JP2901698B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefin using the catalyst. More specifically, the present invention relates to an olefin polymerization catalyst capable of polymerizing an olefin with excellent polymerization activity even when the amount of the organic aluminum oxy compound used is reduced, and a method for polymerizing an olefin using the catalyst. In addition, the present invention can produce a spherical olefin polymer having excellent particle properties such as particle size distribution and bulk specific gravity when employing a slurry polymerization method or a gas phase polymerization method, particularly, a gas phase polymerization method, and more than two kinds. When applied to the copolymerization of olefins, olefin polymerization catalysts capable of producing olefin copolymers having a narrow molecular weight distribution and composition distribution with excellent polymerization activity and a method for polymerizing olefins using this catalyst. Related.

Technical Background of the Invention As a new Ziegler-type olefin polymerization catalyst, a method for producing an ethylene / α-olefin copolymer using a catalyst comprising a zirconium compound and an aluminoxane is disclosed in, for example, JP-A-58-19309, These are described in JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-60-130604 and JP-A-60-260602.

The catalyst formed from the transition metal compound and the aluminoxane proposed in these prior arts has a remarkably superior polymerization activity as compared with a catalyst system formed from a conventionally known transition metal compound and an organoaluminum compound. However, most of the catalyst systems proposed in these are soluble in the reaction system, and often employ a solution polymerization system, which not only limits the production process but also produces a high molecular weight polymer. In such a case, the solution viscosity of the polymerization system was extremely high, and the bulk specific gravity of the polymer obtained by post-treatment of these solution systems was small, and it was difficult to obtain a polymer having excellent particle properties.

On the other hand, using a catalyst in which one or both components of the above-mentioned transition metal compound and aluminoxane are supported on a porous inorganic oxide carrier such as silica, silica / alumina, and alumina, a suspension polymerization system or a gaseous Attempts have been made to carry out olefin polymerization in a phase polymerization system.

For example, JP-A-60-35006, JP-A-60-35007
And JP-A-60-35008 describe that a transition metal compound and an aluminoxane can be supported on silica, silica-alumina, alumina or the like and used as a solid catalyst.

And, JP-A-60-106808 and JP-A-60-10
No. 6809 discloses titanium and / or titanium soluble in a hydrocarbon solvent.
Alternatively, a product obtained by pre-contacting a highly active catalyst containing zirconium with a filler and an organoaluminum compound, and further copolymerizing ethylene or ethylene and an α-olefin in the presence of a polyolefin-compatible filler. Thus, a method for producing a composition comprising a polyethylene polymer and a filler is described.

JP-A-61-31404 discloses that ethylene or ethylene is used in the presence of a mixed catalyst comprising a product obtained by reacting a trialkylaluminum with water in the presence of silicon dioxide or aluminum oxide and water and a transition metal compound. A method for copolymerizing ethylene and an α-olefin is described.

JP-A-61-276805 discloses that a reaction mixture obtained by reacting a trialkylaluminum with a zirconium compound and aluminoxane is further reacted with an inorganic oxide having a surface hydroxyl group such as silica. A method for polymerizing an olefin in the presence of a catalyst consisting of

Further, JP-A-61-108610 and JP-A-61-29
No. 6008 describes a method of polymerizing an olefin in the presence of a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide.

However, even when the olefin is polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system using a solid catalyst component supported on a carrier described in these, the polymerization activity is significantly reduced as compared with the solution polymerization system. However, when the transition metal compound and the aluminoxane are used as the polymerization catalyst, the polymerization activity is not sufficiently high, and there is a problem that the properties of the particles are reduced, such as a decrease in the bulk specific gravity of the produced polymer. Further, these inorganic compounds used as carriers are present as foreign substances in the polymer, and often impair the physical properties and appearance of the product film.

As a method of improving these, JP-A-63-152608 describes that the use of a catalyst component obtained by prepolymerizing an olefin can improve the particle properties such as the bulk specific gravity of the produced polymer.

Also, JP-A-63-280703 discloses that when a catalyst component obtained by prepolymerizing an olefin in the presence of a carrier treated with an organometallic compound is used, a small amount of aluminoxane can be used for excellent polymerization. It is described that an active polymer having good particle properties can be obtained.

However, even when an olefin is polymerized according to the method described in JP-A-63-280703, the polymerization activity per aluminoxane has not yet reached a satisfactory level.

In view of the above points, the present inventors conducted further studies and found that the catalyst was obtained by prepolymerizing an olefin to a catalyst component comprising a carrier, an organoaluminum compound, an organoaluminum oxy compound and a specific transition metal compound. The present inventors have found that a polymer having a sufficiently high polymerization activity and good particle properties can be obtained by using the above-mentioned catalyst component and, if necessary, an organic aluminum compound in combination, thereby completing the present invention.

