JPH05170819A - Catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain an olefin polymer having a narrow molecular weight distribution and narrow compositional distribution in high polymerization activity. CONSTITUTION:The title catalyst comprises a transition metal compound catalyst component prepared by bringing a transition metal compound of the general formula: (R<1>COCR<2>COR<3>)mMX4-m (wherein M is Zr or Hf; X is halogen or-SO3 CF3) into contact with an organometallic compound of the general formula: Cp<1>Y<1> or Y<2>Cp<2>-R<5>-Cp<3>Y<3> (wherein Cp<1>, Cp<2> and Cp<3> are each a group containing a cyclopentadienyl skeleton; and Y<1>, Y<2> and Y<3> are each Li, Na or K) and an organoalminumoxy compound. The title process comprises polymerizing an olefin in the presence of the above catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing an olefin using the catalyst, and more specifically, a transition obtained by bringing a specific transition metal compound into contact with an organometallic compound. The present invention relates to a catalyst comprising a metal compound catalyst component and an organoaluminum oxy compound component, and an olefin polymerization method using this catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a method for producing an α-olefin polymer has been carried out in the presence of a titanium catalyst comprising a titanium compound and an organoaluminum compound or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound. , A method of copolymerizing ethylene and α-olefin is known.

Generally, an ethylene / α-olefin copolymer obtained with a titanium catalyst has a broad molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the ethylene / α-olefin copolymer obtained with the vanadium-based catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium-based catalyst,
And, the transparency, the surface non-tackiness and the mechanical properties are considerably improved, but they are still insufficient for the applications in which these performances are required. -A catalyst that can obtain an α-olefin copolymer is required.

On the other hand, as a new Ziegler type olefin polymerization catalyst, a catalyst comprising a zirconium compound and aluminoxane has been proposed in recent years. For example, JP-A-5
8-19309, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35.
JP-A No. 008, JP-A-61-130314, and JP-A No. 2-41303 disclose transition metal compounds having a pentadienyl group such as a cyclopentadienyl group as a ligand, an alkyl group and / or a halogen atom. It is described that the catalyst system in which the metallocene compound and the aluminoxane are combined is highly active in the polymerization of α-olefin and the obtained polymer has excellent properties.

Also, the Journal of Organometallic Chemis
try, 363 (1989) C12-C14 contains Cp ₂ Zr (CF ₃ SO ₃ ) ₂
(THF) and [Cp ₂ Zr (CF ₃ SO ₃ ) (bipy)] ⁺ CF ₃ SO
₃ ^- are disclosed, the two compounds olefin polymerization activity is low compared to the cyclopentadienyl compound as described above. Further, when the concentration of aluminoxane is low, the olefin polymerization activity is remarkably low.

Under these circumstances, the advent of a new catalyst for olefin polymerization, which is more excellent in olefin polymerization activity and excellent in the properties of the obtained polyolefin, is desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel catalyst for olefin polymerization, and a method for polymerizing olefins using such a catalyst. Is intended to provide.

[0008]

The olefin polymerization catalyst according to the present invention comprises: (A) a transition metal compound represented by the following general formula [I]:¹COCR²COR³)_mMX_4-m [I] (In the formula, M is zirconium or hafnium. R
¹, R²And R³Is a hydrogen atom or a carbon number of 1 to 1.
Alkyl group of 0, the number of carbon atoms substituted with a halogen atom is 1
Alkyl group, aryl group, halogen atom or
Aryl substituted with an alkyl or alkoxy group
Group or a furyl group, R¹And R ²Are each other
It may combine with each other to form a ring. X is a halogen atom
Or-SO₃CF₃Is. m is 1 ≦ m ≦ 4. )
An organometallic compound represented by the following general formula [II] or the following
An organometallic compound represented by the general formula [III], Cp¹Y¹ ... [II] (where Cp¹Is a group having a cyclopentadienyl skeleton
Yes, it may have a substituent. Y¹Is lithium,
Thorium or potassium. ) Y²Cp²-R^Five-Cp³Y³ … [III] (Y in the formula²And Y³Is lithium, sodium or
It is lithium and may be the same or different. C
p²And Cp³Is a group having a cyclopentadienyl skeleton
Yes, they may have a substituent, and they may be the same or different.
It may be. R^FiveIs an alkylene group, substituted alkylate
Group, silylene group, substituted silylene group or -P (C
H₃)-. ) Is prepared by contacting
It is characterized in that it is formed from a transition metal compound catalyst component and (B) an organoaluminum oxy compound component.

