JP3115661B2 - Catalyst for ethylene polymer and method for producing ethylene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst. More specifically, the present invention relates to a method for producing an olefin polymer having a large molecular weight and a narrow molecular weight distribution and composition distribution with high polymerization activity. The present invention relates to an olefin polymerization catalyst that can be used and an olefin polymerization method using the catalyst.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It may be used with the incorporation of coalescence.

[0003]

BACKGROUND OF THE INVENTION Olefin polymers, such as polyethylene and ethylene / α-olefin copolymers, which are frequently used for film applications, have been conventionally used with titanium catalysts composed of a titanium compound and an organoaluminum compound or a vanadium compound. It is manufactured with a transition metal catalyst such as a vanadium catalyst composed of an organic aluminum compound.

In recent years, as such transition metal catalysts,
A zirconium-based catalyst comprising a zirconium compound and an organoaluminum oxy compound which can copolymerize ethylene and α-olefin with high polymerization activity has been proposed. A method for producing an ethylene / α-olefin copolymer using such a zirconium-based catalyst,
For example, Japanese Patent Application Laid-Open Nos.
JP-A-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008
It is proposed in Japanese Patent Publication No.

[0005] The use of the zirconium-based catalysts disclosed in these publications is in comparison with the case where a catalyst formed from a transition metal compound and an organoaluminum compound, which has been known before the appearance of this catalyst, is used. Although olefins, particularly ethylene, can be polymerized with high polymerization activity, there is a problem that it is difficult to obtain a polymer having a high molecular weight.

By the way, olefin polymers used for film applications are desired to be excellent in strength and transparency and also excellent in blocking resistance. However, olefin polymers having a high molecular weight and a narrow molecular weight distribution and a narrow composition distribution are required. Polymers are known to have excellent strength, transparency and blocking resistance.

[0007] Therefore, an olefin polymerization catalyst and a polymerization catalyst capable of polymerizing an olefin with high polymerization activity and producing a high yield of an olefin (co) polymer having a high molecular weight and a narrow molecular weight distribution and composition distribution. The advent of a method was desired.

[0008]

The object of the present invention is to provide an olefin polymer having a high molecular weight and a narrow molecular weight distribution, in which olefins can be polymerized with high polymerization activity. Can be 2
When producing a copolymer of two or more olefins, it is necessary to provide an olefin polymerization catalyst capable of producing an olefin copolymer having a narrow composition distribution and a method for polymerizing an olefin using such a catalyst. It is an object.

[0009]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
[A] a transition metal compound represented by the following formula [I]; ML _x ... [I] [In the formula [I], M is a transition metal atom selected from Group IVB, and L is a transition metal atom M And at least one of the ligands L includes a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms and a substituent R ¹ having 2 carbon atoms.
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. )
[B] An organic aluminum oxy compound.

The olefin polymerization catalyst according to the present invention may further comprise, if necessary, [C] an organoaluminum compound, in addition to the above-mentioned [A] transition metal compound and [B] organoaluminum oxy compound. , [D] a particulate carrier.

Further, the catalyst for olefin polymerization according to the present invention may be a prepolymerized catalyst obtained by prepolymerizing an olefin. The olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the above-mentioned catalyst.

[0012]

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

First, the transition metal compound [A] represented by the following formula [I] forming the olefin polymerization catalyst according to the present invention will be described. ML _x ... [I] In the formula [I], M is a transition metal atom selected from Group IVB, and specifically, zirconium, titanium or hafnium. X is the valence of the transition metal atom M.

L is a ligand that coordinates to the transition metal atom M. At least one of the ligands L is (i) a substituent R ¹ comprising a hydrocarbon group having 1 to 10 carbon atoms. And (ii)
A cyclopentadienyl group having a substituent R ² consisting of a hydrocarbon group having 2 to 10 carbon atoms;
¹ and the substituent R ² are different from each other.

As (i) the substituent R ¹ comprising a hydrocarbon group having 1 to 10 carbon atoms, specific examples include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. . More specifically, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples include an alkyl group such as a decyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neophyl group.

Further, (ii) the substituent R ² consisting of a hydrocarbon group having 2 to 10 carbon atoms is specifically the same as the above-mentioned (i) substituent R ¹ except for a methyl group. can do.

These hydrocarbon groups may be substituted with a halogen atom or a trialkylsilyl group. In the cyclopentadienyl group having different substituents R ¹ and R ² as described above, the substituents R ¹ and R ² are
To the carbon atom forming the cyclopentadienyl group,
They are bonded at the 1,2-position or the 1,3-position.

Such a substituted cyclopentadienyl group is specifically represented by the following formula.

[0019]

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In the above formula, for the sake of convenience, the substitution position of the substituent R ¹ is shown as the 1-position, but it goes without saying that the substitution position of the substituent R ² may be the 1-position. Examples of such a cyclopentadienyl group having different substituents R ¹ and R ² include, for example, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexyl Cyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylbutylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group,
Examples thereof include an ethylhexylcyclopentadienyl group.

In the present invention, such a substituted cyclopentane
In the dienyl group, the substituent R¹And the substituent R^TwoAnd
Preferably, the number of carbon atoms differs by 2 or more.
To R ¹And R^TwoOne of them is a methyl group
Is particularly preferred.

In the above formula [I], the ligand L other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom or a halogen atom. Atom, trialkylsilyl group or hydrogen atom.

