JPH0678386B2 - Olefin Polymerization Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer. More specifically, it relates to a method for producing an olefin polymer by using a solid catalyst component having extremely high activity per transition metal in various polymerization processes (slurry polymerization, gas phase polymerization, etc.). Further, it relates to a method for producing an olefin polymer in which the particle shape of the solid catalyst component is extremely well controlled, the bulk density is high in slurry polymerization, gas phase polymerization and the like, the flowability of fine powder is small, and the molecular weight distribution is wide. Is.

The activity of the catalyst used for producing the olefin polymer (polymerization amount per unit catalyst), especially the high activity per transition metal means that it is not necessary to remove the catalyst residue from the polymer obtained after the polymerization, Needless to say, the polymer has a very high utility value because it can simplify the production process.

On the other hand, a large amount of adhesion to the polymerization tank causes various problems in operation and causes a decrease in operation efficiency. Therefore, it is desirable that the adhesion to the polymerization tank is as small as possible. Further, in the case of carrying out slurry polymerization or gas phase polymerization, it is desirable that the bulk density of the polymer powder is high, the particle size distribution is narrow, and the fluidity is good from the viewpoint of operation stability and operation efficiency.

Further, the molecular weight distribution of the obtained polymer is a factor controlling the processability of the polymer, the appearance of the processed product, and the physical properties. For example, a polymer having a narrow molecular weight distribution or for injection molding, rotational molding, or having a molecular weight distribution A wide range of polymers are suitable for blow molding, extrusion or film forming. Therefore, if the molecular weight distribution of the polymer can be arbitrarily controlled by a simple operation,
This makes it possible to produce a wide range of polymers suitable for various uses, which is extremely advantageous industrially.

<Prior Art> Conventional IVa to V of the periodic table as a catalyst for olefin polymerization
It is well known that a catalyst system (so-called Ziegler catalyst) consisting of a combination of a group Ia transition metal compound and an organometallic compound of a group I to III metal of the periodic table is effective. However, these catalysts generally have low catalytic activity, and it is necessary to remove the catalyst residue from the polymer after the polymerization, which does not necessarily satisfy the above properties and is industrially sufficiently superior. I can't say it. Further, when trying to broaden the molecular weight distribution of a polymer using a conventional olefin polymerization catalyst, the catalytic activity is lowered by a large amount, the amount of catalyst per unit polymer is increased, and a large amount of catalyst is required, which is industrially sufficiently advantageous. It cannot be called a thing.

Various improvements have been made to Ziegler catalysts. For example, (1) hydroxylated organic compound, (2) metallic magnesium, (3) organic oxygenated compound of group IVa, Va, VIa group of periodic table, (4) halogen of group IVa, Va, VIa group of periodic table A catalyst system comprising a compound containing the compound and (5) a heating reaction product of an aluminum halide and an organometallic compound (Japanese Patent Publication No. 52-39714), (1) a dihalide of magnesium, calcium, manganese or zinc, (2)
A catalyst system comprising an organic oxygen compound of titanium, zirconium or vanadium and (3) a solid reaction product of an organoaluminum halogen compound and an organoaluminum compound (Japanese Patent Publication No. 37195/1978), (1) an oxygen-containing organic compound of magnesium Or obtained by reacting a halogen-containing compound, (2) an oxygen-containing organic compound or a halogen-containing compound of titanium, (3) an oxygen-containing organic compound or a halogen-containing compound of zirconium, and (4) an organic aluminum halide compound in a specific amount ratio. A catalyst system comprising a solid catalyst and an organoaluminum compound (Japanese Patent Publication No. 55-8083),
It is obtained by reacting (1) an inert fine particle support material, (2) an organomagnesium compound, (3) a zirconium compound, (4) a halogenated material, and (5) a tetravalent titanium compound in this order in a specific amount ratio. Polymerization catalyst (Japanese Patent Application Laid-Open No. 61-19607)
Gazette), in the presence of a solid inorganic oxide, an organomagnesium compound and boron, silicon, germanium, tin, phosphorus,
A catalyst system comprising a solid catalyst component obtained by reacting a titanium halide, a zirconium compound and an organometallic compound with a reaction product of an antimony, bismuth, zinc halide or an organomagnesium compound and chlorine hydrogen and an organogold layer compound. (JP-A-57-155206). However, even these catalyst systems cannot be said to be industrially satisfactory in terms of the above-mentioned catalytic activity and polymer powder characteristics. Further, all of these catalyst systems, except for JP-B-52-39714, JP-B-55-8083, JP-A-57-155206 and JP-A-60-19607, all give polymers having a narrow molecular weight distribution, Does not give a polymer with a broad molecular weight distribution.

<Problems to be Solved by the Invention> In this situation, the problem to be solved by the present invention, that is, the object of the present invention is to provide a solid having a sufficiently high catalytic activity per transition metal so that the removal of catalyst residue becomes unnecessary. An object of the present invention is to provide a method for producing an olefin polymer having a wide molecular weight distribution, a high bulk density, a small amount of fine powder and good fluidity, which uses a catalyst component.

<Means for Solving Problems> In the present invention, 1. (A) the average particle diameter is 10 to 200 μm, and the pore radius is 7
Silica gel, alumina, silica-alumina, magnesia, zirconia, polyethylene, polypropylene, polystyrene with a pore volume of 5 to 200,000Å of 0.3 ml / g or more,
(B) an organosilicon compound having a Si—O bond, and (C) a general formula Ti (OR ^{1 in} the presence of a single or two or more kinds of porous simple substances selected from the group consisting of styrene-divinylbenzene copolymers. ) LX _4- l (wherein R ¹ is a carbon atom 1 to
It represents a hydrocarbon group containing 20 groups, X represents a halogen atom, and l represents a number of 0 <l ≦ 4. ), And (D) the general formula Zr (OR ² ) mX _4- m, wherein R ² is 1 to 20 carbon atoms.
Represents a hydrocarbon group containing a group, X represents a halogen atom, and m represents a number of 0 <m ≦ 4. ), And / or the general formula Hf (OR ³ ) nX _4- n, wherein R ³ represents a carbon-hydrogen group containing 1 to 20 carbon atoms, X represents a halogen atom, and n Indicates a number of 0 <n ≦ 4. ) Is reacted with a hafnium compound to obtain a reaction mixture (I), and then (E) an organomagnesium compound or a hydrocarbon-soluble complex of an organomagnesium compound and an organometallic compound is added to the reaction mixture (I). The intermediate product (II) is reacted to obtain an intermediate product (II), and the intermediate product (II) is reacted with oxygen (F) to obtain a reaction product (III), and then the reaction product (III) is obtained. And (G) general formula R ⁴ cAlX _3- c
(In the formula, R ⁴ represents a carbon atom group containing 1 to 20 carbon atoms, and c represents a number of 0 <c <3), and is obtained by contacting with an organic aluminum halide compound A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst system comprising a combination of a solid catalyst component and (H) an organoaluminum compound.