In the present invention, as the transition metal compound, the following general formula [IV] (R ⁷ COCR ⁸ COR ⁹ ) _q ZrCl _4-q ... [IV] (wherein R ⁷ , R ⁸ and R ⁹ are carbon numbers) Is an alkyl group having 1 to 6, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an aryl group, and R ⁷ and R ⁸ may be bonded to each other to form a ring, and q is 1 ≦ q ≦ 4) is preferable, and particularly tetrakis (2,4-pentanedionato) -zirconium or dichlorobis (2,4-pentanedionato) -zirconium is used. preferable.

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

[0011]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention 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" means not only homopolymer but also copolymerization. May be used to mean coalesce.

[Transition Metal Compound Catalyst Component] The transition metal compound catalyst component (A) used in the present invention can be prepared by bringing a transition metal compound as described below into contact with an organometallic compound.

The transition metal compound (A) used for the preparation of the catalyst component is sometimes referred to as a transition metal compound represented by the following general formula [I] (hereinafter referred to as "compound [I]"). ).

(R ¹ COCR ² COR ³ ) _m MX _4-m ... [I] In the general formula [I], M is zirconium or hafnium. R ¹ , R ² and R ³ are each a hydrogen atom or a methyl group, an ethyl group, a propyl group, an isopropyl group, t-
A butyl group or other alkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group or other halogen atom-substituted carbon atom is 1
-10 alkyl group, aryl group such as phenyl group, aryl group substituted with alkyl group such as tolyl group, aryl group substituted with alkoxy group such as p-methoxyphenyl group, aryl group substituted with halogen atom or It is a frill group.

R ¹ and R ² may combine with each other to form a ring. X is fluorine, chlorine, bromine, a halogen atom or -SO ₃ CF ₃ iodine.

M is 1≤m≤4, preferably 2≤m≤4
Is. Specific examples of the transition metal compound represented by the general formula [I] include the following compounds.

