JP4021463B2 - Olefin polymerization catalyst and olefin polymerization method using the catalyst - Google Patents

Description

  The present invention relates to a novel organoaluminum oxy compound and a production method thereof, an olefin polymerization catalyst containing the organoaluminum oxy compound, and an olefin polymerization method using the catalyst.

  Conventionally, an olefin polymerization catalyst comprising a transition metal compound and an organometallic compound is known as a catalyst for producing an olefin polymer or olefin copolymer. Among them, as a catalyst capable of producing an olefin polymer or olefin copolymer with high polymerization activity, an olefin polymerization catalyst comprising a transition metal compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known. For example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, and JP-A-60 can be used for producing olefin (co) polymers using such a catalyst. -35007 and JP-A-60-35008 (patent documents 1 to 5).

  Further, in a suspension polymerization system or a gas phase polymerization system 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, silica / alumina, etc. Methods for polymerizing olefins have been proposed in, for example, the above-mentioned JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008 (Patent Documents 3 to 5). In JP-A-61-108610 and JP-A-61-296008 (Patent Documents 6 to 7), in the presence of a catalyst in which a transition metal compound such as metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide. A method for polymerizing olefins is described.

  Furthermore, Japanese Patent Application Laid-Open No. 63-280703 (Patent Document 8) describes a method for prepolymerizing an olefin in the presence of a carrier such as a zirconocene compound, an aluminoxane, an organoaluminum compound and silica.

  By the way, when an olefin (co) polymer is produced 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 size of 100 μm or less (fine powder polymer). In some cases, a large amount of is produced or a polymer having good particle properties cannot be obtained. Further, when a prepolymerized catalyst is prepared by prepolymerizing an olefin in the presence of a transition metal compound, an organoaluminum oxy compound and a carrier, a prepolymerized catalyst having a good particle shape may not be obtained.

As a result of intensive studies under these circumstances, the present inventors have found that when the molar ratio between the alkyl group and the aluminum atom in the organoaluminum oxy compound is within a specific range, the organoaluminum oxy compound and the particulate carrier. The catalyst for olefin polymerization comprising a transition metal compound and a transition metal compound produces a polymer with a small amount of finely divided polymer during polymerization and an excellent particle property. It has been found that it can be prepared, and the present invention has been completed.
JP 58-19309 A JP-A-60-35005 JP-A-60-35006 Japanese Unexamined Patent Publication No. 60-35007 JP 60-35008 A JP-A-61-108610 JP-A 61-296008 JP-A-63-280703

  An object of the present invention is to provide an organoaluminum oxy compound that can be a constituent component of an olefin polymerization catalyst that produces a polymer having a fine particle property with little generation of a fine powder polymer during polymerization, and a method for producing the same. In addition, an object of the present invention is to provide an olefin polymerization catalyst containing the organoaluminum oxy compound and an olefin polymerization method using the catalyst.

The organoaluminum oxy compound according to the present invention is characterized in that the molar ratio of alkyl group to aluminum atom (alkyl group / aluminum atom) is 1.7 to 2.1.
In the first method for producing an organoaluminum oxy compound according to the present invention, an organoaluminum oxy compound is brought into contact with water and / or an inorganic compound so that the molar ratio of alkyl group to aluminum atom (alkyl group / aluminum atom) is It is characterized by preparing an organoaluminum oxy compound of 1.7 to 2.1.

  The second method for producing an organoaluminum oxy compound according to the present invention comprises bringing an organoaluminum oxy compound having a molar ratio of alkyl group to aluminum atom (alkyl group / aluminum atom) exceeding 2.1 and water into contact with the alkyl. An organoaluminum oxy compound having a molar ratio of a group to an aluminum atom of 1.7 to 2.1 is prepared. The water used for the preparation of this organoaluminum oxy compound is, for example, adsorbed water adsorbed on an inorganic compound.

  The third method for producing an organoaluminum oxy compound according to the present invention comprises an organoaluminum oxy compound having an alkyl group / aluminum atom molar ratio (alkyl group / aluminum atom) of less than 1.7, and an inorganic compound containing no water. And an organoaluminum oxy compound having a molar ratio of alkyl group to aluminum atom of 1.7 to 2.1 is prepared.

The first olefin polymerization catalyst according to the present invention comprises:
In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) The organoaluminum oxy compound is supported.

The second olefin polymerization catalyst according to the present invention is:
In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) a solid catalyst component on which the organoaluminum oxy compound is supported;
(C) It consists of an organoaluminum compound.

The third 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;
(B) the organoaluminum oxy compound;
It is characterized by comprising an olefin polymer produced by preliminary polymerization.

The fourth 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;
(B) the organoaluminum oxy compound and (C) the organoaluminum compound;
It is characterized by comprising an olefin polymer produced by preliminary polymerization.

The 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;
(B) the organoaluminum oxy compound and (C) the organoaluminum compound;
A prepolymerization catalyst component comprising an olefin polymer produced by prepolymerization;
(C) It consists of an organoaluminum compound.

  The (B) organoaluminum oxy compound forming the olefin polymerization catalyst according to the present invention usually contains an organoaluminum compound. The olefin polymerization method according to the present invention is characterized in that an olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst.

The organoaluminum oxy compound of the present invention can be a constituent component of an olefin polymerization catalyst in which a fine powder polymer is produced at the time of polymerization and a polymer having excellent particle properties is obtained.
The olefin polymerization catalyst of the present invention produces a polymer having excellent particle properties with a small amount of fine powder polymer produced during polymerization. The prepolymerization catalyst of the present invention is excellent in particle shape.

  According to the method for polymerizing olefins of the present invention, a polymer having a fine particle property can be obtained with a small amount of fine powder polymer produced at the time of polymerization.

  Hereinafter, the organoaluminum oxy compound according to the present invention, a production method thereof, an olefin polymerization catalyst containing the organoaluminum oxy compound, and an olefin polymerization method using the olefin polymerization catalyst will be specifically described.

  In the present invention, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” refers to not only a homopolymer but also a copolymer. It may be used in the meaning that also includes coalescence.

  First, the organoaluminum oxy compound of the present invention will be described. In the organoaluminum oxy compound of the present invention, the molar ratio (R / Al ratio) between the alkyl group (R) and the aluminum atom (Al) in the organoaluminum oxy compound is 1.7 to 2.1, preferably 1. It is desirable to be in the range of 8 to 2.1, more preferably 1.9 to 2.1.

