JP3465310B2 - Method for preparing olefin polymerization catalyst, olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention is directed to a process of preparing an olefin polymerization catalyst, it relates polymerization process of olefin polymerization catalysts and olefin, more particularly a process for the preparation of olefin polymerization catalysts having excellent polymerization activity per catalyst unit weight, this preparation
The present invention relates to an olefin polymerization catalyst obtained by the method and an olefin polymerization method using the olefin polymerization catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer or an ethylene / olefin copolymer, a titanium catalyst comprising a titanium compound and an organoaluminum compound, or a vanadium compound and an organic catalyst. A vanadium-based catalyst composed of an aluminum compound is known.

An olefin polymerization catalyst composed of a zirconium compound and an organoaluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an ethylene / olefin copolymer with high polymerization activity. Examples of the method for producing an ethylene / olefin copolymer using the same include JP-A-58-19309, JP-A-60-35005, and JP-A-60-3.
5006, JP-A-60-35007, JP-A-60-35008, and the like.

Further, in JP-A-60-260602 and JP-A-60-130604, a catalyst formed from a transition metal compound and a mixed organoaluminum compound of an aluminoxane and an organoaluminum compound is used. Methods for polymerizing olefins have been proposed.

The catalysts formed from a transition metal compound and an aluminoxane proposed in these publications are more polymerized than the catalysts formed from a transition metal compound and an organoaluminum compound which are known before the appearance of this catalyst. Excellent activity, especially ethylene polymerization activity. However, most of them are soluble in the reaction system, and in most cases, the production process is limited to the solution polymerization system, and when trying to produce a polymer having a high molecular weight, the viscosity of the solution containing the polymer becomes extremely high. The inconvenience of reduced productivity occurs.

Further, at least one of the transition metal compound and the organoaluminum oxy compound is silica,
A method of polymerizing an olefin in a suspension polymerization system or a gas phase polymerization system using a catalyst supported on a porous inorganic oxide carrier such as alumina or silica-alumina is known.

For example, JP-A-60-35006, JP-A-60-35007 and JP-A-60-
Japanese Patent No. 35008 describes that a catalyst in which a transition metal compound and an aluminoxane are supported on silica, alumina, silica-alumina or the like can be used.

The above publications and JP-A-61-130
No. 314 and JP-A No. 2-41303 disclose a catalyst in which a metallocene compound of a transition metal compound having a pentadienyl group such as a cyclopentadienyl group as a ligand, an alkyl group and / or a halogen atom is combined with an aluminoxane. It is described that the system is highly active in the polymerization of α-olefin, and the properties of the obtained polymer are excellent.

JP-A-61-1108610 and JP-A-61-296008 disclose that an olefin is polymerized in the presence of a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide. How to do is described.

However, when olefins are polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system by using the solid catalyst component supported on the carrier described in these publications, compared with the above solution polymerization system. The polymerization activity was remarkably reduced and was not satisfactory.

As a result of intensive studies in view of the above-mentioned conventional techniques, the present inventors have found that (A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton. , (B) an organoaluminum oxy compound, and (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones,
The catalyst obtained by mixing and contacting these in a specific order is
The inventors have found that a polymer having excellent polymerization activity per unit weight of catalyst and having a uniform particle size (small amount of fine powder polymer) can be polymerized, and thus completed the present invention.

[0012]

SUMMARY OF THE INVENTION The present invention has been made under the above circumstances, and an object thereof is to provide a method for preparing an olefin polymerization catalyst having excellent polymerization activity per unit weight of the catalyst. Olefi obtained by this method of preparation
Emissions polymerization catalyst, and its object is to provide a process for olefin polymerization using the olefin polymerization catalyst.

[0013]

SUMMARY OF THE INVENTION A first method for preparing an olefin polymerization catalyst according to the present invention comprises: (B) an organoaluminumoxy compound; and (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Mixed contact with each other, and then (A) containing a ligand having a cyclopentadienyl skeleton
A transition metal compound of Group 4 of the periodic table and a solid carrier are mixed and brought into contact with each other, and the (A) transition metal compound is added to the solid carrier.
The olefin polymerization catalyst is characterized in that (B) an organoaluminum oxy compound and (C) a carbonyl group-containing compound are supported.

A second method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
The transition metal compound of Group 4 of the periodic table and the solid support are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are added to the solid support. An olefin polymerization catalyst comprising a compound, (C) a carbonyl group-containing compound, and (D) an organoaluminum compound supported thereon.

The third method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
A transition metal compound of Group 4 of the periodic table and a solid carrier are mixed and brought into contact with each other, and the (A) transition metal compound is added to the solid carrier.
(B) An organoaluminum oxy compound and (C) a carbonyl group-containing compound are supported as a solid catalyst component (i), and the solid catalyst component (i) and (E) an organoaluminum compound are mixed and brought into contact with each other. It is characterized by being used as an olefin polymerization catalyst.

The fourth method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
The transition metal compound of Group 4 of the periodic table and the solid support are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are added to the solid support. A solid catalyst component (ii) in which a compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound are supported, and the solid catalyst component (ii) and (E) an organoaluminum compound are mixed and contacted The feature is that it is used as an olefin polymerization catalyst.

A fifth method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
A transition metal compound of Group 4 of the periodic table and a solid carrier are mixed and brought into contact with each other, and the (A) transition metal compound is added to the solid carrier.
(B) An organoaluminum oxy compound and (C) a carbonyl group-containing compound are supported to obtain a solid catalyst component (i), and the solid catalyst component (i) is prepolymerized to obtain a prepolymerization catalyst. It is characterized by that.

The sixth method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
The transition metal compound of Group 4 of the periodic table and the solid support are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are added to the solid support. A compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound are supported to obtain a solid catalyst component (ii), and an olefin is prepolymerized on the solid catalyst component (ii) to form a prepolymerization catalyst. It is characterized by doing.