The use of the present catalyst system achieves the above objectives.

Hereinafter, the present invention will be specifically described.

(A) Porous Carrier As the porous carrier used in the present invention, silica gel,
Solid inorganic oxides such as alumina, silica-alumina, magnesia, and zirconia are mentioned. Further, polymers such as polyethylene, polypropylene, polystyrene, and styrene-divinylbenzene copolymer can be used. These may be used alone or as a mixture of two or more. A solid inorganic oxide is preferably used, and more preferably silica gel, alumina, or silica-alumina is used. The particle size of the porous carrier is preferably in the range of 5-250 μm, more preferably 10-200 μm. The average particle size is preferably 10 to 200 μm, more preferably 20 to 150 μm.
Is. The average pore radius is preferably 50Å or more, more preferably 75Å or more. Also, the pore radius is 75
Pore volume between ~ 20,000Å is preferably 0.3ml / g
It is above, more preferably 0.4 ml / g or above, and particularly preferably 0.6 ml / g or above.

Furthermore, it is preferable to use a porous carrier from which adsorbed water is excluded. Specific examples include a method of calcination at a temperature of about 300 ° C. or higher, or vacuum drying at a temperature of about 100 ° C. or higher, treated with an organometallic compound such as organomagnesium and used.

(B) Organosilicon Compound Having Si-O Bond The organosilicon compound having a Si-O bond used in the synthesis of the solid catalyst component of the present invention is represented by the following general formula.

Si (OR ⁵ ) pR ⁶ _4- p R ⁷ (▲ R ⁸ ₂ ▼ SiO) qSi ▲ R ⁹ ₃ ▼ or (▲ R ¹⁰ ₂ ▼ SiO) r where R ⁵ is a carbon having 1 to 20 carbon atoms. Hydrogen group, R ⁶ , R ⁷ , R ⁸ , R
⁹ and R ¹⁰ are hydrocarbon groups having 1 to 20 carbon atoms or hydrogen atoms, m is a number of 0 <p ≦ 4, q is an integer of 1 to 1000, and r is an integer of 2 to 1000. Is.

Specific examples of the organic silicon compound include the following.

Tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-iso-propoxysilane, di-iso-propoxy-
Di-iso-propylsilane, tetrapropoxysilane,
Dipropoxydipropylsilane, tetra-n-butoxysilane, di-n-butoxy-di-n-butylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, Examples thereof include triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane and phenylhydropolysiloxane.

Preferred of these organosilicon compounds are those of the general formula
An alkoxysilane compound represented by Si (OR ⁵ ) pR ⁶ _4- p, preferably 1 ≦ p ≦ 4, and a tetraalkoxysilane compound having p = 4 is particularly preferable.

(C) Titanium Compound The titanium compound used in the present invention has the general formula Ti (OR
¹ ) lX _4- l (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and l is a number of 0 <l ≦ 4). Specific examples of R ¹ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-.
Amyl, iso-amyl, n-hexyl, n-heptyl,
alkyl groups such as n-octyl, n-decyl and n-dodecyl; aryl groups such as phenyl, cresyl, xylyl and naphthyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; allyl groups such as propenyl; aralkyl groups such as benzyl. It is illustrated. Of these compounds, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use titanium compounds having two or more different OR ¹ groups.

Examples of the halogen atom represented by X include chlorine, bromine and iodine. Especially chlorine gives favorable results.

The value of l of the titanium compound represented by the general formula Ti (OR ¹ ) lX _4- l is 0 <l ≦ 4, preferably 2 ≦ l ≦ 4, and particularly preferably l = 4.

As a method for synthesizing the titanium compound represented by the general formula Ti (OR ¹ ) lX _4- l (0 <l ≦ 4), a known method can be used.
For example, a method of reacting Ti (OR ¹ ) ₄ and TiX ₄ at a predetermined ratio, or a method of reacting TiX ₄ and a corresponding alcohol with a predetermined amount can be used.

(D) zirconium compound and a zirconium compound used in the hafnium compound invention or hafnium compound of the general formula Zr (OR ²⁾ mX ₄ -m or Hf (OR ³⁾ n
X ₄ -n (R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms, X is a halogen atom, and m and n are 0 <m ≦ 4 and 0 <n ≦ 4). Be done. Specific examples of R ² and R ³ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl. , N-decyl, n-
Examples thereof include alkyl groups such as dodecyl, aryl groups such as phenyl, cresyl, xylyl, and naphthyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, allyl groups such as propenyl, and aralkyl groups such as benzyl. Of these compounds, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use titanium compounds having ^two or more different OR ² or OR ³ groups.

Examples of the halogen atom represented by X include chlorine, bromine and iodine. Especially chlorine gives favorable results.

The values of m and n of the zirconium compound or hafnium compound represented by the general formula Zr (OR ² ) xX ₄ -m or Hf (OR ³ ) nX ₄ -n are 0 <m ≦ 4, 0 <n ≦ 4, preferably Is 2 ≦ m
≦ 4, 2 ≦ n ≦ 4, particularly preferably m = 4 and n = 4.

General formula Zr (OR ² ) mX _4- m (0 <m ≤ 4) or Hf (OR ³ ) nX
_{As a} method for synthesizing the zirconium compound or hafnium compound represented by _4- n (0 <n ≦ 4), a known method can be used. For example, a method of reacting ZrX ₄ or HfX ₄ with a corresponding alcohol in a predetermined amount can be used.

(E) Organomagnesium Compound Next, as the organomagnesium used in the present invention, any type of organomagnesium compound containing a bond of magnesium-carbon can be used. In particular, a Grignard compound represented by the general formula R ¹¹ MgX (wherein R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms and X represents a halogen atom) and a general formula R ¹² R ¹³ Mg (wherein R ¹² and R ¹³ each represent a hydrocarbon group having 1 to 20 carbon atoms), and a dialkyl magnesium compound or diaryl magnesium compound represented by the formula (I) is preferably used. Here, R ¹¹ , R ¹² and R ¹³ may be the same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-.
Amyl, iso-amyl, n-hexyl, n-octyl,
2-ethylhexyl, phenyl, benzyl, etc. having 1 carbon atom
To 20 alkyl groups, aryl groups, aralkyl groups, or alkenyl groups.