The hydrocarbon group having 1 to 12 carbon atoms includes an alkyl group, a cycloalkyl group, an aryl group,
Examples include aralkyl groups, and more specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, and pentyl groups. , Hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group,
Examples thereof include a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neophyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,
n-butoxy group, isobutoxy group, sec-butoxy group, t-
Butoxy, pentoxy, hexoxy, octoxy and the like.

Examples of the aryloxy group include a phenoxy group and the like, and examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The transition metal compound [A] represented by the above formula [I] is more specifically represented by the following formula [II] when the valence of the transition metal is 4. You.

R ³ _a R ⁴ _b R ⁵ _c R ⁶ _d M ... [II] In the formula [II], M is zirconium, titanium or hafnium. R ³ is the above substituted cyclopentadienyl group.

R ⁴ , R ⁵ and R ⁶ each represent the same substituted cyclopentadienyl group, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, halogen atom or hydrogen atom as defined for R ^3. Or a group or atom selected from the group consisting of

A is an integer of 1 or more, and a + b + c
+ D = 4. The transition metal compound [A] preferably used in the present invention is a compound represented by the formula (II) wherein R ^{3 is}
A compound in which at least two of R ⁴ , R ⁵ and R ⁶ , that is, R ³ and R ⁴ are substituted cyclopentadienyl groups. The two substituted cyclopentadienyl groups are bonded via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, and a substituted silylene group such as a silylene group, dimethylsilylene and diphenylsilylene. May be.

Hereinafter, the transition metal compound represented by the formula [I] used in the present invention will be specifically exemplified when M is zirconium. Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-propylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-propylcyclopentadienyl) zirconium methyl Chloride, bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dimethyl, bis (1-methyl
3-butylcyclopentadienyl) zirconium methyl chloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium ethoxycyclolide, bis ( 1-methyl-3-butylcyclopentadienyl) zirconium dimethoxide, bis (1-ethyl-3-butylcyclopentadienyl) zirconium dichloride,
Bis (1-benzyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-hexylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-cyclohexylcyclopentadienyl)
Zirconium dichloride, bis (1-ethyl-3-hexylcyclopentadienyl) zirconium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-2-propylcyclopentadienyl) ) Zirconium dimethyl, bis (1-methyl)
2-propylcyclopentadienyl) zirconium methyl chloride, bis (1-methyl-2-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-2
-Butylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-2-butylcyclopentadienyl)
Zirconium methyl chloride, bis (1-methyl-2-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-2-butylcyclopentadienyl) zirconium ethoxycyclolide, bis (1-methyl-2-butylcyclopenta Dienyl) zirconium dimethoxide, bis (1-ethyl-2-butylcyclopentadienyl) zirconium dichloride, bis (1-benzyl-2-methylcyclopentadienyl) zirconium dichloride, bis (1-methyl-2-hexyl) Cyclopentadienyl) zirconium dichloride, bis (1-methyl-2-cyclohexylcyclopentadienyl) zirconium dichloride, bis (1-ethyl-2-hexylcyclopentadienyl) zirconium dichloride.

Of these, the following compounds are particularly preferred. Bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-hexylcyclopentadienyl) zirconium dichloride .

In the exemplified compounds, the respective substituents bonded to the 1,3-position of the cyclopentadienyl group as described above can be exchanged. For example, 1-methyl-3-ethylcyclopentadienyl is
It can also be exemplified as ethyl-3-methylcyclopentadienyl. The same applies to the substituent bonded to the 1,2-position.

In the present invention, as the transition metal compound (A), a transition metal compound in which zirconium is replaced with titanium or hafnium in the above-mentioned zirconium compound may be used.

Next, the organoaluminum oxy compound [B] forming the olefin polymerization catalyst according to the present invention will be described. [B] The organic aluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organic aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride In a suspended hydrocarbon solvent,
A method in which an organoaluminum compound such as trialkylaluminum is added and reacted to recover a hydrocarbon solution. (2) A method in which an organic aluminum compound such as trialkylaluminum is directly allowed to act on water, ice or steam in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover as a hydrocarbon solution.

The aluminoxane may contain a small amount of an organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and the obtained aluminoxane may be redissolved in the solvent.

Specific examples of the organoaluminum compound used in producing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, Tri sec-butyl aluminum, tri tert
-Butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum,
Trialkylaluminums such as tridecylaluminum, tricyclohexylaluminum and tricyclooctylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminums such as diethylaluminum hydride and diisobutylaluminum hydride Hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum is particularly preferred. Further, isoprenyl aluminum represented by the following general formula [III] can be used as the organic aluminum compound.

(I—C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (III) (where x, y, and z are positive numbers and z ≧ 2x) Such 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. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons,
A hydrocarbon solvent such as an alicyclic hydrocarbon halide, in particular, a chlorinated product and a brominated product can be used. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention may be prepared, for example, by contacting a solution of aluminoxane with water or an active hydrogen-containing compound, or by bringing the above-mentioned organoaluminum into contact with water. It can be obtained by a method or the like.

In the first method for obtaining a benzene-insoluble organoaluminum oxy compound, a solution of aluminoxane is brought into contact with water or an active hydrogen-containing compound. Active hydrogen-containing compounds include methanol, ethanol, n-
Alcohols such as propanol and isopropal, 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 preferred, and alcohols are particularly preferred.

