JPH0565308A - Catalyst and process for polymerizing olefin - Google Patents

Abstract

PURPOSE:To provide a catalyst which can give on olefin polymer of good particle properties in high polymerization activity and to provide a process for polymerizing an olefin in the presence of this catalyst. CONSTITUTION:The objective solid catalyst for polymerizing an olefin is prepared by impregnating a particulate carrier (A) with a group IV transition metal compound (B) containing sulfonated ligands and cyclopentadienylated ligands and an organoaluminumoxy compound (C). A catalyst for polymerizing an olefin comprising a solid catalyst component prepared by impregnating component (A) with components (B) and (C), and an organoaluminum compound (D). Besides a process for polymerizing an olefin comprising polymerizing or copolymerizing an olefin in the presence of the above catalyst is included.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for polymerizing an olefin using this catalyst, and more specifically, an olefin capable of producing an olefin polymer with high polymerization activity and excellent polymer particle properties. The present invention relates to a polymerization catalyst and an olefin polymerization method using this catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a method for producing an α-olefin polymer, the presence of a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, or a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound. Below, a method of copolymerizing ethylene and α-olefins is known.

In recent years, a new Ziegler type olefin polymerization catalyst composed of a zirconium compound and aluminoxane has been developed as a catalyst capable of producing an ethylene / α-olefin copolymer with high polymerization activity.
JP-A-58-19309, JP-A-60-3500
5, JP-A-60-35006, JP-A-60-
Japanese Patent Laid-Open No. 35007/1985 and Japanese Patent Application Laid-Open No. 60-35008 propose a method for producing an ethylene / α-olefin copolymer using such a new catalyst.

The catalyst formed from a transition metal compound and an aluminoxane proposed in these prior arts is a catalyst formed from a transition metal compound and an organoaluminum compound known before the appearance of this catalyst. In comparison, the polymerization activity, particularly ethylene polymerization activity, is excellent. However, most of these catalysts are soluble in the reaction system, and in most cases, the production process is limited to the solution polymerization system,
When it is attempted to produce a polymer having a high molecular weight, the viscosity of a solution containing the polymer becomes remarkably high, and the productivity is lowered.

On the other hand, at least one component of the transition metal compound and aluminoxane is silica, alumina,
Attempts have also been made to polymerize olefins in a suspension polymerization system or a gas phase polymerization system using a catalyst supported on a porous inorganic oxide carrier such as silica / alumina.

For example, JP-A-60-35006, JP-A-60-35007 and JP-A-60-
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.

JP-A-60-106808 and JP-A-60-106809 disclose in advance a highly active catalyst component containing a titanium compound and / or a zirconium compound soluble in a hydrocarbon solvent and a filler. Composed of a polyethylene polymer and a filler by copolymerizing ethylene or ethylene and an α-olefin in the presence of a product obtained by contact treatment, an organoaluminum compound, and a filler having affinity for polyolefin. A method of making the composition is described.

In Japanese Patent Laid-Open No. 61-31404, a trialkylaluminum is reacted with water in the presence of silicon dioxide or aluminum oxide, and the product obtained is mixed with a transition metal compound in the presence of a mixed catalyst. , Ethylene or a method of polymerizing or copolymerizing ethylene and an α-olefin.

JP-A-61-1108610 and JP-A-61-296008 disclose that an olefin is present 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. A method for polymerizing is described.

However, when the olefins are polymerized or copolymerized by the suspension polymerization system or the gas phase polymerization system using the solid catalyst components supported on the carriers described above, the polymerization activity is higher than that of the solution polymerization system. It was significantly reduced and was not satisfactory.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has high polymerization activity and excellent particle properties of a polymer even when applied to a suspension polymerization method or a gas phase polymerization method. It is an object of the present invention to provide an olefin polymerization catalyst capable of producing an olefin polymer by the method described above, and to provide a polymerization method using this catalyst.

[0012]

SUMMARY OF THE INVENTION A solid catalyst for olefin polymerization according to the present invention comprises a group IVB group comprising [A] a fine particle carrier and [B] a sulfonic acid group-containing ligand and a ligand having a cyclopentadienyl skeleton. It is characterized in that a transition metal compound and a [C] organoaluminum oxy compound are supported.

Further, the olefin polymerization catalyst according to the present invention is a group IVB transition compound comprising [A] a fine particle carrier and [B] a sulfonic acid group-containing ligand and a ligand having a cyclopentadienyl skeleton. A solid catalyst component comprising a metal compound and a [C] organoaluminum oxy compound supported thereon;
[D] An organoaluminum compound.

The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above catalyst.

[0015]

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

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used not only as a homopolymer but also as a copolymer. May be used to mean coalesce.

The catalyst component [A] used in the present invention is an inorganic or organic compound having a particle size of 10 to 300.
It is a solid in the form of granules or fine particles having a size of μm, preferably 20 to 200 μm.

The inorganic compound is preferably a porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc.,
Or mixtures thereof such as SiO ₂ —MgO, SiO ₂ —
Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
Examples thereof include Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The inorganic compound contains a small amount of Na ₂ CO.
₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It does not matter even if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al ₂ (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

Further, in the present invention, as the catalyst component [A],
It is also possible to use a granular or particulate solid of an organic compound having a particle size of 10 to 300 μm. As these organic compounds, ethylene-propylene, 1-butene, 4-methyl-1-pentene and other (co) polymers containing α-olefins having 2 to 14 carbon atoms as a main component or vinylcyclohexane and styrene are mainly used. Examples thereof include polymers or copolymers as components or ring-opening polymers of norbornene.