Specifically, as the Grignard compound, methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, n-propyl magnesium chloride, n-propyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, sec-butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-amylmagnesium chloride, iso-amylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, R ¹² R ¹³ Diethyl magnesium, di-n-propyl magnesium, di-iso-propyl magnesium, di-n-as compounds represented by Mg Magnesium chill, di -sec- butyl magnesium, di -tert- butyl magnesium, n- butyl -sec- butyl magnesium, di -
Examples thereof include n-amyl magnesium and diphenyl magnesium.

As a synthetic solvent for the above-mentioned organomagnesium compound, diethyl ether, di-n-propyl ether, di-iso
-Propyl ether, di-n-butyl ether, di-is
o-butyl ether, di-n-amyl ether, di-iso
-Amyl ether, di-n-hexyl ether, di-n
Ethers such as octyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole, tetrahydrofuran, tetrahydropyran can be used. Also, hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene,
A hydrocarbon such as xylene, or a mixed solvent of ether and hydrocarbon may be used. The organomagnesium compound is preferably used in the state of an ether solution. In this case, as the ether compound, an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure is used.

Also, a hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and organometallic compound can be used. Examples of the organometallic compound include organic compounds such as Li, Be, B, Al and Zn.

(F) Oxygen As oxygen used in the present invention, oxygen or a mixed gas having an arbitrary mixing ratio of oxygen and an inert gas is used, and as the inert gas, nitrogen, argon, helium or the like is used.

(G) organic aluminum halide compound organic aluminum halide compound used in the present invention have the general formula ^{_{▲ R 4 c ▼ AlX 3 -}} c ( wherein, R ⁴ is 1 to 20 carbon atoms
Represents an organic group containing 1 to 6, preferably 1 to 6, preferably a hydrocarbon group, X represents a halogen atom, and c represents 0 <
Indicates the number of c <3. It is represented by. Chlorine is particularly preferable as X, and c is preferably 1 ≦ c ≦ 2, and particularly preferably c = 1. R ⁴ is preferably selected from alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups.

Examples of the component (G) include ethyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride, diethyl aluminum monochloride, isobutyl aluminum monochloride and the like. Among these, alkyl aluminum dichlorides such as ethyl aluminum dichloride and isobutyl aluminum dichloride can be particularly preferably used.

It is also possible to use a plurality of different organoaluminum halide compounds as component (G), in which case trialkylaluminum such as triethylaluminum, triisobutylaluminum, etc. together with the organoaluminum halide compound may be used for adjusting the amount of halogen. Trialkenylaluminum can also be used.

Synthesis of Solid Catalyst Component The solid catalyst component of the present invention comprises an organosilicon compound having a Si—O bond, a titanium compound represented by the general formula Ti (OR ¹ ) 1X ₄ -l and a general formula Zr ( OR ¹ ) zirconium compound represented by mX _4- m and / or general formula Hf (OR ₃ ) n
A reaction product of an intermediate product (II) obtained by reacting a reaction mixture (I) with a hafnium compound represented by X _4- n with an organomagnesium compound and an oxidizing compound (II
Obtained by contacting I) with an organic aluminum halide compound. At this time, it is desirable that the solid is extruded on the porous carrier due to the reaction with the organomagnesium compound, the solid product retains the shape of the porous carrier, and fine powder is not generated.

The synthesis of the solid catalyst component is carried out under an atmosphere of an inert gas such as nitrogen or argon except for the contact with oxygen. In the presence of the porous carrier, the reaction between the organosilicon compound of component (B), the titanium compound of component (C) and the zirconium compound and / or hafnium compound of component (D) is carried out by reacting component (B), component (C) The component (D) is used as it is or after being dissolved or diluted in a suitable solvent, usually at a temperature of −50 to 150 ° C. for a few minutes to a few hours. The method of adding the component (B), the component (C) and the component (D) is arbitrary, and the method of adding the component (C) and the component (D) to the component (B), the component (C) and the component (D). Any of the method of adding the component (B) to the composition or the method of simultaneously adding the component (B), the component (C) and the component (D) can be used. The reaction ratio of the component (B) to the component (C) and the component (D) is 1 in terms of the atomic ratio of the silicon atom in the component (B) to the component (C) and the transition metal (Ti + Zr + Hf) atom in the component (D). : 50 to 50: 1, preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1. The reaction ratio of the component (C) and the component (D) is 1:50 to 50: 1, preferably 1 in the atomic ratio of titanium atoms in the component (C) and zirconium and / or hafnium atoms in the component (D). It is preferably carried out in the range of: 20 to 20: 1, particularly preferably 1:10 to 10: 1 for obtaining a solid catalyst component which gives a polymer having a wider molecular weight distribution.

The amount of the porous carrier used is in the range of 20 to 90% by weight, preferably 30 to 75% by weight, in the solid catalyst component.

Examples of the solvent used in this reaction include pentane,
Hexane, heptane, octane, and other aliphatic hydrocarbons, benzene, toluene, xylene, chlorobenzene, and other aromatic hydrocarbons, cyclohexane, cyclopentane, and other alicyclic hydrocarbons, and diethyl ether, dibutyl ether, tetrahydrofuran, and other ethers. A compound etc. are mentioned. These solvents are used alone or as a mixture.

Next, the reaction mixture (I) is reacted with the organomagnesium compound component of the component (E) to obtain the intermediate product (II). In this reaction, the reaction mixture (I) and the component (E) are used as they are or by dissolving or diluting them in a suitable solvent.
It is carried out at a temperature of 150 ° C., preferably −30 to 50 ° C. for a few minutes to a few hours, preferably 30 minutes to 5 hours. The method of adding the reaction mixture (I) and the component (E) is arbitrary, and the method of adding the component (E) to the reaction mixture (I), the method of adding the reaction mixture (I) to the component (E), and the reaction mixture Any method of simultaneously adding (I) and component (E) can be used. The reaction ratio between the reaction mixture (I) and the component (E) is 1:10 by the atomic ratio of the sum of silicon atoms and transition metal atoms in the reaction mixture (I) and the magnesium atom in the component (E).
10: 1, preferably 1: 5 to 5: 1, more preferably 1: 2 to 2: 1
It is performed in the range of. Examples of the solvent used in this reaction include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cyclopentane and diethyl. Examples thereof include ether compounds such as ether, dibutyl ether, tetrahydrofuran and dioxane. These solvents are used alone or as a mixture. The intermediate product (I
I) is used as it is, or after it is dried to dryness, separated and dried, thoroughly washed with a solvent and then contacted with the component (F).

The reaction between the intermediate product (II) and the component (F) can be carried out by various methods. For example, a method in which the intermediate product (II) is dissolved or suspended in a suitable solvent, and then oxygen is passed through or dissolved in the solvent to bring it into contact with an oxidizing compound, and the intermediate product (II) is treated with a gaseous oxidizing agent. For example, there is a method of bringing them into contact with each other in a substantially dry state in an atmosphere containing them.