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

The contact reaction between the aluminoxane solution and water or an active hydrogen-containing compound is usually carried out in a solvent, for example, a hydrocarbon solvent. As such a hydrocarbon solvent, the aforementioned hydrocarbons are used. Among these solvents, 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, per Al atom in the aluminoxane solution. The concentration in the reaction system is converted into Al atoms,
Usually, it is desirable to be in the range of 1 × 10 ^{−3 to} 5 g atom / l, preferably 1 × 10 ^{−2 to} 3 g atom / l, and the concentration of water in the reaction system is usually 2 × 10 3 g / l.
The concentration is desirably ^{-4 to} 5 mol / l, preferably 2 × 10 ^{-3 to} 3 mol / l.

As a method for bringing the aluminoxane solution into contact with water or an active hydrogen-containing compound, the following method is specifically mentioned. (1) A method in which a solution of aluminoxane is brought into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound. (2) A method in which water or an active hydrogen-containing compound vapor is blown into a solution of aluminoxane to bring the aluminoxane into contact with the vapor. (3) A method in which a solution of aluminoxane is brought into direct contact with water, ice or an active hydrogen-containing compound. (4) Aluminoxane solution is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a water of crystallization or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound is adsorbed. And contacting the water with the adsorbed water or water of crystallization.

The aluminoxane solution described above may contain other components as long as the reaction between the aluminoxane and water or an active hydrogen-containing compound is not adversely affected.

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

In the second method for obtaining a benzene-insoluble organoaluminum oxy compound, an organoaluminum is brought into contact with water. Water is used in such an amount that the organic aluminum atoms dissolved in the reaction system become 20% or less based on all the organic aluminum atoms.

The water to be brought into contact with the organoaluminum compound is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, hexane, etc., an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of steam or ice. be able to. As water, it was adsorbed on water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or on inorganic compounds or polymers such as silica, alumina and aluminum hydroxide. Adsorbed water or the like can also be used.

The contact reaction between the organoaluminum compound and water is usually performed in a hydrocarbon solvent. As the hydrocarbon solvent, the above-mentioned hydrocarbon solvent is used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. The concentration of water in the reaction system is usually 1 × 10 ^{−3 to} 5 mol / l, preferably 1 × 10 ^{−2 to} 3 mol / l. At this time, the organic aluminum atoms dissolved in the reaction system are desirably 20% or less, preferably 10% or less, more preferably 0 to 5% based on all the organic aluminum atoms.

The method for bringing the organoaluminum compound into contact with water includes the following method. (1) A method in which a hydrocarbon solution of an organic aluminum is brought into contact with a hydrocarbon solvent containing water. (2) A method in which water vapor is blown into a hydrocarbon solution of organic aluminum to bring the organic aluminum into contact with water vapor. (3) A method in which a hydrocarbon solution of an organic aluminum is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and the organic aluminum is brought into contact with the adsorbed water or the water of crystallization. (4) A method in which ice is brought into contact with a hydrocarbon solution of an organic aluminum.

The hydrocarbon solution of organoaluminum as described above may contain other components as long as the reaction between the organoaluminum and water is not adversely affected. The contact reaction between the organoaluminum compound and water is usually -100.
C. to 150.degree. C., preferably -70 to 100.degree. C., more preferably -50 to 80.degree. Although the reaction time varies greatly depending on the reaction temperature, it is usually 1 to 20.
It is 0 hour, preferably about 2 to 100 hours.

Such a benzene-insoluble organoaluminum oxy compound is obtained by dissolving Al in the benzene at 60 ° C.
The component is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, 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 milligram atoms of Al in 100 ml of benzene, mixing the mixture at 60 ° C. with stirring for 6 hours, and adding a jacketed G-5. A hot filter was performed at 60 ° C. using a glass filter, and the solid portion separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the amount of Al atoms present in the entire filtrate was determined. x mmol) (x mmol)
%).

The benzene-insoluble organic compound used in the present invention
In the case of aluminum oxy compounds, the compounds are analyzed by infrared spectroscopy.
Analyzed by IR method (IR)^-1Nearby
Absorbance (D₁₂₂₀) And 1260cm^-1In the vicinity
Absorbance (D₁₂₆₀) And the ratio (D ₁₂₆₀/ D₁₂₂₀) Is 0.0
9 or less, preferably 0.08 or less, particularly preferably 0.0
It is desirable to be in the range of 4 to 0.07.

The infrared spectroscopic analysis of the organic aluminum oxy compound is performed as follows. First, an organic aluminum oxy compound and nujol are ground in an agate mortar in a nitrogen box to form a paste. next,
The paste-like sample is sandwiched between KBr plates, and the IR spectrum is measured in a nitrogen atmosphere by IR-810 manufactured by JASCO Corporation. From the IR spectrum thus obtained, D
₁₂₆₀ / _D1220 is obtained, and the value of _D1260 / _D1220 is obtained as follows.

(A) Around 1280 cm ^-1 and 1240 cm
A maximum point near ^-1 is connected, and this is defined as a baseline L1. (B) Transmittance at the minimum absorption point near 1260 cm ^-1 (T
%) And a line perpendicular to the wave number axis (horizontal axis) is drawn from the minimum point, the transmittance (T ₀ %) at the intersection of the perpendicular and the baseline L1 is read, and the absorbance (D ₁₂₆₀ ) around ₁₂₆₀ cm ⁻¹ is read. = Log T ₀ / T).