These particulate carriers may contain a hydroxyl group or water. In that case, the surface hydroxyl group is 1.
It is desirable that it is 0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight, and water is 1.0% by weight or more, preferably 1.2 to 1.2% by weight. It is desirable that the content is 20% by weight, more preferably 1.4 to 15% by weight. The water contained in the fine particle carrier [A] means adsorbed water adsorbed on the surface of the fine particle carrier.

The surface hydroxyl group contained in the particulate carrier can be determined by the following method. That is, 200
The weight of the carrier obtained by drying for 4 hours under a nitrogen atmosphere at a temperature of ° C was defined as X (g), and the carrier was 1000
The weight of the calcined product obtained by calcining at 20 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is defined as Y (g) and calculated by the following formula.

Surface hydroxyl group (% by weight) = {(X−Y) / X} × 100 In order to quantify the water contained in the particulate carrier, the heating weight loss method can be used. In the present invention, the weight loss when dried at 200 ° C. for 4 hours under the flow of a dry gas such as air or nitrogen is defined as the amount of adsorbed water.

By using such a particulate carrier having a specific amount of adsorbed water and a surface hydroxyl group, a solid catalyst for olefin polymerization capable of producing an olefin polymer having high polymerization activity and excellent particle properties can be obtained.

The catalyst component [B] used in the present invention is, for example,
For example, a transition metal compound represented by the following general formula [I]
It R¹ _kR² _lR³ _mM (SO₃R^Four) [I] (In the formula [I], M is a group IVB transition metal, and R is
¹ Is a group having a cyclopentadienyl skeleton,
A group having a cyclopentadienyl skeleton has a substituent
You may stay. R²And R³Is cyclopentadienyl
Group having a skeleton (which may have a substituent), SO₃
R^Four, Halogen atom, R^Four, OR^Four, NR^Four _n, S (O)_q
R^Four, SiR^Four ₃, P (O)_qR^Four ₃Is. Where R^FourIs
Alkyl groups, alkyl groups substituted with halogen atoms,
Substituted with reel group, halogen atom or alkyl group
It is an aryl group. R¹ , R², R³Two of them are al
Xylene group, substituted alkylene group, silylene group, substituted silile
It may be bound via a phenyl group. Also, k is k ≧ 1
Where k + 1 + m = 3 and n is 1, 2 or 3
Yes, q is 0, 1 or 2. ) The above general formula [I]
In, M is a group IVB transition metal,
Is zirconium, titanium or hafnium.

Examples of the group having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group and dimethylcyclopentadienyl group. Examples thereof include alkyl-substituted cyclopentadienyl groups such as trimethylcyclopentadienyl group and pentamethylcyclopentadienyl group, indenyl group, fluorenyl group and the like.

Of these, alkyl-substituted cyclopentadienyl groups and indenyl groups are preferred. Examples of the alkylene group include ethylene group and propylene group, examples of the substituted alkylene group include isopropylidene group and diphenylmethylene group, and examples of the substituted silylene group include dimethylsilylene group.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group and butyl group, and examples of the aryl group include phenyl group and tolyl group.

Halogen is fluorine, chlorine, bromine or iodine. Specific examples of the transition metal compound represented by the above general formula [I] are shown below. Bis (cyclopentadienyl) -zirconium (IV) -bis (methanesulfonato),
Bis (cyclopentadienyl) -zirconium (IV) -bis (p-toluenesulfonato), bis (cyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (cyclopentadienyl) -Zirconium (IV) -trifluoromethanesulfonatomonochloride bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) -zirconium (I
V) -trifluoromethanesulfonatomonochloride, bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride,
Bis (1,3,5-trimethylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (1,3,5-trimethylcyclopentadienyl)
-Zirconium (IV) -trifluoromethanesulfonatomonochloride,

Ethylene bis (indenyl) -zirconium (IV) -bis (trifluoromethane sulfonate), ethylene bis (indenyl) -zirconium (IV) -bis (methane sulfonate), ethylene bis (indenyl)-
Zirconium (IV) -bis (p-toluenesulfonato),
Ethylenebis (indenyl) -zirconium (IV) -bis (p-chlorobenzenesulfonato), ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV)- Trifluoromethanesulfonatomonobromide, ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonofluoride,
Ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonoiodide, ethylenebis (indenyl) -zirconium (IV) -methanesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV) -p-toluenesulfo Nato monochlorid,

Ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methyl,
Ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methyl, ethylenebis (indenyl)
-Zirconium (IV)-(trifluoromethanesulfonato) phenyl, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) phenyl, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methoxy , Ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methoxy, ethylenebis (indenyl) -zirconium (I
V)-(trifluoromethanesulfonato) dimethylamino, ethylenebis (indenyl) -zirconium (IV)-
(Methanesulfonato) dimethylamino, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methylmercapto, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato)
Methyl mercapto, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) thiophenyl, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) thiophenyl,

Ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methylsulfone, ethylenebis (indenyl) -zirconium (I
V)-(methanesulfonato) methyl sulfone, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methylsulfoxide, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methylsulfoxide, Ethylene bis (indenyl)
-Zirconium (IV)-(trifluoromethanesulfonato) trimethylsilyl, ethylene bis (indenyl)-
Zirconium (IV)-(methanesulfonato) trimethylsilyl, ethylene bis (indenyl) -zirconium (I
V)-(trifluoromethanesulfonato) trimethylphosphine, ethylenebis (indenyl) -zirconium (I
V)-(Methanesulfonato) trimethylphosphine, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) triphenylphosphine, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) triphenyl Phosphine,

Ethylenebis (indenyl) -hafnium (IV) -bis (trifluoromethanesulfonato), ethylenebis (indenyl) -hafnium (IV) -bis (methanesulfonato), ethylenebis (indenyl) -hafnium (IV) -Bis (p-toluenesulfonato), ethylenebis (indenyl) -hafnium (IV) -bis (p-chlorobenzenesulfonato), ethylenebis (indenyl)-
Hafnium (IV) -trifluoromethanesulfonatomonochloride, ethylenebis (indenyl) -hafnium (I
V) -trifluoromethanesulfonatomonobromide, ethylenebis (indenyl) -hafnium (IV) -trifluoromethanesulfonatomonofluoride, ethylenebis (indenyl) -hafnium (IV) -trifluoromethanesulfonatomonoiodo, ethylenebis ( Indenyl) -hafnium (IV) -methanesulfonatomonochloride, ethylenebis (indenyl) -hafnium (IV) -p-toluenesulfonatomonochloride,

Ethylene bis (indenyl) -titanium (I
V) -bis (trifluoromethanesulfonato), ethylene bis (indenyl) -titanium (IV) -bis (methanesulfonato), ethylene bis (indenyl) -titanium (IV) -bis (p-toluenesulfonato), ethylene Bis (indenyl) -titanium (IV) -bis (p-chlorobenzenesulfonato), ethylenebis (indenyl) -titanium (IV) -trifluoromethanesulfonatomonochloride, ethylenebis (indenyl) -titanium (IV) -trifluoro Romethanesulfonatomonobromide, ethylenebis (indenyl) -titanium (IV) -trifluoromethanesulfonatomonofluoride, ethylenebis (indenyl) -titanium (IV) -trifluoromethanesulfonatomonoiodine, ethylenebis (indenyl) -titanium (IV) -Methanesulfonatomonochloride, ethylenebis (indenyl) -thi Emissions (IV)-p-toluenesulfonate monochloride,

Dimethylsilylbis (indenyl) -zirconium (IV) -bis (trifluoromethanesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -bis (methanesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -bis (p-toluenesulfonato), dimethylsilylbis (indenyl)
-Zirconium (IV) -bis (p-chlorobenzenesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride, dimethylsilylbis (indenyl) -zirconium (IV) -trifluoromethanesulfone Natomonobromide,
Dimethylsilylbis (indenyl) -zirconium (I
V) -trifluoromethanesulfonatomonofluoride, dimethylsilylbis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonoiodo, dimethylsilylbis (indenyl) -zirconium (IV) -methanesulfonatomonochloride, dimethylsilyl Bis (indenyl) -zirconium (IV) -p-toluenesulfonatomonochloride, diphenylmethylenebis (indenyl) -zirconium (IV) -bis (trifluoromethanesulfonato), diphenylmethylenebis (indenyl) -zirconium (IV)- Bis (methanesulfonato), diphenylmethylenebis (indenyl) -zirconium (IV) -bis (p-toluenesulfonato), diphenylmethylenebis (indenyl) -zirconium (IV) -bis (p-chlorobenzenesulfonato),

Diphenylmethylene bis (indenyl)-
Zirconium (IV) -trifluoromethanesulfonatomonochloride, diphenylmethylenebis (indenyl)-
Zirconium (IV) -trifluoromethanesulfonato monobromide, diphenylmethylene bis (indenyl)-
Zirconium (IV) -trifluoromethanesulfonato monofluoride, diphenylmethylene bis (indenyl)-
Zirconium (IV) -trifluoromethanesulfonatomonoiodide, diphenylmethylenebis (indenyl) -zirconium (IV) -methanesulfonatomonochloride, diphenylmethylenebis (indenyl) -zirconium (I
V) -p-toluenesulfonatomonochloride and the like.

The [B] transition metal compound used in the present invention includes, for example, a compound represented by the following general formula [II], R ¹ _k R ² _l R ³ _m MX ... [II] (in the formula [II] , M is a group IVB transition metal, R
¹ is a group having a cyclopentadienyl skeleton, and this group having a cyclopentadienyl skeleton may have a substituent. R ² and R ³ are a group having a cyclopentadienyl skeleton (which may have a substituent), SO ₃ R
⁴ , halogen atom, R ⁴ , OR ⁴ , NR ⁴ _n , S (O) _q R
⁴ , SiR ⁴ ₃ , and P (O) _q R ⁴ ₃ . R ⁴ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an alkyl group. ^{Two of} R ¹ , R ² and R ³ may be bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. Also, k is k ≧ 1, k + 1 + m = 3, n is 1, 2 or 3, and q is 0, 1 or 2. X is halogen. ) From a sulfonic acid derivative represented by the following general formula [III], R ⁴ SO ₃ Y ... [III] (In the formula [III], R ⁴ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, It is an aryl group substituted with a halogen atom or an alkyl group, and Y is Ag, an alkali metal such as Na or K, or an ammonium group such as triethylammonium or tri (n-octyl) ammonium.) Produced according to the following reaction formula. be able to.

