JP2741890B2 - Olefin polymerization catalyst and olefin polymerization method using the catalyst - Google Patents

Description

Description: TECHNICAL FIELD 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 an olefin polymer having excellent polymerization activity and a large molecular weight. The present invention relates to a novel catalyst for olefin polymerization which can be obtained and a method for polymerizing olefin using the catalyst.

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Conventionally, as a catalyst for producing an α-olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and organoaluminum or vanadium has been used. Vanadium-based catalysts comprising a compound and an organoaluminum compound are known.

These organoaluminum compounds were themselves liquid or soluble in a hydrocarbon solvent even if they were solid.

On the other hand, 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 has been recently proposed.

For example, JP-A-58-19309 discloses that the following formula (cyclopentadienyl) ₂ MeRHal [where R is cyclopentadienyl, C ₁ -C ₆ alkyl or halogen, and Me is a transition metal Yes, Hal is halogen]
And a transition metal-containing compound represented by the following formula: Al ₂ OR ₄ (Al (R) —O) _n [where R is methyl or ethyl, and n is 4 to 20]
Or a linear aluminoxane represented by the following formula: In the presence of a catalyst comprising a cyclic aluminoxane represented by the formula: wherein R and n are the same as defined above, one or more of ethylene and a C _{3 to} C ₁₂ α-olefin may be used. A method for producing an ethylene / α-olefin copolymer which is polymerized at a temperature of −50 ° C. to 200 ° C. is described. The publication teaches that to control the density of the resulting polyethylene, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat longer chain α-olefins or mixtures. I have.

JP-A-59-95292 discloses the following formula: [Where n is 2 to 40, R is C _{1 to} C ₆ ] and a linear aluminoxane represented by the following formula: [Wherein the definitions of n and R are the same as described above], the invention relating to a method for producing a cyclic aluminoxane represented by the formula: The publication discloses that, for example, when methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method are mixed and olefin is polymerized, 1 g of transition metal and It is stated that over 25 million g of polyethylene are obtained per hour.

JP-A-60-35005 discloses the following formula: Wherein R ¹ is C ₁ -C ₁₀ alkyl and R ⁰ is R ¹ or is bonded to and represents —O—. The aluminoxane compound represented by the formula A method is disclosed for producing a olefin polymerization catalyst by chlorinating the reaction product and treating it with a compound of Ti, V, Zr or Cr. And in the publication, it is described as being particularly suitable for the copolymerization of a mixture of the catalyst and α- olefin of ethylene and C ₃ -C _12.

JP-A-60-35006 discloses, as a catalyst system for producing a reactor blend polymer, mono-, di- or tri-cyclopentadienyl of two or more different transition metals or a derivative (a) thereof and alumino. Combinations with xane (b) are disclosed. In Example 1 of the publication, ethylene and propylene were polymerized using a catalyst composed of bis (pentamethylcyclopentadienyl) zirconium dimethyl and aluminoxane to obtain a number average molecular weight of 15,300,
It is disclosed that a polyethylene having a weight average molecular weight of 36,400 and a propylene component of 3.4% can be obtained. In Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dichloride, and a catalyst comprising bis (methylcyclopentadienyl) zirconium dichloride and aluminoxane. , A toluene-soluble portion containing a propylene component having a number average molecular weight of 2,200, a weight average molecular weight of 11,900 and 30 mol%, a number average molecular weight of 3,000, and a weight average molecular weight of 7,4.
A blend of polyethylene and an ethylene-propylene copolymer containing a propylene component having a number-average molecular weight of 2,000, a weight-average molecular weight of 8,300 and a 7.1-mol% consisting of a toluene-insoluble portion containing 00 and 4.8% of a propylene component is obtained. Similarly, in Example 3, the molecular weight distribution (w / n) was 4.
A blend of LLDPE and an ethylene-propylene copolymer comprising 57 and a soluble portion of 20.6 mol% of the propylene component and a molecular weight distribution of 3.04 and an insoluble portion of 2.9 mol% of the propylene component is described.

JP-A-60-35007 discloses ethylene alone or a mixture of ethylene and an α-olefin having 3 or more carbon atoms with a metallocene and a compound represented by the following formula: [Where R is an alkyl group having 1 to 5 carbon atoms, and n is 1
Or an aluminoxane represented by the following formula: R (R-Al-O) _n AlR ₂ wherein R is an alkyl group having 1 to 5 carbon atoms, and n is defined as The same applies to the above], and a method of polymerizing in the presence of a catalyst system containing a linear aluminoxane represented by the formula: According to the publication, the polymer thus obtained has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.