The seventh method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
A transition metal compound of Group 4 of the periodic table and a solid carrier are mixed and brought into contact with each other, and the (A) transition metal compound is added to the solid carrier.
(B) An organoaluminum oxy compound and (C) a carbonyl group-containing compound are supported to obtain a solid catalyst component (i), and the solid catalyst component (i) is prepolymerized with an olefin to carry out a prepolymerization catalyst component (i). In addition, the prepolymerization catalyst component (i) and the organoaluminum compound (E) are mixed and contacted with each other to obtain an olefin polymerization catalyst.

The eighth method for preparing an olefin polymerization catalyst according to the present invention comprises mixing (B) an organoaluminumoxy compound with (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. Contacted, then containing (A) a ligand having a cyclopentadienyl skeleton
The transition metal compound of Group 4 of the periodic table and the solid support are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are added to the solid support. A compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound are supported as a solid catalyst component (ii), and the solid catalyst component (ii) is prepolymerized with an olefin to carry out a prepolymerization catalyst component ( ii), and further, the prepolymerization catalyst component (ii) and (E) the organoaluminum compound are mixed and brought into contact with each other to obtain an olefin polymerization catalyst.

The olefin polymerization catalyst according to the present invention is as described above.
It is characterized by being obtained by a preparation method such as
It The olefin polymerization method according to the present invention is characterized by polymerizing an olefin in the presence of a catalyst obtained by the above-mentioned method for preparing an olefin polymerization catalyst.

[0022]

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

In the present invention, the term "polymerization" may be used in the sense of including not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also homopolymer. It may be used to include a polymer.

First, each component used in the olefin polymerization catalyst of the present invention will be described. Includes (A) a ligand having a cyclopentadienyl skeleton used in the present invention
The transition metal compound of Group 4 of the periodic table (hereinafter sometimes referred to as “component (A)”) is a transition metal compound represented by the following general formula (I).

ML _x (I) (In the formula, M represents a transition metal atom selected from Group 4 of the periodic table , L represents a ligand coordinated to the transition metal, and at least one L is cyclo. L is a ligand having a pentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
An aryloxy group, a trialkylsilyl group, a SO ₃ R ¹ group (wherein 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 Indicates the valence of the transition metal. In the above general formula (I), M is a transition metal atom selected from Group 4 of the periodic table , specifically a zirconium atom, a titanium atom or a hafnium atom, preferably a zirconium atom.

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

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

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

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

The ligand represented by SO ₃ R ¹ is p-
Examples thereof include a toluene sulfonate group, a methane sulfonate group, and a trifluoro methane sulfonate group. Such a transition metal compound containing a ligand having a cyclopentadienyl skeleton is more specifically represented by the following general formula (Ia) when the valence of the transition metal is 4.

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

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) Zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) ) Zirconium bis (methane sulfonate), ethylene bis (indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirco Umbis (trifluoromethanesulfonato), ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopenta) Dienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl)
Zirconium bis (trifluoromethane sulfonate),
Dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride , Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopenta Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl Benzalkonium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) (Enyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, Bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene) Le) zirconium dichloride, bis (methyl-butylcyclopentadienyl) zirconium dichloride, bis (methyl-butylcyclopentadienyl)
Zirconium bis (methanesulfonato), 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 cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4. -Includes substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert.
-Including isomers such as.

In the present invention, in the zirconium compound as described above, a compound in which a zirconium atom is replaced with a titanium atom or a hafnium atom can be used.
The organoaluminum oxy compound (B) used in the present invention (hereinafter sometimes referred to as “component (B)”) is
It may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

In the above method, the aluminoxane is recovered as a hydrocarbon solution. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then the obtained aluminoxane may be redissolved in the solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Trialkyl aluminum such as aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula (II) can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (II) (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) Such organoaluminum compounds may be used alone or in combination.

The solvent used for the preparation of the aluminoxane includes aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbons such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The benzene-insoluble organoaluminum oxy compound that can be used in the present invention can be obtained by contacting a solution of aluminoxane with water or a compound containing active hydrogen, or by contacting the organoaluminum compound with water as described above. Can be obtained. In such a benzene-insoluble organoaluminum oxy compound, the Al component soluble in benzene at 60 ° C. is A
It is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of 1 atom, and is insoluble or hardly soluble in benzene.

The organoaluminum oxy compound (B) as described above is usually commercially available or handled as a toluene solution. The organoaluminum oxy compound (B) used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum.

The carbonyl group-containing compound (C) used in the present invention is the following keto alcohol or the following β-diketone. Examples of the keto alcohol used in the present invention include acetol (acetol), 1-hydroxy-2-butanone (1-hydroxy-2-butanone), 3-hydroxy-2-butanone (3-hydroxy-2-butanone), 3 -Acetyl-1-propanol, 3-hydroxy-3-methyl-2
-Butanone (3-hydroxy-3-methyl-2-butanone), 4-hydroxy-3-methyl-2-butanone (4-hydroxy-3-methyl-2-b)
utanone), 4-hydroxy-4-methyl-2-pentanone (4-h
ydroxy-4-methyl-2-pentanone) and the like.

The β-diketone used in the present invention includes 2,4-pentanedione (acetylacetone, 2,4-pentane).
anedione), 2-methyl-1,3-butanedione (2-methyl-1,
3-butanedione), 1,3-butanedione (1,3-butanedion)
e), 3-phenyl-2,4-pentanedione (3-phenyl-2,4-p
entanedione), 1,1,1-trifluoro-2,4-pentanedione (1,1,1-trifluoro-2,4-pentanedione), 1,1,1-trifluoro-5,5-dimethyl-2,4 -Hexanedione (1,1,1-triflu
oro-5,5-dimethyl-2,4-hexanedione), 2,2,6,6-tetramethyl-3,5-heptanedione (2,2,6,6-tetramethyl-3,5
-heptanedione), 3-methyl-2,4-pentanedione (3-me
thyl-2,4-pentanedione), 2-acetylcyclopentanone, 2-acetylcyclohexanone, 1-heptafluoropropyl-3-t-butyl-1,3-propanedione ( 1-heptafluor
opropyl-3-t-butyl-1,3-propanedione), 1,3-diphenyl-1,3-propanedione
ne), 1,3-diphenyl-2-methyl-1,3-propanedione (1,3-diphenyl-2-methyl-1,3-propanedione), 1-ethoxy-1,3-butanedione -1,3-butanedion
e) and the like.