This reaction is usually -70 to 150 ° C, preferably -30 to 80 ° C.
At a temperature of several minutes to several tens of hours, preferably 30 minutes to 10 hours. The reaction ratio between the intermediate product (II) and the component (F) can be selected within a wide range. Generally, the rate of oxidation of the transition metal compound can be adjusted by the treatment time or the amount of oxidizing compound used. The amount of the oxidizing compound used is preferably 0.1 mol or more per 1 mol of the transition metal. Generally, by increasing the reaction ratio of oxygen to the intermediate product (II), the molecular weight distribution of the obtained polymer can be broadened. Examples of the solvent used in this reaction include aliphatic hydrocarbons such as pentane, hexine, heptane and octane, halogenated hydrocarbons such as carbon tetrachloride and dichloroethane, aromatic carbons having a degree of benzene, toluene, xylene and chlorobenzene. Examples thereof include hydrogen. These solvents are used alone or as a mixture.
In this way, the reaction product (III) is obtained.

The reaction product (III) is contacted with the component (G) at a temperature of −70 to 200 ° C., preferably −30 to 150 ° C., more preferably 30 to 100 ° C. for a few minutes to a few hours in a slurry state. Done. The method of adding the reaction product (III) and the component (G) is arbitrary, and the method of adding the component (G) to the reaction product (III) and the method of adding the reaction product (III) to the component (G) The method of adding the reaction product (III) and the component (G) at the same time may be the same. Reaction product (II
The reaction ratio between I) and component (G) can be selected within a wide range. The molecular weight distribution of the polymer can be adjusted by changing the reaction ratio of the reaction product (III) and the component (G). Generally, the molecular weight distribution of the polymer can be broadened by increasing the reaction ratio of the component (G) to the reaction product (III). Usually, it is preferable to select the amount of the component (G) per 1 g of the reaction product (III) in the range of 0.01 to 0.1 gram equivalent based on the halogen atom contained in the component (G). Examples of the solvent used in this reaction include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, halogenated hydrocarbons such as carbon tetrachloride and dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene. Examples thereof include hydrogen, alicyclic hydrocarbons such as cyclohexane and cyclopentane. These solvents are used alone or as a mixture.
In this way, a solid catalyst component is obtained.

The solid catalyst component obtained as described above retains the shape of the porous carrier, has no fine powder and has a narrow particle size distribution, high bulk density, and good fluidity. Further, this solid catalyst component contains magnesium, titanium, zirconium and / or hafnium and further halogen, and generally shows amorphous or extremely weak crystallinity, almost no X-ray diffraction peak is observed, or interplanar spacing d = 5.9. , 2.8 and 1.8Å often give very broad or weak diffraction peaks.

The solid product is usually thoroughly washed with a hydrocarbon diluting agent and then used as it is or after drying as an olefin polymerization catalyst component.

In carrying out the process of the present invention, prior to carrying out the olefin polymerization, the intermediate product (II), the reaction product (III) or the solid catalyst component is an organometallic compound of a metal of group I to III of the periodic table by a known method. under presence may small amounts of olefins (such as ethylene, a- olefins such as the C ₃ -C ₁₀₎ and carrying out the preliminary polymerization or pre-copolymerization process. The prepolymerization treatment is preferably carried out in the presence of some hydrogen. The polymerization temperature is in the range of room temperature to 100 ° C, preferably room temperature to 50 ° C. The amount of pre-polymerization is intermediate product (II), reaction product (II
I) or 0.005 to 20 g per 1 g of final solid catalyst component, especially 0.01
It is preferably carried out in the range of up to 10 g.

(H) Organoaluminum Compound In the present invention, the organoaluminum compound used in combination with the above-mentioned solid catalyst component has at least 1 in the molecule.
It has one Al-carbon bond. A typical one is shown below by a general formula.

R ¹⁴ aAlY ₃ −a R ¹⁵ R ¹⁶ Al—O—AlR ¹⁷ R ¹⁸ Here, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are hydrocarbon groups having 1 to 8 carbon atoms, and Y is It represents a halogen atom, a hydrogen atom or an alkoxy group. a is a number represented by 2 ≦ a ≦ 3.

Specific examples of the organic aluminum compound include triethyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, diethyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride, dialkyl aluminum halide such as diethyl aluminum chloride, and trialkyl aluminum. Examples thereof include mixtures of dialkylaluminum halides and alkylalumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.

Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride and tetraethyldialumoxane are preferable. .

The amount of the organoaluminum compound used can be selected in a wide range such as 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst, but the range of 5 to 600 mol is particularly preferable.

(I) Olefin Polymerization Method There are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that it is supplied in an inert gas such as nitrogen or argon in the absence of water.

The solid catalyst component and the organoaluminum compound component may be supplied individually or may be contacted in advance and supplied.

The polymerization can be carried out up to -30 to 200 ° C.

The polymerization pressure is not particularly limited, but a pressure of about 3 to 100 atm is desirable from the viewpoint of being industrial and economical. The polymerization method may be either continuous or batch. Further, slurry polymerization using an inert hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, octane, liquid phase polymerization without solvent or gas phase polymerization is also possible.

The olefin used in the present invention has 2 to 20 carbon atoms,
Preferable examples are olefins having 2 to 10 ends and having unsaturated terminals such as ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, and octene-1.

It is also possible to copolymerize a plurality of these olefins and copolymerize these olefins with diolefins having preferably 4 to 20 carbon atoms. Examples of diolefins are 1,4-hexadiene, 1,7-octadiene, vinylcyclohexene, 1,3-divinylcyclohexene, cyclopentadiene, 1,5-cyclooctadiene, dicyclopentadiene, norbornadiene, 5-vinylnorbornene and ethylidene. Examples thereof include norbornene, butadiene, isoprene and the like.

The invention is particularly directed to ethylene homopolymers or ethylene containing at least 90 mol% ethylene and other olefins (especially propylene, butene-1,4-methylpentene-1, hexene-1, octene-1). It can be effectively applied to the production of copolymers.

Also, heteroblock copolymerization in which the polymerization is carried out in two or more stages can be easily carried out.

It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer.

Further, a known electron donating compound may be added to the polymerization system for the purpose of controlling stereoregularity and molecular weight distribution of the polymer. Typical examples of the compound as the electron-donating compound include organic carboxylic acid esters such as methyl methacrylate and methyl toluate, phosphite esters such as triphenylphosphite, tetraethoxysilane, phenyltriethoxysilane and the like. Examples include silicate esters.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

The properties of the polymers in the examples were measured by the following methods.

The density was determined according to JIS K-6760 and the bulk density was determined according to JIS K-6721.