The JP 60-35008 discloses, by using a catalyst system comprising at least two metallocenes and aluminoxane, and α- olefin polyethylene or ethylene and C ₃ -C ₁₀ having a width broader molecular weight distribution Is described as being produced. The publication describes that the copolymer has a molecular weight distribution (w / n) of 2 to 50.

JP-A-60-260602 and JP-A-60-130604 disclose a method of polymerizing an olefin using a catalyst formed from a mixed organoaluminum compound comprising a transition metal compound, an aluminoxane and an organoaluminum compound. And that the addition of an organoaluminum compound improves the polymerization activity per unit transition metal.

Further, JP-A-62-36390 teaches that an aluminoxane can be obtained by reacting an organoaluminum compound with an iron compound containing water of crystallization. The gazette teaches that aluminoxane can be obtained by reacting an organoaluminum compound with a compound containing water of crystallization selected from the group consisting of a magnesium compound, a nickel compound and a lanthanide compound. Kaisho
JP-A-63-56507 and JP-A-63-56508 use a high-speed, high-breaking-force induction impeller or ultrasonic waves.
It is taught that aluminoxane can be obtained by directly reacting water and an organoaluminum compound in an inert hydrocarbon solvent.

When an aluminoxane compound is used as one component of the catalyst in producing the α-olefin (co) polymer in this way, the α-olefin (co) polymer having excellent polymerization activity and a narrow molecular weight distribution and composition distribution can be obtained. Can be manufactured.

The aluminoxane compounds used in the conventionally known olefin polymerization are all recovered in a state of being soluble in benzene or toluene, and their molecular weights are measured by dissolving in benzene and measuring by a freezing point depression method. Was. The structure of the aluminoxane has also been determined by dissolving it in benzene and measuring the freezing point.

However, when an α-olefin is polymerized in the presence of a ligand having a cycloalkadienyl skeleton such as a cyclopentadienyl group and a catalyst comprising aluminoxane soluble in benzene and toluene, the molecular weight of the resulting polymer is reduced. In order to increase the molecular weight, the polymer had to be polymerized at a low temperature.

The present inventors have conducted further intensive studies in view of the above points, and found that a coordination having a cycloalkadienyl skeleton and an organoaluminum oxy compound which was insoluble or hardly soluble in benzene and toluene, and which had never been known before. The inventors have found that a combination with a transition metal compound containing no metal has excellent catalytic activity for olefin polymerization and produces a polymer having a large molecular weight, thereby completing the present invention.

An object of the present invention is to use an organoaluminum oxy compound, which was hitherto unknown at all, as a component of a catalyst, to have excellent catalytic activity and to obtain an olefin polymer having a large molecular weight. It is an object of the present invention to provide a catalyst and a method for polymerizing an olefin using the catalyst.

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises: [A] an Al component soluble in benzene at 60 ° C.
Less than 10%, An organoaluminum oxy compound having an alkyloxyaluminum unit represented by the formula: and [B] MLm (where M is titanium, vanadium, zirconium, hafnium or chromium, and L is an alkyl group, aryl group, cycloalkyl group, aralkyl Group, halogen, hydrogen, alkoxy group, aryloxy group, 2,4-
A monodentate or polydentate ligand selected from a pentanedionate group and an ester residue, and m is the valence of the transition metal.

Further, the olefin polymerization method according to the present invention is characterized in that an α-olefin is polymerized or copolymerized using the olefin polymerization catalyst as described above.

Since the catalyst for olefin polymerization according to the present invention comprises [A] an organic aluminum oxy compound insoluble or hardly soluble in benzene and [B] the transition metal compound as described above, polymerization excellent in olefin polymerization is achieved. An olefin polymer having an activity and a large molecular weight can be obtained.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the olefin polymerization catalyst according to the present invention and the olefin polymerization method using the olefin polymerization 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. May be used.

The olefin polymerization catalyst according to the present invention comprises [A] a benzene-insoluble organoaluminum oxy compound and [B] a transition metal compound as described above.

[A] Benzene-insoluble organoaluminum oxy compound [A] The benzene-insoluble organoaluminum oxy compound used in the present invention is Al
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 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%).