Of these, 2,4-pentanedione, 2-methyl-1,3-butanedione and 1,3-butanedione are preferable, and 2,4-pentanedione is particularly preferable. Two or more kinds of these keto alcohols and β-diketones can be used.

Examples of the (D) organoaluminum compound (hereinafter sometimes referred to as "component (D)") used in the present invention include organoaluminum compounds represented by the following general formula (III). be able to. ^{_{R 6 n AlX 3-n ...}} (III) ( wherein, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, X
Is a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula (III), R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group,
Examples thereof include a heptyl group, a nonyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

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

As the organoaluminum compound (D),
It is also possible to use a compound represented by the following general formula (IV)
it can. R⁶ _nAlY_3-n  … (IV) (In the formula, R⁶Is the same as above, and Y is -OR⁷Group,-
OSiR⁸ ₃Group, -OAlR ⁹ ₂Group, -NR^Ten ₂Group, -SiR
¹¹ ₃Group or -N (R¹²) AlR¹³ ₂And n is 1 to
2 and R⁷, R⁸, R⁹And R¹³Is a methyl group, ethi
Group, isopropyl group, isobutyl group, cyclohexyl
Group, phenyl group, etc., R^TenIs a hydrogen atom, methyl
Group, ethyl group, isopropyl group, phenyl group, trimethyl
Such as a rusilyl group, R¹¹And R¹²Is a methyl group,
For example, a chill group. ) Such an organoaluminum compound
As the product, specifically, the following compounds are used.
Be done. (1) R⁶ _nAl (OR⁷)_3-nThe compound represented by
For example, dimethyl aluminum methoxide, diethyl aluminum
Aluminum ethoxide, diisobutylaluminum methoxy
Such as (2) R⁶ _nAl (OSiR⁸ ₃)_3-nA compound represented by
For example Et₂Al (OSiMe₃), (Iso-Bu)₂A
l (OSiMe₃), (Iso-Bu)₂Al (OSiE
t₃)Such; (3) R⁶ _nAl (OAlR⁹ ₂)_3-nA compound represented by
For example, Et₂AlOAlEt₂, (Iso-Bu)₂Al
OAl (iso-Bu)₂Such; (4) R⁶ _nAl (NR^Ten ₂)_3-nThe compound represented by
For example, Me₂AlNEt₂, Et₂AlNHMe, Me₂A
lNHEt, Et₂AlN (SiMe₃)₂, (Iso-B
u)₂AlN (SiMe₃)₂Such; (5) R⁶ _nAl (SiR¹¹ ₃)_3-nA compound represented by
For example (iso-Bu)₂AlSiMe₃Such; (6) R⁶ _nAl (N (R¹²) AlR¹³ ₂)_3-nRepresented by
Compounds such as Et₂ AlN (Me) AlEt₂,
(Iso-Bu)₂AlN (Et) Al (iso-Bu)₂Na
What.

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

The olefin polymerization catalyst according to the present invention is as described above.
Each component such as is supported on a solid carrier as shown below.
There is. The solid carrier used in the present invention is inorganic or
Organic compounds with a particle size of 10-300 μm, preferably
Or a solid of 20 to 200 μm in the form of granules or fine particles.
The body is used. Among them, the inorganic carrier is porous oxide
Preferred is SiO.₂, Al₂O₃, Mg
O, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, Ba
O, ThO₂Or a mixture thereof, such as Si
O₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, S
iO₂-V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-M
Examples thereof include gO. Among these SiO
₂And Al ₂O₃At least 1 selected from the group consisting of
Those having a seed component as a main component are preferable.

The inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxides may be contained.

The properties of such a solid carrier differ depending on the type and production method, but the solid carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g,
It is preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 2.5 cm ² / g. The solid carrier is used after firing at a temperature of 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Further, examples of the solid carrier which can be used in the present invention include granular or fine particle solids of an organic compound having a particle size of 10 to 300 μm. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having 2 to 2 carbon atoms.
Produced mainly from 14 α-olefins (co)
Examples thereof include polymers, and polymers or copolymers containing vinylcyclohexane or styrene as a main component.

Next, the olefin polymerization catalyst of the present invention will be described more specifically. The first olefin polymerization catalyst according to the present invention includes (A) a ligand having a cyclopentadienyl skeleton in a solid support.
A solid catalyst comprising a transition metal compound of Group 4 of the periodic table , (B) an organoaluminum oxy compound, and (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones. .

The olefin polymerization catalyst (solid catalyst component (i)) is prepared by mixing and contacting the components (A), (B), (C) and the solid carrier in an inert hydrocarbon. You can

At this time, the order of mixing the respective components is arbitrary, but it is desirable that the component (B) and the component (C) are mixed and brought into contact with each other, and then the component (A) or the solid carrier is brought into contact with them.

The second olefin polymerization catalyst according to the present invention contains (A) a ligand having a cyclopentadienyl skeleton in a solid carrier.
A transition metal compound of Group 4 of the periodic table , (B) an organoaluminum oxy compound, (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones, and (D) an organoaluminum compound. It is a supported solid catalyst.

This olefin polymerization catalyst (solid catalyst component (ii)) is a component (A), a component (B), a component (C), a component (D) and a solid carrier which are the above-mentioned inert hydrocarbon solvents. It can be prepared by mixing in.

At this time, the order of mixing the respective components is arbitrary, but first, the component (B) and the component (C) are mixed and contacted, and then the component (A) or the solid carrier and then the component (D) are mixed and contacted. Preferably.

In the present invention, when the above components are mixed, the component (A) is added in an amount of 10 ^{−5 to} 5 per 1 g of the solid carrier.
It is used in an amount of x10 ^-3 mol, preferably 5 x 10 ^-5 to 10 ^-3 mol, and the concentration of component (A) is 10 ^-4 to 2 x 10 ^-2.
Mol / liter-solvent, preferably 2 × 10 ^-4 to 10 ^-2
Mol / l-solvent range. The component (B) has an atomic ratio (Al / transition metal) of aluminum (Al) derived from the component (B) and the transition metal derived from the component (A), and is 10 to 500, preferably 20 to 200. Used in an amount of. The component (C) is 0.01 to 0.25 mol, preferably 0.02 to 0.20 mol, and more preferably 0.03 to 1 mol of aluminum derived from the component (B).
Used in an amount of 0.15 mol. Further, when the component (D) is used, the aluminum atom (Al-d) in the component (D) and the aluminum atom (Al- in the component (B) are included.
The gram atom ratio (Al-d / Al-b) with b) is 0.01-
It is used in an amount of 1, preferably 0.02 to 0.5.