Object of the Invention The present invention has been made in view of the prior art as described above, even when the amount of the organoaluminum oxy compound is small, for example, when used for two or more olefins, the molecular weight distribution and An object of the present invention is to provide an olefin polymerization catalyst from which an olefin polymer having a narrow composition distribution and excellent particle properties can be obtained, and to provide an olefin polymerization method using a catalyst having such good properties. I have.

SUMMARY OF THE INVENTION The first olefin polymerization catalyst according to the present invention comprises: [A] a carrier, [B] an organoaluminum compound, [C] an organoaluminum oxy compound, and [D] an n-propyl group, n-butyl. And a transition metal compound selected from zirconium and hafnium having a cyclopentadienyl group having a substituent having n-hexyl group or n-hexyl group as a ligand. It is characterized by becoming.

Further, the second olefin polymerization catalyst according to the present invention provides an olefin prepolymer formed by prepolymerizing an olefin with a catalyst component formed from the above components [A], [B], [C], and [D]. It is characterized by comprising a polymerization catalyst and [E] an organoaluminum compound.

Further, the olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst as described above.

When olefin polymerization is carried out in the presence of the olefin polymerization catalyst according to the present invention, the particle properties are excellent, the molecular weight distribution is narrow, and the molecular weight distribution and the composition distribution are narrow particularly when applied to copolymerization of two or more olefins. Ethylene copolymers can be obtained with high polymerization activity in olefin copolymers and the like.

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

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. Sometimes used in

First, the first olefin polymerization catalyst will be described.

[A] As the carrier, a finely divided inorganic carrier or a finely divided organic carrier having an average particle size of usually 10 to 300 µm, preferably 20 to 200 µm is used.

As the particulate inorganic carrier as described above, a porous oxide is preferable, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
_{TiO 2, B 2 O 3,} CaO, ZnO, BaO, 1 or such as ThO _2, or 2
Mixtures of more species, for example, _{SiO 2 -MgO, SiO 2 -Al 2} O 3, Si
_{O 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO
Are used. Among them, a carrier containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component is preferable.

In addition, a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaC
O ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
Carbonate, sulfate, and oxide components such as (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O may be contained.

Such porous inorganic carrier is property by its type and production method different, as the support according to the present invention, a specific surface area of 50~1000m ² / g, especially 100~700m ² / g, a pore volume of 0 .
Is preferably a 3~2.5cm ² / g, optionally 150-1000
C., preferably at 200 to 800.degree.

In addition, as a particulate organic carrier, the particle size is 10 ~ 300μ
m, for example, a polymer or copolymer mainly composed of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane And a polymer or copolymer containing styrene as a main component.

Next, the organoaluminum compound [B] used in the present invention will be described in detail.

As this [B] organoaluminum compound, for example, R _n ⁶ AlX _3-n (where R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3 Can be exemplified.

In the above formula, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. Group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum,
Trialkyl aluminums such as triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum and tri 2-ethylhexyl aluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide.

Alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminium sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

[B] As an organoaluminum compound, R ⁶ _n AlY
_3-n (wherein R ⁶ is the same as above, Y is -OR ⁷ group, -OSiR
⁸ ₃ group, -OAlR ⁹ ₂ group, -NR ¹⁰ ₂ group, -SiR ¹¹ ₃ group or Wherein n is 1-2, R ⁷ , R ⁸ , R ⁹ and R ¹³ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹⁰ is hydrogen,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ¹¹ and R ¹² are a methyl group, an ethyl group, and the like. ) Can also be used.

As such an organoaluminum compound, specifically, the following compounds are used.

_{^{(I) R 6 n Al (}} OR 7) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R 6 n Al}} (OSiR 8 3) 3-n Et 2 Al (OSiMe ₃₎ (such as _{iso-Bu) 2 Al (OSiMe} 3) (iso-Bu) 2 Al (OSiEt 3), (iii) R 6 n Al (OAlR 9 2) 3-n Et 2 AlOAlEt 2 (iso-Bu) ₂ AlOAl (iso-Bu) ₂ etc., (iV) R ⁶ _n Al (NR ¹⁰ ₂ ) _3-n Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHEt Et ₂ AlN (Me ₃ Si) ₂ (iso-Bu) ₂ AlN (Me ₃ Si) ₂ etc., (V) R ⁶ _n Al (SiR ¹¹ ₃ ) _3-n (iso-Bu) ₂ AlSiMe ₃ etc. Organoaluminum compounds mentioned above, R ⁶ ₃ A
_{^{l, R 6 n Al (OR}} 7) 3-n, can be mentioned organoaluminum compounds represented by ^{_{R 6 n Al (OAlR 9 2}} ) 3-n Suitable examples, in particular R ⁶ is located at isoalkyl group , N = 2 are preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

Next, the [C] organoaluminum oxy compound used in the present invention will be described.

