresented by
Compounds such as Et₂AlN (Me) AlEt₂,
(Iso-Bu)₂AlN (Et) Al (iso-Bu)₂What
What.

Among the organoaluminum compounds represented by the above general formulas (III) and (IV), the general formula R ⁶ ₃ A
l, R ⁶ _n Al (OR ⁷ ) _3-n , R ⁶ _n Al (OAl
A compound represented by R ⁹ ₂ ) _3-n is preferable, and a compound in which R ⁶ is an isoalkyl group and n = 2 is preferable.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components. In the first catalyst for olefin polymerization according to the present invention, the transition metal compound (A) and the organoaluminum oxy compound (B) are supported on the particulate carrier.

Such an olefin polymerization catalyst (solid catalyst component) can be prepared by mixing and contacting the above particulate carrier, component (A) and component (B) in an inert hydrocarbon solvent. When the components are mixed and brought into contact with each other, an organoaluminum compound similar to the component (C) may be added.

The mixing order at this time is arbitrarily selected, and there is also a method in which the particulate carrier and the component (B) are brought into mixed contact, and then the component (A) is brought into mixed contact. It is desirable to bring the mixture of (A) and the particulate carrier into contact with each other.

Specific examples of the inert hydrocarbon solvent used in the preparation of the olefin polymerization catalyst in the present invention include:
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic carbonization such as benzene, toluene, xylene Hydrogen; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or a mixture thereof can be used.

When the above components are mixed, the component (A) is usually 5 × 10 ^-6 to 1 g of the particulate carrier.
It is used in an amount of 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol, and the concentration of the component (A) is about 10 ⁻⁴ to 2 × 1.
0 ^-2 mol / liter (solvent), preferably 2 x 10 ^-4 ~
It is in the range of 10 ^-2 mol / liter (solvent). The atomic ratio (Al / M) between the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the component (A) is usually 10 to 500, preferably 20 to 200.

The mixing temperature at the time of mixing the above components is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

The second olefin polymerization catalyst according to the present invention comprises the transition metal compound (A) on the fine particle carrier.
And a solid catalyst component carrying the organoaluminum oxy compound (B) and the organoaluminum compound (C).

Such an olefin polymerization catalyst comprises the above-mentioned first olefin polymerization catalyst (solid catalyst component),
And (C) an organoaluminum compound.
A second olefin polymerization catalyst according to the present invention is the first olefin polymerization catalyst described above.
Of the olefin polymerization catalyst (solid catalyst component), and the component (C) in an amount of 500 mol or less, preferably 5 to 200 mol, per gram atom of the transition metal atom derived from the component (A) in the solid catalyst component. Is preferably formed from

Such first and second catalysts for olefin polymerization according to the present invention can produce an olefin polymer excellent in particle properties, with a small amount of finely divided polymer particles having a size of 100 μm or less being produced.

The third catalyst for olefin polymerization according to the present invention comprises the fine particle carrier and the transition metal compound (A).
And an organoaluminum oxy compound (B) and an olefin polymer produced by prepolymerization.

Such an olefin polymerization catalyst can be prepared by using the above fine particle carrier, the component (A) and the component (B) in the presence of
It can be prepared by introducing an olefin into an inert hydrocarbon solvent. The solid catalyst component is preferably formed from the particulate carrier, the component (A) and the component (B). In this case, the component (B) may be added in addition to the solid catalyst component.

The olefin used in the prepolymerization is an α-olefin having 2 to 30 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1.
Examples thereof include-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and the like.
Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

As the inert hydrocarbon solvent used in the prepolymerization, the same hydrocarbon as the inert hydrocarbon solvent used in the preparation of the first olefin polymerization catalyst is used.

In the prepolymerization, the component (A) is usually 1 in terms of the transition metal compound derived from the component (A).
It is used in an amount of 0 ^{−6 to} 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent), and the component (A) is used per 1 g of the particulate carrier. , Usually 5
× 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 1
It is used in an amount of 0 ⁻⁴ mol, and the atomic ratio (Al / M) of the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the component (A) is usually 10 to 500. , Preferably 20 to 200. Prepolymerization temperature is -20 to 80
C., preferably 0 to 50.degree. C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

It is desirable that the amount of the polymer produced by the prepolymerization is in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g per 1 g of the fine particle carrier. Further, the prepolymerization catalyst carries about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atom of transition metal atom per 1 g of the particulate support, 10 ^{−3 to} 5 × 10 ⁻² gram atom,
It is desirable that 2 × 10 ^{−3 to} 2 × 10 ⁻² gram atom of aluminum atom is supported.