The organoaluminum oxy compound is considered to contain an alkylaluminumoxy compound represented by the following formula (i) as a main component and a small amount of an organoaluminum compound such as trialkylaluminum. Therefore, in the present invention, the alkyl group in the organoaluminum oxy compound is the total of the alkyl group in the alkylaluminum oxy compound and the alkyl group in the organoaluminum compound, and the aluminum atom in the organoaluminum oxy compound is alkyl. This is the total of aluminum atoms in the aluminum oxy compound and aluminum atoms in the organoaluminum compound.

(Wherein R is an alkyl group and n is n ≧ 2 )
Next, how to determine the R / Al ratio will be described by taking the case where R is a methyl group as an example. A sufficiently nitrogen-substituted flask is charged with 2 mmol of an organoaluminum oxy compound solution in terms of aluminum atoms. At this time, toluene is added and adjusted so that the total amount of the solution becomes 40 ml. After cooling the system to 10 ° C., 10 ml of 0.5N aqueous sulfuric acid solution is added dropwise. Methane gas generated by this operation is collected by a gas burette. After confirming that the generation of methane gas has completely stopped, the amount of methane gas generated (a milliliter) and the gas temperature (t ° C.) are measured and determined by the following formula. The amount of aluminum atoms in the organoaluminum oxy compound is measured by plasma emission spectroscopy.
R / Al = (a × 273) / {22.4 × (t + 273) × 2}}
In the organoaluminum oxy compound of the present invention, the ratio of the organoaluminum compound in the organoaluminum oxy compound is preferably within a specific range. For example, when the organoaluminum oxy compound is methylaluminoxane containing trimethylaluminum, the peak area derived from protons in trimethylaluminum (TMA) determined from ¹ H-NMR and the peak area derived from protons in methylaluminoxane The ratio of the peak area derived from protons in trimethylaluminum to the sum of (TMA (Area)) is 0.25 to 0.40, preferably 0.27 to 0.40, more preferably 0.30 to 0. Is preferably in the range of .40.

The peak area derived from protons in methylaluminoxane and the peak area derived from protons in trimethylaluminum (TMA) are measured as follows. That is, the sample tube having an inner diameter of 5 mm, perform sample prepared by mixing a toluene solution 0.5ml and deuterated benzene 0.1ml organoaluminum oxy-compound 0.5 to 1.5 mol / l, Part ¹ The H-NMR spectrum was measured under the conditions of normal temperature, measurement frequency 500 MHz, spectrum width 7507.5 Hz, pulse repetition time 6.2 seconds, and pulse width 45 °. The broad peak seen from −0.6 ppm to 0.3 ppm is assigned as the peak derived from protons in methylaluminoxane, and the sharp peak near −0.28 ppm is assigned as the peak derived from protons in trimethylaluminum (TMA). (See FIG. 2). The peak area is obtained by curve fitting using a Lorentz function (see FIG. 3).

  An olefin polymerization catalyst containing such an organoaluminum oxy compound produces an olefin polymer having a small amount of fine powder polymer during polymerization and excellent particle properties. In addition, when prepolymerization is performed on an olefin polymerization catalyst containing the organoaluminum oxy compound, a prepolymerization catalyst excellent in particle formation can be prepared.

Such an organoaluminum oxy compound of the present invention can be prepared, for example, by the following method.
(A) A method of adjusting the R / Al ratio by bringing water into contact with a conventionally known organoaluminum oxy compound such as a commercially available aluminoxane.
(B) A method of adjusting the R / Al ratio by contacting a conventionally known organoaluminum oxy compound such as a commercially available aluminoxane with an inorganic compound not containing water.

  In addition, although aluminoxane is usually marketed as a solution, in this case, this solution can be used as it is. The aluminoxane solution may contain other components as long as the reaction is not adversely affected.

Hereinafter, the organoaluminum oxy compound for adjusting the R / Al ratio may be referred to as a raw material organoaluminum oxy compound.
In the method (a), since the organoaluminum compound in the raw material organoaluminum oxy compound reacts with water by bringing the raw material organoaluminum oxy compound into contact with water, the R / Al ratio can be adjusted. In this case, a raw material organoaluminum oxy compound having an R / Al ratio of 1.7 to 2.1 can be prepared by contacting a raw material organoaluminum oxy compound with an R / Al ratio exceeding 2.1 and water, The R / Al ratio was adjusted to 1.7 to 2.1 (raw material) and the organoaluminum oxy compound was brought into contact with water to adjust the R / Al ratio to a specific value within the range of 1.7 to 2.1. May be.

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

In the present invention, the adsorbed water of the particulate carrier described later can also be used as water to be brought into contact with the raw material 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 carried out in an organic medium.

Examples of the organic medium used here include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene;
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane;
Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclohexane;
Hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and light oil;
Or halogenated hydrocarbons such as the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides, especially chlorinated products, brominated products;
Mention may be made of ethers such as ethyl ether and tetrahydrofuran.

Of these organic media, aromatic hydrocarbons are particularly preferred.
The water used for the contact between the raw material organic aluminum oxy compound and water is 0.01 to 0.3 mol, preferably 0.02 to 0.2 mol, more preferably relative to the aluminum atoms in the raw material organic aluminum oxy compound. Is used in an amount of 0.03 to 0.15 mol. The concentration of the raw material organic aluminum oxy compound in the reaction system is usually 1 × 10 ^{−3 to} 5 gram atom / liter (solvent), preferably 1 × 10 ⁻² in terms of aluminum atoms in the raw material organic aluminum oxy compound. The concentration of water in the reaction system is usually 0.01 to 1 mol / liter (solvent), preferably 0.02 × 0.5 mol. A concentration of 1 / liter (solvent) is desirable.

  The contact between the raw material organoaluminum oxy compound and water is usually carried out at a temperature of -50 to 150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C. The contact time varies greatly depending on the contact temperature, but is usually 0.5 to 300 hours, preferably about 1 to 150 hours.

In order to bring the raw material organoaluminum oxy compound into contact with water, specifically, the following may be performed.
(1) A method in which a raw material organic aluminum oxy compound and a compound containing adsorbed water are mixed and the raw material organic aluminum oxy compound and adsorbed water are brought into contact with each other. (Note that the compound containing adsorbed water includes the following particulate carrier)
(2) A method in which a raw material organic aluminum oxy compound and a compound containing crystallization water are mixed and the raw material organic aluminum oxy compound and crystallization water are brought into contact with each other.
(3) A method of bringing a raw material organoaluminum oxy compound into contact with a hydrocarbon solvent containing (dissolved or dispersed) water.
(4) A method of bringing the raw material organic aluminum oxy compound and water vapor into contact with each other by blowing water vapor into the solution of the raw material organic aluminum oxy compound.
(5) A method in which the raw material organoaluminum oxy compound is directly brought into contact with water or ice.