The outflow ratio (MFR) was used as a measure of melt flowability. M
FR is the melt index (MI) in ASTM 1238-57T
In the above measurement method, it is expressed as the ratio of the outflow rate when a load of 21.60 kg is applied to the outflow rate (MI) when a load of 2.160 kg is applied.

It is generally known that the wider the molecular weight distribution of a polymer, the larger the MFR value.

The particle size distribution of the polymer powder was measured by the following method. That is, the generated polymer powder is classified using a JIS standard sieve with a mesh opening of 0.125 to 1.68 mm, the weight of the polymer remaining on each sieve is weighed, and the ratio to the total polymer weight is calculated and accumulated from the small particle size side. did.

Example 1 (1) Synthesis of organomagnesium compound 3 equipped with stirrer, reflux condenser, dropping funnel, thermometer
Air and moisture were removed by adding 96.0 g of ground magnesium for Grignard and thoroughly replacing the inside of the system with argon. N-Butyl chloride in the dropping funnel
360 g and 1500 ml of di-n-butyl ether were charged and about 90 ml was dropped into the flask to start the reaction. 50 ℃ after starting the reaction
Then, the reaction was continued for about 4 hours, and after the dropping was completed, the reaction was continued at 60 ° C. for another hour. Then, the reaction solution was cooled to room temperature, and the solid content was separated.

When n-butylmagnesium chloride in this di-n-butyl ether was hydrolyzed with 1N sulfuric acid and back-titrated with 1N aqueous sodium hydroxide solution to determine the concentration (phenolphthalein was used as an indicator), the concentration was 2.03
It was mol /.

(2) Synthesis of reaction mixture (I) and intermediate product (II) After a flask having an inner volume of 3 equipped with a stirrer and a dropping funnel was replaced with argon, silica gel manufactured by Fuji Davisson Chemical Co., Ltd. As a result, pore radius 75-20,000
The pore volume between Å (hereinafter abbreviated as dvp (ml / g)) is d
The vp was 0.89 ml / g and the average pore radius was 350Å. ) Was calcined in an argon atmosphere at 800 ° C for 6 hours, and 200 g of n-
1000 ml of butyl ether was added, and 560 ml of the organomagnesium compound synthesized in (1) was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 80 ° C. with stirring, and further treated at the same temperature for 1 hour. . After that, washing with 1000 ml of n-butyl ether and once with 1000 ml of n-heptane was repeated twice, followed by drying under reduced pressure to obtain 2555 g of an organomagnesium-treated product of silica gel.

Next, after replacing the flask with an internal volume of 800 ml equipped with a stirrer and a dropping funnel with argon, 31.0 g of the organomagnesium-treated product of silica gel obtained above, 120 ml of n-heptane, and Ti
_{(O-n-C 4 H} 9) 4 1.3g (4.1mmol), previously prepared Zr
_{(O-n-C 4 H} 9) 4 of n- heptane solution 11.3 ml (Zr (O
_{-N-C 4 H 9) 4} 19.0mmol) was added and stirred at 20 ° C. 10 min. Furthermore, Si (OC ₄ H ₉ ) ₄ 9.5 g (25.0 mmol) was added at 20 ° C for 15
After dropwise addition over a period of 20 minutes, stirring was continued at 20 ° C. for 20 minutes to obtain a pale yellow slurry solution (reaction mixture (I)).

After cooling the reaction mixture (I) to 5 ° C, the temperature is raised to 5 ° C.
While maintaining the temperature at 0 ° C., the n-C ₄ H ₉ MgCl di-
23.6 ml (47.9 mmol) of n-butyl ether solution was added dropwise over 45 minutes. The reaction solution turned brown with the dropping. After the dropping was completed, the reaction was continued for another 2 hours at 20 ° C.
The liquid phase was removed by filtration, washed with 120 ml of n-heptane five times, repeated repeatedly, and dried under reduced pressure at room temperature to obtain 29.9 g of a brown powder (intermediate product (II)). Analysis of this powder revealed that Ti 0.6%, Zr 5.3%, Mg 3.5%, Cl 5.3%, (n-C ₄
It contained 0.6% of H ₉ ) ₂ O (all by weight).

(3) Synthesis of reaction product (III) 10.0 g of the intermediate product (II) synthesized in (2) above was collected, and 100 ml of n-heptane was added thereto, and then stirred at room temperature with 10% oxygen and nitrogen. A dry gas containing 90% was flowed at a rate of 12 l / h for 2 hours for reaction. After completion of the reaction, the liquid phase was removed by filtration, washed with 100 ml of n-heptane 5 times and repeated, and dried under reduced pressure at room temperature to obtain 9.4 g of a pale yellow powder.

(4) Synthesis of solid catalyst component 8.5 g of the reaction product (III) synthesized in (3) above was sampled, 25 ml of n-heptane was added thereto, and then C ₂ H ₅ AlCl ₂
12.3 ml (C ₂ H ₅ AlCl ₂ 42.5 mmol) of n-heptane solution of
The mixture was added dropwise at 30 ° C over 30 minutes, and after completion of the reaction, the mixture was reacted at 65 ° C for 1 hour. After completion of the reaction, the liquid phase was removed by filtration, washed with 50 ml of n-heptane 5 times and repeated repeatedly, and dried under reduced pressure at room temperature to obtain 7.9 g of a brown powder. Analysis of this powder revealed that Ti 0.5
%, Zr 5.5%, Mg 3.9, Cl 19.9%, Al 1.2% (all in weight%).

Microscopic observation of this powder revealed that it was almost spherical and had a narrow particle size distribution.

(5) Polymerization of ethylene After the autoclave with an electromagnetic induction stirrer of 1 was sufficiently replaced with nitrogen, 500 ml of n-heptane and 1.0 mmol of triisobutylaluminum were added. After heating to 70 ° C, hydrogen is added until the total pressure reaches 5 kg / cm ² , and then ethylene is added at a total pressure of 15 kg / cm ^2.
Added until cm ² . Polymerization was initiated by adding 13.6 mg of the fixed catalyst component synthesized in (4) above. Then, polymerization was carried out at 70 ° C. for 1 hour while continuously feeding ethylene and keeping the total pressure constant.

After completion of the polymerization, the produced polymer was filtered and dried under reduced pressure at 60 ° C. The polymer yield was 31.7 g. The catalytic activity in this case was 42,400 g polymer / g transition metal, hr. The MI of this polymer was 0.51 g / 10 minutes, the MFR was 99, the bulk density was 0.40 g / cm ³ , the shape of the polymer powder was almost spherical, and the fluidity with a narrow particle size distribution as shown in Table 1 was used. It was a good one. The fine particles having a particle diameter of 125 μm or less were 0.4 wt%, which was a very small amount.