The organoaluminum oxy compound may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound found by the present inventors.

The aluminoxane as described above 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 A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension 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 organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used when producing the solution of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, and trisec-. Trialkyl aluminum such as butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide ,
Dialkyl aluminum halides such as diisobutyl aluminum chloride, diethyl aluminum hydride, dialkyl aluminum hydrides such as diisobutyl aluminum hydride, dimethyl aluminum methoxide, dialkyl aluminum alkoxides such as diethyl aluminum ethoxide, and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. Can be

Of these, trialkyl aluminum is particularly preferred.

Further, as the organoaluminum compound represented by the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z (x, y, z are each a positive number, the z ≧ 2x) represented by Isoprenyl aluminum can also be used.

The above-mentioned organoaluminum compounds are used alone or in combination.

Solvents used in the solution of aluminoxane include:
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, cyclopentane, sichlorohexane, cyclooctane, methylcyclopentane, etc. Petroleum fractions such as alicyclic hydrocarbons, gasoline, kerosene and light oil, or hydrocarbon solvents such as the above aromatic hydrocarbons, aliphatic hydrocarbons and halides of alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. No. 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 has an Al component soluble in benzene at 60 ° C. of not more than 10%, preferably not more than 5%, particularly preferably not more than 2% in terms of Al atom. Insoluble or poorly soluble.

The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligram atoms of Al in 100 ml of benzene, mixing at 60 ° C. with stirring for 6 hours, and applying a jacket. Using a G-5 glass filter, filtration was carried out while heating at 60 ° C., and the solid part separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and then the total amount of Al atoms present in the total filtrate was measured. It is determined by measuring the abundance (x mmol) (x%).

Analysis of the benzene-insoluble organoaluminum oxy compound as described above by infrared spectroscopy (IR) shows that
1220cm absorbance at around ^-1 (D _1220), the ratio of the absorbance at around _{^{1260cm -1 (D 1260) (D}} 1260 / D 1220) , the
0.09 or less, preferably 0.08 or less, particularly preferably 0.04 to 0.07
Is desirably within the range.

The infrared spectroscopic analysis of the organic aluminum oxy compound is performed as follows.

First, in a nitrogen box, the organoaluminum oxy compound and Nujol are ground in an agate pestle to form a paste.

Next, the paste-like sample is sandwiched between KBr plates, and an IR spectrum is measured by IR-810 manufactured by JASCO Corporation under a nitrogen atmosphere.

Of the organoaluminum oxy compound used in the present invention
FIG. 1 shows the IR spectrum.

From the IR spectrum thus obtained, D ₁₂₆₀ / D
_The value of D ₁₂₆₀ / D ₁₂₂₀ is obtained as follows.

(B) 1280cm ^-1 signed a maximum point in the vicinity of and around 1240cm ^-1,
This is referred to as base line L _1.

(Ii) the transmittance of the absorption minimum point of 1260 cm ^-1 and (T%), the wave number of minimum point axis a vertical line with respect to (horizontal axis), the transmittance of the intersection of the perpendicular line and the baseline L ₁ ( T ₀ %) and read the absorbance around ₁₂₆₀ cm ⁻¹ (D ₁₂₆₀ = log T ₀ / T).

(C) Similarly bear maximum point in the vicinity of 1280 cm ^-1 and near 1180 cm ^-1, which is the baseline L _2.

(D) Transmittance at the minimum absorption point near 1220 cm ^-1 (T '%)
From this minimum point, a perpendicular is drawn to the wave number axis (horizontal axis), and the transmittance (T ′) at the intersection of this perpendicular and the baseline L ₂ is drawn.
₀ %) and absorbance near ₁₂₂₀ cm ^-1 (D ₁₂₂₀ = log)
T ′ ₀ / T ′) is calculated.

(E) D ₁₂₆₀ / D ₁₂₂₀ is calculated from these values.

FIG. 2 shows the IR spectrum of a conventionally known benzene-soluble organoaluminum oxy compound. As can be seen from FIG. 2, the benzene-soluble organoaluminum oxy compound has a D ₁₂₆₀ / D ₁₂₂₀ value of about 0.10 to 0.13.
The benzene-insoluble organoaluminum oxy compound used in the present invention is clearly different from the conventionally known benzene-soluble organoaluminum oxy compound in the D ₁₂₆₀ / D ₁₂₂₀ value.