  In the method of (b), the R / Al ratio is less than 1.7, or the raw material organoaluminum oxy compound exceeding 2.1 is brought into contact with an inorganic compound that does not substantially contain water, and the R / Al ratio is 1. An organoaluminum oxy compound that is .7 to 2.1 can be prepared. In the present invention, “substantially not containing water” means that the amount of adsorbed water of the inorganic compound is 0.1% by weight or less.

  By bringing the inorganic compound substantially free of water into contact with the raw material organic aluminum oxy compound, a specific component in the raw material organic aluminum oxy compound, for example, an alkylaluminum oxy compound having a specific R / Al ratio is converted into the inorganic compound. It is considered that the R / Al ratio changes due to the adsorption and separation. Therefore, an inorganic compound that does not substantially contain water is used. Among these inorganic compounds, those having a surface hydroxyl group can 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, aluminum hydroxide and the like. The surface hydroxyl group amount 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. It is desirable that the amount is not more than wt%, preferably not more than 0.01 wt%.

The inorganic compound has a particle size of 10 to 300 μm, 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 adsorbed water amount (% by weight) and the surface hydroxyl group amount (% by weight) of the inorganic compound are determined as follows.
[Amount of adsorbed water]
The weight loss when dried for 4 hours at a temperature of 200 ° C. under normal pressure and nitrogen flow is a value expressed as a percentage of the weight before drying.
[Surface hydroxyl group content]
X (g) is the weight of the inorganic compound obtained by drying at 200 ° C. under normal pressure and nitrogen flow for 4 hours, and further the surface hydroxyl group obtained by calcining the inorganic compound at 1000 ° C. for 20 hours. The weight of the fired product with disappearance is Y (g) and is calculated according to the following formula.
Surface hydroxyl group content (% by weight) = {(XY) / X} × 100
Contact between the raw material organic aluminum oxy compound and the inorganic compound is usually carried out in an organic medium. Examples of the organic medium used at this time include the above 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%, more preferably 10 to 40 mol% with respect to aluminum atoms in the raw material organic aluminum oxy compound. Used in quantity. The concentration of the raw material organic aluminum oxy compound in the reaction system is usually 1 × 10 ^{−3 to} 5 gram atom / liter (solvent), preferably 1 × 10 ⁻² in terms of aluminum atoms in the raw material organic aluminum oxy compound. Desirably, it is in the range of ~ 3 gram atoms / liter (solvent).

  The contact between the raw material organic aluminum oxy compound and the inorganic compound not containing water is usually carried out at a temperature of -50 to 150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C. The contact time varies greatly depending on the contact temperature, but is usually 0.5 to 300 hours, preferably about 1 to 150 hours.

  Furthermore, in this invention, you may prepare the organoaluminum oxy compound whose R / Al ratio is 1.7-2.1 combining the method of (a) and the method of (b). For example, the R / Al ratio of the (raw material) organoaluminum oxy compound prepared by adjusting the R / Al ratio to 1.7 to 2.1 by the method (a) is 1.7 to 2.1 by the method (b). The R / Al ratio of the organoaluminum oxy compound (raw material) prepared by adjusting the R / Al ratio to 1.7 to 2.1 by the method of (b) may be adjusted to a specific value within the range of The R / Al ratio may be adjusted to a specific value within the range of 1.7 to 2.1 by the method (a).

Next, the olefin polymerization catalyst according to the present invention will be described.
The catalyst for olefin polymerization according to the present invention includes a particulate carrier as described below, a transition metal compound (A) of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, and the organoaluminum oxy It is formed from the compound (B) and, if necessary, the organoaluminum compound (C).

FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.
First, each component which forms such an olefin polymerization catalyst of the present invention will be described.
The particulate carrier forming the olefin polymerization catalyst of the present invention is an inorganic or organic compound, and is a granular or particulate solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm.

Among these, as the inorganic compound, a porous oxide is preferable. Specifically, SiO ₂ , Al ₂ O ₃
MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or mixtures thereof such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , Si
Examples thereof include O ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. 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 are preferred.

The inorganic oxide is composed of a small amount of Na ₂ CO 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 ) ₂ , Al (NO ₃ ) ₃ , N
Carbonic acid salts such as a ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

The properties of such a particulate carrier vary depending on the type and production method, but the particulate carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100.
~700m a ² / g, it is desirable that the pore volume is 0.3~2.5cm ³ / g. The fine particle carrier is used after being calcined at a temperature of 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

  In such a particulate carrier, the amount of adsorbed water is desirably 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. It is desired to be 0% by weight, particularly preferably 2.0 to 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 in the same manner as the inorganic compound.
The transition metal compound of group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton forming the catalyst for olefin polymerization of the present invention is a transition metal compound represented by the following general formula (I) It is.

ML _x (I)
Wherein 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 is a coordination having a cyclopentadienyl skeleton. L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R ¹ group (where 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 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, preferably a zirconium atom.

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

Among the ligands coordinated to these transition metal atoms, 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, It may be bonded via an alkylene group such as propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, a substituted silylene group such as a silylene group or a dimethylsilylene group, 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,
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group include a phenyl group and a tolyl group.
Examples of the aralkyl group include a benzyl group and a neophyll group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group.
Examples of aryloxy groups include phenoxy groups,
Examples of the trialkylsilyl group include a trimethylsilyl group.
Examples of the ligand represented by SO ₃ R ¹ include a p-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like.