The mixing temperature for mixing the above components is −
50 to 150 ° C, preferably -20 to 120 ° C,
The contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. Further, the mixing temperature may be changed during the mixing contact.

In the present invention, the component (B) and the component (C)
Is preferably mixed and contacted in advance in an inert hydrocarbon to prepare a solution containing a mixed contact product of the component (B) and the component (C), and then the solution and other components are mixed and contacted. .

When the component (B) and the component (C) are mixed and brought into contact with each other, the concentration of the component (B) is 0.01 to 5 mol / mol.
It is in the range of liter-solvent, preferably 0.1 to 3 mol / liter-solvent. The component (C) is 0.01 to 0.25 mol, preferably 0.02 to 0.20 mol, and more preferably 0.03 to 0.15 mol, relative to 1 mol of aluminum derived from the component (B). Is desirable. The mixing temperature for mixing and contacting the component (B) and the component (C) is
The temperature is −20 to 150 ° C., preferably 0 to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.

As described above, when the component (C) is used in the preparation of the catalyst, it is possible to prepare a solid catalyst component having a larger amount of each component supported than the conventional supported catalyst. In particular,
First, the component (B) and the component (C) are mixed and contacted to prepare a solution containing a mixed contact product of the component (B) and the component (C), and then the solution and then the other component are mixed and contacted. By doing so, a solid catalyst component in which the amount of each component supported is large can be prepared.

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

First Olefin Polymerization Catalyst According to the Present Invention
(Solid catalyst component (i)) is derived from component (A)
5 × 10 5 metal transfer atoms per 1 g of solid carrier^-6~ 5
× 10 ^-FourGram atom, preferably 10^-Five~ 2 x 10^-FourGu
Aluminum supported in the amount of lamb atoms and derived from component (B)
10 atoms of nickel^-3~ 5 x 10^-2Gram atom, preferably
Is 2 × 10^-3~ 2 x 10^-2Supported in the amount of gram atoms,
Ingredient (C) is 10^-Four~ 5 x 10^-3Mol, preferably 2
× 10^-Four~ 2 x 10^-3Must be supported in molar amounts
desirable.

Second Olefin Polymerization Catalyst According to the Present Invention
(Solid catalyst component (ii)) is derived from component (A)
A transfer metal atom. 5 × 10 per 1 g of solid carrier^-6~ 5
× 10 ^-FourGram atom, preferably 10^-Five~ 2 x 10^-FourGu
Supported in the amount of lamb atoms, component (B) and component (D)
10 aluminum atoms derived from^-3~ 5 x 10^-2Gra
Mu atom, preferably 2 × 10^-3~ 2 x 10^-2Gram atom
And the amount of component (C) is 10^-Four~ 5 x 10^-3Mo
Le, preferably 2 × 10^-Four~ 2 x 10^-3Carried in molar amounts
It is desirable that

The third olefin polymerization catalyst according to the present invention is formed from the solid catalyst component (i) and (E) an organoaluminum compound. The component (E) is a transition metal atom 1 derived from the component (A) in the solid catalyst component (i).
500 moles or less per gram atom, preferably 5 to 20
It is preferably used in an amount of 0 mol.

The fourth olefin polymerization catalyst according to the present invention is formed from the solid catalyst component (ii) and (E) an organoaluminum compound. The component (E) is a transition metal atom 1 derived from the component (A) in the solid catalyst component (ii).
500 moles or less per gram atom, preferably 5 to 20
It is preferably used in an amount of 0 mol.

Examples of the organoaluminum compound (E) used in the third and fourth olefin polymerization catalysts of the present invention include the same compounds as the organoaluminum compound (D).

A fifth olefin polymerization catalyst according to the present invention comprises (A) a ligand having a cyclopentadienyl skeleton in a solid carrier.
A solid catalyst component carrying a transition metal compound of Group 4 of the periodic table , (B) an organoaluminum oxy compound, and (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones, It is a prepolymerization catalyst obtained by prepolymerizing olefins.

The olefin polymerization catalyst (preliminary polymerization catalyst component (i)) is obtained by prepolymerizing olefin in the presence of the component (A), the component (B), the component (C) and a solid carrier. However, the olefin is usually prepolymerized in the presence of the solid catalyst component (i).

The sixth olefin polymerization catalyst according to the present invention contains (A) a ligand having a cyclopentadienyl skeleton in a solid carrier.
A transition metal compound of Group 4 of the periodic table , (B) an organoaluminum oxy compound, (C) at least one carbonyl group-containing compound selected from keto alcohols and β-diketones, and (D) an organoaluminum compound. It is a prepolymerization catalyst in which an olefin is prepolymerized on a supported solid catalyst component.

The olefin polymerization catalyst (preliminary polymerization catalyst component (ii)) comprises components (A), (B), (C),
It can be obtained by prepolymerizing an olefin in the presence of the component (D) and a solid carrier. Usually, the olefin is prepolymerized in the presence of the solid catalyst component (ii).

In the preliminary polymerization, the component (A) is 10 ^-6
It is used in an amount of ˜2 × 10 ⁻² mol / liter (polymerization volume), preferably 5 × 10 ⁻⁵ -10 ⁻² mol / liter, and the component (A) is 5 × as a transition metal per 1 g of the solid support. 1
0 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴
Used in molar amounts. The component (B) has an atomic ratio (Al / transition metal) of aluminum (Al) of the component (B) to the transition metal of the component (A), and is preferably 10 to 500, preferably 2
Used in an amount of 0-200. The component (C) is 0.01 to 0.25 mol, preferably 0.02 to 0.20 mol, and more preferably 0.03 mol, relative to 1 mol of the component (B).
Used in an amount of ˜0.15 mol. Further, when the component (D) is used, the aluminum atom (Al-d) in the component (D) and the aluminum atom (Al- in the component (B) are included.
It is used in an amount of 0.01 to 1, preferably 0.02 to 0.5 in terms of atomic ratio (Al-d / Al-b) with b).