The benzene-insoluble organoaluminum oxy compound as described above is [Wherein, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms].

In the above alkyloxyaluminum unit, R ¹
Is specifically exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl, cyclooctyl, etc. it can. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

This benzene-insoluble organoaluminum oxy compound is In addition to the alkyloxyaluminum unit represented by [Wherein R ¹ is the same as above, and R ² has 1 to 12 carbon atoms.]
A hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms and 6 carbon atoms
-20 aryloxy, hydroxyl, halogen or hydrogen, and R ¹ and R ² represent different groups from each other]. In that case, the alkyloxyaluminum unit Is preferably an organoaluminum oxy compound having an alkyloxyaluminum unit containing at least 30 mol%, preferably at least 50 mol%, particularly preferably at least 70 mol%.

Next, a method for producing the benzene-insoluble organic aluminum oxy compound as described above will be specifically described.

This benzene-insoluble organoaluminum oxy compound is obtained by contacting a solution of aluminoxane with water or an active hydrogen-containing compound.

Examples of the active hydrogen-containing compound include alcohols such as methanol, ethanol, n-propanol and isopropanol; diols such as ethylene glycol and hydroquinone; and organic acids such as acetic acid and propionic acid. Of these, alcohols and diols are preferred, and alcohols are particularly preferred.

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

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out in a solvent such as a hydrocarbon solvent. Examples of the solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, cyclopentane and cyclohexane. , Cyclooctane, alicyclic hydrocarbons such as methylcyclohexane, hydrocarbon solvents such as gasoline, kerosene, petroleum fractions such as light oil, and the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons And halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran. Among these media, aromatic hydrocarbons are particularly preferred.

Water or an active hydrogen-containing compound used in the catalytic reaction is 0.1 to 0.1% of Al atoms in the solution of aluminoxane.
It is used in an amount of 5 mol, preferably 0.2 to 3 mol. The concentration in the reaction system is usually 1 ×
The concentration is preferably in the range of 10 ^{-3 to} 5 gram atoms / preferably 1 × 10 ^{-2 to} 3 gram atoms /, and the concentration of water in the reaction system is usually 2 × 10 ^{-4 to} 5 mol / preferably. 2x
The concentration is preferably 10 ^{-3 to} 3 mol /.

The contact of the aluminoxane solution with water or an active hydrogen-containing compound may be carried out specifically as follows.

(1) A method in which an aluminoxane solution is brought into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound.

(2) A method of contacting aluminoxane with steam by blowing steam of water or an active hydrogen-containing compound into a solution of aluminoxane.

(3) A method in which an aluminoxane solution is brought into direct contact with water, ice or an active hydrogen-containing compound.

(4) Aluminoxane is mixed with a solution of an aluminoxane and a hydrocarbon suspension of a compound containing adsorbed water or a compound of water of crystallization or a hydrocarbon suspension of a compound on which an active hydrogen-containing compound is adsorbed. And contacting the water with the adsorbed water or water of crystallization.

The aluminoxane solution as described above may contain other components as long as the reaction between the aluminoxane and water or the 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 at 0 to 1 ° C.
The reaction is carried out at a temperature of 20 ° C, more preferably 20 to 100 ° C.
The reaction time varies greatly depending on the reaction temperature,
Usually, it is about 0.5 to 300 hours, preferably about 1 to 150 hours.

The benzene-insoluble organoaluminum oxy compound can also be obtained directly by bringing the above-mentioned organoaluminum into contact with water. In this case, water is used in such an amount that the amount of the organic aluminum atoms dissolved in the reaction system is 20% or less based on all the organic aluminum atoms.

Water to be brought into contact with the organoaluminum compound can be used by dissolving or dispersing it in a hydrocarbon solvent such as benzene, toluene, and hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of steam or ice. . 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. Examples of the hydrocarbon solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclohexane, petroleum fractions such as gasoline, kerosene and light oil, and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether tetrahydrofuran can be used. Of these media, aromatic hydrocarbons are particularly preferred.

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

The contact between the organoaluminum compound and water may be specifically performed as follows.

(1) A method in which a hydrocarbon solution of organoaluminum 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 of mixing a hydrocarbon solution of an organoaluminum and a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization and bringing the organic aluminum 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 organoaluminum.

The organic aluminum hydrocarbon solution as described above may contain other components as long as the reaction between the organic aluminum and water is not adversely affected.

The contact reaction between the organoaluminum compound and water is usually
100-150 ° C, preferably -70-100 ° C, more preferably -5
It is performed at a temperature of 0 to 80 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually about 1 to 200 hours, preferably about 2 to 100 hours.