[0038] The reaction conditions in this reaction differ depending on the composition of the compound [I] to be obtained, but the compound [III] is usually 1 to 10 times mol, preferably 1 to 10 times the mol of the compound [II].
Used in a 3-fold molar amount. The reaction temperature is -20 to
180 ° C., preferably 0 to 130 ° C., reaction time is 0.5 to 48 hours, preferably 2 to 12 hours
Time is desirable.

The solvent used in the reaction includes aliphatic hydrocarbons such as hexane and decane, benzene, toluene,
Aromatic hydrocarbons such as xylene, carbon tetrachloride, chloroform, halogenated hydrocarbons such as methylene chloride, acetone,
Ketones such as methyl isobutyl ketone and acetonitrile are used. Of these, toluene and xylene are particularly preferable. Such a hydrocarbon solvent is a compound [I
I], usually 1 to 1000 times, preferably 50 times
Used in an amount up to 500 times.

The catalyst component [C] used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound. 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, and ceric chloride hydrate A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same. (2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution. (3) Addition of an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene,
A method of reacting an organic tin oxide such as dimethyltin oxide or dibutyltin oxide.

The aluminoxane may contain a small amount of organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec. -Butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum,
Trialkylaluminums such as tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide,
Dialkyl aluminum halides such as diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. Be done.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula [IV] can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [IV] (In the formula [IV], x, y, and z are positive numbers, and z ≧
2x. ) The above organoaluminum compounds are used alone or in combination.

Solvents used for the aluminoxane solution include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Of hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Hydrocarbon solvents such as halides, especially chlorides and bromides, 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 used in the present invention can be obtained by, for example, bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound.

As the active hydrogen-containing compound, alcohols such as methanol, ethanol, n-propanol and isopropanol, diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid are used. Of these, alcohols and diols are preferable, and alcohols are particularly preferable.

Water or an active hydrogen-containing compound which is brought into contact with the solution of aluminoxane is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene or hexane, an ether solvent such as tetrahydrofuran or an amine solvent such as triethylamine, or It can be used in the vapor or solid state. In addition, as water, it is adsorbed to water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and ceric chloride, or to inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide. Adsorbed water or the like can also be used.

The catalytic reaction between the solution of aluminoxane and water or the compound containing active hydrogen is usually carried out in a solvent, for example, a hydrocarbon solvent. As the solvent used at this time, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane; cyclopentane, cyclohexane , Cyclooctane, alicyclic hydrocarbons such as methylcyclohexane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, etc. It is also possible to use halogenated hydrocarbons such as chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran.

Of these media, aromatic hydrocarbons are particularly preferred. The water or active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, based on the Al atoms in the aluminoxane solution. The concentration in the reaction system is preferably in the range of 1 × 10 ^{−3 to} 5 gram atom / liter, preferably 1 × 10 ^{−2 to} 3 gram atom / liter, in terms of aluminum atom. The concentration of water in the system is usually 2 × 10 ^{−4 to} 5 mol / liter, preferably 2
It is desirable that the concentration is × 10 ^{-3 to} 3 mol / liter.

Specific examples of the method for bringing the aluminoxane solution into contact with water or an active hydrogen-containing compound include the following methods. (1) A method of bringing a solution of aluminoxane into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound. (2) A method of bringing the aluminoxane into contact with the vapor by, for example, blowing steam of water or an active hydrogen-containing compound into a solution of the aluminoxane. (3) A method of directly contacting a solution of aluminoxane with water or ice or a compound containing active hydrogen. (4) An aluminoxane is mixed with a solution of an aluminoxane and a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization or a hydrocarbon suspension of a compound to which a compound containing active hydrogen is adsorbed. Method of contacting with adsorption water or crystal water.

The aluminoxane solution as described above may contain other components as long as it does not adversely affect the reaction between the aluminoxane and water or the compound containing active hydrogen.

The catalytic reaction between a solution of aluminoxane and water or an active hydrogen-containing compound is usually -50 to 150.
C, preferably 0 to 120 C, more preferably 20 to 1
It is carried out at a temperature of 00 ° C. The reaction time is usually 0.5 to 300 hours, preferably 1 to 150 hours, though it varies greatly depending on the reaction temperature.

Such a benzene-insoluble organoaluminum oxy compound is an Al that dissolves in benzene at 60 ° C.
The component is usually 10% or less, preferably 5% in terms of Al atom.
The content is particularly preferably 2% or less, and is insoluble or hardly soluble in benzene.

The solubility of the organoaluminum oxy compound in benzene was determined by suspending the organoaluminum oxy compound corresponding to 100 mg of Al in 100 ml of benzene, mixing the mixture with stirring at 60 ° C. for 6 hours, and then applying a jacket. Using a G-5 glass filter, 6
The amount of Al atoms present in the whole filtrate (x mmol) after filtration was carried out while hot at 0 ° C. and the solid portion separated on the filter was washed 4 times with 50 ml of benzene at 60 ° C.
Is obtained (x%).

Examples of the catalyst component [D] optionally used in the present invention include organic aluminum compounds represented by the following formula [V]. R ⁷ _n AlX _3-n ... [V] (In the formula [V], R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3).
Is. ) In the above formula [V], R ⁷ has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, Examples thereof include an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
Trialkyl aluminum such as trioctyl aluminum and tri-2-ethylhexyl aluminum; alkenyl aluminum such as isoprenyl aluminum; dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide; methyl Aluminum sesquichloride, ethylaluminium sesquichloride,
Alkyl aluminum sesquihalides such as isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; diethyl aluminum hydride, diisobutyl aluminum Alkyl aluminum hydride such as hydride.

As the catalyst component [D], the following formula [VI]
It is also possible to use an organoaluminum compound represented by R ⁷ _n AlY _3-n ... [VI] (In the formula [VI], R ⁷ is the same as above, and Y is −
OR ⁸ group, -OSiR ⁹ ₃ group, -OAlR ¹⁰ ₂ group, -NR
¹¹ ₂ group, —SiR ¹² ₃ group or —N (R ¹³ ) AlR ^{1 4} ₂ group, n is 1 to 2, R ⁸ , R ⁹ , R ¹⁰ and R
¹⁴ is a methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., R ¹¹ is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ¹² and R ¹³ is a methyl group, an ethyl group or the like. ) Specific examples of such an organoaluminum compound include the following compounds. (I) a compound represented by R ⁷ _n Al (OR ⁸ ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc., (ii) R ⁷ _n Al (OSiR ⁹ ₃ ) _{3 -n} , for example, Et ₂ Al (OSiMe ₃ ) (iso-Bu) ₂ Al (OSiMe ₃ ) (iso-Bu) ₂ Al (OSiEt ₃ ), etc., (iii) R ⁷ _n Al (OAlR ^10). ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc., (iv) R ⁷ _n Al (NR ¹¹ ₂ ) _3-n Compounds such as Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHEt Et ₂ AlN (SiMe ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ etc., (v) R ⁷ _n Al (SiR ¹² ₃ ) _3-n A compound represented by, for example, (iso-Bu) ₂ AlSiMe _{3 and the} like,

[0059]

[Chemical 1]

Among the organoaluminum compounds represented by the above general formulas [V] and [VI], R ⁷ ₃ Al and R ⁷ _n Al (OR
⁸ ) _3-n and R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n can be mentioned as preferable examples of the organoaluminum compound.
⁷ is an isoalkyl group, and n = 2 is particularly preferable. These organoaluminum compounds may be used as a mixture of two or more kinds.

In the present invention, the above catalyst components [A] to [D] are used.
Besides, water can be used as the catalyst component [E]. Examples of the water used in the present invention include water dissolved in a polymerization solvent as described below, or adsorbed water containing a compound or salt used in producing the catalyst component [C], crystal water, and the like. You can

The olefin polymerization catalyst according to the present invention comprises the above catalyst components [A] to [C] and, if desired, the catalyst components [D] and / or [E] in an inert hydrocarbon solvent or in an olefin medium. It can be prepared by mixing and contacting with each other. The catalyst component [D] is preferably added at the time of polymerization together with the solid catalyst component in which the catalyst components [B], [C] and optionally [D] are supported by the catalyst component [A].

The mixing order at this time is arbitrarily selected, but preferably [A] the particulate carrier and [C] the organoaluminum oxy compound are mixed and contacted, and then [B] the transition metal compound is mixed and contacted, and If desired, [E] water may be mixed and contacted, or a mixture of the [C] organoaluminum oxy compound and [B] transition metal compound may be mixed and contacted with the [A] fine particle carrier, and, if desired, [E] water. Are mixed or contacted, or [A] the fine particle carrier, [C] the organoaluminum oxy compound and [E] water are mixed and contacted, and then the [B] transition metal compound is mixed and contacted.

FIG. 1 shows a catalyst for olefin polymerization according to the present invention.
The process for preparing the medium will be described. Catalyst components [A] to [C] and desired
Mix catalyst component [D] and / or [E] with
In addition, the catalyst component [B] is equivalent to 1 g of the catalyst component [A].
Ordinary 10 ^-Five~ 5 x 10^-3Mol, preferably 5 × 10
^-Five-10^-3Concentration of catalyst component [B] used in molar amounts
Is about 10^-Four~ 2 x 10^-2Mol / l, preferably
2 x 10^-Four-10^-2It is in the range of mol / liter. catalyst
Transition of component [C] aluminum and catalyst component [B]
The atomic ratio with the metal (Al / transition metal) is usually 10 to 30.
00, preferably 20 to 2000.

The molar ratio (Al _C / H ₂ O) between the aluminum atom (Al _C ) of the catalyst component [C] and water (H ₂ O) of the catalyst component [E] that is optionally used is 0. 5-5
The range is 0, preferably 1 to 40.

The mixing temperature for mixing the catalyst components [A] to [C] and the catalyst component [E] is usually -50 to 15.
The temperature is 0 ° C., preferably −20 to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.
Further, the mixing temperature may be changed during the mixing contact.