When a fifth olefin polymerization catalyst is prepared by prepolymerizing an olefin in the presence of the solid catalyst component (i), the solid catalyst component (i) is the same as that in the solid catalyst component (i). Converted to component (A), 10 ^-6 to 2 x 10 ^-2
Mol / liter (polymerization volume), preferably 5 × 10 ⁻⁵
Used in an amount of 10 ^-2 mol / l. At this time, an organoaluminum compound (D) may be used if necessary. When the organoaluminum compound (D) is used as described above, 200 mol or less per gram atom of the transition metal atom derived from the component (A) in the solid catalyst component (i),
It is preferably used in an amount of 3 to 150 mol.

When a sixth olefin polymerization catalyst is prepared by prepolymerizing an olefin in the presence of the solid catalyst component (ii), the solid catalyst component (ii) is the same as the solid catalyst component (ii). Converted to component (A), 10 ^-6 to 2 x 10 ^-2
Mol / liter (polymerization volume), preferably 5 × 10 ⁻⁵
Used in an amount of 10 ^-2 mol / l. At this time, an organoaluminum compound (D) may be used if necessary. When the organoaluminum compound (D) is used as described above, 200 mol or less per gram atom of the transition metal atom derived from the component (A) in the solid catalyst component (ii),
It is preferably used in an amount of 3 to 150 mol.

The prepolymerization temperature is −20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 0.5 ° C.
It is 100 hours, preferably about 1 to 50 hours. For the prepolymerization, an olefin similar to the olefin used in the later-described polymerization is used, but an olefin containing ethylene as a main component is preferable.

The prepolymerization may be batch type, semi-continuous type or continuous type.
The offset method can also be implemented. like this
A fifth olefin polymerization catalyst according to the present invention prepared according to
The medium (preliminary polymerization catalyst component (i)) is derived from the component (A).
5 x 10 transition metal atoms per g of solid support^-6
~ 5 x 10^-FourGram atom, preferably 10^-Five~ 2 x 10
^-FourIt is supported in the amount of gram atom and is derived from the component (B).
10 aluminum atoms^-3~ 5 x 10^-2Gram atom, preferred
2 × 10^-3~ 2 x 10^-2Supported in the amount of grams atom
And component (C) is 10^-Four~ 5 x 10^-3Mol, preferably
Is 2 × 10^-Four~ 2 x 10 ^-3Preliminary weight, supported in molar amounts
The polymer produced at the time of synthesis is 0.1 g per 1 g of the solid carrier.
~ 500g, preferably 0.3-300g, especially preferred
More preferably, it is contained in an amount of 1 to 100 g.

In the sixth olefin polymerization catalyst (preliminary polymerization catalyst component (ii)) according to the present invention, the transition metal atom derived from the component (A) is 5 × 10 5 per 1 g of the solid support.
^{-6 to} 5 x 10 ^-4 gram atom, preferably 10 ^-5 to 2 x 1
The amount of aluminum atom derived from the component (B) and the component (D) is 10 ^{−3 to} 5 × 10, which is supported in an amount of 0 ⁻⁴ gram atom.
^-2 gram atom, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² gram atom, and the component (C) is 10 ^{−4 to} 5 × 1.
The amount of the polymer formed in the preliminary polymerization is 0.1 to 500 g, preferably 0.1 to 500 g, preferably 0.1 to ^-3 mol, preferably 2 × 10 ^-4 to 2 × 10 ^-3 mol. 3 to 30
It is desirable that the content is 0 g, particularly preferably 1 to 100 g.

The seventh olefin polymerization catalyst according to the present invention is formed from the prepolymerization catalyst component (i) and (E) an organoaluminum compound. The component (E) is preferably used in an amount of 500 mol or less, preferably 5 to 200 mol, per gram atom of the transition metal atom derived from the component (A) in the prepolymerization catalyst component (i).

The eighth olefin polymerization catalyst according to the present invention is formed from the prepolymerization catalyst component (ii) and (E) an organoaluminum compound. The component (E) is preferably used in an amount of 500 mol or less, preferably 5 to 200 mol, per gram atom of the transition metal atom derived from the component (A) in the prepolymerization catalyst component (ii).

Examples of the (E) organoaluminum compound used in the seventh and eighth olefin polymerization catalysts of the present invention include the same compounds as the above (D) organoaluminum compound.

The olefin polymerization catalyst of the present invention is
In addition to the above components, other components useful for olefin polymerization may be included. Such an olefin polymerization catalyst according to the present invention has excellent polymerization activity per unit weight of catalyst and has a uniform particle size (there is little fine polymer).
A polymer is obtained.

Next, the olefin polymerization method according to the present invention will be described. In the present invention, olefin polymerization is carried out in the presence of the above 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 as used in the above catalyst preparation can be used as a solvent, and the olefin itself can be used as a solvent.

Using the olefin polymerization catalyst of the present invention,
In carrying out the polymerization of the reffin, the above catalyst is
The concentration of transition metal atoms derived from the component (A) in the polymerization system
Then 10^-8-10^-3Gram atom / liter (polymerization volume
Product), preferably 10^-7-10 ^-FourGram atom / liter
It is desirable to be used in an amount of (polymerization volume). this
At this time, if desired, using an organoaluminum oxy compound
Good. The amount of organoaluminum oxy compound used is
0 per gram atom of transition metal atom derived from minute (A)
It is desirable to be in the range of to 500 mol.