Example 2 Example 1 was repeated except that 1.0 mmol of triethylaluminum and 18.3 mg of a solid catalyst component were used in place of triisobutylaluminum in the polymerization of ethylene in Example 1.
Polymerization was carried out in the same manner as in (5) to obtain 46.8 g of a polymer. The catalytic activity in this case was 46,500 g polymer / g transition metal, hr. The MI of this polymer was 0.52 g / 10 minutes, the MFR was 65, the bulk density was 0.39 g / m ³ , the shape of the polymer powder was almost spherical, and the fluidity with a narrow particle size distribution was good. .

Comparative Example 1 Example 1 (5) except that 45.3 mg of the intermediate product (III) synthesized in Example 1 (2) was used as the solid catalyst component.
Polymerization of ethylene was carried out in the same manner as, but only a trace amount of the polymer was obtained.

Comparative Example 2 Example 1 (5) except that 49.3 mg of the reaction product (III) synthesized in Example 1 (3) was used as the solid catalyst component.
Ethylene was polymerized in the same manner as in, but only a trace amount of the polymer was obtained.

Comparative Example 3 (1) Synthesis of solid catalyst component 7.0 g of the intermediate product (II) synthesized in Example 1 (2) was collected and treated with C ₂ H ₅ AlCl _{2 in} the same manner as in Example 1 (4). The reaction was performed to obtain 6.7 g of brown powder. Analysis of this powder revealed that Ti
It contained 0.6% by weight and 5.4% by weight of Zr.

(2) Polymerization of ethylene Polymerization of ethylene was carried out in the same manner as in Example 1 (5) except that 24.5 mg of the brown powder obtained in (1) above was used to obtain 39.2 g of ethylene.
A polymer of The catalyst activity in this case is 26,700 g polymer /
The catalyst activity per transition metal was inferior to that of Example 1 since the amount was g transition metal and hr.

Comparative Example 4 (1) Reaction mixture (1), the intermediate product synthesis Ti of (II) (O-n- C 4 H 9) 4 5.0g (14.6mmol) n- heptane
Dissolved in 150 ml. Then the previously prepared _{Zr (O-n-C 4} H
_{9) 4} of n- heptane solution 43.6ml (Zr (O-n- C 4 H 9) 4
72.9 mmol) was added and the mixture was stirred at room temperature for 10 minutes. Further Si
After 20.0 g (90.0 mmol) of (OC ₂ H ₅ ) _{4 was} added dropwise at room temperature over 15 minutes, stirring was continued at room temperature for 20 minutes to obtain a pale yellow homogeneous solution (reaction mixture (I)).

After cooling the reaction mixture (I) to 5 ° C, the temperature is raised to 5 ° C.
Was added dropwise Example 1 (1) synthesized n-C ₄ H ₉ MgCl di n- butyl ether solution 93.0ml of (189 mmol) over a period of 35 minutes while maintaining the. With the dropping, the reaction liquid turned brown and solid was produced. After the dropping was completed, the reaction was continued at 20 ° C for another 2 hours, and the liquid phase was removed by filtration to remove n-heptane.
It was washed 5 times with 350 ml and repeated repeatedly, and dried under reduced pressure at room temperature to obtain 41.4 g of a brown powder (intermediate product (II)). Analysis of this powder revealed that Ti 1.8%, Zi 17.8%, Mg 11.6%, Cl
16.1% and contained _{(n-C 4 H 9)} 2 O 0.7% ( both by weight).

(2) Synthesis of reaction product (III) Except for collecting 10.0 g of the intermediate product synthesized in (1) above, it was reacted with an oxidizing compound in the same manner as in Example 1 (3) to give brown powder 9.0 g. Got

(3) Synthesis of solid catalyst component 8.0 g of the reaction product (III) synthesized in (2) above was sampled, 23 ml of n-heptane was added thereto, and then C ₂ H ₅ AlCl ₂
N-heptane solution of 46.2 ml (C ₂ H ₅ AlCl ₂ 80 mmol) of 60 ° C.
Was added dropwise over 30 minutes, and after completion of the reaction, the mixture was reacted at 65 ° C. for 1 hour. After completion of the reaction, the liquid phase was removed by filtration to remove n-heptane.
It was washed with 50 ml 5 times and repeated repeatedly, and dried under reduced pressure at room temperature to obtain 4.8 g of a brown powder.

Analysis of this powder revealed that Ti 1.9%, Zr 18.2%, Mg 1
It contained 3.0%, Cl 61.9%, and Al 3.3% (all in weight%).

(4) Polymerization of ethylene Polymerization of ethylene was carried out in the same manner as in Example 1 (5) except that 3.8 mg of the solid synthesized in (3) above was used as a solid catalyst component to obtain 35.0 g of a polymer. The catalytic activity in this case is 4
It was 5,600 g polymer / g transition metal, hr. The bulk density of this polymer was 0.36 g / cm ³ , and as shown in Table 1, the polymer powder was unsatisfactory in terms of bulk density and fluidity. Further, the amount of fine particles having a particle diameter of 125 μm or less was 5.2% by weight, which was more than that in Example 1.

Comparative Example 5 In the synthesis of the solid product of Example 1 (2), as the silica gel, used was Super Microbeads Silica Gel 4B type (dvp = 0.15 ml / g) manufactured by Fuji Devison Chemical Co., Ltd., which was vacuum dried at 100 ° C. A solid catalyst component was synthesized in the same manner as in Example 1 except that it was used. Analysis of this powder revealed that Ti
It contained 0.6% and Zr 5.5% (both by weight).

Polymerization of ethylene was carried out in the same manner as in Example 1 (5) except that 30.2 mg of the above solid was used as a solid catalyst component to obtain 16.2 g of a polymer. The catalytic activity in this case was 8,800 g polymer / g transition metal, hr, and the catalytic activity per transition metal was inferior. The bulk density of this polymer is 0.35 g / cm ³ ,
As shown in 1, the polymer powder was unsatisfactory in terms of bulk density and fluidity. In addition, fine particles with a particle size of 125 μm or less
The amount was 3.9 wt%, which was higher than that in Example 1.