Examples of halogen include fluorine, chlorine, bromine and iodine.
A transition metal compound containing a ligand having such a cyclopentadienyl skeleton is more specifically represented by the following general formula (Ia) when the valence of the transition metal is 4, for example.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (Ia)
(In the formula, M represents a transition metal atom, R ² represents a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ represent groups having a cyclopentadienyl skeleton (arrangement) A ligand), an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO ₃ R ¹ group, a halogen atom or a hydrogen atom, and k is 1
It is the above integer, and k + l + m + n = 4. )
In the present invention, in the transition metal compound represented by the general formula (Ia), a compound in which at least one of R ³ , R ⁴ and R ⁵ is a group (ligand) having a cyclopentadienyl skeleton, such as R ^A compound in which ² and R ³ are a group (ligand) having a cyclopentadienyl skeleton is preferably used. Thus, when the compound represented by the general formula (Ia) includes two or more groups (ligands) having a cyclopentadienyl skeleton, a group having two cyclopentadienyl skeletons ( Ligand) are bonded via an alkylene group such as ethylene or propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene, or methylphenylsilylene group. It may be. When R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton, R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, An aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R ¹ , a halogen atom or a hydrogen atom;

Below, a specific compound is illustrated about the transition metal compound whose M is a zirconium.
Bis (indenyl) zirconium dichloride,
Bis (indenyl) zirconium dibromide,
Bis (indenyl) zirconium bis (p-toluenesulfonate),
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,
Ethylene bis (indenyl) zirconium bis (methanesulfonate),
Ethylene bis (indenyl) zirconium bis (p-toluenesulfonate),
Ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (indenyl) zirconium dichloride,
Dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (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) cyclohexyl zirconium monochloride,
Bis (cyclopentadienyl) phenylzirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride,
Bis (cyclopentadienyl) methylzirconium monohydride,
Bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenylzirconium,
Bis (cyclopentadienyl) dibenzylzirconium,
Bis (cyclopentadienyl) zirconium methoxychloride,
Bis (cyclopentadienyl) zirconium ethoxy chloride,
Bis (cyclopentadienyl) zirconium bis (methanesulfonate),
Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate),
Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium ethoxy chloride,
Bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (methylethylcyclopentadienyl) 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 examples, the di-substituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the tri-substituted product includes 1,2,3- and 1,2,4-substituted products. including. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.

  In the present invention, in the zirconium compound as described above, a compound in which a zirconium atom is replaced with a titanium atom or a hafnium atom can also be used. The catalyst for olefin polymerization of the present invention contains the particulate carrier, the transition metal compound, and the organoaluminum oxy compound as essential components, but contains (C) an organoaluminum compound as described later. Also good.

Examples of the organoaluminum compound (C) used as necessary include an organoaluminum compound represented by the following general formula (III).
R ⁶ _n AlX _3-n (III)
(In the formula, R ⁶ represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3.)
In the general formula (III), R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically includes a methyl group, an ethyl group, and an n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group, heptyl group, nonyl group, octyl group and other alkyl groups, cyclopentyl group, cyclohexyl group and other cycloalkyl groups, phenyl group, tolyl group Aryl groups such as

Specific examples of such an organoaluminum compound (C) include the following compounds.
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum;
Alkenyl aluminum such as isoprenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum, 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, Alkyl aluminum hydrides such as di-sec-nonyl aluminum hydride.

Moreover, the compound represented by the following general formula (IV) can also be used as the organoaluminum compound (C).
R ⁶ _n AlY _3-n (IV)
(Wherein R ⁶ is the same as above, Y is —OR ⁷ group, —OSiR ⁸ ₃ group, —OAlR ⁹ ₂ group,
—NR ¹⁰ ₂ group, —SiR ¹¹ ₃ group or —N (R ¹² ) AlR ¹³ ₂ group, n is 1 to 2, and R ⁷ , R ⁸ , R ⁹ and R ¹³ are methyl group, ethyl group , Isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., R ¹⁰ is a hydrogen atom, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ¹¹ and R ¹² are methyl group, ethyl group, etc. Group. )
Specific examples of such an organoaluminum compound include the following compounds.
(1) Compounds represented by R ⁶ _n Al (OR ⁷ ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide,
(2) R ⁶ _n Al (OSiR ⁸ ₃ ) _3-n compounds such as Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al
(OSiEt ₃ ) etc .;
(3) a compound represented by R ⁶ _n Al (OAlR ⁹ ₂ ) _3-n , for example,
Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) ₂ etc .;
(4) Compounds represented by R ⁶ _n Al (NR ¹⁰ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ etc .;
(5) a compound represented by R ⁶ _n Al (SiR ¹¹ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ ;
(6) R ⁶ _n Al (N (R ¹² ) AlR ¹³ ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso- Bu) ₂ etc.

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

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.
The first olefin polymerization catalyst according to the present invention comprises:
In the particulate carrier,
The transition metal compound (A) [component (A)];
The organoaluminum oxy compound (B) [component (B)] is supported.

  Such an olefin polymerization catalyst (solid catalyst component) can be prepared by mixing and contacting the particulate carrier, component (A) and component (B) in an inert hydrocarbon solvent. In addition, when the components are mixed and contacted, an organoaluminum compound similar to the organoaluminum compound (C) can be further added.

In this case, the mixing order is arbitrarily selected. Preferably, the fine particle carrier and component (B) are mixed and contacted, and then component (A) is mixed and contacted, or
It is selected to bring the mixture of component (B) and component (A) into contact with the particulate carrier.

Specific examples of the inert hydrocarbon solvent used for the preparation of the catalyst for olefin polymerization in the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene;
Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Examples thereof include halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

When mixing the above components, the component (A) is usually used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol, per 1 g of the particulate carrier. The concentration of component (A) is in the range of about 10 ⁻⁴ to 2 × 10 ⁻² mol / liter (solvent), preferably 2 × 10 ⁻⁴ to 10 ⁻² mol / liter (solvent). 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.

  The mixing temperature at the time of mixing each said component is -50-150 degreeC normally, Preferably it is -20-120 degreeC, and contact time is 1-1000 minutes, Preferably it is 5-600 minutes. Further, the mixing temperature may be changed during the mixing contact.

The second olefin polymerization catalyst according to the present invention is:
In the particulate carrier,
The transition metal compound (A);
A solid catalyst component on which the organoaluminum oxy compound (B) is supported;
It is formed from the organoaluminum compound (C) [component (C)].

Such an olefin polymerization catalyst is formed from the first olefin polymerization catalyst (solid catalyst component) and (C) an organoaluminum compound.
The second olefin polymerization catalyst according to the present invention comprises 500 mol per gram atom of transition metal atoms derived from the first olefin polymerization catalyst (solid catalyst component) and the component (A) in the solid catalyst component. Hereinafter, it is preferably formed from component (C) in an amount of 5 to 200 mol.

  Such first and second olefin polymerization catalysts according to the present invention can produce an olefin polymer having a small amount of fine powder polymer of 100 μm or less and excellent particle properties.