Dichlorobis (2,4-pentanedionato)-
Zirconium (IV), dichlorobis (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionato)-
Zirconium (IV), dichlorobis (1,1,1-trifluoro-2,4-pentanedionato) -zirconium (IV), dichlorobis (1,1,1,5,5,5-hexafluoro-2,4 -Pentanedionate) -Zirconium (IV), dichlorobis (4,4,4
-Trifluoro-1-phenyl-1,3-butanedionate) -zirconium (IV), dichlorobis (2,2,6,6-tetramethyl
-3,5-heptanedionato) -zirconium (IV), dichlorobis (4,4,4-trifluoro-1- (2-furyl) -1,3-butanedionato) -zirconium (IV), dichlorobis (3-)
Phenyl-2,4-pentanedionato) -zirconium (I
V), dichlorobis (1,1,1-trifluoro-5,5-dimethyl
-2,4-Hexandionato) -zirconium (IV), dichlorobis (2-acetylcyclohexanonato) -zirconium (IV), dichlorobis (2-acetylcyclopentanonato) -zirconium (IV), dichlorobis (3-methyl) -2,
4-pentanedionato) -zirconium (IV), dichlorobis (1,3-di (p-methoxyphenyl) -1,3-propanedionate) -zirconium (IV), dichlorobis (1,3-diphenyl-1, 3-Propanedionato) -Zirconium (I
V), chlorotris (2,4-pentanedionato) -zirconium (IV), chlorotris (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedio Nato) -zirconium (IV), chlorotris (1,1,1-trifluoro-2,4-
Pentandionato) -zirconium (IV), chlorotris (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) -zirconium (IV), chlorotris (4,4,4-tri) Fluoro-1-phenyl-1,3-butanedionate) -zirconium (IV), chlorotris (2,2,6,6-tetramethyl-3,5
-Heptanedionate) -zirconium (IV), chlorotris (4,4,4-trifluoro-1- (2-furyl) -1,3-butanedionate) -zirconium (IV), chlorotris (3-phenyl-2,4- Pentandionato) -zirconium (IV), chlorotris (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) -zirconium (IV), chlorotris (2-acetylcyclohexanonato) -Zirconium (I
V), chlorotris (2-acetylcyclopentanonato)-
Zirconium (IV), chlorotris (3-methyl-2,4-pentanedionato) -zirconium (IV), chlorotris (1,3-di (p-methoxyphenyl) -1,3-propanedionato) -zirconium ( IV), chlorotris (1,3-diphenyl-1,3-propanedionato) -zirconium (IV), tetrakis (2,4-pentanedionato) -zirconium (I
V), tetrakis (1,1,1,2,2,3,3-heptafluoro-7,7-
Dimethyl-4,6-octanedionate) -zirconium (I
V), tetrakis (1,1,1-trifluoro-2,4-pentanedionato) -zirconium (IV), tetrakis (1,1,1,5,
5,5-hexafluoro-2,4-pentanedionato) -zirconium (IV), tetrakis (4,4,4-trifluoro-1-phenyl-1,3-butanedionate) -zirconium (IV), tetrakis ( 2,2,6,6-Tetramethyl-3,5-heptanedionato) -zirconium (IV), tetrakis (4,4,4-trifluoro-1- (2-furyl) -1,3-butanedionate) -zirconium (IV), tetrakis (3-phenyl-2,4-pentanedionato) -zirconium (IV), tetrakis (1,1,1-
Trifluoro-5,5-dimethyl-2,4-hexanedionate)-
Zirconium (IV), Tetrakis (2-acetylcyclohexanonato) -zirconium (IV), Tetrakis (2-acetylcyclopentanonato) -zirconium (IV), Tetrakis (3-methyl-2,4-pentanedionato)- Zirconium (IV), Tetrakis (1,3-di (p-methoxyphenyl) -1,3-propanedionato) -Zirconium (IV), Tetrakis (1,3-diphenyl-1,3-propanedionato)- Zirconium (IV) etc.

In the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with hafnium metal can also be used. In the present invention, it is preferable to use a compound represented by the following general formula [IV] as the transition metal compound.

(R ⁷ COCR ⁸ COR ⁹ ) _q ZrCl _4-q ... [IV] In the formula [IV], R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom or a methyl group, an ethyl group, a propyl group or an isopropyl group. , Alkyl groups having 1 to 6 carbon atoms such as t-butyl group, alkyl groups having 1 to 6 carbon atoms substituted with halogen atoms such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, phenyl It is an aryl group such as a group, and R ⁷ and R ⁸ may combine with each other to form a ring.

Q is 1 ≦ q ≦ 4, preferably 2 or 4
Is. In addition, tetrakis (2,4-
Particular preference is given to using pentanedionato) -zirconium or dichlorobis (2,4-pentanedionato) -zirconium.

The organometallic compound used for preparing the transition metal compound catalyst component (A) according to the present invention is represented by the following general formula [II] (hereinafter referred to as "compound [II]"). There are things to do).

Cp ¹ Y ¹ ... [II] In the general formula [II], Cp ¹ is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group or an n-butylcyclopentadienyl group. ,
Examples thereof include alkyl-substituted cyclopentadienyl groups such as dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group and fluorenyl group.

Y ¹ is lithium, sodium or potassium. Specific examples of the organometallic compound represented by the general formula [II] include cyclopentadienyl lithium, cyclopentadienyl sodium, and cyclopentadienyl potassium. Lithium is preferably used.

In preparing the (A) transition metal compound catalyst component according to the present invention, an organometallic compound represented by the following general formula [III] (hereinafter sometimes referred to as "compound [III]"). Can also be used.