The [D] organoaluminum compound optionally used is 0 to 5 per gram atom of the transition metal atom.
It is desirable to use it in an amount of 00 mol, preferably 5 to 200 mol.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components. Specific examples of the inert hydrocarbon medium used in the preparation of the olefin polymerization catalyst according to the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane. Alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the catalyst preparation method can be used, and the olefin itself can also be used as the solvent.

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the catalyst component [B]
Is usually 10 ⁻⁸ to 10 ⁻¹ gram atom / liter, preferably 10 as the concentration of the transition metal atom in the polymerization reaction system.
It is preferably used in an amount of ^{-7 to} 5 x 10 ^-2 gram atom / liter. At this time, alumino-okiosan may be used if desired.

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

The olefins which can be polymerized by such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene and 4 -Methyl-1
-Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5- Methyl-2-norbornene, tetracyclododecene, 2-methyl
1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0073]

The olefin polymerization catalyst according to the present invention is
Even when applied to a suspension polymerization method or a gas phase polymerization method, an olefin polymer can be produced with high polymerization activity and excellent particle properties of the polymer, and when two or more kinds of monomers are copolymerized, A copolymer having a narrow composition distribution can be obtained.

[0074]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

The molecular weight distribution (Mw / Mn) was measured in accordance with "Gel Permeation Chromatography", published by Takeuchi, Maruzen Co., Ltd. [Production of transition metal compound]

[0076]

[Production Example 1] [Bis (cyclopentadienyl) -zirconium (IV)-
Bis (trifluoromethanesulfonato) (catalyst component [B
-1])]] To a glass reactor having an internal volume of 300 ml which had been sufficiently replaced with nitrogen, 250 ml of dry toluene and 0.73 g (2.5 mmol) of zirconocene dichloride were charged.
Stir at room temperature until uniform. 100 ml of a toluene solution of 1.28 g (5.0 mmol) of silver trifluoromethanesulfonate was added dropwise to this reaction solution at room temperature over 30 minutes. After continuing the reaction at room temperature for 3 hours, the reaction was continued at 60 ° C. for 4 hours.

The produced salt was filtered through a glass filter under a nitrogen stream, and the obtained filtrate was concentrated under reduced pressure. The obtained solid is purified by sublimation (1 × 10 ⁻⁴ mmHg / 100 to 120
C.) to give 0.45 g of a white solid.

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0079]

[Production Example 2] [Production of bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (catalyst component [B-2])] Bis (methylcyclopentadiene instead of zirconocene dichloride) Dienyl) -zirconium (I
The procedure of Production Example 1 was repeated except that 1.60 g (5 mmol) of V) -dichloride and 2.59 g (10 mmol) of silver trifluoromethanesulfonate were used to obtain 0.55 g of yellow crystals.

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0081]

[Production Example 3] [Production of bis (methylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride (catalyst component [B-3])] Instead of zirconocene dichloride, bis (methylcyclopentadiene) 1.53 g (4.8 mmol) of (enyl) -zirconium (IV) -dichloride was used and 1.29 g (5.0) of silver trifluoromethanesulfonate was used.
The same operation as in Production Example 1 was carried out except that the amount of yellow crystals was 1.44 g.

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0083]

[Production Example 4] [Production of bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride (catalyst component [B-4])] Instead of zirconocene dichloride, bis ( 1,3-dimethylcyclopentadienyl)-
Zirconium (IV) -dichloride (1.60 g, 4.6 mmol) was used and silver trifluoromethanesulfonate (1.2) was used.
The same operation as in Preparation Example 1 was carried out except that 4 g (4.8 mmol) was used to obtain 0.25 g of yellow crystals.

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0085]

Production Example 5 [Ethylenebis (indenyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (catalyst component [B-
5]) Production] 600 ml of dry toluene and 1.88 g (4.5 mmol) of ethylenebis (indenyl) -zirconium (IV) -dichloride were charged into a glass reactor having an internal volume of 1 liter which had been sufficiently replaced with nitrogen. And stirred at room temperature until uniform. To this reaction solution was added a toluene solution 1 containing 2.34 g (9 mmol) of silver trifluoromethanesulfonate.
00 ml was added dropwise at room temperature over 30 minutes. After further stirring at room temperature for 3 hours, the reaction was continued at 60 ° C. for 4 hours. The produced salt was filtered through a glass filter under a nitrogen stream, and the obtained filtrate was concentrated under reduced pressure. The obtained solid was recrystallized from 60 ml of toluene to give 1.5 orange crystals.
4 g was obtained.

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0087]

[Table 1]

[Polymerization of ethylene]

[0089]

Example 1 <Preparation of water-adsorbed silica> Inner diameter 45 mm loaded in electric furnace
150g silica (F-9 made by Fuji Devison Co., Ltd.
48), and under nitrogen flow at 200 ° C for 4 hours, then 70
It was dried at 0 ° C. for 7 hours.

Next, 30 g of the dried silica obtained above was placed in a 500 ml eggplant flask, and 1.8 ml of it was placed under a nitrogen atmosphere.
Water was added and the mixture was rotated for 1 hour and stirred. In this way, water adsorbed silica was obtained.

20 g of the water-adsorbed silica was taken and dried at 200 ° C. for 4 hours in a nitrogen atmosphere to give 1.14.
A weight loss of g was observed. Therefore, the amount of water in the water-adsorbed silica is 5.70% by weight.