The third olefin polymerization catalyst according to the present invention is:
The particulate carrier;
The transition metal compound (A);
The organoaluminum oxy compound (B);
And an olefin polymer produced by preliminary polymerization.

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

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

As the inert hydrocarbon solvent used in the preliminary polymerization, the same hydrocarbon as the inert hydrocarbon solvent used for the preparation of the first olefin polymerization catalyst is used.
In prepolymerization, component (A), in terms of the transition metal compound derived from said components (A), usually 10 ^-6 ~2 × 10 ^-2 mol / l (solvent), preferably 5 × 10 ^- It is used in an amount of ⁵ to 10 ⁻² mol / liter (solvent), and the component (A) is usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 per 1 g of the particulate carrier. 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 10 ⁻⁴ mol. 500, preferably 20-200. The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 50 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The amount of the polymer produced by the prepolymerization is desirably 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. The prepolymerization catalyst carries about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atoms, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atoms, of transition metal atoms per gram of the fine particle support. It is desirable to carry aluminum atoms of 10 ^{−3 to} 5 × 10 ⁻² gram atoms, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² gram atoms.

  The third olefin polymerization catalyst according to the present invention is excellent in particle shape. When the olefin is polymerized using such a catalyst, it is possible to produce an olefin polymer having a small amount of fine powder polymer of 100 μm or less and excellent particle properties.

The fourth olefin polymerization catalyst according to the present invention is:
The particulate carrier;
The transition metal compound (A);
The organoaluminum oxy compound (B);
The organoaluminum compound (C);
And an olefin polymer produced by preliminary polymerization.

  Such an olefin polymerization catalyst (preliminary polymerization catalyst component) is obtained by introducing an olefin into an inert hydrocarbon solvent in the presence of the particulate carrier, component (A), component (B) and component (C). Can be prepared. The solid catalyst component is preferably formed of the particulate carrier, component (A) and component (B). In this case, in addition to the solid catalyst component, component (B) may be further added.

Examples of the olefin used in the prepolymerization include the same α-olefins having 2 to 30 carbon atoms as described above. Among these, ethylene or a combination of ethylene and an α-olefin used for polymerization is particularly preferable.

As the inert hydrocarbon solvent used in the preliminary polymerization, the same hydrocarbon as the inert hydrocarbon solvent used for the preparation of the first olefin polymerization catalyst is used.
In prepolymerization, component (A), in terms of the transition metal compound derived from said components (A), usually 10 ^-6 ~2 × 10 ^-2 mol / l (solvent), preferably 5 × 10 ^- It is used in an amount of ⁵ to 10 ⁻² mol / liter (solvent), and the component (A) is usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 per 1 g of the particulate carrier. Used in an amount of × 10 ^-4 moles,
The atomic ratio (Al / M) of the aluminum atom (Al) in B) and the transition metal atom (M) in component (A) is usually 10 to 500, preferably 20 to 200. The ratio (Al-C / Al-B) of the aluminum atom (Al-C) of the component (C) to the aluminum atom (Al-B) of the component (B) is usually 0.02 to 3, preferably 0. It is the range of 05-1.5. The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 50 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The amount of the polymer produced by the prepolymerization is desirably 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. The prepolymerization catalyst carries about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atoms, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atoms of transition metal atom per gram of the fine particle carrier. The aluminum atoms derived from (B) and component (C) are supported in an amount of about 10 ^{−3 to} 5 × 10 ⁻² gram atoms, preferably 2 × 10 ⁻³ to 2 × 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 the olefin is polymerized using such a catalyst, it is possible to produce an olefin polymer having a small amount of fine powder polymer of 100 μm or less and excellent particle properties.

The fifth olefin polymerization catalyst according to the present invention is:
The particulate carrier;
The transition metal compound (A);
The organoaluminum oxy compound (B);
The organoaluminum compound (C);
A pre-polymerization catalyst component produced by pre-polymerization;
It is formed from the organoaluminum compound (C).

  Such an olefin polymerization catalyst is formed from the fourth olefin polymerization catalyst (preliminary polymerization catalyst component) and (C) an organoaluminum compound. The fifth olefin polymerization catalyst according to the present invention is 500 mol or less, preferably 5 or less per gram atom of transition metal atoms derived from the prepolymerization catalyst (component) and the component (A) in the prepolymerization catalyst component. Desirably formed from component (C) in an amount of ~ 200 moles.

Such a fifth olefin polymerization catalyst according to the present invention can produce an olefin polymer having a small amount of fine powder polymer of 100 μm or less and excellent particle properties.
In addition, the 1st-5th olefin polymerization catalyst which concerns on this invention can contain the other component useful for olefin polymerization other than each 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 performed in the presence of the 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, the same inert hydrocarbon solvent used in the catalyst preparation described above can be used, and the olefin itself can be used as a solvent.
When the olefin polymerization is carried out using the first or second olefin polymerization catalyst of the present invention, the above-mentioned catalyst is usually 10 as the concentration of transition metal atoms derived from the component (A) in the polymerization system. It is desirable to use in an amount of ^-8 to 10 ^-3 gram atoms / liter, preferably 10 ^-7 to 10 ^-4 gram atoms / liter. At this time, in addition to the organoaluminum oxy compound (component (B)) supported on the carrier, an unsupported organoaluminum oxy compound may be used.

Further, when performing olefin polymerization using an olefin polymerization catalyst in which an olefin is prepolymerized, such as the third, fourth or fifth olefin polymerization catalyst according to the present invention, the catalyst as described above, The concentration of the transition metal atom derived from the component (A) in the polymerization system is usually 10 ⁻⁸ to 10 ⁻³ gram atom / liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter. Is desirable. At this time, in addition to the organoaluminum oxy compound (component (B)) supported on the carrier, an unsupported organoaluminum oxy compound may be used.

The polymerization temperature of the olefin is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when the slurry polymerization method is performed, and is usually 0 when the liquid phase polymerization method is performed. It is desirable to be in the range of -250 ° C, preferably 20-200 ° C. In 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 normal pressure to 100 kg / cm ² , preferably normal pressure to
A condition of 50 kg / cm ^2, the polymerization reaction is a batch, semi-continuous, can be carried out by any of the methods of continuous. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.
Examples of the olefin that can be polymerized by the olefin polymerization catalyst according to the present invention include α-olefins having 2 to 20 carbon atoms, such as 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;
A cyclic olefin having 5 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene and the like. Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Modification of methylaluminoxane]
Toluene solution of methylaluminoxane (Al; 1.44 mol / liter, CH ₃ / Al molar ratio; 2.23, TMA (Area); 0.42) in a glass flask thoroughly purged with nitrogen
100 ml was charged.