Next, the [D] transition metal compound belonging to Group IVB of the Periodic Table IV having a substituted cyclopentadienyl group having a hydrocarbon group having 3 to 10 carbon atoms as a substituent according to the present invention will be described.

A transition metal compound containing a ligand having such a substituted cyclopentadienyl skeleton has the formula ML _x (where M is zirconium or hafnium;
Is a ligand that coordinates to a transition metal, and at least one L is a ligand consisting of a substituted cyclopentadienyl group having an n-propyl group, an n-butyl group, or an n-hexyl group as a substituent. L other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, halogen or hydrogen, and x is a valence of a transition metal. ).

Examples of the substituted cyclopentadienyl group having an n-propyl group, an n-butyl group, or an n-hexyl group as a substituent include, for example, an n-propylcyclopentadienyl group, n
Mono-substituted cyclopentadienyl group such as -butylcyclopentadienyl group, n-hexylcyclopentadienyl group, methyl-n-propylcyclopentadienyl group, n
Examples thereof include a disubstituted cyclopentadienyl group such as -butyl-methylcyclopentadienyl group and a trisubstituted cyclopentadienyl group such as n-butyldimethylcyclopentadienyl group.

The ligand other than the ligand having the substituted cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group.Examples of the aralkyl group include a benzyl group, A neofil group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Hereinafter, specific examples of the transition metal compound containing a ligand having a substituted cycloalkadienyl skeleton substituted with a specific hydrocarbon group as described above, wherein M is zirconium, will be given.

Bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) )
Zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl)
Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride, bis (n-butyl) Cyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, Bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride Enyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride.

In addition, a transition metal compound in which zirconium metal is replaced with hafnium metal in the zirconium compound as described above can also be used.

As the [E] organoaluminum compound used as required in the present invention, the same compounds as the above [B] organoaluminum compounds can be exemplified.

The first olefin polymerization catalyst according to the present invention is formed by prepolymerizing an olefin in the presence of the catalyst components [A], [B], [C] and [D].

Prior to the prepolymerization, the catalyst component [D], or the catalyst components [C] and [D], or the catalyst components [B], [C] and [D] are preliminarily supported on the carrier [A]. Alternatively, the respective catalyst components may be mixed and brought into contact at the time of preliminary polymerization. The order of the contact operation is preferably [A] → [B] → [C] → [D].

This prepolymerization is carried out by polymerizing 0.05 to 100 g, preferably 0.1 to 50 g, more preferably 0.2 to 30 g of olefin per 1 g of the carrier [A]. Examples of the olefin include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, and among them, ethylene is preferable.

This prepolymerization is carried out without solvent or in an inert hydrocarbon solvent. The amount of the [A] organoaluminum compound per 1 g of the [A] carrier during the prepolymerization is 0.2 to 20 mmol, preferably 0.5 to 10 mmol, and the amount of the [C] organoaluminum oxy compound is based on aluminum atoms. It is 1 to 50 mg atoms, preferably 2 to 20 mg atoms, and the amount of the [D] transition metal compound is 0.02 to 2 mg atoms, preferably 0.05 to 1 mg atom, in terms of transition metal atoms. Range.

The atomic ratio (Al _B / Al _C ) between the aluminum atom (Al _B ) of the component [ _B ] and the aluminum atom (Al _C ) of the component [C]
Is usually 0.02 to 3, preferably 0.05 to 1.5, and the atomic ratio (Al _C / M) of the aluminum atom (Al _C ) of the component [ _C ] to the transition metal atom (M) of the component [D] is usually 5 to 5. 250, preferably in the range of 10 to 150.

Further, when the prepolymerization is carried out in an inert hydrocarbon solvent, the concentration of the component [D] in this solvent is usually 0.1 to 10 mg atom /, preferably 0.5 to 5 mg atom / in terms of transition metal atom concentration. Range.

In addition, the temperature of the polymerization system in the case of performing such preliminary polymerization is in the range of -20 to 70C, preferably -10 to 60C, and more preferably 0 to 50C.

Such a prepolymerization can be either a batch type or a continuous type, and can be performed under any of reduced pressure, normal pressure and pressurized conditions. In such a prepolymerization, a molecular weight regulator such as hydrogen may be used. However, even when such a molecular weight regulator is used, the intrinsic viscosity [η] measured in decalin at least at 135 ° C. Is preferably 0.2 dl / g or more, preferably 0.5 to 10 dl / g.