<Support of aluminoxane> 85 ml of toluene was added to a 400 ml glass flask purged with nitrogen.
65.2 ml of an organoaluminum oxy compound (methylaluminoxane manufactured by Schering Co., Ltd., dried and redissolved in toluene; Al concentration: 1.15 mol / liter) was added, and the system was heated to 0 ° C. with stirring. To this, 9.0 g of the water-adsorbed silica obtained above was added over 30 minutes in a nitrogen atmosphere. Then, the mixture was reacted at 20 to 25 ° C for 1 hour and at 80 ° C for 3 hours. Thus, aluminoxane-supported silica was obtained.

<Support of zirconium compound> The aluminoxane-supported silica obtained above was stirred in a nitrogen-substituted 50 ml glass flask to obtain 10 mmol of aluminum atom, and bis (methyl) obtained in Preparation Example 2 was used. Cyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (catalyst component [B-2]) was added at 0.04 mmol in terms of zirconium atom, and the mixture was added at 30 ° C.
After stirring for 2 hours, a supported catalyst was obtained.

<Polymerization> 1 liter of purified n-decane was placed in a glass flask having an internal volume of 1 liter which had been sufficiently replaced with nitrogen, and hydrogen was passed at 1 liter / hr and ethylene was passed at 250 liter / hr, and the temperature was raised to 75 ° C. at 10 ° C. Hold for a minute.

Then, triisobutylaluminum was charged at 0.5 mg atom in terms of aluminum atom, and the supported catalyst prepared above was charged at 0.02 mg atom in terms of zirconium atom. After polymerization was carried out at 75 ° C. for 2 hours, the polymerization was stopped by adding a small amount of isobutanol.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0097]

Example 2 Instead of the catalyst component [B-2], the catalyst component [B-
Ethylene was polymerized in the same manner as in Example 1 except that [3] was used.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0099]

[Reference Example 1] Ethylene was polymerized in the same manner as in Example 1 except that bis (cyclopentadienyl) -zirconium (IV) -dichloride was used in place of the catalyst component [B-2] and triisobutylaluminum was not used. did.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0101]

Example 3 Instead of the catalyst component [B-2], the catalyst component [B-
4] was used, and ethylene was polymerized in the same manner as in Example 1.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0103]

Example 4 Instead of the catalyst component [B-2], the catalyst component [B-
4] was used and ethylene was polymerized in the same manner as in Example 1 except that triisobutylaluminum was not used.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0105]

[Reference Example 2] The same as Example 1 except that bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -dichloride was used in place of the catalyst component [B-2], and triisobutylaluminum was not used. Then, ethylene was polymerized.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0107]

Example 5 Instead of the catalyst component [B-2], the catalyst component [B-
Ethylene was polymerized in the same manner as in Example 1 except that [5] was used.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0109]

Reference Example 3 Ethylene was polymerized in the same manner as in Example 1 except that ethylene bis (indenyl) -zirconium (IV) -dichloride was used in place of the catalyst component [B-2] and triisobutylaluminum was not used.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0111]

[Table 2]

[Polymerization of Propylene]

[0113]

Example 6 125 ml of toluene and a toluene solution of an organoaluminum oxy compound (a methylaluminoxane manufactured by Schering Co. was dried to dryness and then re-dissolved in toluene) in a 400 ml glass flask thoroughly replaced with nitrogen.
74.6 ml of Al concentration; 1.34 mol / liter) was added and the mixture was cooled to 0 ° C. Silica (F-948 manufactured by Fuji Devison Co., Ltd.) was added to this solution at 130 ° C. for 5
What was dried at mmHg for 5 hours (hydroxyl group content; 2.7% by weight) was added over 30 minutes. At this time, the temperature in the system is set to 0
It was kept at ℃. Then, at room temperature for 1 hour and at 80 ° C for 3 hours.
A time reaction was performed. 30 ml of the resulting suspension (Al; 1
5 mmol) was transferred to another glass flask and a toluene solution of the catalyst component [B-5] (Zr; 0.00231 mol /
Liter) 26.0 ml (0.06 mmol) and added 5
After stirring for a minute, the toluene solution was removed by decantation and replaced with n-hexane. In this way, a solid catalyst was obtained. It was confirmed by elemental analysis that all the zikonium was supported on silica.

150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was placed in a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Then, return to normal pressure by introducing propylene gas,
The inside of the system was set to 50 ° C. Next, 0.01 mg of zirconium atom-converted solid catalyst prepared above and 0.5 mmol of triisobutylaluminum were added to the autoclave. Then, propylene gas was introduced and the total pressure was adjusted to 7 kg / cm ² -G to start the polymerization. In addition, replenish only propylene gas to bring the total pressure to 7
Polymerization was carried out at 50 ° C. for 1 hour while keeping it at kg / cm ² -G.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It was dried under reduced pressure at 0 ° C overnight. As a result, 18.4 g of propylene polymer having an intrinsic viscosity [η] of 0.31 dl / g and a bulk specific gravity of 0.245 g / cm ³ (polymerization activity; 1840 gPP
/ Mmol-Zr · hr) was obtained.