(C) Similarly, 1280 cm^-1Nearby and 118
0cm^-1The local maximum points are connected, and this is connected to the baseline L2.
And (D) 1220cm^-1Near the absorption minimum point (T ')
%) And a line perpendicular to the wave number axis (horizontal axis) from this minimum point.
, The transmittance at the intersection of this perpendicular and the baseline L2
(T₀'%) And read 1220 cm^-1Near absorbance
(D₁₂₂₀= Log T ₀'/ T').

(E) D ₁₂₆₀ / D ₁₂₂₀ is calculated from these values. Benzene-soluble organoaluminum oxy compound is D
₁₂₆₀ / D ₁₂₂₀ value is approximately between 0.10 and 0.13,
Benzene-insoluble organoaluminum oxy-compound is an organic aluminum oxy compound conventionally known benzene-soluble, have clearly different in the D _{12 60} / D ₁₂₂₀ value.

It is estimated that the benzene-insoluble organoaluminum oxy compound as described above has an alkyloxyaluminum unit (i) represented by the following formula [IV].

[0062]

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In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. As such a hydrocarbon group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a cyclohexyl group, and a cyclooctyl group. Of these, a methyl group and an ethyl group are preferred, and a methyl group is particularly preferred.

The benzene-insoluble organoaluminum oxy compound contains an oxyaluminum unit (ii) represented by the following formula [V] in addition to the alkyloxyaluminum unit (i) represented by the above formula [IV]. May be.

[0065]

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In the formula, R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, halogen, or hydrogen.
R ⁸ and R ⁷ in the above formula [IV] represent different groups.

In the case of containing an aluminum oxyaluminum unit (ii), an alkyloxyaluminum unit containing the alkyloxyaluminum unit (i) in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more Organoaluminum oxy compounds having units are preferred.

The olefin polymerization catalyst according to the present invention may contain an organic aluminum compound [C] as necessary. As such an organic aluminum compound [C], an organic aluminum compound represented by the following formula [VI] can be exemplified.

R ⁹ _n AlX _3-n ... [VI] In the formula, R ⁹ 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.

The hydrocarbon group having 1 to 12 carbon atoms is, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group.

As such organoaluminum compounds, specifically, the following compounds are used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride; Dialkylaluminum halides such as diisobutylaluminum chloride and dimethylaluminum bromide; methylaluminum sesquichloride, ethylauminium sesquichloride, isopropylaluminum sesquichloride,
Alkylaluminum sesquihalides such as butylaluminum sesquichloride and ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminums such as diethylaluminum hydride and diisobutylaluminum hydride Hydride and the like.

Further, as the organoaluminum compound [C], a compound represented by the following formula [VII] can also be used. R ⁹ _n AlY _3-n ... [VII] In the formula, R ⁹ is the same as in the above formula [VI], and Y is -OR ¹⁰
Group, -OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR
¹³ ₂ group, an -SiR ¹⁴ ₃ group or -N (R ¹⁵⁾ AlR ¹⁶ ₂ group. R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group and the like. n is 1-2.

As such organoaluminum compounds, specifically, the following compounds are used. _{^{(i) R 9 n Al (}} OR 10) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R 9 n Al}} (OSi R 11 3 A) a compound represented by _3-n ;
For example, such _{Et 2 Al (OSi Me 3)} (iso-Bu) 2 Al (OSi Me 3) (iso-Bu) 2 Al (OSi Et 3), (iii) R 9 n Al (OAlR 12 2) 3- a compound represented by _{n, e.g., Et 2 AlOAlEt 2 (iso-} Bu) such as _{2 AlOAl (iso-Bu) 2} , (iv) R 9 n Al (NR 13 2) a compound represented by _3-n, e.g. _{, Me 2 AlNEt 2 Et 2 AlNHMe} Me 2 AlNHEt Et 2 AlN (Si Me 3) 2 (iso-Bu) such as _{2 AlN (SiMe 3) 2,} (V) R 9 n Al (Si R 14 3) 3-n A compound represented by, for example, (iso-Bu) ₂ AlSi Me ₃

[0074]

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[0075] The above general formula [VI], in an organic aluminum compound represented by [VII] _{^{is, R 9 3 Al, R 9}} n Al
(OR ¹⁰⁾ _3-n, can be mentioned organoaluminum compounds represented by _{^{R 9 n Al (OAlR 12 2}} ) 3-n Suitable examples, R ⁹ is an isoalkyl group, compounds which are n = 2 Is particularly preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

The olefin polymerization catalyst according to the present invention preferably contains [D] a particulate carrier. As such a fine particle carrier [D], a fine particle inorganic carrier composed of an oxide of at least one element selected from the group II, group III, and group IV, and an organic carrier such as polyethylene, polypropylene, and polystyrene are used. .

As the particulate inorganic carrier, a porous oxide is used.
Preferably, specifically, SiO_Two, Al _TwoO_Three, MgO, ZrO
_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_TwoWhat
Or a mixture containing them, for example, SiO 2_Two-Mg
O, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five,
SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-Example of MgO
be able to. Among them, SiO_Two, Al_TwoO_ThreeAnd M
at least one component selected from the group consisting of gO
Carriers contained as components are preferred.