Comparative Example 6 (1) Synthesis of solid catalyst component 19.8 g of the organomagnesium-treated silica gel obtained in Example 1 (2), 120 ml of n-heptane, Ti (O-n-C)
₄ H ₉ ) ₄ 0.9 g (2.6 mmol), previously prepared Zr (O-n-C ₄
H ₉ ) ₄ n-heptane solution 8.7 ml (Zr (O-n-C ₄ H ₉ ) ₄
14.6 mmol) was added and the mixture was stirred at 20 ° C. for 30 minutes. After cooling this slurry solution to 5 ° C, 13.0 ml (26.3 mmol) of the di-n-butyl ether solution of n-C ₄ H ₉ MgCl synthesized in Example 1 (1) was kept for 40 minutes while maintaining the temperature at 5 ° C. It dripped over. The reaction solution turned brown with the dropping. After completion of the dropping, the reaction was continued at 20 ° C. for another 2 hours, the liquid phase was removed by filtration, the mixture was washed 5 times with 120 ml of n-heptane, repeated repeatedly, and dried under reduced pressure at room temperature to obtain 23.0 g of a brown powder. Next, 12.3 g of this brown powder was sampled, and n-heptane 130
After adding ml, it was reacted with an oxidation compound in the same manner as in Example 1 (3) to obtain 12.0 g of a light brown powder. Further, 9.8 g of this powder was collected and treated with C ₂ H _{5 in the same} manner as in Example 1 (4).
Reaction with AlCl ₂ gave 9.1 g of a brown powder. When this powder was analyzed, it contained 1.4% by weight of Ti and 7.3% by weight of Zr.

(2) Polymerization of ethylene The weight of ethylene was the same as in Example 1 (5) except that 18.2 mg of the brown powder synthesized in (1) above was used as the solid catalyst component to obtain 28.0 g of a polymer. The catalytic activity in this case was 17,700 g polymer / g transition metal, hr, and the contact activity per transition metal was poor.

The MI of this polymer is 0.38 g / 10 minutes, MFR is 58, and bulk density is
It was 0.37 g / cm ³ , and as shown in Table 1, the polymer powder was unsatisfactory in terms of bulk density and fluidity. Also 125 μm
The following fine particles were 2.7 wt% and were more than in Example 1.

Comparative Example 7 (1) Synthesis of solid catalyst component 10.1 g of silica gel treated with organomagnesium obtained in Example 1 (2), 60 ml of n-heptane, Ti (O-n-C)
₄ H ₉ ) ₄ 0.5 g (1.5 mmol), Si (OEt) ₄ 2.0 g (9.7 mmol)
Was added and stirred at 20 ° C. for 30 minutes. After cooling this slurry solution to 5 ° C., Example 1 while maintaining the temperature at 5 ° C.
18.2 ml (37 mmol) of a solution of n-C ₄ H ₉ MgCl synthesized in (1) in di-n-butyl ether was added dropwise over 40 minutes. The reaction solution turned brown with the dropping. After the dropping was completed, the reaction was continued for another 2 hours at 20 ° C., and then the liquid phase was removed by filtration.
-Washing with 120 ml of heptane 5 times and repeating the process, and drying under reduced pressure at room temperature gave 14.8 g of a brown powder. Then this brown powder 10.
0 g was collected and reacted with an oxidizing compound in the same manner as in Example 1 (3) to obtain 9.8 g of a light brown powder. Furthermore, 7.2 g of this light brown powder
Was reacted with C ₂ H ₅ AlCl _{2 in} the same manner as in Example 1 (4) to obtain 6.8 g of a brown powder. Analysis of this powder revealed that Ti
It contained 2.2% by weight.

(2) Polymerization of ethylene Polymerization of ethylene was carried out in the same manner as in Example 1 (5) except that 8.2 mg of the brown powder synthesized in (1) above was used as a solid catalyst component, to obtain 25.4 g of a polymer. The catalytic activity in this case was 118,000 g polymer / g transition metal, hr.

The MI of this polymer is 8.5 g / 10 minutes, MFR is 32, and bulk density is 0.36.
It was g / cm ³ and was unsatisfactory in that the MFR was small.

Comparative Example 8 (1) Synthesis of solid catalyst component 11.2 g of the organomagnesium-treated silica gel obtained in Example 1 (2), 60 ml of n-heptane, and Zr prepared in advance
_{(O-n-C 4 H} 9) 4 of n- heptane solution 4.5 ml (Zr (O
-N-C ₄ H ₉ ) ₄ 7.8 mmol), Si (OEt) ₄ 2.0 g (9.7 mmo
l) was added and stirred at 20 ° C. for 30 minutes. After cooling this slurry solution to 5 ° C., Example 1 while maintaining the temperature at 5 ° C.
Synthesized n-C ₄ H ₉ MgCl di -n- butyl ether solution 18.2ml of (37 mmol) was added dropwise over 40 minutes at (1). The reaction solution turned brown with the dropping. After the addition was completed, the reaction was continued at 20 ° C. for another 2 hours, then the liquid phase was removed by filtration, washed with 120 ml of n-heptane 5 times, repeated repeatedly and dried under reduced pressure at room temperature to obtain 18.9 g of a brown powder. Then this brown powder 1
1.1 g was collected and reacted with an oxidizing compound in the same manner as in Example 1 (3) to obtain 11.0 g of a light brown powder. Further, 10,0 g of this light brown powder was added to C ₂ H ₅ AlCl _{2 by} the same method as in Example 1 (4).
Was reacted with to obtain 9.1 g of brown powder. The powder was analyzed and found to contain 7.8 wt% Zr.

(2) Polymerization of ethylene Polymerization of ethylene was carried out in the same manner as in Example 1 (5) except that 38.4 mg of the brown powder synthesized in (1) above was used as a solid catalyst component to obtain 27.3 g of a polymer. The catalytic activity in this case was 9,100 g polymer / g transition metal, hr, and the catalytic activity per transition metal was inferior.

The MI of this polymer was 0.05 g / 10 minutes, the MFR was 73, and the bulk density was
It was 0.38 g / cm ³ .

Example 3 The autoclave with an electromagnetic dielectric stirrer of Example 1 was thoroughly replaced with nitrogen, and then 200 g of butane and 10 parts of triisobutylaluminum were used.
mmol, butene-1, 50 g were added. After raising the temperature to 65 ° C,
Hydrogen was added until the total pressure reached 5 kg / cm ² , then ethylene was added until the total pressure reached 15 kg / cm ² . Polymerization was initiated by adding 11.3 mg of the solid catalyst component synthesized in Example 1 (5). After that, while continuously supplying ethylene, keeping the total pressure constant
Copolymerization of ethylene and butene-1 was performed at 65 ° C for 1 hour. After the polymerization was completed, the produced polymer was filtered and dried under reduced pressure at 60 ° C. The polymer yield was 29.4 g. The catalytic activity in this case was 47,300 g polymer / g transition metal, hr. In this copolymer, there are 16.4 ethyl groups per 1000 carbon atoms, the density is 0.928 g / cm ³ , the MI is 0.48 g / 10 minutes, and the MF
The R was 81 and the bulk density was 0.39 g / cm ³ , and the shape of the polymer powder was almost spherical and the fluidity with a narrow particle size distribution was good.