The olefin polymerization temperature is -50 to 100 ° C., preferably 0 to 100 ° C. when carrying out the slurry polymerization method.
It is preferably in the range of 90 ° C, and when carrying out the liquid phase polymerization method, it is 0 to 250 ° C, preferably 20 to 200 ° C.
It is desirable that the range is. When carrying out the gas phase polymerization method, the polymerization temperature is 0 to 120 ° C., preferably 20.
It is preferably in the range of -100 ° C. The polymerization pressure is
Atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 kg
/ Cm and under conditions of ^2, the polymerization reaction is batch, semi-continuous can be carried out by any of the methods of continuous. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Examples of olefins that can be polymerized by the olefin polymerization catalyst of the present invention include ethylene and 3 to 2 carbon atoms.
0 α-olefins such as propylene, 1-butene, 1
-Pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; carbon number 5
~ 20 cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano
-1,2,3,4,4a, 5,8,8a-octahydronaphthalene etc. can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0090]

EFFECT OF THE INVENTION The olefin polymerization catalyst according to the present invention is excellent in polymerization activity per unit weight of catalyst and is capable of polymerizing a polymer having a uniform particle size (small polymer powder).

[0091]

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

The melt flow rate of the polymer (M
FR), density, average particle size and amount of fine powder were measured as follows. [Melt flow rate (MFR)] According to ASTM D785,
It was measured under the conditions of 190 ° C. and 2.16 kg load.

[Density] The density was measured by the density gradient tube method. [Average Particle Size and Amount of Fine Powder] The average particle size and the amount of fine powder of 100 μm or less were measured by a sieve.

[0094]

[Example 1] [Modification of methylaluminoxane] A toluene solution of methylaluminoxane (Shelling Co., Ltd.) (Lot No.
3, Al; 1.45 mol / l) 150 ml was charged.

After cooling the system to 0 ° C., a solution prepared by diluting 1.66 ml of acetylacetone with 25 ml of toluene was added dropwise over 20 minutes. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes and further at 40 ° C. for 4 hours. The toluene solution of the reaction product of methylaluminoxane thus obtained and acetylacetone (hereinafter referred to as "modified methylaluminoxane (a)") was a uniform pale yellow color.

[Preparation of Solid Catalyst Component (A-1)] In a glass flask having an inner volume of 200 ml which had been sufficiently replaced with nitrogen, 50 ml of the modified methylaluminoxane (a) solution, 50 ml of toluene and bis (1,3-n- 18.7 ml of a toluene solution of butylmethylcyclopentadienyl) zirconium dichloride (Zr; 23.8 mmol / l) was charged and the reaction was carried out at 40 ° C. for 1 hour.

Then, 6.3 g of silica dried at 250 ° C. for 10 hours was added dropwise over 20 minutes. At that time, the temperature in the system was kept at 40 ° C. Subsequently, the temperature was raised to 60 ° C., and the reaction was carried out at that temperature for 6 hours.

After completion of the reaction, the supernatant was removed by decantation, and once with 200 ml of toluene and hexane 2 times.
Solid catalyst component (A-1) was obtained by washing twice with 00 ml.
Got 170 g of aluminum and 3.7 mg of zirconium were contained in 1 g of this solid catalyst component (A-1).

[Preparation of Prepolymerization Catalyst (B-1)] 1 containing 5.6 mmol of diisobutylaluminum hydride
The solid catalyst component (A-1) 2.7 was added to 00 ml of hexane.
By adding 5 g of the prepolymerized ethylene at 50 ° C. for 3 hours, a prepolymerized catalyst (B-1) containing 3.7 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst component (A-1) was obtained.

[Polymerization] 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liter which had been sufficiently replaced with nitrogen, and the system was replaced with ethylene. Then, 40 ml of 1-hexene was charged and the temperature inside the system was raised to 70 ° C. Subsequently, polymerization was initiated by pressurizing 112 mg of ethylene with 0.75 mmol of triisobutylaluminum and the prepolymerized catalyst (B-1) prepared above as solid catalysts.

Then, polymerization was carried out at 8 kg / cm ² -G and 80 ° C. for 1.5 hours while continuously supplying ethylene. After completion of the polymerization, the polymer was recovered by filtration and dried at 80 ° C. under reduced pressure overnight to obtain 190 ° C. and 2.
MFR was measured under a 16kg load was 0.13 g / 10 min, density of 0.922 g / cm ^3, a bulk specific gravity of 0.44 g / cm ^3, an average particle size of 630 .mu.m, 100 [mu] m or less Fine polymer content of 0.05% by weight
As a result, 336 g of an ethylene / 1-hexene copolymer was obtained.
The activity per solid catalyst was 3000 g-polymer / g-catalyst.

[0102]

Comparative Example 1 [Preparation of Solid Catalyst Component (A-2)] Methylaluminoxane (Lot No. TB 6.1-503) manufactured by Schering Co. was used instead of the toluene solution of the modified methylaluminoxane (a). A solid catalyst component was prepared in the same manner as in Example 1. 88 g of aluminum and 1.6 mg of zirconium were contained in 1 g of the obtained solid catalyst component (A-2).

[Preparation of Prepolymerization Catalyst (B-2)] 2 containing 5.6 mmol of diisobutylaluminum hydride
The solid catalyst component (A-2) 6.3 in 00 ml of hexane
1 g was added, and ethylene was prepolymerized at 50 ° C. for 3 hours to prepare a prepolymerized catalyst (B-2) containing 1.1 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst component (A-2).

[Polymerization] Instead of the prepolymerization catalyst (B-1), the prepolymerization catalyst (B-2) was used as a solid catalyst for 415 m.
Copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1 except that g was used, the MFR was 0.18 g / 10 min, the density was 0.923 g / cm ³ , and the bulk specific gravity was 0. .
36 g / cm ³ and an average particle size of 440 μm,
383 g of ethylene / 1-hexene copolymer having a fine polymer amount of 100 μm or less and 0.20% by weight was obtained. The activity per solid catalyst was 920 g-polymer / g-catalyst.

[0105]

[Example 2] [Modification of methylaluminoxane] Same as Example 1 except that methylaluminoxane (Lot No.TB 6.1-373) manufactured by Schering Co. was used instead of methylaluminoxane (Lot No.TB 6.1-503). Then, methylaluminoxane was reacted with acetylacetone. The toluene solution of the obtained reaction product of methylaluminoxane and acetylacetone (hereinafter referred to as “modified methylaluminoxane (b)”) was a uniform pale yellow color.