  After cooling the system to 0 ° C., 1.8 g of silica containing 0.26 g of water was added dropwise over 30 minutes. At that time, the temperature in the system was kept at 0 to 2 ° C. After completion of dropping, the reaction was performed at 0 ° C. for 30 minutes.

Subsequently, the temperature in the system was raised to 40 ° C. over 30 minutes and reacted at that temperature for 6 hours. Thereafter, the inside of the system was cooled to room temperature, and the supernatant was recovered. The modified methylaluminoxane solution thus obtained is a colorless and transparent uniform solution with a CH ₃ / Al molar ratio of 2.00.
And TMA (Area) was 0.32.
[Preparation of solid catalyst]
A glass flask thoroughly purged with nitrogen was charged with 6.9 g of silica (specific surface area: 357 m ² / g, average particle diameter: 47 μm) dried at 250 ° C. for 10 hours and 100 ml of toluene, and then cooled to 0 ° C. Thereafter, 64 ml of the toluene solution of methylaluminoxane prepared above (Al; 0.830 mol / liter) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 3 ° C. Then, it was made to react at 0 degreeC for 20 minutes, then, it heated up to 95 degreeC over 1 hour, and was made to react at the temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene, and then toluene was added and resuspended so that the total volume became 125 ml. 50 ml of this suspension was transferred to another glass flask to which a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 23.8 mmol / l) 6 .4 ml was added at room temperature (added so that Al / Zr = 130 molar ratio in the reaction system), and further reacted at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.5 mg of zirconium and 138 mg of aluminum per 1 g.
[Preparation of prepolymerization catalyst]
By adding 3.9 g of the solid catalyst obtained above and 0.53 ml of 1-hexene to 130 ml of hexane containing 7.7 mmol of triisobutylaluminum, and performing prepolymerization of ethylene at 35 ° C. for 2 hours, A prepolymerized catalyst containing 3.3 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst was obtained.

At this time, adhesion of the prepolymerization catalyst to the reactor and the stirring blade was not recognized, and the obtained prepolymerization catalyst had a good shape. The particle structure of this prepolymerized catalyst is shown in FIG.
[polymerization]
1 liter of hexane was charged into a 2 liter stainless steel autoclave thoroughly purged with nitrogen, and the system was replaced with ethylene. Thereafter, 40 ml of 1-hexene was charged, and the temperature in the system was raised to 70 ° C. Subsequently, 0.75 mmol of triisobutylaluminum and the prepolymerized catalyst prepared above as zirconium were used to inject 0.005 mmol with ethylene to initiate polymerization.

Thereafter, while continuously supplying ethylene, polymerization was carried out at 8 kg / cm ² -G, 80 ° C. for 1.5 hours.
The polymer was recovered by filtration and dried at 80 ° C. under reduced pressure overnight, whereby the melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg was 0.15 g / 10 min and the density was 0. a .924g / cm ^3, a bulk specific gravity of 0.45 g / cm ^3, average particle size was obtained ethylene-1-hexene copolymer 346g is 600 .mu.m.

At this time, adhesion of the polymer to the polymerization vessel wall and the stirring blade was not observed.
[Comparative Example 1]
[Preparation of solid catalyst]
In Example 1, a catalyst was prepared in the same manner except that unmodified methylaluminoxane was used instead of modified methylaluminoxane. 1 g of this solid catalyst contained 115 mg of aluminum and 3.0 mg of zirconium.
[Preparation of prepolymerization catalyst]
By adding 3.9 g of the solid catalyst obtained above and 0.53 ml of 1-hexene to 130 ml of hexane containing 6.4 mmol of triisobutylaluminum, and performing prepolymerization of ethylene at 35 ° C. for 2 hours, A prepolymerized catalyst containing 2.7 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst was obtained.

At this time, adhesion of the prepolymerization catalyst was observed on the reactor and the stirring blade, and adhesion of cotton-like polymer was observed on the surface of the obtained prepolymerization catalyst. The particle structure of this prepolymerized catalyst is shown in FIG.
[polymerization]
The polymerization in Example 1 was carried out in the same manner except that 0.005 mmol of the prepolymerized catalyst prepared as described above was used as zirconium. The MFR was 0.17 g / 10 min and the density was 0.925 g / cm ³ . In addition, 304 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.44 g / cm ³ and an average particle diameter of 540 μm was obtained. In addition, adhesion of the polymer was recognized on the polymerization vessel wall and the stirring blade.
[Comparative Example 2]
[Modification of methylaluminoxane]
Toluene solution of methylaluminoxane (Al; 1.44 mol / liter, CH ₃ / Al molar ratio; 2.23, TMA (Area); 0.42) in a glass flask thoroughly purged with nitrogen
100 ml was charged.

After cooling the system to 0 ° C., 3.0 g of silica containing 0.65 g of water was added dropwise over 45 minutes. Subsequent operations were carried out in the same manner as in Example 1, and the CH ₃ / Al molar ratio was 1.69.
A modified methylaluminoxane solution having a TMA (Area) of 0.24 was obtained.
[Preparation of solid catalyst]
A catalyst was prepared in the same manner as in Example 1 except that the modified methylaluminoxane was used instead of the modified methylaluminoxane prepared in Example 1. 1 g of this solid catalyst contained 143 mg of aluminum and 3.6 mg of zirconium.
[Preparation of prepolymerization catalyst]
3.8 g of the solid catalyst obtained above and 0.50 ml of 1-hexene are added to 130 ml of hexane containing 7.6 mmol of triisobutylaluminum, and prepolymerization of ethylene is carried out at 35 ° C. for 1.7 hours. Thus, a prepolymerized catalyst containing 3.5 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst was obtained.

At this time, no adhesion of the prepolymerized catalyst to the reactor or the stirring blade was observed, but the shape of the obtained prepolymerized catalyst was bad.
[polymerization]
The polymerization in Example 1 was carried out in the same manner except that 0.005 mmol of the prepolymerized catalyst prepared above was used as zirconium, and the MFR was 0.14 g / 10 min and the density was 0.924 g / cm ³ . In addition, 272 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.40 g / cm ³ and an average particle diameter of 470 μm was obtained. In addition, although the adhesion of the polymer was not recognized on the polymerization vessel wall or the stirrer, the pulverization of the polymer was observed (in Example 1, the amount of the fine powder polymer of 100 μm or less was 0.01% by weight or less However, in this comparative example, it was 0.23% by weight).