The third olefin polymerization catalyst according to the present invention as described above is excellent in particle shape. When an olefin is polymerized using such a catalyst, an amount of a finely divided polymer having a particle size of 100 μm or less is small, and an olefin polymer having excellent particle properties can be produced.

The fourth olefin polymerization catalyst according to the present invention comprises the fine-particle support and the transition metal compound (A).
And the organoaluminum oxy compound (B), the organoaluminum compound (C), and an olefin polymer produced by prepolymerization.

Such an olefin polymerization catalyst (preliminary polymerization catalyst component) contains an olefin in an inert hydrocarbon solvent in the presence of the fine particle carrier, the component (A), the component (B) and the component (C). It can be prepared by introducing. In addition, it is preferable that the solid catalyst component is formed by the particulate carrier, the component (A) and the component (B). In this case, the component (B) may be added in addition to the solid catalyst component.

As the olefin used in the prepolymerization, the same α-olefin having 2 to 30 carbon atoms as mentioned above can be exemplified. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

As the inert hydrocarbon solvent used in the prepolymerization, the same hydrocarbon as the inert hydrocarbon solvent used in the preparation of the first olefin polymerization catalyst is used.

In the prepolymerization, the component (A) is usually 1 in terms of the transition metal compound derived from the component (A).
It is used in an amount of 0 ^{−6 to} 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent), and the component (A) is used per 1 g of the particulate carrier. , Usually 5
× 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 1
It is used in an amount of 0 ⁻⁴ mol, and the atomic ratio (Al / M) of the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the component (A) is usually 10 to 500. , Preferably 20 to 200. Aluminum atom (Al-C) of component (C) and aluminum atom (Al-B) of component (B)
The ratio (Al-C / Al-B) is usually 0.02 to 3, and preferably 0.05 to 1.5. The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 50 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably 1 to 50 hours.
It's about time.

It is desirable that the amount of the polymer produced by the prepolymerization is in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g of the fine particle carrier. Further, the prepolymerization catalyst carries about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atom of transition metal atom per gram of the particulate support, Aluminum atoms derived from (B) and component (C) are supported in an amount of about 10 ^{-3 to} 5 x 10 ^-2 gram atoms, preferably 2 x 10 ^-3 to 2 x 10 ^-2 gram atoms. Is desirable.

The fourth olefin polymerization catalyst (preliminary polymerization catalyst component) according to the present invention is excellent in particle shape. When an olefin is polymerized using such a catalyst, an amount of a finely divided polymer having a particle size of 100 μm or less is small, and an olefin polymer having excellent particle properties can be produced.

The fifth olefin polymerization catalyst according to the present invention comprises the fine particle carrier and the transition metal compound (A).
, The organoaluminum oxy compound (B), the organoaluminum compound (C), a prepolymerization catalyst component produced by prepolymerization, and the organoaluminum compound (C).

Such an olefin polymerization catalyst comprises the above-mentioned fourth olefin polymerization catalyst (preliminary polymerization catalyst component),
And (C) an organoaluminum compound.
The fifth catalyst for olefin polymerization according to the present invention comprises 50 parts per gram atom of transition metal atom derived from the prepolymerization catalyst (component) and the component (A) in the prepolymerization catalyst component.
It is desired to be formed from component (C) in an amount of 0 mol or less, preferably 5 to 200 mol.

Such a fifth catalyst for olefin polymerization according to the present invention can produce an olefin polymer excellent in particle properties with a small amount of a finely divided polymer having a particle size of 100 μm or less being produced.

The first to fifth olefin polymerization catalysts according to the present invention may contain other components useful for olefin polymerization in addition to the above components. Next, the olefin polymerization method according to the present invention will be described.

In the present invention, olefin polymerization or copolymerization of two or more olefins is carried out in the presence of the above-mentioned olefin polymerization catalyst. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, it is used when preparing the above-mentioned catalyst.
It is possible to use the same inert hydrocarbon solvent that was used.
However, the olefin itself can be used as a solvent.
Using the first or second olefin polymerization catalyst of the present invention
When carrying out olefin polymerization,
Is the concentration of transition metal atoms derived from the component (A) in the polymerization system.
As a degree, usually 10^-8-10^-3Grams atom / liter,
Preferably 10 ^-7-10^-FourIn the amount of grams atom / liter
It is desirable to be used. At this time, it is supported on the carrier
In addition to existing organoaluminum oxy compound (component (B))
Unsupported organoaluminum oxy compound
May be used.