[Preparation of solid catalyst component (A-3)] 250 ml in a glass flask with an internal volume of 400 ml which had been sufficiently replaced with nitrogen.
10.1 g of silica dried at 10 ° C for 10 hours and 15 parts of toluene
0 ml was charged and the temperature in the system was cooled to 0 ° C. Then, 76.4 ml of a toluene solution of the modified methylaluminoxane (b) (Al; 1.02 mol / liter) was added dropwise over 45 minutes. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 30 minutes, and reacted at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., the supernatant was removed by decantation, and the mixture was washed twice with toluene.

3.7 g of the solid component thus obtained
Was suspended in 60 ml of toluene, and a solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Zr; 23.8 mmol / liter) 6.
Charge 2 ml (Al / Zr molar ratio = 130), 80 ° C
Was reacted for 2 hours. Then, the supernatant liquid was removed, and the solid catalyst component (A-3) was obtained by washing twice with hexane. 1 g of this solid catalyst component (A-3) contained 150 mg of aluminum and 3.8 mg of zirconium.

[Preparation of prepolymerization catalyst (B-3)] 150 m containing 7.4 mmol of triisobutylaluminum
1 hexane, to the total amount of the solid catalyst component (A-3) and 1-
After adding 0.66 ml of hexene and prepolymerizing ethylene at 35 ° C for 2 hours, 1 g of the solid catalyst component (A-3) was obtained.
A prepolymerized catalyst (B-3) containing 3.7 mg of zirconium and 3 g of polymer was obtained.

[Polymerization] Instead of the prepolymerization catalyst (B-1), the prepolymerization catalyst (B-3) was used as a solid catalyst in an amount of 123 m
The copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1 except that g was used, the MFR was 0.11 g / 10 min, the density was 0.923 g / cm ³ , and the bulk specific gravity was 0. .
43 g / cm ³ and an average particle size of 610 μm,
308 g of an ethylene / 1-hexene copolymer having a fine polymer amount of 100 μm or less and 0.02% by weight was obtained. The activity per solid catalyst was 2500 g-polymer / g-catalyst.

[0110]

Comparative Example 2 [Preparation of Solid Catalyst Component (A-4)] Methylaluminoxane (Lot No. TB 6.1-373) manufactured by Schering Co. was used in place of the toluene solution of the modified methylaluminoxane (b), except that The solid catalyst component was prepared in the same manner as in Example 2. 1 g of the obtained solid catalyst component (A-4) contained 110 mg of aluminum and 2.9 mg of zirconium.

[Preparation of prepolymerization catalyst (B-4)] 130 m containing 6.4 mmol of triisobutylaluminum
3.90 g of the solid catalyst component (A-4) and 0.52 ml of 1-hexene were added to 1 hexane, and ethylene was prepolymerized at 35 ° C. for 2 hours to give a solid catalyst component (A-
4) 2.6 mg of zirconium and polymer 3 per gram
A prepolymerized catalyst (B-4) containing g was obtained.

[Polymerization] Instead of the prepolymerization catalyst (B-1), the prepolymerization catalyst (B-4) was used as a solid catalyst for 179 m.
Copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1 except that g was used, MFR was 0.14 g / 10 min, density was 0.924 g / cm ³ , and bulk specific gravity was 0. .
45 g / cm ³ and an average particle size of 540 μm,
304 g of an ethylene / 1-hexene copolymer having a fine polymer content of 100 μm or less and 0.20% by weight was obtained. The activity per solid catalyst was 1700 g-polymer / g-catalyst.

[0113]

Example 3 [Modification of methylaluminoxane] Methylaluminoxane was reacted with acetylacetone in the same manner as in Example 1 except that the amount of acetylacetone used was changed to 1.10 ml. A toluene solution of the obtained reaction product of methylaluminoxane and acetylacetone (hereinafter referred to as "modified methylaluminoxane (c)") was obtained.

[Preparation of Solid Catalyst Component (A-5)] The solid catalyst component was prepared in the same manner as in Example 1 except that the toluene solution of the modified methylaluminoxane (c) was used in place of the modified methylaluminoxane (a). Was prepared. 1 g of the obtained solid catalyst component (A-5) contained 140 m of aluminum.
It contained 3.5 mg of g and zirconium.

[Preparation of Preliminary Polymerization Catalyst (B-5)] Preliminary polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component (A-5) was used in place of the solid catalyst component (A-1). The prepolymerization catalyst (B-5) containing 3.4 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst component (A-5) was obtained.

[Polymerization] Instead of the prepolymerization catalyst (B-1), the prepolymerization catalyst (B-5) was used as a solid catalyst for 121 m.
Copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1 except that g was used, MFR was 0.18 g / 10 min, density was 0.924 g / cm ³ , and bulk specific gravity was 0. .
44 g / cm ³ and an average particle size of 610 μm,
327 g of an ethylene / 1-hexene copolymer having a fine polymer amount of 100 μm or less and 0.02% by weight was obtained. The activity per solid catalyst was 2700 g-polymer / g-catalyst.

The above results are shown in Table 1.

[0118]

[Example 4] [Modification of methylaluminoxane] 1.66 m of 4-hydroxy-3-methyl-2-butanone was used instead of acetylacetone.
Aluminoxane was reacted with 4-hydroxy-3-methyl-2-butanone in the same manner as in Example 1 except that 1 was used.
The solution of the obtained reaction product of aluminoxane and 4-hydroxy-3-methyl-2-butanone (hereinafter referred to as "modified aluminoxane (d)") was a uniform pale yellow color.

[Preparation of solid catalyst component (A-6)] The solid catalyst component was prepared in the same manner as in Example 1 except that the toluene solution of the modified methylaluminoxane (d) was used in place of the modified methylaluminoxane (a). Was prepared. 170 g of aluminum is contained in 1 g of the obtained solid catalyst component (A-6).
It contained 3.6 mg of g and zirconium.

[Preparation of Preliminary Polymerization Catalyst (B-6)] Prepolymerization was carried out in the same manner as in Example 1 except that the solid catalyst component (A-6) was used in place of the solid catalyst component (A-1). Then, a prepolymerized catalyst (B-6) containing 3.5 mg of zirconium and 3 g of polyethylene per 1 g of the solid catalyst component (A-5) was obtained.