[0078] The [D] particulate carrier has an average particle diameter of usually 1 to 300 [mu] m, it is desirable and preferably 10~200μm range, specific surface area 50~1000m ² / g, preferably 100~700m ² / g, and the pore volume is desirably 0.3 to 2.5 cm ³ / g.

In the particulate carrier [D], the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl groups are 1.0% by weight or more, preferably 1.5% by weight.
４4.0 wt%, particularly preferably 2.0-3.5 wt%.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) are determined as follows. [Amount of adsorbed water] at a temperature of 200 ° C. under normal pressure and nitrogen flow
The weight loss after drying for an hour is defined as the amount of adsorbed water. [Amount of surface hydroxyl groups] The weight of a carrier obtained by drying at a temperature of 200 ° C. under a normal pressure under a nitrogen stream for 4 hours is defined as X (g),
Further, the weight of the sintered body in which the surface hydroxyl groups disappeared obtained by sintering the carrier at 1000 ° C. for 20 hours is defined as Y (g),
It is calculated by the following formula.

[0081]

(Equation 1)

By using the [D] particulate carrier having a specific amount of adsorbed water and a surface hydroxyl group,
An olefin polymerization catalyst capable of polymerizing an olefin with high polymerization activity and producing an olefin polymer having excellent particle properties can be obtained.

The catalyst for olefin polymerization according to the present invention comprises the above-mentioned [A] transition metal compound, [B] organoaluminum oxy compound and preferably [D] a particulate carrier, and if necessary, [C] organoaluminum. It is formed by contacting a compound.

At this time, the contacting order is arbitrarily selected, but preferably [D] is mixed and contacted with the [B] organoaluminum oxy compound, and then [A] contains a substituted cyclopentadienyl group. A transition metal compound selected from Group IVB is mixed and contacted, and if necessary, [C] an organoaluminum compound is mixed, or [D] a particulate carrier, [B] an organoaluminum oxy compound, and [A] substituted cycloalkyl. A mixture with a mixture of a transition metal compound selected from Group IVB containing a pentadienyl group is brought into contact with the mixture, and then, if necessary, an organoaluminum compound [C] is mixed.

FIG. 1 shows a process for preparing the catalyst for olefin polymerization according to the present invention. When mixing the component [A], the component [B], the component [D] and the component [C] as required, the component [A] is usually 5 × 10 ⁻⁶ per 1 g of the component [D].
５5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol, and the concentration of the component [A] is about 10 ^-4 to 2 ×
10 ^-2 mol / l, preferably 2 × 10 ^-4 to 10 ^-2
It is in the mole / liter range. The molar ratio (OH / Al-B) between the surface hydroxyl group (OH) of [D] and the aluminum (Al-B) of the component [B] is usually 0.1 to 0.4, preferably 0.15. ~ 0.3.

The aluminum of component [B] and the component [A]
The atomic ratio with the transition metal (Al / transition metal) is usually 1
It is 0 to 500, preferably 20 to 200. The aluminum atom (Al-
The atomic ratio (Al-C / Al-B) of the component (B) and the aluminum atom (Al-B) of the component [B] is usually in the range of 0.02 to 3, preferably 0.05 to 1.5. Component [A],
Component [B], component [D] and optionally component [C]
Is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 10
00 minutes, preferably 5 to 600 minutes. In particular, the reaction temperature of the component [D] and the component [B] is usually 50 to 1
The temperature is 20C, preferably 60-100C. Further, the mixing temperature may be changed during the mixing contact.

The above contact can be carried out in an inert hydrocarbon solvent as described below. Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene Hydrogen; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

The olefin polymerization catalyst of the present invention obtained as described above is used in an amount of about 5 × 10 ^-6 to 1 g per component [D].
5 × 10 ⁻⁴ gram atoms, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴
Gram atoms of transition metal atoms are supported, and about 10 ^-3 to
5 × 10 ⁻² gram atoms, preferably 2 × 10 ⁻³ to 2 × 1
^Preferably, 0 ^-2 gram atoms of aluminum atoms are carried.

The olefin polymerization catalyst according to the present invention
Component [A], Component [B], Component [D] and
If necessary, prepolymerize olefin to component [C]
The obtained prepolymerized catalyst may be used. For pre-polymerization
In general, the above-mentioned [A] transition metal compound is usually 10^-6~ 2x
10^-2Mol / liter, preferably 5 × 10^-Five-10 ^-2
It is used in an amount of mol / l and the prepolymerization temperature is -20.
-80 ° C, preferably 0-50 ° C, and prepolymerization
Time is 0.5 to 100 hours, preferably about 1 to 50 hours
Degrees.

The olefin used for the prepolymerization is selected from olefins used for the polymerization, and preferably contains ethylene as a main component. Further, the amount of the polymer produced by the prepolymerization is about 0.1 to 5 per gram of the component [D].
It is desirably in the range of 00 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g. Also, about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atoms per 1 g of the component [D],
Preferably, 10 ^{-5 to} 2 × 10 ^-4 gram atoms of transition metal atoms are supported, and about 10 ^{-3 to} 5 × 10 ^-2 gram atoms,
Preferably, 2 × 10 ^{−3 to} 2 × 10 ⁻² gram atoms of aluminum atoms are supported.

The prepolymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system. In the olefin polymerization method according to the present invention, the olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst as described above.