Further, the third, fourth or fifth aspect of the present invention
Olefin polymerization catalysts such as
The combined olefin polymerization catalyst is used to
When carrying out the polymerization, the catalyst as described above should not be used in the polymerization system.
The concentration of transition metal atoms derived from the component (A) is usually 1
0^-8-10^-3Gram atom / liter, preferably 10 ^-7
-10^-FourCan be used in amounts of grams atom / liter
desirable. At this time, the organic aluminum supported on the carrier
In addition to the umoxy compound (component (B))
A non-organoaluminum oxy compound may be used.

The olefin polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C. when carrying out the slurry polymerization method, and when carrying out the liquid phase polymerization method. , Usually 0 to 250 ° C., preferably 20 to
It is preferably in the range of 200 ° C. Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C.
The polymerization pressure is usually from atmospheric pressure to 100 kg / cm ² , preferably from atmospheric pressure to 50 kg / cm ² , and the polymerization reaction may be carried out by any of batch, semi-continuous and continuous methods. You can In addition, polymerization is performed under different reaction conditions 2
It is also possible to divide into more than one step.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. As the olefin that can be polymerized by the olefin polymerization catalyst according to the present invention, an α-olefin having 2 to 20 carbon atoms,
For example ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; carbon number 5-20
Cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,
Examples include 3,4,4a, 5,8,8a-octahydronaphthalene. Furthermore, styrene, vinyl cyclohexane,
Diene and the like can also be used.

[0096]

INDUSTRIAL APPLICABILITY The olefin polymerization catalyst of the present invention produces a finely divided polymer in a small amount during the polymerization, and a polymer having excellent particle properties can be obtained. Further, the prepolymerized catalyst of the present invention is excellent in particle shape.

[0097]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0098]

Example 1 [Preparation of catalyst] 107 ml of toluene, 32 ml of a toluene solution of methylaluminoxane (Al; 1.33 mol / liter, CH ₃ / Al molar ratio; 1.69) were placed in a glass flask sufficiently replaced with nitrogen, and Toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 22 mmol / l) 15 m
After charging l, the temperature was raised to 40 ° C. and the reaction was carried out at that temperature for 1 hour.

Thereafter, the silica was dried at 250 ° C. for 10 hours (specific surface area: 321 m ² / g, average particle size: 54 μm).
6.4 g was added, the temperature was further raised to 60 ° C., and the reaction was performed for 2 hours. Then, the supernatant liquid was removed, and the solid catalyst containing 3.2 mg of zirconium per 1 g was obtained by washing twice with hexane.

Then, in 130 ml of hexane containing 1.1 mmol of triisobutylaluminum, 3.0 g of the solid catalyst obtained above and 0.8 ml of 1-hexene.
Was added and prepolymerization of ethylene was carried out at 35 ° C. for 2 hours to obtain a prepolymerized catalyst (a) containing 2.8 mg of zirconium and 3 g of the polymer per 1 g of the solid catalyst.

At this time, no adhesion of the prepolymerized catalyst to the reactor or the stirring blade was observed, and the obtained prepolymerized catalyst had a good shape. [Polymerization] 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liter which had been sufficiently replaced with nitrogen, and the system was replaced with ethylene. Then 1-hexene 40 ml
Was charged and the temperature in the system was raised to 70 ° C. Subsequently, 0.75 mmol of triisobutylaluminum and 0.05 of zirconium were used as the prepolymerized catalyst (a) prepared above.
Polymerization was initiated by pressurizing 05 mmol with ethylene. After that, while continuously feeding ethylene,
Polymerization was carried out at 80 ° C. for 1.5 hours at kg / cm ² -G.

The polymer was recovered by filtration and placed under reduced pressure for 8 hours.
By drying at 0 ° C. overnight, 387 g of an ethylene / 1-hexene copolymer was obtained. At this time, adhesion of the polymer to the wall of the polymerization vessel or the stirring blade was not observed.

The ethylene / 1-hexene copolymer obtained had an MFR of 0.16 g / 10 minutes measured at 190 ° C. under a load of 2.16 kg and a density of 0.925 g / cm 3.
³ , the bulk specific gravity was 0.35 g / cm ³ , and the average particle size was 740 μm. The results are shown in Table 1.