[Modification of methylaluminoxane]
Toluene solution of methylaluminoxane (Al; 1.56 mol / liter, CH ₃ / Al molar ratio; 2.13, TMA (Area); 0.42) in a glass flask thoroughly purged with nitrogen
100 ml was charged.

After cooling the system to 0 ° C., 1.7 g of silica containing 0.15 g of water was added dropwise over 30 minutes. Subsequent operations were performed in the same manner as in Example 1, and the CH ₃ / Al molar ratio was 2.03,
A colorless and transparent modified methylaluminoxane solution having a TMA (Area) of 0.37 was obtained.
[Preparation of solid catalyst]
A catalyst was prepared in the same manner as in Example 1 except that the modified methylaluminoxane was used instead of the modified methylaluminoxane prepared in Example 1. 1 g of this solid catalyst contained 140 mg of aluminum and 3.5 mg of zirconium.
[Preparation of prepolymerization catalyst]
Add 3.9 g of the solid catalyst obtained above and 0.53 ml of 1-hexene to 130 ml of hexane containing 7.6 mmol of triisobutylaluminum, and carry out prepolymerization of ethylene at 35 ° C. for 1.7 hours. Thus, a prepolymerized catalyst containing 3.4 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst was obtained.

At this time, adhesion of the prepolymerization catalyst to the reactor and the stirring blade was not recognized, and the obtained prepolymerization catalyst had a good shape.
[polymerization]
The polymerization in Example 1 was carried out in the same manner except that 0.005 mmol of the prepolymerized catalyst prepared above was used as zirconium, and the MFR was 0.13 g / 10 min and the density was 0.925 g / cm ³ . 362 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.44 g / cm ³ and an average particle diameter of 640 μm was obtained. In addition, adhesion of the polymer to a polymerization vessel wall or a stirrer was not recognized.

[Modification of methylaluminoxane]
A toluene solution of methylaluminoxane (Al; 1.77 mol / liter, CH ₃ / Al molar ratio; 2.11, TMA (Area); 0.41) in a glass flask thoroughly substituted with nitrogen
100 ml was charged.

After cooling the system to 0 ° C., 1.7 g of silica containing 0.16 g of water was added dropwise over 30 minutes. Subsequent operations were carried out in the same manner as in Example 1, and the CH ₃ / Al molar ratio was 1.97; TMA
A colorless transparent modified methylaluminoxane solution (Area); 0.35 was obtained.
[Preparation of solid catalyst]
A catalyst was prepared in the same manner as in Example 1 except that the modified methylaluminoxane was used instead of the modified methylaluminoxane prepared in Example 1. 1 g of this solid catalyst contained 137 mg of aluminum and 3.6 mg of zirconium.
[Preparation of prepolymerization catalyst]
Add 3.9 g of the solid catalyst obtained above and 0.53 ml of 1-hexene to 130 ml of hexane containing 7.6 mmol of triisobutylaluminum, and carry out prepolymerization of ethylene at 35 ° C. for 1.8 hours. Thus, a prepolymerized catalyst containing 3.5 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst was obtained.

At this time, adhesion of the prepolymerization catalyst to the reactor and the stirring blade was not recognized, and the obtained prepolymerization catalyst had a good shape.
[polymerization]
The polymerization in Example 1 was carried out in the same manner except that 0.005 mmol of the prepolymerized catalyst prepared above was used as zirconium, and the MFR was 0.16 g / 10 min and the density was 0.924 g / cm ³ . In addition, 346 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.44 g / cm ³ and an average particle diameter of 610 μm was obtained. In addition, adhesion of the polymer to a polymerization vessel wall or a stirrer was not recognized.

[Modification of methylaluminoxane]
Toluene solution of methylaluminoxane (Al; 1.56 mol / liter, CH ₃ / Al molar ratio; 1.68, TMA (Area); 0.24) in a glass flask thoroughly purged with nitrogen
100 ml was charged.

After cooling the system to 0 ° C., the amount of adsorbed water was 0.005% by weight and the surface hydroxyl group amount was 3.0.
2.4% by weight of silica was added dropwise over 30 minutes. Subsequent operations were carried out in the same manner as in Example 1 to obtain a colorless and transparent modified methylaluminoxane solution having a CH ₃ / Al molar ratio of 1.72 and a TMA (Area) of 0.32.
[Preparation of solid catalyst]
A catalyst was prepared in the same manner as in Example 1 except that the modified methylaluminoxane was used instead of the modified methylaluminoxane prepared in Example 1. 1 g of this solid catalyst contained 138 mg of aluminum and 3.4 mg of zirconium.
[Preparation of prepolymerization catalyst]
Add 3.9 g of the solid catalyst obtained above and 0.53 ml of 1-hexene to 130 ml of hexane containing 7.5 mmol of triisobutylaluminum and carry out prepolymerization of ethylene at 35 ° C. for 1.7 hours. Thus, a prepolymerized catalyst containing 3.3 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst was obtained.

At this time, adhesion of the prepolymerization catalyst to the reactor and the stirring blade was not recognized, and the obtained prepolymerization catalyst had a good shape.
[polymerization]
The polymerization in Example 1 was carried out in the same manner except that 0.005 mmol of the prepolymerized catalyst prepared above was used as zirconium. The MFR was 0.15 g / 10 min and the density was 0.925 g / cm ³ . 357 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.44 g / cm ³ and an average particle diameter of 620 μm was obtained. In addition, adhesion of the polymer to a polymerization vessel wall or a stirrer was not recognized.

  The above results are summarized in Table 1.

[Modification of methylaluminoxane]
Into a stainless steel reactor thoroughly purged with nitrogen, a toluene solution of methylaluminoxane (Al; 1.44 mol / liter, CH ₃ / Al molar ratio; 2.23, TMA (Area); 0.42
) 47.8 kg (77.5 mol as Al) was charged.

After the system was cooled to 0 ° C., 775 g of silica containing 140 g of water was added dropwise over 65 minutes. At that time, the temperature in the system was kept at 0 to 5 ° C. After completion of dropping, the reaction was performed at 0 ° C. for 30 minutes.