In the polymerization, [A] the transition metal compound is
Usually 10 ^-8 to 10 ^-3 gram atoms, preferably 10 ^-7 to 10 ^-4 , in terms of transition metal atoms per liter of polymerization volume.
Preferably, it is used in an amount of gram atoms. On this occasion,
If necessary, an organoaluminum compound or an aluminoxane may be used. As the organoaluminum compound used at this time, the same compounds as the above-mentioned organoaluminum compound [C] can be mentioned. The amount used is desirably in the range of 0 to 500 mol, preferably 5 to 200 mol, per gram atom of the transition metal atom.

The olefin used in the present invention includes:
Ethylene and an α-olefin having 3 to 20 carbon atoms,
For example, 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, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4
a, 5,8,8a-Octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, dienes and the like can be used.

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,
The olefin itself can be used as a solvent.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of -50 to 150 ° C, preferably 0 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² .
kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages under different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

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

[0097]

According to the olefin polymerization catalyst and the olefin polymerization method using the same according to the present invention, an olefin can be polymerized with high polymerization activity, and an olefin polymer having a high molecular weight and a narrow molecular weight distribution can be produced. In addition, when two or more olefins are copolymerized, an olefin copolymer having a narrow composition distribution can be produced.

[0098]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

The amount of the n-decane-soluble component of the ethylene copolymer obtained according to the present invention (the smaller the soluble amount, the narrower the composition distribution) is that about 3 g of the copolymer is mixed with 450 ml of n-decane.
In addition, after melting at 145 ℃, cooled to 23 ℃
The measurement was performed by removing the n-decane-insoluble portion by filtration and recovering the n-decane-soluble portion from the filtrate.

The density was measured with a density gradient tube after heat-treating the strand obtained at the time of MFR measurement at 190 ° C. under a load of 2.16 kg at 120 ° C. for 1 hour and gradually cooling it to room temperature over 1 hour.

The average particle size of the polymer and
The amount of fine powder of m or less was measured by a sieve.

[0102]

Example 1 [Polymerization] One liter of decane was charged into a 1.5-liter glass autoclave sufficiently purged with nitrogen, and the temperature in the system was raised to 70 ° C. Thereafter, 0.5 m of a decane solution of triisobutylaluminum (Al; 1 mol / liter) was used.
1, 4.1 ml of a toluene solution of an organic aluminum oxy compound (Methylaluminoxane manufactured by Schering, dried and redissolved in toluene, Al; 1.21 mol / l) and bis (1-n-butyl-3-) 1.82 ml of a toluene solution of methylcyclopentadienyl) zirconium dichloride (Zr; 0.011 mol / l) were added in this order. Then, polymerization was started by flowing a mixed gas of ethylene and hydrogen (250 L / h and 0.25 L / h, respectively). The MF measured at 190 ° C. under a load of 2.16 kg by performing polymerization at 75 ° C. for 1 hour under normal pressure while continuously supplying the above mixed gas.
47.8 g of a polymer having an R of 2.52 g / 10 min and an Mw / Mn of 2.3 was obtained.

[0103]

Example 2 [Polymerization] In the polymerization of Example 1, bis (1-n-butyl-3
Except that 1.25 ml of a toluene solution of bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride (Zr; 0.016 mol / l) was used instead of -methylcyclopentadienyl) zirconium dichloride. Was polymerized in the same manner to obtain 43.8 g of a polymer having an MFR of 2.10 g / 10 min and an Mw / Mn of 2.4.

[0104]

Comparative Example 1 [Polymerization] In the polymerization of Example 1, bis (1-n-butyl-3
-Methylcyclopentadienyl) zirconium dichloride instead of bis (n-butylcyclopentadienyl) zirconium dichloride in toluene solution (Zr; 0.02)
(0 mol / l) Polymerization was carried out in the same manner except that 1.0 ml was used and hydrogen was not used, and the MFR was 4.91 g / 10 min.
And 71.0 g of a polymer having an Mw / Mn of 2.3 was obtained.

[0105]

[Example 3] [Preparation of solid catalyst (zirconium catalyst)] Silica (HTG-30603 manufactured by Fuji Devison Co.) was dried at 250 ° C for 10 hours in a nitrogen stream in a 400 ml glass flask sufficiently purged with nitrogen (adsorption). Water (0.1% by weight or less, hydroxyl group content 2.7% by weight) (10.3 g) and toluene (158 ml) were put into a suspension, and the mixture was cooled to 0 ° C. To this suspension, 53.5 ml of a toluene solution of an organic aluminum oxy compound (Methylaluminoxane Al manufactured by Schering Co .; 1.47 mol / l) was added dropwise over 1 hour, and the temperature in the system was reduced to 0 ° C. Kept. Thereafter, the reaction was carried out at 0 ° C. for 1 hour, at room temperature for 1 hour, and further at 80 ° C. for 4 hours. Thereafter, the supernatant was removed by decantation, and toluene 150 was removed.
Washed three times with ml. Again, toluene was added so that the volume of the suspension became 200 ml, and 66.8 ml of the suspension was added to another 2 ml.
Transferred to a 00 ml flask. Bis (1-n-
(Butyl-3-methylcyclopentadienyl) toluene solution of zirconium dichloride (Zr: 0.0153 mol /
21.8 ml) were added dropwise over 15 minutes. After completion of the dropwise addition, the temperature was raised to 30 ° C., and the mixture was stirred at that temperature for 1.5 hours. Thereafter, the solvent was removed by decantation, followed by washing with 100 ml of hexane three times. Thus, 1 g of silica
8.8 mg zirconium and 18 aluminum
A solid catalyst containing 3 mg was obtained.