In the prepolymerized catalyst thus obtained, [A] component [D] per 1 g of the carrier is 0.1 to 50 milligrams, preferably 0.3 to 50 milligrams as measured by the amount of transition metal atoms contained in this component. 30 mg, more preferably 0.5 to 20 mg, and the atomic ratio of Al atoms derived from components [B] and [C] to the amount of transition metal atoms in component [D] (Al / transition metal atom) Is 5-200, preferably 10-15
0, more preferably in the range of 15 to 100.

The olefin polymerization catalyst according to the present invention is obtained by prepolymerizing an olefin with the catalyst component consisting of the components [A], [B], [C] and [D] in any of the first and second olefin polymerization catalysts. When the olefin prepolymerization catalyst is obtained by the reaction, components such as an electron donor may be contained in addition to these components. Such electron donors include:
Carboxylic acids, esters, ethers, ketones, aldehydes, alcohols, phenols, acid amides, metal atoms such as aluminum and silicon, oxygen-containing compounds such as -OC bond-containing compounds, nitriles, amines , Phosphines and the like. This electron donor is usually 1 mol or less or 1 g atom or less, preferably 0.1 to 0.6 mol or 0.1 to 0.6 g, per 1 g of transition metal atom in the transition metal compound contained in the prepolymerization catalyst. It is contained in the catalyst component in atomic amount.

INDUSTRIAL APPLICABILITY The present invention is effective for producing an olefin polymer, particularly an ethylene polymer and a copolymer of ethylene and an α-olefin. Examples of olefins that can be used in the olefin polymerization method of the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene,
-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 and the like can be mentioned.

In the process of the present invention, the polymerization of the olefin is usually carried out in a gas phase or a liquid phase such as a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

Specific examples of such an inert hydrocarbon include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane; methylcyclopentane; cyclohexane; Examples thereof include alicyclic hydrocarbons such as octane, aromatic hydrocarbons such as benzene, toluene, and xylene, and petroleum fractions such as gasoline, kerosene, and light oil. Of these, aliphatic hydrocarbons, alicyclic hydrocarbons, and petroleum fractions are preferred.

When the polymerization of the olefin according to the present invention is carried out by a slurry polymerization method, the polymerization temperature is usually -50 to 100C, preferably 0 to 90C.

When the polymerization of the olefin according to the present invention is carried out by a gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C.
Range.

When the polymerization of the olefin according to the present invention is carried out by a gas phase polymerization method or a slurry polymerization method, the amount of the transition metal compound to be used is usually represented by the concentration of the transition metal atom in the polymerization reaction system, and is usually 10%.
^-8 to 10 ^-2 gram atoms / preferably, 10 ^-7 to 10 ^-3 gram atoms /.

The [E] organoaluminum compound used as required has an atomic ratio of Al to transition metal atom (Al _E / transition metal atom) of 5 to 300, preferably 10 to 200, more preferably 15 to 300.
It is in the range of ~ 150.

The polymerization pressure in this case is usually under normal pressure to 100 kg / cm ² , preferably ² to 50 kg / cm ² .

The polymerization can be carried out by any of batch, semi-continuous and continuous methods.

Further, the polymerization can be performed in two or more stages having different reaction conditions.

Effect of the Invention When the olefin polymerization catalyst according to the present invention is used for the polymerization of olefin, particularly, ethylene or ethylene and α
-When the olefin is polymerized by a slurry polymerization method or a gas phase polymerization method, the polymer does not adhere to the reactor and has excellent particle properties,
Moreover, when applied to copolymerization of two or more olefins, an olefin copolymer having a narrow molecular weight distribution and composition distribution can be obtained.

Further, according to the olefin polymerization method of the present invention performed using such an olefin polymerization catalyst, the molecular weight distribution is narrow as described above, and an olefin polymer excellent in particle properties can be obtained. Olefins can be polymerized. Further, even when the amount of the organic aluminum oxy compound used is reduced, a sufficiently high polymerization activity is exhibited.

Examples Examples of the present invention will be shown below, but the present invention is not limited to these examples.

First, in the following examples, methods for measuring and evaluating polymer physical properties will be described.

a) Amount of n-decane-soluble component About 3 g of the polymer was added to 450 ml of n-decane, and the solution was heated at 145 ° C.
After the temperature was raised to dissolve the polymer, the solution was cooled to 23 ° C., and then the solution was filtered to remove the n-decane-insoluble portion, and the n-decane-soluble portion was separated and weighed. , N
-The amount of decane soluble components was determined.

The smaller the amount of the n-decane-soluble component, the narrower the composition distribution of the polymer.

b) Use a strand of 120 when measuring the density MFR (190 ° C, 2.16 kg load).
After heat treatment at 1 ° C. for 1 hour and then cooling to room temperature over 1 hour, the density was measured with a density gradient tube.

c) Melting point: Perkin-Elmer DSC-7 type differential thermal analyzer
Differential thermal analysis was performed at 10 ° C./min, and the temperature at the maximum endothermic peak position was defined as the melting point.