Example 4 (1) Synthesis of solid catalyst component As silica gel, 952 grade silica gel (dvp = 0.94 ml / g) manufactured by Fuji Devison Chemical Co., Ltd. was calcined at 800 ° C. for 6 hours 30.0 g, n-heptane 120 ml, Ti _{(O-n-C 4 H} 9)
₄ 1.4g (4mmol), was added _{Zr (O-n-C 4} H 9) 4 of n- heptane solution 11.4ml (Zr (O-n- C 4 H 9) 4 19mmol), 10 minutes at 20 ° C. It was stirred. Furthermore, Si (OE
t) ₄ 5.2 g (25 mmol) was added dropwise at 20 ° C over 15 minutes, and then 2
Stirring was continued for 20 minutes at 0 ° C. Next, while maintaining the temperature at 5 ° C., 64 ml (48 mmo) of a solution of Mg (n-C ₆ H ₁₃ ) ₂ in n-heptane was used.
l) was added dropwise over 45 minutes. 2 more at 20 ℃ after dropping
After continuing the reaction for a period of time, the liquid phase was removed by filtration, washed with 150 ml of n-heptane 5 times, repeated filtration, and dried under reduced pressure at room temperature to obtain 38.5 g of a brown powder. 20 g of this powder was sampled, and dry oxygen gas was passed directly through it. The reaction was performed at room temperature at a rate of 10 / hr for 2 hours. After completion of the reaction, 100 ml of n-heptane
It was washed 5 times with, repeated over, and dried under reduced pressure at room temperature to obtain 16.5 g of pale yellow powder. 14.3 g of this powder was sampled and n-
After addition of heptane 23ml, C ₂ H ₅ AlCl ₂ of n- heptane solution 20.6ml of _{(C 2 H 5 AlCl 2 71.5mmol} ) was added dropwise over 30 minutes at 60 ° C., 1 hour at 65 ° C. After completion of the dropwise addition Let After completion of the reaction, the liquid phase was removed by filtration, washed with 50 ml of n-heptane 5 times, repeated filtration, and dried under reduced pressure at room temperature to give 12.9 g of brown powder.
Got Analysis of this powder revealed that Ti 3.0% by weight, Zr
It contained 5.1% by weight.

(2) Polymerization of ethylene Polymerization of ethylene was carried out in the same manner as in Example 1 (5) except that 11.8 mg of the solid synthesized in (1) above was used as a solid catalyst component to obtain 22.8 g of a polymer. The catalytic activity in this case was 33,900 g polymer / g transition metal, hr. The polymer had an MI of 0.80 g / 10 minutes, an MFR of 70 and a bulk density of 0.40 g / cm ^3.
The flowability was narrow and the particle size distribution was narrow.

Examples 5 to 10 Using various compounds, the solid catalyst component was synthesized and ethylene was polymerized in the same manner as in Example 1. Table 2 shows the synthesis conditions of the solid catalyst component, and Table 2 shows the ethylene polymerization results.
3 shows.

Example 11 In the synthesis of the reaction mixture of Example 1 (2), a styrene-divinylene copolymer (dvp
= 1.05 ml / g, average pore radius 370Å, average particle diameter 31 μm)
A solid catalyst component was synthesized in the same manner as in (1) to (4) of Example 1 except that the one dried under reduced pressure at 80 ° C. for 5 hours was used instead of silica gel. When the obtained brown powder was analyzed, the contents of Ti and Zr were 0.6% by weight and 5.4% by weight, respectively. The powder had a substantially spherical shape and a narrow particle size distribution.

Except that 18.3 mg of the above powder was used as the solid catalyst component,
Ethylene was polymerized in the same manner as in Example 1 (5) to give 38.3
g of polymer was obtained. The catalytic activity in this case was 35,000 g polymer / g transition metal, hr. The MI of this polymer is 0.42 g / 1.
At 0 minutes, the MFR was 79, the bulk density was 0.42 g / cm ³ , and the fluidity was good with a narrow particle size distribution. Also, the particle size diameter is 125
Fine particles having a size of μm or less were 0.2% by weight.

<Effects of the Invention> In the method for polymerizing olfine of the present invention, since the catalyst activity per transition metal is high, the amount of the catalyst remaining in the produced polymer is small and the catalyst removal step can be omitted. Further, there is little adhesion to the polymerization tank during polymerization, and when slurry polymerization or gas phase polymerization is carried out, the particle size distribution is narrow, and a substantially spherical or oblong bulk density gives a polymer powder with good fluidity, The pelletizing step can be omitted, and the polymerization efficiency and operability are extremely excellent. In addition, since the molecular weight distribution of the polymer produced can be controlled by selecting the type of each component used in the production of the solid catalyst component and the amount used, a wide range of applications such as injection molding, rotational molding, extrusion molding, film molding, and hollow molding. A polymer suitable for the above can be produced.

[Brief description of drawings]

FIG. 1 is a flow chart for facilitating the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (2)

[Claims] 1. (A) Silica gel, alumina, silica-alumina, magnesia, zirconia, polyethylene, polypropylene having an average particle diameter of 10 to 200 μm and a pore volume of 0.3 ml / g or more at a pore radius of 75 to 200,000Å. (B) an organosilicon compound having a Si—O bond, and (C) a general formula Ti, in the presence of a single or two or more kinds of porous simple substances selected from the group consisting of, polystyrene, and a styrene-divinylbenzene copolymer. (OR ¹ ) lX _4- l (wherein R ¹ is a carbon atom 1 to
It represents a hydrocarbon group containing 20 groups, X represents a halogen atom, and l represents a number of 0 <l ≦ 4. ), And (D) the general formula Zr (OR ² ) mX _4- m, wherein R ² is 1 to 20 carbon atoms.
Represents a hydrocarbon group containing a group, X represents a halogen atom, and m represents a number of 0 <m ≦ 4. ), And / or the general formula Hf (OR ³ ) nX _4- n, wherein R ³ represents a hydrocarbon group containing 1 to 20 carbon atoms, X represents a halogen atom, and n Indicates a number of 0 <n ≦ 4. ) Is reacted with a hafnium compound to obtain a reaction mixture (I), and then (E) an organomagnesium compound or a hydrocarbon-soluble complex of an organomagnesium compound and an organometallic compound is added to the reaction mixture (I). The intermediate product (II) is reacted to obtain an intermediate product (II), and the intermediate product (II) is reacted with oxygen (F) to obtain a reaction product (III), and then the reaction product (III) is obtained. And (G) general formula R ⁴ cAlX _3- c
(In the formula, R ⁴ represents a carbon atom group containing 1 to 20 carbon atoms, and c represents a number of 0 <c <3), and is obtained by contacting with an organic aluminum halide compound Solid catalyst component, and 2. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst system comprising (H) an organoaluminum compound in combination.