Subsequently, the temperature in the system was raised to 40 ° C. over 1 hour and reacted at that temperature for 6 hours. Thereafter, the inside of the system was cooled to room temperature, and the supernatant was recovered. The modified methylaluminoxane solution thus obtained was a colorless and transparent uniform solution, the CH ₃ / Al molar ratio was 2.00, and TMA (Area) was 0.32.
[Preparation of solid catalyst]
Silica dried at 250 ° C. for 10 hours (specific surface area: 307 m ² / g, average particle size: 45 μm
) 4.4 kg was suspended in 80 liters of toluene and then cooled to 0 ° C. Thereafter, 24.7 liters of the toluene solution (Al; 1.36 mol / liter) of methylaluminoxane prepared above was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 5 ° C. Then, it was made to react at 0 degreeC for 30 minutes, then, it heated up to 95 degreeC over 1.5 hours, and was made to react at the temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. To this system, 8.6 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 29.9 mmol / liter) was added dropwise at 80 ° C. over 30 minutes. The reaction was carried out at 2 ° C for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per 1 g.
[Preparation of prepolymerization catalyst]
By adding 1.47 kg of the solid catalyst obtained above and 132 g of 1-hexene to 80 liters of hexane containing 2.9 mol of triisobutylaluminum, and prepolymerizing ethylene at 35 ° C. for 4 hours, A prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the catalyst was obtained.
[polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was performed at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. In order to maintain a constant gas composition during the polymerization, the prepolymerized catalyst prepared above was continuously supplied at a rate of 0.11 mmol / h in terms of zirconium atom and triisobutylaluminum at a rate of 5 mmol / h. 1-hexene, hydrogen, and nitrogen were continuously supplied (gas composition; 1-hexene / ethylene = 0.024, hydrogen / ethylene = 2.5 × 10 ⁻⁴ , ethylene concentration = 47%). The yield of the ethylene / 1-hexene copolymer thus obtained was 8.3 kg / h, the MFR was 1.10 g / 10 min, and the density was 0.918 g / cm ³ .

  Furthermore, as shown in Table 2, the polymerization conditions were changed, and copolymers having different MFR and density were synthesized. During this time, the polymerization was very stable, and when the inside of the polymerization apparatus was inspected after one week of continuous operation, no polymer adhesion to the vessel wall was observed.

It is explanatory drawing which shows the preparation process of the olefin polymerization catalyst which concerns on this invention. It is a figure which shows an example of the < ¹ > H-NMR spectrum chart of an organoaluminum oxy compound. It is explanatory drawing of the curve fitting using a Lorentz function. 1 is a diagram (micrograph) showing the particle structure of a prepolymerized catalyst prepared in Example 1. FIG. 2 is a view showing a particle structure (micrograph) of a prepolymerized catalyst prepared in Comparative Example 1. FIG.

Claims (6)

In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) a methylaminoxan composition comprising a methylaluminumoxy compound represented by the following formula (i) as a main component and a small amount of trimethylaluminum,
(Wherein R is a methyl group and n is n ≧ 2 )
Methyl ratio of methyl group to aluminum atom (methyl group / aluminum atom) is 1.7 to 2.1, peak area derived from protons in trimethylaluminum (TMA) determined from ¹ H-NMR and methylaluminum A methylaminoxan composition in which the ratio of the peak area derived from the proton in trimethylaluminum to the sum of the peak area derived from the proton in the oxy compound (TMA (Area)) is in the range of 0.25 to 0.40 . And a catalyst for olefin polymerization. In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) a methylaminoxan composition comprising a methylaluminumoxy compound represented by the following formula (i) as a main component and a small amount of trimethylaluminum,
(Wherein R is a methyl group and n is n ≧ 2 )
Methyl ratio of methyl group to aluminum atom (methyl group / aluminum atom) is 1.7 to 2.1, peak area derived from protons in trimethylaluminum (TMA) determined from ¹ H-NMR and methylaluminum A methylaminoxan composition in which the ratio of the peak area derived from the proton in trimethylaluminum to the sum of the peak area derived from the proton in the oxy compound (TMA (Area)) is in the range of 0.25 to 0.40 . A solid catalyst component on which is supported, and
(C) An olefin polymerization catalyst comprising an organoaluminum compound. In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) a methylaminoxan composition comprising a methylaluminumoxy compound represented by the following formula (i) as a main component and a small amount of trimethylaluminum,
(Wherein R is a methyl group and n is n ≧ 2 )
Methyl ratio of methyl group to aluminum atom (methyl group / aluminum atom) is 1.7 to 2.1, peak area derived from protons in trimethylaluminum (TMA) determined from ¹ H-NMR and methylaluminum A methylaminoxan composition in which the ratio of the peak area derived from the proton in trimethylaluminum to the sum of the peak area derived from the proton in the oxy compound (TMA (Area)) is in the range of 0.25 to 0.40 . A solid catalyst component on which is supported, and
An olefin polymerization catalyst comprising an olefin polymer produced by preliminary polymerization. In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) a methylaminoxan composition comprising a methylaluminumoxy compound represented by the following formula (i) as a main component and a small amount of trimethylaluminum,
(Wherein R is a methyl group and n is n ≧ 2 )
Methyl ratio of methyl group to aluminum atom (methyl group / aluminum atom) is 1.7 to 2.1, peak area derived from protons in trimethylaluminum (TMA) determined from ¹ H-NMR and methylaluminum A methylaminoxan composition in which the ratio of the peak area derived from the proton in trimethylaluminum to the sum of the peak area derived from the proton in the oxy compound (TMA (Area)) is in the range of 0.25 to 0.40 . A solid catalyst component on which is supported, and
(C) an organoaluminum compound;
An olefin polymer produced by pre-polymerization;
An olefin polymerization catalyst comprising: In the particulate carrier,
(A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton;
(B) a methylaminoxan composition comprising a methylaluminumoxy compound represented by the following formula (i) as a main component and a small amount of trimethylaluminum,
(Wherein R is a methyl group and n is n ≧ 2 )
Methyl ratio of methyl group to aluminum atom (methyl group / aluminum atom) is 1.7 to 2.1, peak area derived from protons in trimethylaluminum (TMA) determined from ¹ H-NMR and methylaluminum A methylaminoxan composition in which the ratio of the peak area derived from the proton in trimethylaluminum to the sum of the peak area derived from the proton in the oxy compound (TMA (Area)) is in the range of 0.25 to 0.40 . A solid catalyst component on which is supported, and
(C) an organoaluminum compound;
A prepolymerization catalyst component comprising an olefin polymer produced by prepolymerization;
(C) An olefin polymerization catalyst comprising an organoaluminum compound.   An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1.