Example 1 [Preparation of Preliminary Polymerization Catalyst] In a 400 ml glass flask sufficiently purged with nitrogen, 1.61 g of silica (F-948, manufactured by Fuji Devison Co., Ltd.) calcined at 700 ° C. for 6 hours and 20 ml of decane were added. Suspended. 4.02 ml of a decane solution of triisobutylaluminum (Al: 1 gram atom /) was added to this suspension, and 35
Stirred for minutes.

Next, 18.7 ml of an organoaluminum oxy compound (resisting in toluene after removing toluene from a methylaluminoxane toluene solution manufactured by Schering Co .; Al: 1.79 g atom /) was added to the suspension, and further added. Stirred at room temperature for 30 minutes.

Thereafter, 24.8 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0108 gram atom /) was added to the suspension, and the mixture was stirred for 20 minutes. (Normal pressure)
Was preliminarily polymerized at 30 ° C. for 4 hours.

After this prepolymerization, the solvent was removed by decantation, and then hot washing (60 ° C.) three times with 150 ml of hexane,
Further, washing (room temperature) was performed three times with 150 ml of hexane. By this operation, zirconium was added to 1 g of silica at 8.
A prepolymerized catalyst containing 2 mg, 200 mg of aluminum and 9.1 g of polyethylene was obtained.

[Polymerization] 150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 and sufficiently purged with nitrogen, and dried under reduced pressure at 90 ° C for 1 hour. Then, the pressure was returned to normal pressure by introducing ethylene gas, and the temperature in the autoclave was raised to 80.
° C. Then, a prepolymerized catalyst of 0.015 mg atom in terms of zirconium was charged into the autoclave, and 50 Nml of hydrogen and ethylene were immediately introduced, and the polymerization was started at a total pressure of 8 kg / cm ² -G. As a result, the temperature in the autoclave immediately rose to 85 ° C.

After that, only ethylene gas was replenished, and the total pressure was 8 kg / cm ²
-G, polymerization was carried out at 85 ° 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 and then dried under reduced pressure at 80 ° C. overnight. As a result, 285 g of a spherical polymer having a bulk specific gravity of 0.40 kg / cm ³ , an MFR measured at 190 ° C. under a load of 2.16 kg of 0.53 g / 10 min, and an average particle size of 370 μm was obtained. Was done.

Comparative Example 1 [Preparation of Preliminary Polymerization Catalyst] 2.30 g of calcined silica (F-948, manufactured by Fuji Devison Co., Ltd.) at 700 ° C. for 6 hours and 40 ml of decane were placed in a 400 ml glass flask sufficiently purged with nitrogen. Suspended. To this suspension was added 10.6 ml of a triisobutylaluminum decane solution (Al: 1 gram atom /),
Stirred for minutes.

Next, 24.5 ml of an organoaluminum oxy compound (resisting in toluene after removing toluene from a methylaluminoxane toluene solution manufactured by Schering Co .; Al: 1.79 g atom /) was added to the suspension, and further added. Stirred at room temperature for 30 minutes.

Thereafter, a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr: 0.04
After adding 8.85 ml of gram atom /) and stirring for 30 minutes, 42 ml of decane was further added, and prepolymerization was performed at 30 ° C. for 4 hours while continuously introducing ethylene gas (normal pressure).

The subsequent operation was performed in the same manner as in Example 1, to obtain a prepolymerized catalyst containing 7.3 mg of zirconium, 254 mg of aluminum, and 7.6 g of polyethylene based on 1 g of silica.

[Polymerization] The pre-polymerized catalyst of Example 1 was used in an amount of 0.
Using 01 mg atom and polymerizing in the same manner as in Example 1 except that 100 Nml of hydrogen was introduced, the bulk specific gravity was 0.1%.
Was 40 g / cm ^3, MFR is 0.33 g / 10 min, an average particle size of 24
81 g of a spherical polymer having a diameter of 0 μm was obtained.

Example 2 [Preparation of Preliminary Polymerization Catalyst] In a 400 ml glass flask sufficiently purged with nitrogen, 1.05 g of silica (F-948, manufactured by Fuji Devison Co., Ltd.) calcined at 700 ° C. for 6 hours and 20 ml of decane were added. Suspended. 2.62 ml of a triisobutylaluminum decane solution (Al: 1 gram atom /) was added to this suspension,
Stirred for minutes.