[0116]

Example 7 Polymerization of propylene was carried out in the same manner as in Example 6 except that triisobutylaluminum was not used.

As a result, the intrinsic viscosity [η] was 0.25 dl /
g, propylene polymer having a bulk specific gravity of 0.226 g / cm ³ 17.8 g (polymerization activity; 1780 g PP / mmol-
Zr · hr) was obtained.

[0118]

[Reference Example 4] Polymerization of propylene was carried out in the same manner as in Example 6 except that ethylenebis (indenyl) -zirconium (IV) -dichloride was used in place of the catalyst component [B-5], and triisobutylaluminum was not used. It was

As a result, the intrinsic viscosity [η] was 0.32 dl /
g, a propylene polymer having a bulk specific gravity of 0.185 g / cm ³ of 12.8 g (polymerization activity; 1280 g PP / mmol-
Zr · hr) was obtained.

The above results are summarized in Table 3.

[0121]

[Table 3]

[Polymerization of ethylene / butene]

[0123]

Example 8 125 ml of toluene and a toluene solution of an organoaluminum oxy compound (methylaluminoxane manufactured by Schering Co. were dried to dryness and re-dissolved in toluene) in a 400 ml glass flask thoroughly purged with nitrogen.
(Concentration: 1.34 mol / l) 74.6 ml was added to 0
Cooled to ° C. Silica (F-948 manufactured by Fuji Devison Co., Ltd.) was added to this solution at 130 ° C. for 5 mmH using an evaporator.
dried at 5g for 5 hours (hydroxyl group content; 2.7% by weight)
Was added over 30 minutes. At this time, the temperature in the system was kept at 0 ° C. Then, the reaction was carried out at room temperature for 1 hour and further at 80 ° C. for 3 hours.

30 ml (Al; 15 mmol) of the obtained suspension was transferred to another glass flask and the catalyst component [B-2] was added.
Toluene solution of Zr (Zr; 0.0635 mol / l)
4.7 ml (0.30 mmol) was added and after stirring for 5 minutes,
The toluene solution was removed by decantation and replaced with n-hexane. In this way, a solid catalyst was obtained. It was confirmed by elemental analysis that all Zr was supported on silica.

150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Then, the pressure was returned to normal pressure by introducing a mixed gas of ethylene and 1-butene (1-butene content; 5.9 mol%), and the temperature inside the system was raised to 75 ° C. Then, 0.01 mg of zirconium atom-converted solid catalyst prepared above and 0.5 mmol of triisobutylaluminum were added to the autoclave. After that, 50 Nml of hydrogen was introduced, and further the mixed gas of ethylene and 1-butene was introduced, and the total pressure was 8 kg / cm ² -G to start the polymerization.
The temperature in the system immediately rose to 80 ° C. Furthermore, replenishing only the mixed gas, keeping the total pressure at 8 kg / cm ² -G,
Polymerization was carried out for a time.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It was dried under reduced pressure at 0 ° C overnight. As a result, 2.16 at 190 ℃
The MFR measured under a load of kg is 2.70 g / 10 minutes, the bulk specific gravity is 0.307 g / cm ³ , and the density is 0.3.
Ethylene-butene copolymer 4 having a weight of 924 g / cm ^3.
9.6 g (polymerization activity; 4960 g polymer / mmol-Z)
r.hr) was obtained.

[0127]

Example 9 Without using triisobutylaluminum,
Ethylene-butene copolymerization was carried out in the same manner as in Example 8 except that 20 Nml of hydrogen was introduced.

As a result, the MFR measured at 190 ° C. under a load of 2.16 kg was 2.57 g / 10 minutes, the bulk specific gravity was 0.200 g / cm ³ , and the density was 0.933 g / cm ^3.
15.9 g of ethylene-butene copolymer having a cm ³ (polymerization activity; 1590 g polymer / mmol-Zr · hr) was obtained.

[0129]

[Reference Example 5] Ethylene-in the same manner as in Example 8 except that bis (methylcyclopentadienyl) -zirconium (IV) -dichloride was used in place of the catalyst component [B-2], and triisobutylaluminum was not used. Butene copolymerization was performed.

As a result, the MFR measured at 190 ° C. under a load of 2.16 kg was 51.2 g / 10 minutes, the bulk specific gravity was 0.096 g / cm ³ , and the density was 0.942 g / cm ^3.
cm ³ of ethylene-butene copolymer (polymerization activity; 1050 g polymer / mmol-Zr · hr) was obtained.

The above results are summarized in Table 4.

[0132]

[Table 4]

[Brief description of drawings]

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

Claims (4)

[Claims] 1. A transition metal compound of Group IVB containing [B] a sulfonic acid group-containing ligand and a ligand having a cyclopentadienyl skeleton in [A] a fine particle carrier, and [C] an organoaluminum oxy. A solid catalyst for olefin polymerization, comprising a compound supported on the solid catalyst. 2. A transition metal compound of Group IVB containing [B] a sulfonic acid group-containing ligand and a ligand having a cyclopentadienyl skeleton in a [A] fine particle carrier, and [C] an organoaluminum oxy. An olefin polymerization catalyst comprising a solid catalyst component carrying a compound and [D] an organoaluminum compound. 3. An olefin polymerization method characterized by polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 1. 4. An olefin polymerization method characterized by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 2.