Y ² Cp ² -R ⁵ -Cp ³ Y ³ [III] In the formula [III], Y ² and Y ³ are lithium, sodium or potassium, and Y ² and Y ³ are the same. May also be different.

Cp ² and Cp ³ are cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group,
Examples thereof include alkyl-substituted cyclopentadienyl groups such as dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group and fluorenyl group.

Cp ² and Cp ³ may be the same or different. R ⁵ is a methylene group, an alkylene group such as an ethylene group, a substituted alkylene group such as a dimethylmethylene group, a silylene group, a substituted silylene group such as a dimethylsilylene group, or —P (CH ₃ ).

Specific examples of the organometallic compound represented by the general formula [III] include the following compounds.

[0030]

[Chemical 1]

In the above formula, Cp is a cyclopentadienyl group and Ind is an indenyl group. Further, in the above compound, a compound in which a lithium atom is replaced with a sodium atom or a potassium atom can also be used.

[Preparation of Transition Metal Catalyst Component] The transition metal catalyst component (A) according to the present invention is a compound [I] as described above.
And compound [II] or compound [III] in a solvent. When the compound [I] is contacted with the compound [II] or the compound [III], the compound [II] or the compound [III] is
It is generally used in an amount of 1 to 20 times, preferably 1 to 8 times, the amount of the compound [I]. The contact temperature is -5.
It is desired that the temperature is 0 to 180 ° C., preferably −20 to 100 ° C., and the contact time is 0.5 to 120 hours, preferably 1 to 60 hours.

As the solvent used at the time of contact, aliphatic hydrocarbons such as hexane and decane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as ethyl ether, tetrahydrofuran and the like are used. Of these, benzene and toluene are particularly preferable. Such an aromatic hydrocarbon solvent is generally used in an amount of 1 to 1000 times, preferably 50 to 500 times the amount of the compound [I].

The desired transition metal compound catalyst component can be prepared by the method as described above. [Organoaluminum Oxy Compound Component] In the present invention, the (A) transition metal compound catalyst component and the (B) organoaluminum oxy compound component used as a catalyst for olefin polymerization are the organoaluminum oxy compounds usually used for olefin polymerization. Used as is.

Such an organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Good.

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) 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.

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 a solution of aluminoxane 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,
Trialkyl aluminum such as tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum 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. To be

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

(I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z ... [V] (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) As described above. Such organoaluminum compounds are used alone or in combination.

As the solvent used in the production of the aluminoxane solution, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, etc. Aliphatic 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, alicyclics Hydrocarbon halides, in particular, hydrocarbon solvents such as chlorinated compounds and brominated compounds. Other,
Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The olefin polymerization catalyst according to the present invention is
It can be prepared by mixing (A) the transition metal compound catalyst component and (B) the organoaluminum oxy compound component in an inert hydrocarbon solvent or in an olefin medium. The mixing order at this time is arbitrarily selected.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. When mixing the catalyst components (A) and (B), the atomic ratio (Al / transition metal) of aluminum in the catalyst component (B) to the transition metal in the catalyst component (A) is usually 10 to 10,000, Preferably 20-50
And the concentration of the catalyst component (A) is about 10 ^-8 to 10
^-1 mol / liter, preferably in the range of 10 ^{-7 to} 5 × 10 ^-2 mol / liter.

[Polymerization Method] The olefin polymerization method according to the present invention is carried out by the above transition metal compound catalyst component (A).
And the olefin is polymerized in the presence of the organoaluminum oxy compound component (B).

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as a slurry polymerization method, a solution polymerization method or a suspension polymerization method, or a gas phase polymerization method. In the liquid phase polymerization, an inert hydrocarbon solvent or olefin itself can be used as a solvent.

Specifically as the hydrocarbon medium, butane,
Isobutane, pentane, hexane, octane, decane,
Aliphatic hydrocarbons such as dodecane, hexadecane, octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene; gasoline, kerosene, Examples include petroleum fractions such as light oil.