Next, 4.87 ml of the organic aluminum oxy compound was added to the suspension in the same manner as in Example 1, and the mixture was further stirred at room temperature for 35 minutes.

Thereafter, 16.2 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0108 gram atom /) was added to the suspension, and the mixture was stirred for 30 minutes. Preliminary polymerization was performed at 30 ° C. for 4 hours while continuously introducing gas (normal pressure).

After this pre-polymerization, the solvent was removed by decantation, and then hot washing (60 ° C.) three times with 200 ml of hexane,
Further, washing (room temperature) was performed three times with 200 ml of hexane. With this operation, zirconium is added to 1 g of silica 9.
A prepolymerized catalyst containing 3 mg, 152 mg of aluminum and 18 g of polyethylene was obtained.

[Polymerization] 150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 and sufficiently purged with nitrogen, and dried under reduced pressure at 90 ° C for 1 hour. Then, ethylene and 1
-Butene mixed gas (1-butene content 6.9 mol%)
To return to normal pressure and reduce the temperature in the autoclave to 75
° C. Next, a prepolymerized catalyst of 0.005 mg atom in terms of zirconium and triisobutylaluminum 0.5
The mixture was charged into the autoclave, and 50 Nml of hydrogen and a mixed gas of ethylene and 1-butene (the content of 1-butene was 6.9 mol%) were immediately introduced, and the total pressure was increased to 8 kg / cm. ^The polymerization was started as ^2- G. As a result, the temperature in the autoclave immediately rose to 85 ° C.

After that, only the mixed gas was supplied, and the total pressure was 8 kg / cm ²
-G, polymerization was carried out at 85 ° 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 and then dried under reduced pressure at 80 ° C. overnight. As a result, a bulk density 0.38 g / cm ^3, an MFR of 2.45 g / 10 min as measured under a load of 2.16kg at 190 ° C., density 0.9
10 g / cm ³ , a melting point of 109.4 ° C. measured by a differential calorimeter (DSC), a ratio of decane-soluble components at 23 ° C. of 1.45% by weight, and an average particle diameter of 370 μm. 147 g of a combined product were obtained.

Example 3 In the polymerization of Example 2, a mixed gas of ethylene and 1-butene having a 1-butene content of 6.5 mol% was used, and the amount of triisobutylaluminum mixed with the prepolymerization catalyst was reduced.
The same procedures as in Example 2 were carried out except that the amount was 0.25 mmol, the bulk specific gravity was 0.37 g / cm ³ , the MFR was 4.82 g / 10 min, the density was 0.916 g / cm ³ , and the differential calorimeter was used. (DSC)
The melting point measured in step is 111.6 ° C, the ratio of the decane-soluble component at 23 ° C is 0.67% by weight, and the average particle size is 340μ.
Thus, 92 g of a spherical polymer having a molecular weight of m was obtained.

Example 4 In the polymerization of Example 2, ethylene was used in place of the mixed gas of ethylene and 1-butene, the amount of the prepolymerized catalyst was 0.0075 mg atom in terms of zirconium, and the amount of triisobutylaluminum mixed with the prepolymerized catalyst was used. To 0.
Example 2 except that the polymerization temperature was 90 ° C. and 19 mmol.
As a result, the bulk specific gravity is 0.44 g / cm ³ and the MFR is
It was 0.42 g / 10 minutes, and 211 g of a spherical polymer having an average particle size of 380 μm was obtained.

[Brief description of the drawings]

FIG. 1 shows the benzene-insoluble aluminum oxy compound.
FIG. 2 shows the IR spectrum of the benzene-soluble aluminum oxy compound.
It is an IR spectrum.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-89505 (JP, A) JP-A-63-260903 (JP, A) JP-A-1-315407 (JP, A) JP-A-1- 210404 (JP, A) JP-A-63-152608 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (4)

(57) [Claims] 1. A carrier, [B] an organoaluminum compound, [C] an organoaluminum oxy compound, and [D] a cyclopentadiene having an n-propyl, n-butyl or n-hexyl group as a substituent. An olefin polymerization catalyst formed by prepolymerizing an olefin with a catalyst component comprising a compound of a transition metal selected from zirconium and hafnium having an enyl group as a ligand. 2. [A] a carrier, [B] an organoaluminum compound, [C] an organoaluminum oxy compound, and [D] a cyclopentadiene having an n-propyl, n-butyl or n-hexyl group as a substituent. An olefin prepolymerization catalyst formed by prepolymerizing an olefin with a catalyst component comprising a compound of a transition metal selected from zirconium and hafnium having an enyl group as a ligand; and [E] an organoaluminum compound. A catalyst for olefin polymerization characterized by the following. 3. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1. 4. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 2.