2.3 g of the solid catalyst prepared above were suspended in 75 ml of hexane, and 8.4 mmol of triisobutylaluminum were added to the suspension. Thereafter, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 35 ° C. for 90 minutes. As a result, a prepolymerized catalyst containing 6.4 mg of zirconium, 165 mg of aluminum, and 4.2 g of polyethylene per 1 g of silica was obtained. At this time, no adhesion of the polymer to the reactor wall was observed.

[Polymerization] 150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, and dried at 90 ° C. for 1 hour under reduced pressure. Thereafter, the pressure was returned to normal pressure by introducing a mixed gas of ethylene and 1-butene (1-butene content: 5.0 mol%), and the system was heated to 70 ° C.

Next, the solid catalyst prepared as described above was added to an autoclave of 0.004 mg atom in terms of zirconium atom and 0.5 mmol of triisobutylaluminum.

Thereafter, a mixed gas of the above ethylene and 1-butene was introduced, and polymerization was started at a total pressure of 8 kg / cm ² -G.
The temperature in the system immediately rose to 80 ° C. Thereafter, only the mixed gas was supplied, the total pressure was kept at 8 kg / cm ² -G, and polymerization was carried out at 80 ° C. for 1 hour.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It dried under reduced pressure at 1 degreeC for 1 hour. As a result, the MFR was 0.56 g.
/ A 10min, a density of 0.907 g / cm ^3, a bulk density 0.46 g / cm ^3, a Mw / Mn is 2.5, n-decane soluble content of 2.0 weight %, The average particle size of the polymer is 640 μm, and the amount of the finely divided polymer of 100 μm or less is 0.1% by weight.
1 g was obtained.

[0111]

[Example 4] [Preparation of solid catalyst (zirconium catalyst)] In Example 3, bis (1-methyl) was used instead of bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride.
-3-n-Propylcyclopentadienyl) zirconium dichloride, except that 1 g of silica was used.
8.1 mg zirconium and 20 aluminum
A prepolymerized catalyst containing 0 mg and 3.9 g of polyethylene was obtained.

[Polymerization] In the polymerization of Example 3, the prepolymerized catalyst prepared above was used in an amount of 0.0 in terms of zirconium atoms.
The same procedure as in Example 3 was carried out except that 05 milligram atoms were used. The MFR was 0.51 g / 10 min, and the density was 0.907 g.
/ cm ³ , bulk specific gravity 0.45 g / cm ³ , Mw / Mn
Is 2.6%, the amount of n-decane-soluble components is 2.1% by weight, the average particle size of the polymer is 650 μm,
Ethylene / 1 with the following fine polymer content of 0.1% by weight
-Butene copolymer 214 g was obtained.

[0113]

Comparative Example 2 [Preparation of solid catalyst (zirconium catalyst)] 5.9 g of silica and 91 ml of toluene as in Example 3 were put into a suspension and cooled to 0 ° C. In this suspension, a toluene solution of an organoaluminum oxy compound (Methylaluminoxane Al manufactured by Schering Co .; 1.66 mol / l) 27.
3 ml was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Then 1 hour at 0 ° C., 1 hour at room temperature,
The reaction was performed at 4 ° C. for 4 hours. Thereafter, the supernatant was removed by decantation and washed three times with 150 ml of toluene. Again, toluene was added so that the volume of the suspension was 120 ml. To this suspension, 10.3 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0432 mol / l) is added.
In minutes. After completion of the dropwise addition, the temperature was raised to 30 ° C., and the mixture was stirred at that temperature for 2 hours. Thereafter, the solvent was removed by decantation, followed by washing with 100 ml of hexane three times. Thus, 6.5 mg of zirconium per 1 g of silica,
A solid catalyst containing 152 mg of aluminum was obtained.

3.0 g of the solid catalyst prepared above was suspended in 100 ml of hexane, and 4.9 mmol of triisobutylaluminum was added to the suspension. Thereafter, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 35 ° C. for 90 minutes. As a result, a prepolymerized catalyst containing 4.0 mg of zirconium, 129 mg of aluminum, and 4.0 g of polyethylene based on 1 g of silica was obtained. At this time, no adhesion of the polymer to the reactor wall was observed.

[Polymerization] In the polymerization of Example 3, the prepolymerized catalyst prepared above was used in an amount of 0.0 in terms of zirconium atoms.
The same procedure as in Example 3 was carried out except that 02 milligram atoms were used. The MFR was 2.24 g / 10 min, and the density was 0.908 g.
/ cm ³ , bulk specific gravity 0.43 g / cm ³ , Mw / Mn
Is 2.4, the amount of n-decane-soluble components is 1.7% by weight, the average polymer particle diameter is 650 μm,
Ethylene / 1 with the following fine polymer content of 0.1% by weight
138 g of -butene copolymer was obtained.