In carrying out the slurry polymerization method in the present invention, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the liquid phase polymerization method, the polymerization temperature is usually 0 to 250 ° C., preferably 20 to 200 ° C.
When carrying out the gas phase polymerization method, the polymerization temperature is usually 0.
It is desirable to be in the range of 120 to 120 ° C, preferably 20 to 100 ° C.

In the present invention, a slurry polymerization method, a solution polymerization
When polymerizing olefins by the method or vapor phase polymerization method,
(A) The transition metal compound catalyst component is used for the transition in the polymerization reaction system.
Usually, the concentration of transferred metal atoms is 10^-8-10^-1Gram Hara
Child / liter, preferably 10 ^-7~ 5 x 10^-2Gram Hara
It is preferably used in a quantity of offspring / liter. (A)
Of the transition metal in the component and the aluminum in the component (B)
The atomic ratio (Al / transition metal) is usually 10 to 10,000,
It is preferably 20 to 5000.

The polymerization pressure is usually atmospheric pressure to 100 kg.
/ Cm ² , preferably under normal pressure to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system. 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. The olefins that can be polymerized by the olefin polymerization method according to the present invention include ethylene and α-C3-20.
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; 3 to 20 carbon atoms
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 and the like can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, it is possible to copolymerize two or more components using the above-mentioned olefins. For example, ethylene / propylene, ethylene / 1-butene, ethylene / propylene / diene, ethylene / tetracyclododecene and the like.

In the present invention, the transition metal compound catalyst component (A) and / or the organoaluminum oxy compound component (B) can be used by supporting it on a carrier such as silica, alumina, silica-alumina or zirconia.

In the present invention, the olefin may be prepolymerized with the olefin polymerization catalyst upon the polymerization of the olefin. In the prepolymerization, the olefin polymer is 0.05 to 500 g, preferably 0.1 to 300 g, and more preferably 0.2 to 100 g per 1 g of the olefin polymerization catalyst.
Is preferably prepolymerized in an amount of.

As the olefin for prepolymerization, ethylene and α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
Examples thereof include 1-tetradecene, 3-methyl-1-butene, 3-methyl-1-pentene and the like. Of these, preferred are olefins used during polymerization.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

[0058]

According to the olefin polymerization catalyst and the olefin polymerization method of the present invention, an olefin polymer having excellent polymerization activity and having a narrow molecular weight distribution and a narrow composition distribution can be obtained.

[0059]

EXAMPLES The catalyst for olefin polymerization and the method for olefin polymerization according to the present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.

In the present invention, the intrinsic viscosity [η] is 1
Measured in decalin at 35 ° C. and expressed in dl / g.

[0061]

Example 1 [Preparation of catalyst component (A)] Internal volume 5 with sufficient nitrogen substitution
In a 0 ml glass reactor, dry toluene 18.0 m
1, tetrakis (2,4-pentanedionato) -zirconium 177 mg, and lithium cyclopentadienylide 209 mg were charged. Subsequently, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 5 hours. After the reaction, solid-liquid separation was performed by filtration to obtain a toluene solution of the catalyst. This was used as it was for the polymerization.

[Coupling] Internal volume with sufficient nitrogen substitution 50
200 ml of purified toluene in a 0 ml glass flask
Was charged, and the mixture was kept at 60 ° C. for 10 minutes while circulating ethylene at 100 liter / hr.

Next, methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and re-dissolved in toluene) was charged in an amount of 16.2 mg atom in terms of aluminum atom. Further, the zirconium complex was charged at 0.073 mg atom in terms of zirconium atom. After performing the polymerization at 60 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with n-hexane, and dried under reduced pressure for 24 hours. The polyethylene obtained was 1.42 g, and the polymerization activity was 10700 g / mmol-Zr / hr.

[0065]

Example 2 [Preparation of catalyst component (A)] Internal volume 5 with sufficient nitrogen substitution
In a 0 ml glass reactor, dry toluene 17.5 m
1, tetrakis (2,4-pentanedionato) zirconium 169 mg, and lithium cyclopentadienylide 1
Charged 00 mg. Subsequently, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 5 hours. After the reaction, solid-liquid separation was performed by filtration to obtain a toluene solution of the catalyst.

[Coupling] 50 with internal volume fully replaced with nitrogen
200 ml of purified toluene in a 0 ml glass flask
Was charged, and the mixture was kept at 60 ° C. for 10 minutes while circulating ethylene at 100 liter / hr.

Next, 16.2 mg of methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and re-dissolved in toluene) was charged in terms of aluminum atom. Further, the zirconium complex was charged at 0.073 mg atom in terms of zirconium atom. After performing the polymerization for 15 minutes at 60 ° C., the polymerization was stopped by adding a small amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with n-hexane and dried under reduced pressure for 24 hours. The polyethylene obtained was 1.81 g, and the polymerization activity was 9000 g / mmol-Zr / hr.

[0069]

Example 3 [Preparation of catalyst component (A)] Inner volume 5 sufficiently replaced with nitrogen
In a 0 ml glass reactor, dry toluene 20.0 m
1, 216 mg dichlorobis (2,4-pentanedionato) -zirconium, and 43 mg lithium cyclopentadienylide were charged. Subsequently, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 5 hours. After the reaction, solid-liquid separation was performed by filtration to obtain a toluene solution of the catalyst.

[Coupling] Inner volume 50 fully replaced with nitrogen
200 ml of purified toluene in a 0 ml glass flask
Was charged, and the mixture was kept at 60 ° C. for 10 minutes while circulating ethylene at 100 liter / hr.

Then, methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and re-dissolved in toluene) was charged in an amount of 16.2 mg atom in terms of aluminum atom. Further, the zirconium complex prepared above was charged in an amount of 0.073 mg atom in terms of zirconium atom. After polymerizing at 60 ° C. for 20 minutes,
The polymerization was stopped by adding a small amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with n-hexane, and dried under reduced pressure for 24 hours. The polyethylene obtained was 1.10 g, the polymerization activity was 4100 g / mmol-Zr / hr, and the intrinsic viscosity [η] was 4.07 dl / g.

[0073]

Example 4 [Preparation of catalyst component (A)] Internal volume 5 with sufficient nitrogen substitution
In a 0 ml glass reactor, dry toluene 33.5 m
l, dichlorobis (4,4,4-trifluoro-1-phenyl-1,
Charged were 634 mg of 3-butanedionato) -zirconium and 96 mg of lithium cyclopentadienylide.
Subsequently, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 5 hours. After the reaction, solid-liquid separation was performed by filtration to obtain a toluene solution of the catalyst.

[Coupling] 50 with internal volume fully replaced with nitrogen
200 ml of purified toluene in a 0 ml glass flask
Was charged, and the mixture was kept at 60 ° C. for 10 minutes while circulating ethylene at 100 liter / hr.

Then, methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and re-dissolved in toluene) was charged at 54.0 mg atom in terms of aluminum atom. Further, the zirconium complex prepared above was charged in an amount of 0.073 mg atom in terms of zirconium atom. After polymerizing at 60 ° C. for 20 minutes,
The polymerization was stopped by adding a small amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with n-hexane, and dried under reduced pressure for 24 hours. The polyethylene obtained was 1.03 g, the polymerization activity was 3900 g / mmol-Zr / hr, and the intrinsic viscosity [η] was 4.08 dl / g.

[0077]

Example 5 [Preparation of catalyst component (A)] Internal volume 5 with sufficient nitrogen substitution
In a 0 ml glass reactor, dry toluene 40.0 m
1, tetrakis (2,4-pentanedionato) zirconium 199 mg, and lithium cyclopentadienylide 1
Charged 13 mg. Subsequently, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 3 hours. After the reaction, solid-liquid separation was performed by filtration to obtain a toluene solution of the catalyst.

[Coupling] 50% of internal volume with sufficient nitrogen substitution
160 ml of purified toluene in a 0 ml glass flask
1 and 40 ml of 4-methyl-1-pentene were charged, and ethylene was passed at 100 liter / hr at 30 ° C.
For 10 minutes.

Next, methylaluminoxane (methylaluminoxane manufactured by Schering Co., which was dried and re-dissolved in toluene) was charged in an amount of 40.5 mg atom in terms of aluminum atom. Further, the zirconium complex prepared above was charged in an amount of 0.182 milligram atom in terms of zirconium atom. After polymerizing at 30 ° C. for 30 minutes,
The polymerization was stopped by adding a small amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with n-hexane and dried under reduced pressure for 24 hours. The copolymer of ethylene and 4-methyl-1-pentene obtained was 1.89 g, and the polymerization activity was 1900 g / mm.
It was ol-Zr / hr.

The above results are shown in Table 1.

[0082]

[Table 1]

[Brief description of drawings]

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

Continued Front Page (72) Inventor Shuji Minami 580-32, Takuji Nagaura, Sodegaura City, Chiba Prefecture 32 Mitsui Petrochemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A transition metal compound represented by the following general formula [I]: (A) (a-1)
And, (R¹COCR²COR³)_mMX_4-m [I] (In the formula, M is zirconium or hafnium. R
¹, R²And R³Is a hydrogen atom or a carbon number of 1 to 1.
Alkyl group of 0, the number of carbon atoms substituted with a halogen atom is 1
Alkyl group, aryl group, halogen atom or
Aryl substituted with an alkyl or alkoxy group
Group or a furyl group, R¹And R ²Are each other
It may combine with each other to form a ring. X is a halogen atom
Or-SO₃CF₃Is. m is 1 ≦ m ≦ 4. ) (A-2) Organometallic compound represented by the following general formula [II]
And Cp¹Y¹ ... [II] (where Cp¹Is a group having a cyclopentadienyl skeleton
Yes, it may have a substituent. Y¹Is lithium,
Thorium or potassium. ) To contact
A catalyst for olefin polymerization characterized by being formed from a transition metal compound catalyst component prepared by
Medium. 2. (A) (a-1) A transition metal compound represented by the following general formula [I]:
And, (R¹COCR²COR³)_mMX_4-m [I] (In the formula, M is zirconium or hafnium. R
¹, R²And R³Is a hydrogen atom or a carbon number of 1 to 1.
Alkyl group of 0, the number of carbon atoms substituted with a halogen atom is 1
Alkyl group, aryl group, halogen atom or
Aryl substituted with an alkyl or alkoxy group
Group or a furyl group, R¹And R ²Are each other
It may combine with each other to form a ring. X is a halogen atom
Or-SO₃CF₃Is. m is 1 ≦ m ≦ 4. ) (A-3) organometallic compound represented by the following general formula [III]
Things, Y²Cp²-R^Five-Cp³Y³ … [III] (Y in the formula²And Y³Is lithium, sodium or
And is the same or different.
Cp²And Cp³Is a group having a cyclopentadienyl skeleton
And may have a substituent, and each may be the same.
May be different. R^FiveIs an alkylene group, substituted alk
Ren group, silylene group, substituted silylene group or -P (CH
₃)-. ) Prepared by contacting
A catalyst for olefin polymerization, which is formed from a metal-transfer compound catalyst component and (B) an organoaluminumoxy compound component.
Medium. 3. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound is a compound represented by the following general formula [IV]. ^{(R 7 COCR 8 COR 9)} q ZrCl 4-q ... [IV] ( wherein, R ^7, R ⁸ and R ⁹ carbon atoms substituted with an alkyl group, a halogen atom having 1 to 6 carbon atoms 1 Are alkyl groups, aryl groups, or furyl groups of 6 to 6, and R ⁷ and R ⁸ may combine with each other to form a ring.
Is 1 ≦ q ≦ 4. ) 4. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound is tetrakis (2,4-pentanedionato) -zirconium. 5. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound is dichlorobis (2,4-pentanedionato) -zirconium. 6. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst according to any one of claims 1 to 5.