[0104]

Example 2 [Preparation of catalyst] In the "preparation of catalyst" of Example 1, C
A prepolymerization catalyst (b) was prepared in the same manner as in Example 1 except that methylaluminoxane having a CH ₃ / Al molar ratio of 1.63 was used instead of methylaluminoxane having an H ₃ / Al molar ratio of 1.69. ) Was prepared.

At this time, no adhesion of the prepolymerized catalyst to the reactor or the stirring blade was observed, and the obtained prepolymerized catalyst had a good shape. [Polymerization] An ethylene / 1-hexene copolymer was polymerized in the same manner as in Example 1 except that the prepolymerization catalyst (b) was used in place of the prepolymerization catalyst (a) in the "polymerization" of Example 1. . At this time, adhesion of the polymer to the wall of the polymerization vessel or the stirring blade was not observed. The results are shown in Table 1.

[0106]

Example 3 [Preparation of catalyst] In the "preparation of catalyst" of Example 1, C
A prepolymerization catalyst (c) was prepared in the same manner as in Example 1 except that methylaluminoxane having a CH ₃ / Al molar ratio of 1.57 was used instead of using methylaluminoxane having an H ₃ / Al molar ratio of 1.69. ) Was prepared.

At this time, no adhesion of the prepolymerized catalyst to the reactor or the stirring blade was observed, and the obtained prepolymerized catalyst had a good shape. [Polymerization] An ethylene / 1-hexene copolymer was polymerized in the same manner as in Example 1 except that the prepolymerization catalyst (c) was used in place of the prepolymerization catalyst (a) in the "polymerization" of Example 1. . At this time, adhesion of the polymer to the wall of the polymerization vessel or the stirring blade was not observed. The results are shown in Table 1.

[0108]

[Table 1]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (10)

[Claims] 1. A transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton in a particulate carrier, and (B) a molar ratio of an alkyl group and an aluminum atom ( An olefin polymerization catalyst, which comprises an organoaluminum oxy compound having an alkyl group / aluminum atom) of 1.3 or more and less than 1.7. 2. A transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton in a particulate carrier, and (B) an alkyl group and an aluminum atom in a molar ratio ( An olefin comprising (C) an organoaluminum compound and a solid catalyst component carrying an organoaluminum oxy compound having an alkyl group / aluminum atom) of 1.3 or more and less than 1.7. Polymerization catalyst. 3. A particulate support, a transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, and (B) a molar ratio of an alkyl group to an aluminum atom ( An olefin polymerization catalyst comprising an organoaluminum oxy compound having an alkyl group / aluminum atom ratio of 1.3 or more and less than 1.7 and an olefin polymer produced by prepolymerization. 4. A particulate carrier, a transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, and (B) a molar ratio of an alkyl group to an aluminum atom ( An alkylaluminum group / aluminum atom) in the range of 1.3 or more and less than 1.7, (C) an organoaluminum compound, and an olefin polymer produced by prepolymerization. Olefin polymerization catalyst. 5. A particulate support, a transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, and (B) a molar ratio of an alkyl group to an aluminum atom ( A prepolymerization catalyst component comprising an organoaluminum oxy compound having an alkyl group / aluminum atom) of 1.3 or more and less than 1.7, (C) an organoaluminum compound, and an olefin polymer produced by prepolymerization. And (C) an organoaluminum compound. 6. The organoaluminum oxy compound (B) is brought into contact with an organoaluminum oxy compound and water to give a molar ratio of an alkyl group to an aluminum atom (alkyl group / aluminum atom) of 1.3 or more and 1 or less. The catalyst for olefin polymerization according to any one of claims 1 to 5, which is an organoaluminum oxy compound in a range of less than 0.7. 7. The catalyst for olefin polymerization according to claim 6, wherein the water is adsorbed water adsorbed by an inorganic compound. 8. The organoaluminum oxy compound (B) is brought into contact with an organoaluminum oxy compound and an inorganic compound containing substantially no water to give a molar ratio of an alkyl group and an aluminum atom (alkyl group / aluminum atom). ) Is an organoaluminum oxy compound having a ratio of 1.3 or more and less than 1.7, and the catalyst for olefin polymerization according to any one of claims 1 to 5. 9. The catalyst for olefin polymerization according to claim 1, wherein the organoaluminum oxy compound (B) is an organoaluminum oxy compound containing an organoaluminum compound. 10. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 9.