[Polymerization] Instead of the prepolymerization catalyst (B-1), the prepolymerization catalyst (B-6) was used as a solid catalyst in an amount of 123 m
Copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1 except that g was used, MFR was 0.10 g / 10 min, density was 0.924 g / cm ³ , and bulk specific gravity was 0. .
42 g / cm ³ and an average particle size of 600 μm,
295 g of an ethylene / 1-hexene copolymer having a fine polymer amount of 100 μm or less and 0.04% by weight was obtained. The activity per solid catalyst was 2400 g-polymer / g-catalyst.

The above results are shown in Table 1.

[0123]

[Table 1]

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/60-4/70 EUROPAT (QUESTEL) WPI / L (QUESTEL)

Claims (10)

(57) [Claims] 1. An organoaluminum oxy compound (B) and (C) at least one carbonyl group-containing compound selected from a keto alcohol and a β-diketone are brought into mixed contact, and then (A) a cyclopentadienyl skeleton is added. Including ligands
A transition metal compound of Group 4 of the periodic table and a solid support are mixed and brought into contact with each other, and (A) a transition metal compound, (B) an organoaluminumoxy compound, and (C) a carbonyl group-containing compound are added to the solid support. A method for preparing an olefin polymerization catalyst, characterized in that the olefin polymerization catalyst is supported. 2. An organoaluminum oxy compound (B) and (C) at least one carbonyl group-containing compound selected from a keto alcohol and a β-diketone are brought into mixed contact, and then (A) a cyclopentadienyl skeleton is added. Including ligands
The transition metal compound of Group 4 of the periodic table and the solid carrier are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and (B) organoaluminum oxy are mixed on the solid carrier. A method for preparing an olefin polymerization catalyst, which comprises a compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound supported thereon. 3. An organoaluminum oxy compound (B) and (C) at least one carbonyl group-containing compound selected from a keto alcohol and a β-diketone are brought into mixed contact, and then (A) a cyclopentadienyl skeleton is added. Including ligands
A transition metal compound of Group 4 of the periodic table and a solid support are mixed and brought into contact with each other, and (A) a transition metal compound, (B) an organoaluminumoxy compound, and (C) a carbonyl group-containing compound are added to the solid support. A method for preparing an olefin polymerization catalyst, which comprises forming a supported solid catalyst component (i), and further mixing and contacting the solid catalyst component (i) with an organoaluminum compound (E) to form an olefin polymerization catalyst. 4. An organoaluminum oxy compound (B) and (C) at least one carbonyl group-containing compound selected from a keto alcohol and a β-diketone are brought into mixed contact, and then (A) a cyclopentadienyl skeleton is added. Including ligands
The transition metal compound of Group 4 of the periodic table and the solid support are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are added to the solid support. A solid catalyst component (ii) in which a compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound are supported, and the solid catalyst component (ii) and (E) an organoaluminum compound are mixed and contacted A method for preparing an olefin polymerization catalyst, which comprises allowing the olefin polymerization catalyst. 5. (B) Organoaluminum oxy compound and (C) at least one carbonyl group-containing compound selected from keto alcohol and β-diketone are brought into mixed contact, and then (A) cyclopentadienyl skeleton is added. Including ligands
A transition metal compound of Group 4 of the periodic table and a solid support are mixed and brought into contact with each other, and (A) a transition metal compound, (B) an organoaluminumoxy compound, and (C) a carbonyl group-containing compound are added to the solid support. A method for preparing an olefin polymerization catalyst, which comprises forming a supported solid catalyst component (i), and preliminarily polymerizing an olefin on the solid catalyst component (i) to prepare a prepolymerization catalyst. 6. (B) Organoaluminum oxy compound and (C) at least one carbonyl group-containing compound selected from keto alcohol and β-diketone are brought into mixed contact, and then (A) cyclopentadienyl skeleton is added. Including ligands
The transition metal compound of Group 4 of the periodic table and the solid carrier are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are mixed on the solid carrier. A compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound are supported to obtain a solid catalyst component (ii), and the solid catalyst component (ii) is prepolymerized with an olefin to obtain a prepolymerization catalyst. A method for preparing an olefin polymerization catalyst comprising: 7. (B) Organoaluminum oxy compound and (C) at least one carbonyl group-containing compound selected from keto alcohol and β-diketone are brought into mixed contact, and then (A) cyclopentadienyl skeleton is added. Including ligands
A transition metal compound of Group 4 of the periodic table and a solid support are mixed and brought into contact with each other, and (A) a transition metal compound, (B) an organoaluminumoxy compound, and (C) a carbonyl group-containing compound are added to the solid support. The supported solid catalyst component (i) is preliminarily polymerized with olefin on the solid catalyst component (i) to give the prepolymerized catalyst component (i), and the prepolymerized catalyst component (i) and (E) organoaluminum. A method for preparing an olefin polymerization catalyst, which comprises mixing and contacting a compound to obtain an olefin polymerization catalyst. 8. (B) Organoaluminum oxy compound and (C) at least one carbonyl group-containing compound selected from keto alcohol and β-diketone are brought into mixed contact, and then (A) cyclopentadienyl skeleton is added. Including ligands
The transition metal compound of Group 4 of the periodic table and the solid carrier are mixed and contacted, and further (D) the organoaluminum compound is mixed and contacted, and the (A) transition metal compound and the (B) organoaluminum oxy are mixed on the solid carrier. A solid catalyst component (ii) comprising a compound, a (C) carbonyl group-containing compound, and (D) an organoaluminum compound supported on the solid catalyst component (ii). ii), and further, the prepolymerization catalyst component (ii) and (E) the organoaluminum compound are mixed and brought into contact with each other to prepare an olefin polymerization catalyst, which is a method for preparing an olefin polymerization catalyst. 9. An olefin polymerization catalyst obtained by the method for preparing an olefin polymerization catalyst according to any one of claims 1 to 8. 10. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of an olefin polymerization catalyst obtained by the method for preparing an olefin polymerization catalyst according to any one of claims 1 to 8.