[0116]

Comparative Example 3 [Preparation of solid catalyst (zirconium catalyst)] 12.5 g of silica as in Example 3 and 200 ml of toluene were put into a suspension and cooled to 0 ° C. In this suspension, a toluene solution of an organic aluminum oxy compound (Methylaluminoxane Al manufactured by Schering Co .; 1.47 mol / L)
65.2 ml was added dropwise over 1 hour.
C. Thereafter, the reaction was carried out at 0 ° C. for 1 hour, at room temperature for 1 hour, and further at 80 ° C. for 4 hours. Thereafter, the supernatant was removed by decantation and washed three times with 150 ml of toluene. Again, toluene was added so that the volume of the suspension was 300 ml, and 150 ml of it was transferred to another 400 ml flask. 14.9 ml of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr: 0.0300 mol / l) was added to this suspension.
Was added dropwise over 10 minutes. After completion of the dropwise addition, the temperature was raised to 30 ° C., and the mixture was stirred at that temperature for 2 hours. Thereafter, the solvent was removed by decantation, and the resultant was washed three times with 200 ml of hexane. Thus, a solid catalyst containing 6.5 mg of zirconium and 192 mg of aluminum per 1 g of silica was obtained.

4.0 g of the solid catalyst prepared above was suspended in 130 ml of hexane, and 15.2 mmol of triisobutylaluminum was added to the suspension. Thereafter, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 35 ° C. for 70 minutes. As a result, a prepolymerized catalyst containing 5.7 mg of zirconium, 182 mg of aluminum, and 1.5 g of polyethylene per 1 g of silica was obtained. At this time, no adhesion of the polymer to the reactor wall was observed.

[Polymerization] In the polymerization of Example 3, the prepolymerized catalyst prepared above was used in an amount of 0.0 in terms of zirconium atoms.
The same procedure as in Example 3 was carried out except that 05 milligram atoms were used, the MFR was 0.01 g / 10 min or less, and the bulk specific gravity was 0.1.
229 g of ethylene / 1-butene copolymer having 42 g / cm ³ , Mw / Mn of 4.1, an average polymer particle diameter of 580 μm, and a fine powder polymer amount of 100 μm or less of 0.2% by weight. Obtained.

[Brief description of the 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 (56) References JP-A-1-207248 (JP, A) JP-A-3-185005 (JP, A) JP-A-2-218706 (JP, A) JP-A-3-234710 (JP) JP-A-63-89505 (JP, A) JP-A-63-280703 (JP, A) JP-A-5-112611 (JP, A) JP-A-6-510808 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] [A] a transition metal compound represented by the following formula [I]: ML _x ... [I] [In the formula [I], M is a transition metal atom selected from Group IVB, and L is A ligand coordinating to the transition metal atom M, wherein at least one of the ligands L is a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms,
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. [B] An ethylene-based polymer catalyst comprising an organoaluminum oxy compound. 2. A [A] below equation transition metal compound represented by [I]; in ML _x ... [I] [Formula [I], M is a transition metal atom selected from Group IVB, L is A ligand coordinating to the transition metal atom M, wherein at least one of the ligands L is a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms,
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. ] A catalyst for an ethylene polymer , comprising: [B] an organic aluminum oxy compound and [C] an organic aluminum compound. 3. A [A] below equation transition metal compound represented by [I]; in ML _x ... [I] [Formula [I], M is a transition metal atom selected from Group IVB, L is A ligand coordinating to the transition metal atom M, wherein at least one of the ligands L is a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms,
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. [E] an ethylene resin comprising: [B] an organoaluminum oxy compound; and [D] a particulate carrier.
Catalysts for polymer-based polymers . 4. A [A] a transition metal compound represented by the following formula [I]; in ML _x ... [I] [Formula [I], M is a transition metal atom selected from Group IVB, L is A ligand coordinating to the transition metal atom M, wherein at least one of the ligands L is a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms,
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. ] Ethylene to [B] an organoaluminum oxy compound, and [C] an organic aluminum compound, characterized by consisting of [D] particulate carrier
Catalysts for polymer-based polymers . 5. A [A] a transition metal compound represented by the following formula [I]; in ML _x ... [I] [Formula [I], M is a transition metal atom selected from Group IVB, L is A ligand coordinating to the transition metal atom M, wherein at least one of the ligands L is a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms,
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. ] It is obtained by prepolymerizing an olefin on an olefin polymerization catalyst comprising [B] an organoaluminum oxy compound and [D] a particulate carrier.
Prepolymerization catalyst for ethylene polymers . 6. [A] a transition metal compound represented by the following formula [I]: ML _x ... [I] [In the formula [I], M is a transition metal atom selected from Group IVB, and L is A ligand coordinating to the transition metal atom M, wherein at least one of the ligands L is a substituent R ¹ composed of a hydrocarbon group having 1 to 10 carbon atoms,
A cyclopentadienyl group having a substituent R ² (where R ¹ and R ² are different from each other) consisting of 10 to 10 hydrocarbon groups, and the ligand L other than the cyclopentadienyl group has a carbon number of 1 to 12 are a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. ] It is obtained by prepolymerizing an olefin on an olefin polymerization catalyst comprising [B] an organoaluminum oxy compound, [C] an organoaluminum compound, and [D] a particulate carrier.
Prepolymerization catalyst for ethylene polymers . 7. The ethylene according to claim 1, wherein
7. A catalyst for a system polymer or according to any one of claims 5 to 6.
In the presence of ethylene polymer-body prepolymerized catalyst, ethylene, characterized in that the polymerization or copolymerization of olefins
A method for producing a polymer .