When the [A] benzene-insoluble organoaluminum oxy compound as described above is analyzed by infrared spectroscopy (IR), the absorbance (D ₁₂₂₀ ) around ₁₂₂₀ cm ⁻¹ and the 1260 c
The ratio to the absorbance (D ₁₂₂₀ ) around m ^-1 (D ₁₂₆₀ /
D ₁₂₂₀ ) is 0.09 or less, preferably 0.08 or less, and particularly preferably 0.04 to 0.07.

In the present specification, infrared spectroscopy of an organoaluminum 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) 1280 cm ^-1 bear maximum point in the vicinity of and around 1240 cm ^-1, which is the baseline L _1.

(B) the transmittance (T%) at the absorption minimum point near 1260 cm ^-1 ,
A perpendicular line is drawn from this minimum point to the wave number axis (horizontal axis), the transmittance (T ₀ %) at the intersection of this perpendicular line and the baseline L ₁ is read, and the absorbance (D ₁₂₆₀ = logT ₀ ) around ₁₂₆₀ cm ⁻¹ / 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 around ₁₂₂₀ cm ^-1 (D ₁₂₂₀ = logT ')
₀ / T ').

(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 approximately between 0.10 and 0.13, and the benzene-insoluble organoaluminum oxy compound used in the present invention is: The _D1260 / _D1220 value is clearly different from the conventionally known benzene-soluble organoaluminumoxy compound.

[A] 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.

[A] The 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 groups, hydroxyl groups, halogens 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, the method for producing the above-mentioned [A] benzene-insoluble organic aluminum oxy compound will be specifically described.

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

The aluminoxane solution used here 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 reacted with 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.

Also, iso 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, which is a z ≧ 2x) represented by Prenyl 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, cyclohexane, 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.

In the present invention, as described above, by contacting the above aluminoxane solution with water or an active hydrogen-containing compound, [A] a benzene-insoluble organic aluminum oxy compound can be obtained.

Examples of the active hydrogen-containing compound used in the present invention include alcohols such as methanol, ethanol, n-propanol and isopropal, 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, methylcyclohexane and other alicyclic hydrocarbons, gasoline, kerosene, light oil and other petroleum fractions and other hydrocarbon solvents, and halogenated carbonization of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons In particular, halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and toterahydrofuran can also be used. 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 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 ^{−4 to} 5 mol / l. l preferably 2 × 10 ^-3
Preferably, the concentration is 3 mol / l.

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 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 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 [A] used in the present invention can also be directly obtained by contacting the above-mentioned organoaluminum 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 gas oil, or 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 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
The concentration is preferably 5 mol / l, preferably 1 × 10 ^{-2 to} 3 mol / l. At this time, the organic aluminum atoms dissolved in the reaction system are 20% of the total organic aluminum atoms.
% Or less, preferably 10% or less, more preferably 0 to 5%
It is desirable that

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

(1) A method of contacting a hydrocarbon solution of organoaluminum with a hydrocarbon solvent containing water (2) A method of contacting organoaluminum with steam by blowing steam into the hydrocarbon solution of organoaluminum .

(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 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.

The above [A] organoaluminum oxy compound may be used by being supported on a solid inorganic compound such as silica, alumina, magnesium oxide and magnesium chloride, or a solid organic compound such as polyethylene, polypropylene and polystyrene. it can.

[B] Transition metal compound The olefin polymerization catalyst according to the present invention comprises the above-mentioned [A] benzene-insoluble organoaluminum oxy compound and the following [B] a ligand having a cycloalkadienyl skeleton. And a transition metal compound that does not contain the same.

In the present invention, as the above-mentioned [B] transition metal compound, a general formula MLm (where M is a transition metal, L is an alkyl group,
Aryl group, cycloalkyl group, aralkyl group, halogen, hydrogen, alkoxy group, aryloxy group, 2,4-pentanedionate group, monodentate or polydentate ligand selected from ester residue, m is a transition metal Which is a valence), and specifically, the following compounds can be used.

^{_{Ti (OR 3) n X 4}} -n, Ti (OR 3) n X 3-n, TiR 3 4, VO (OR 3)
_n X _3-n , V (OR ³ ) _n X _4-n , V (OR ³ ) _n X _3-n , Zr (OR ³ ) _n X _4-n , ZrR
^{_{3 4, Hf (OR 3)}} n X 4-n, HfR 3 4, Cr (OCOR 3) 3, Cr (acac) 3, V
(acac) ₃ , VO (acac) ₂ , In the above formula, R ³ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, specifically, a methyl group, an ethyl group,
n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group,
R ⁴ is a phenylene group, a biphenyl group, a binaphthyl group, or the like; and Y is a sulfur, methylene group, a carbonyl group, or the like. X is halogen or hydrogen, and n is 0-4.

Such [B] transition metal compounds may be used in combination of two or more.

Olefin Polymerization Method FIG. 3 is a flowchart illustrating the olefin polymerization method according to the present invention.

In the present invention, [A] a benzene-insoluble organoaluminum oxy compound as described above and [B] MLm (wherein M
Is titanium, vanadium, zirconium, hafnium or chromium, L is an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, a halogen, a hydrogen, an alkoxy group, an aryloxy group, a 2,4-pentanedionate group,
Is a monodentate or polydentate ligand selected from ester residues, and m is the valence of the transition metal), by polymerizing an olefin using an olefin polymerization catalyst comprising Produce an olefin polymer. Examples of the olefin that can be polymerized by the olefin polymerization catalyst according to the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene.
1-butene, 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,
4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned.

Further, in the present invention, styrene, vinylcyclohexane, diene 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 solution polymerization or suspension polymerization or a gas phase polymerization method.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually -50 to 200 ° C, preferably 0 to 150 ° C.
It is in the range of ° C. The polymerization pressure is usually from normal pressure to 100 kg / c.
m ² , preferably normal pressure to 50 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.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, [A] the benzene-insoluble organoaluminum oxy compound is usually 10 ^{-6 to} 0.1 g atom-Al / l, preferably 10 ^-5 to 10 ^-2 g atom-Al / l
The transition metal compound [B] is preferably used in an amount of usually 10 ^-7 to 10 ^-2 mol / l, preferably 10 ^-6 to 10 ^-3 mol / l.

The olefin polymerization catalyst according to the present invention, which is formed from the above-mentioned [A] benzene-insoluble organic aluminum oxy compound and [B] the above-mentioned transition metal compound, has excellent polymerization performance. . That is, the olefin polymerization catalyst according to the present invention can obtain a polymer having a higher molecular weight than a conventionally known olefin polymerization catalyst formed from a benzene-soluble aluminoxane and a metallocene-based compound.

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

Effect of the Invention The olefin polymerization catalyst according to the present invention comprises [A] an organic aluminum oxy compound insoluble or hardly soluble in benzene, and [B] MLm (where M is titanium, vanadium,
Zirconium, hafnium or chromium, and L is an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, a halogen, hydrogen, an alkoxy group, an aryloxy group,
A monodentate or polydentate ligand selected from a 2,4-pentanedionate group and an ester residue, and m is a valence of the transition metal). When the olefin is polymerized using this catalyst, the olefin polymer having a high molecular weight can be obtained.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 [Preparation of aluminoxane] Al ₂ (SO ₄ ) _3.
After charging 37 g of 14H ₂ O and 125 ml of toluene and cooling to 0 ° C., trimethylaluminum 5 diluted with 125 ml of toluene was added.
00 mmol was added dropwise. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours. After completion of the reaction, solid-liquid separation was performed by filtration, and further toluene was removed from the filtrate.
12 g of aluminoxane as a white solid was obtained.

[Preparation of benzene-insoluble organoaluminum oxy compound] A toluene solution of 59.7 ml of toluene and aluminoxane (A12.
(48 mol-Al / l) 40.3 ml and 25 g of a Teflon cylinder (φ2 mm × 1.2 mm) as a dispersant were charged. Then-
After cooling to 5 ° C., 0.72 ml of water was slowly added with a pipette.
Subsequently, the reaction was carried out at -5 ° C for 40 minutes, and then 80 hours over 1 hour.
C., and the reaction was continued at that temperature for another 3 hours.
After the reaction for 3 hours, the Teflon cylinder was removed with a sieve, and solid-liquid separation was further performed by filtration to obtain a benzene-insoluble organic aluminum oxy compound. When the concentration of aluminum dissolved in the filtrate was measured, the detection limit was 5 mg.
−Al / l or less.

The benzene-insoluble organoaluminum oxy compound obtained above was placed in a 200 ml reactor equipped with a stirrer in an amount of 100 in terms of Al atoms.
Milligram atoms were added, and 100 ml of benzene was further added, followed by stirring and mixing at 60 ° C. for 6 hours. This suspension was subjected to hot filtration using a jacketed G5 glass filter while keeping the silicone oil poured into the jacket at 60 ° C., and further washed four times with 50 ml of benzene at 60 ° C. The filtrate was collected, and the amount of Al in the filtrate was measured. As a result, 0.7 mmol of Al was detected. That is, the amount of the Al component of the organic aluminum oxy compound dissolved in benzene at 60 ° C. is
It was considered to be 0.7% in terms of Al atom. In addition, IR measurement of the above solid organoaluminum oxy compound showed absorption in the Al-O-Al atomic group at 600 to 800 cm ^-1 in the IR spectrum, and absorbance at ₁₂₂₀ cm ^-1 (D ₁₂₂₀ ). To the absorbance at 1206 cm ^-1 (D ₁₂₆₀ ) (D
₁₂₆₀ / D ₁₂₂₀ ) was 0.053. In addition, methane was generated by decomposition with water.

[Polymerization] 250 ml of n-decane was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and heated to 45 ° C. while flowing a mixed gas of ethylene and propylene (60 l / h and 40 l / h, respectively). Warmed. Subsequently, 1.88 milligram atoms of a benzene-insoluble organic aluminum oxy compound in terms of aluminum atoms and 0.025 millimol of titanium tetrachloride were added to initiate polymerization. The polymerization was carried out at 50 ° C. for 30 minutes under normal pressure while continuously flowing the mixed gas. After terminating the polymerization by adding a small amount of methanol to the polymerization system, the polymer was recovered by pouring the obtained polymer solution into 4 l of methanol. The recovered polymer was dried overnight at 130 ° C. under reduced pressure to have an ethylene content of 86.6 mol% and an MFR of 0.06 g / 10 min.
10.5 g of a propylene copolymer was obtained.

Examples 2 to 5 The same procedure as in Example 1 was carried out except that the polymerization was carried out under the conditions described in Table 1.

 Table 1 shows the results.

Comparative Examples 1 to 3 Polymerization was carried out in the same manner as in Example 1 except that the organoaluminum compound shown in Table 2 was used instead of the benzene-insoluble organoaluminum oxy compound.

 Table 2 shows the results.

Comparative Example 4 In Example 1, 0.025 mmol of bis (cyclopentadienyl) titanium dichloride was used in place of TiCl ₄ , and the aluminoxane synthesized in Example 1 was used in place of the benzene-insoluble organoaluminumoxy compound. Polymerization was carried out in the same manner as in Example 1 except that milligram atoms were used.
0.2 mol%, measured in decalin at 135 ° C. [η]
0.4 g of an ethylene / propylene copolymer having a value of 0.75 dl / g was obtained.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a benzene-insoluble organoaluminum oxy compound used in the present invention, and FIG. 2 is an IR spectrum of a conventionally known benzene-soluble organoaluminum compound. FIG. 3 is a flowchart illustrating the olefin polymerization method according to the present invention.

Claims (2)

(57) [Claims] [1] An Al component dissolved in benzene at 60 ° C.
10% or less in terms of Al atom, An organic aluminum oxy compound having an alkyloxyaluminum unit represented by the formula: [B] MLm (where M is titanium, vanadium, zirconium, hafnium or chromium, and L is an alkyl group, an aryl group, a cycloalkyl group, Aralkyl, halogen, hydrogen, alkoxy, aryloxy, 2,4-
A monodentate or polydentate ligand selected from a pentanedionate group and an ester residue, and m is a valence of a transition metal). 2. [A] The Al component dissolved in benzene at 60 ° C.
10% or less in terms of Al atom, An organic aluminum oxy compound having an alkyloxyaluminum unit represented by the formula: [B] MLm (where M is titanium, vanadium, zirconium, hafnium or chromium, and L is an alkyl group, an aryl group, a cycloalkyl group, Aralkyl, halogen, hydrogen, alkoxy, aryloxy, 2,4-
A monodentate or polydentate ligand selected from a pentanedionate group and an ester residue, and m is the valence of the transition metal) in the presence of a catalyst for olefin polymerization formed from a transition metal compound represented by the formula: A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins.