JP2741893B2 - Method for producing benzene-insoluble organoaluminum oxy compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an organoaluminum oxy compound which is insoluble in a hydrocarbon solvent such as benzene, and more particularly to benzene and the like used as a catalyst component of a catalyst for olefin polymerization. The present invention relates to a method for producing an organic aluminum oxy compound insoluble in a hydrocarbon solvent.

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.

In general, ethylene / α- obtained using a titanium-based catalyst
The olefin copolymer has a problem that the molecular weight distribution and the composition distribution are wide and the transparency, the surface non-adhesiveness, and the mechanical properties are poor. In addition, the ethylene-α-olefin copolymer obtained using a vanadium-based catalyst has a narrower molecular weight distribution and composition distribution than the ethylene-α-olefin copolymer obtained using a titanium-based catalyst, and has a higher transparency. Although the surface non-stickiness and the mechanical properties were considerably improved, the polymerization activity was low, and a decalcification operation was required. Therefore, there is a need for a catalyst system with improved performance.

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 wherein R is cyclopentadienyl, C _{1 to} C ₆ alkyl or halogen, and Me is a transition metal And Hal is a halogen], and a transition metal-containing compound represented by the formula:
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: [Wherein, definition of R and n are as defined above] the presence of a catalyst comprising a cyclic aluminoxane represented by one α- olefin ethylene and C ₃ -C _12, or two or more 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 adjust 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: [Here, the definitions of n and R are the same as above.] The invention relating to a method for producing a cyclic aluminoxane represented by the following formula is described. 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% was 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 number-average molecular weight of 2,000 and a weight-average molecular weight of 8.3 consisting of a toluene-insoluble portion containing 00 and 4.8 mol% of a propylene component.
A blend of polyethylene and ethylene / propylene copolymer containing 00 and 7.1 mol% of propylene component is obtained. Similarly, in Example 3, the molecular weight distribution (w / n)
A blend of LLDPE and an ethylene-propylene copolymer comprising 4.57 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 an integer of 1 to about 20], or the following formula R (R-Al-O) _n AlR ₂ [ Here, R is an alkyl group having 1 to 5 carbon atoms, and the definition of n is the same as described above.] And a linear aluminoxane represented by the following formula: I have. 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.

However, the emergence of aluminoxane-based organoaluminum compounds having even more excellent polymerization activity for α-olefins and capable of obtaining α-olefin (co) polymers having a narrow molecular weight distribution and composition distribution is strong. Is desired.

By the way, the aluminoxane compounds that have been used in the above-mentioned known olefin polymerization are themselves liquid or solid, and are all soluble in hydrocarbon solvents such as benzene or toluene. It was recovered in a state, and its molecular weight was measured by a freezing point depression method after dissolving it in benzene. The structure of the aluminoxane has also been determined by dissolving it in benzene and measuring the freezing point.

The present inventors have further studied in view of the above points, obtained from a solution of aluminoxane,
The present inventors have found that a novel organoaluminum oxy compound insoluble or hardly soluble in benzene and toluene, which has never been known before, has excellent catalytic activity for olefin polymerization, and completed the present invention.

Object of the Invention The present invention has been completed in view of the prior art as described above, and can provide an olefin (co) polymer having excellent catalytic activity and having a narrow molecular weight distribution and composition distribution. It is an object of the present invention to provide a method for producing such a novel catalyst component for olefin polymerization.

SUMMARY OF THE INVENTION The method for producing a benzene-insoluble organoaluminum oxy compound according to the present invention is characterized by contacting a solution of aluminoxane with water, and the obtained benzene-insoluble organoaluminum oxy compound has a temperature of 60 ° C. Al component dissolved in benzene is 10% or less in terms of Al atom, Has an alkyloxyaluminum unit represented by

The benzene-insoluble organoaluminum oxy compound obtained in the present invention, when used as a component of an olefin polymerization catalyst, exhibits excellent polymerization activity for olefin polymerization,
Moreover, an olefin (co) polymer having a narrow molecular weight distribution and composition distribution can be provided.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing a benzene-insoluble organoaluminum oxy compound according to the present invention will be specifically described.

The benzene-insoluble organoaluminum oxy compound according to the present invention is obtained by contacting a solution of aluminoxane with water.

The aluminoxane solution used in the present invention 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.

As the organoaluminum compound, isoprenyl aluminum represented by the general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (x, y, and z are positive numbers and z ≧ 2x) 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, butane, isobutane, pentane, hexane, octane, aliphatic hydrocarbons such as decane, dodecane, hexadecane, octadecane, cyclopentane, cyclohexane, cyclooctane, cyclodecane, Alicyclic hydrocarbons such as cyclododecane, petroleum fractions such as gasoline, kerosene and light oil, and hydrocarbons such as the above aromatic hydrocarbons, aliphatic hydrocarbons and halides of alicyclic hydrocarbons, especially chlorinated products and brominated products Hydrogen solvents are mentioned. 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, a benzene-insoluble organoaluminum oxy compound can be obtained by contacting the above aluminoxane solution with water.

Water to be brought into contact with the solution of aluminoxane is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, and hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or used in a state of steam or ice. be able to. 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 solution of aluminoxane and water is usually carried out in a solvent such as a hydrocarbon solvent. As the solvent used at this time, benzene, toluene, xylene,
Aromatic hydrocarbons such as aromatic hydrocarbons such as cumene and cymene, butanes, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, alicyclics such as cyclopentane, cyclohexane, cyclooctane, cyclodecane, cyclododecane Solvents such as petroleum fractions such as aromatic hydrocarbons, gasoline, kerosene, and gas oil, or halogenated aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. Ethers such as hydrocarbons, ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The water used for the contact reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, based on the Al atoms in the aluminoxane solution. The concentration in the reaction system is 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 solution is usually 2 × 10 ^{−4 to} 5 mol atom / l, preferably 2 × 10 ^{−3 to} 3 mol atom / l.

The contact of the aluminoxane solution with water may be carried out specifically as follows.

(1) A method of contacting a solution of aluminoxane with a hydrocarbon solvent containing water.

(2) A method of contacting aluminoxane with water vapor by, for example, blowing water vapor into a solution of aluminoxane.

(3) A method of bringing a solution of aluminoxane into direct contact with water or ice.

(4) mixing a solution of aluminoxane with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization,
A method in which aluminoxane is brought into contact with adsorbed water or water of crystallization.

In addition, the solution of aluminoxane as described above does not adversely affect the reaction between aluminoxane and water,
Other components may be included.

The contact reaction between the aluminoxane solution and water as described above is usually carried out at a temperature of -50 to 150C, preferably 0 to 120C, more preferably 20 to 100C. The reaction time varies greatly depending on the reaction temperature, but is usually 0.5 to 300.
The time is preferably about 1 to 150 hours.

In the organoaluminum oxy compound obtained as described above, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble in benzene 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, hot filtration was performed at 60 ° C., and the solid part separated on the filter was washed four times with 50 ml of 60 ° C. benene, 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 absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D ₁₂₆₀ / D ₁₂₂₀₎
Is 0.09 or less, preferably 0.08 or less, particularly preferably 0.04 to
It is desirable to be in the range of 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 mortar 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.

FIG. 1 shows the IR spectrum of the organoaluminum oxy compound thus obtained.

From this IR spectrum, D ₁₂₆₀ / D ₁₂₂₀ is obtained.
_The value ₁₂₆₀ / _D1220 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 read the absorbance around 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 obtained in the present invention is clearly different from the conventionally known benzene-soluble organoaluminum oxy compound in the value of D ₁₂₆₀ / D ₁₂₂₀ .

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.

The above benzene-insoluble organoaluminum oxy compound has the formula 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%.

The benzene-insoluble organoaluminum oxy compound obtained in the present invention is used as a catalyst component of a catalyst for olefin polymerization.

Such a benzene-insoluble organoaluminum oxy compound can be used as a catalyst for olefin polymerization, for example, in combination with a transition metal compound containing a ligand having a cycloalkadienyl skeleton, and preferably further with an organoaluminum compound.

The transition metal compound containing a ligand having a cycloalkadienyl skeleton used as an olefin polymerization catalyst together with the benzene-insoluble organoaluminum oxy compound obtained in the present invention is represented by the formula ML _x (where M is a transition metal. , L is a ligand that coordinates to a transition metal, and at least one L is a ligand having a cycloalkadienyl skeleton, and contains at least two or more ligands having a cycloalkadienyl skeleton In such a case, the ligand having at least two cycloalkadienyl skeletons may be bonded via a lower alkylene group, and L other than the ligand having a cycloalkadienyl skeleton has 1 to 1 carbon atoms. 12 is a hydrocarbon group, an alkoxy group, an aryloxy group, halogen or hydrogen, and x is a valence of a transition metal.)

In the above formula, M is a transition metal, and specifically, is preferably zirconium, titanium or hafnium, or chromium or vanadium, and among them, zirconium and hafnium are particularly preferable.

As the ligand having a cycloalkadienyl skeleton,
For example, alkyl-substituted cyclopentane such as cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, t-butylcyclopentadienyl group, dimethylcyclopentadienyl group and pentamethylcyclopentadienyl group Examples thereof include a dienyl group, an indenyl group, and a fluorenyl group.

The ligand having a cycloalkadienyl skeleton as described above may be coordinated to two or more transition metals. In this case, the ligand having at least two cycloalkadienyl skeletons is It may be bonded via a lower alkylene group.

The ligand other than the ligand having a 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 cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium Monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) Zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclope Tadienyl) zirconium dibenzyl, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (methylcyclopentadienyl) zirconium ethoxycyclolide, bis (cyclo (Pentadienyl) zirconium phenoxycyclolide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ethyl zirconium mono Chloride, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (a (Denyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ) Methyl zirconium monochloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylene bis ( 4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) Zirconium dichloride, ethylene (5-methoxy-1-indenyl) zirconium dichloride, ethylene bis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylene bis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylene bis (4, 7-dimethoxy-1-indenyl)
Zirconium dichloride.

Further, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal or vanadium metal in the above zirconium compound can also be used.

Further, the benzene-insoluble organic aluminum oxy compound obtained in the present invention can be used as a catalyst component for olefin polymerization together with other organic aluminum compounds. In this case, the organoaluminum compound used is, for example, R ⁶ _n AlX _3-n (wherein, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3
).

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, decyl group, cyclopentyl group,
Cyclohexyl, phenyl, tolyl and the like.

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

Trimethyl aluminum, triethyl aluminum,
Trialkylaluminums such as triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

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

Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylauminium sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide.

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

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

As other organoaluminum compounds, for example, R ⁶ _n AlY _3-n (wherein R ⁶ is the same as above, and 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, is ^{_{R 6 n Al (OAlR 9 2}} ) 3-n Preferably, especially
Preferably, R ⁶ is an isoalkyl group and n = 2.
These organoaluminum compounds can be used as a mixture of two or more kinds.

The benzene-insoluble organoaluminum oxy compound obtained in the present invention is preferably used as a catalyst for olefin polymerization together with the above-mentioned transition metal compound containing a ligand having a cycloalkadienyl skeleton, more preferably an organoaluminum compound. When combined with an organoaluminum compound, it is preferred because it exhibits excellent polymerization activity for olefin polymerization.

Examples of the olefin that can be polymerized with such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene and 1-olefin.
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, 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, the benzene-insoluble organoaluminum oxy compound is usually 10 ^{-6 to} 0.1 g atom-Al / l, preferably 10 ^-5 to 10 ^-2. Gram atom-Al / l, and the transition metal compound having a cycloalkadienyl skeleton is usually 10 ^-8 to 10 ^-3 mol / l, preferably 10 ^-7 to 10 ^-4 mol / l, Further, the organoaluminum compound is usually 0
To 0.1 mol / l, preferably 10 ^-4 to 10 ^-2 mol / l. Further, the ratio of the benzene-insoluble organoaluminum compound (in terms of Al atom) to the organoaluminum compound is desirably used in the range of 0.01 to 5, preferably 0.02 to 2.

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.

The olefin polymerization catalyst formed from the above-mentioned benzene-insoluble organic aluminum oxy compound, a transition metal compound having a cycloalkadienyl skeleton, and an organic aluminum compound has excellent polymerization activity. That is, the olefin polymerization catalyst containing the benzene-insoluble organoaluminum oxy compound according to the present invention has a unit organoaluminum as compared with a conventionally known olefin polymerization catalyst formed from a benzene-soluble aluminoxane and a metallocene-based compound. Per oxy compound weight,
About 1.2 to 20 times the olefin polymer can be obtained.

Further, when an olefin is copolymerized using the olefin polymerization catalyst containing a benzene-insoluble organic aluminum oxy compound according to the present invention, an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained.

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 When the benzene-insoluble organoaluminum oxy compound according to the present invention is used as a component of an olefin polymerization catalyst, it exhibits excellent polymerization activity for olefin polymerization and has a narrow molecular weight distribution and a narrow composition distribution. Obtainable.

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

Reference 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 toluene was removed from the filtrate to obtain 12 g of aluminoxane as a white solid.

Example 1 A 400-ml glass flask purged with nitrogen was spheronized with 100 ml of toluene and a 32-mesh sieve, and 3.4 g of Al ₂ (SO ₄ ) ₃ .14H ₂ O remaining on the sieve was charged and suspended. It became cloudy. At room temperature, 93 ml of a toluene solution of aluminoxane (2.14 mol-Al / l) prepared in Reference Example 1 was added at room temperature. Subsequently, the temperature was raised to 40 ° C., and stirring was continued at that temperature for 10 days. Thereafter, the aluminum sulfate compound was removed by sieving with an 80-mesh sieve under a nitrogen atmosphere, and a suspension composed of fine solid particles and toluene that passed through the sieve was recovered. Further, this suspension was filtered using a G4 glass filter to remove the toluene solution part, and the solid part was recovered and then re-suspended in toluene. From the measurement results of the sulfate groups in the resuspension, the amount of Al sulfate in the resuspension was
It could be regarded as 0.1 mol% or less in the atom. Further, a part of the solid was recovered without resuspension in toluene, and dried under reduced pressure at room temperature, and the dried solid (organoaluminum oxy compound) obtained was transferred to a 200 ml reactor equipped with a stirrer in 100 ml in terms of Al atom.
Mmol, then 100 ml of benzene,
For 6 hours. Using a G5 glass filter with a jacket, this suspension was filtered while hot while maintaining the silicone oil poured into the jacket at 60 ° C.
Washing was performed 4 times using 50 ml of benzene at 50 ° C. The filtrate was recovered, and the amount of Al in the filtrate was measured.Since Al equivalent to 0.4 mmol was detected, the amount of the Al component dissolved in benzene at 60 ° C. of the solid organoaluminum oxy compound was calculated as Al atoms. At 0.4%. Other, was carried out. IR measurement of the solid organoaluminum oxy-compound, Al-O-in 600 to 800 ^-1 in the IR spectrum
Absorption was observed in the Al atomic and absorbance at 1220 cm ^-1 and (D _1220), the ratio of the absorbance at _{^{1260cm -1 (D 1260) (D}} 1260 / D 1220) was 0.068. Generation of methane was observed by decomposition with water, and the specific surface area was 30 g / m ² .

A polymerization activity test of the benzene-insoluble organoaluminum oxy compound prepared as described above was performed as follows.

After 900 ml of 4-methyl-1-pentene was charged into a 2 l stainless steel autoclave sufficiently purged with nitrogen, the temperature was raised to 50 ° C., and the solid component obtained in Example 1, ie, a benzene-inactive organic aluminum oxy compound toluene 0.22 ml of the suspension (0.44 mol-Al / l) and (i-Bu) ₂ -Al-O-Al (iB
u) 1 ml of a toluene solution of ₂ (1 mol-Al / l) was added.
After the temperature was further raised to 75 ° C., a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (0.
1 ml of (001 mol-Zr / l) was injected together with ethylene to initiate polymerization. Total pressure 8kg / cm while continuously supplying ethylene
^{When 2-} G was polymerized at 80 ° C. for 40 minutes, the MFR was 1.20.
a g / 10 min, a density of 0.888g / cm ^3, w / n is 2.
Ethylene-4-methyl-1-pentene copolymer 9 which is 2
2.4 g were obtained.

Example 2 A 400 ml glass flask sufficiently purged with nitrogen was charged with 32.8 ml of toluene and 0.78 g of pulverized magnesium chloride hexahydrate to form a slurry. Thereto, 25 ml of a toluene solution of aluminoxane (2.31 mol-Al / l) prepared in Reference Example 1 was added at room temperature. Thereafter, the temperature was raised to 80 ° C., and stirring was continued at that temperature for 7 hours. Thereafter, solid-liquid separation was performed by filtration to obtain a benzene-insoluble organic aluminum oxy compound. The concentration of aluminum dissolved in the filtrate was measured and found to be 5 mg-Al / l or less, which is the detection limit.

The solubility of the solid component obtained above in benzene at 60 ° C. was measured in the same manner as in Example 1, and found to be 0.3%.

A polymerization activity test of the benzene-insoluble organoaluminum oxy compound prepared as described above was performed as follows.

After charging 900 ml of 4-methyl-1-pentene into a 2 l stainless steel autoclave sufficiently purged with nitrogen, the temperature was raised to 50 ° C., and the solid component obtained in Example 2, ie, toluene suspension of the benzene-insoluble organic aluminum oxy compound, was added. 0.22 ml of a suspension (0.44 ml-Al / l) and (i-Bu) ₂ -Al-O-Al (iB
u) 1 ml of a toluene solution of ₂ (1 mol-Al / l) was added. After the temperature was further raised to 75 ° C., a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (0.00%
1 ml of 1 mol-Zr / l) was injected together with ethylene to initiate polymerization. Total pressure 8 kg / cm ² while continuously supplying ethylene
-G, after polymerization for 40 minutes at 80 ℃, MFR 1.51g
/ 10 min, the density is 0.885 g / cm ³ , w / n is 2.1
Ethylene-4-methyl-1-pentene copolymer 9
5.4 g were obtained.

Examples 3 to 11 Under the conditions shown in Table 1, benzene-insoluble organoaluminum oxy compounds were prepared in the same manner as in Example 2. Table 2 shows the results of a polymerization activity test performed in the same manner as in Example 2.

Example 12 In a 400 ml glass flask sufficiently purged with nitrogen, 59.7 ml of toluene and 40.3 ml of a toluene solution of aluminoxane (Al2.48 mol-Al / l) prepared in the same manner as in Reference Example 1 were added.
Teflon cylinder (φ2mm x 1.2mm) 25 as a dispersant
g was charged. Thereafter, the mixture was cooled to -5 ° C, and 0.72 ml of water was gradually added with a pipette. Subsequently, the reaction was carried out at -5 ° C for 40 minutes, then the temperature was raised to 80 ° C over 1 hour, 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. The concentration of aluminum dissolved in the filtrate was measured and found to be 5 mg-Al / l or less, which is the detection limit.

When the solubility in benzene at 60 ° C. was examined in the same manner as in Example 1, it was 0.7%.

The absorbance at 1220 cm ^-1 and (D _1220), the ratio of the absorbance at _{^{1260cm -1 (D 1260) (D}} 1260 / D 1220) was 0.053.

A polymerization activity test of the benzene-insoluble organoaluminum oxy compound prepared as described above was performed in the same manner as in Example 2.

 Table 2 shows the results.

Example 13 [Preparation of aluminoxane] A hexane solution (Al) of aluminoxane (containing 70 mol% of alkyloxyaluminum units, where the alkyl group is a methyl group) was placed in a glass flask sufficiently purged with nitrogen. = 1.73mol / l) 14.5ml and decane 27.2
ml was added. While stirring the system, wet nitrogen gas (20.5
It was fed into the liquid over mg-H ₂ O / 1 liters -N ₂₎ 2 hours 8.8 liters. The temperature in the system was kept at 23 ° C. Thereafter, 20.8 ml of decane was further added, and the mixture was stirred for 1 hour to obtain a white suspension of aluminoxane. The Al component of this aluminoxane dissolved in benzene at 60 ° C. was 0.2% in terms of Al atoms.

[Polymerization] 900 ml of heptane was charged into a 2-liter stainless steel autoclave which had been sufficiently purged with nitrogen, and propylene was further introduced so that the pressure inside the system was 6.2 kg / cm ² -G at 80 ° C. Then, ethylene was introduced until it reached 8 kg / cm ² -G. Thereafter, the polymerization was initiated by injecting 0.9 mmol of triisobutylaluminum, 0.1 mmol of the aluminoxane prepared above in terms of Al atom and 0.001 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride with nitrogen. . Thereafter, the total pressure was reduced to 8 kg / cm ² by continuously supplying ethylene only.
-G, polymerization was carried out at 80 ° C. for 1 hour. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted monomers were purged. The obtained polymer solution was poured into a large excess of methanol to precipitate a polymer. The polymer was collected by filtration and dried at 130 ° C. under reduced pressure overnight. As a result, 58 g of an ethylene / propylene copolymer having an ethylene content of 81.7 mol% and an intrinsic viscosity [η] of 2.89 dl / g was obtained.

Comparative Example 1 [Polymerization] The same procedure was performed except that the aluminoxane prepared in Example 13 was replaced with the unprepared aluminoxane used as a raw material instead of using the aluminoxane prepared in Example 13, and the ethylene content was 81.0 mol%. 29.5 g of an ethylene / propylene copolymer having a viscosity [η] of 2.43 dl / g was obtained.

Example 14 20 ml of a hexane solution (Al = 1.73 mol / L) of aluminoxane before preparation used as a raw material in Example 13 and 20 ml of decane were added to a glass flask sufficiently purged with nitrogen. After the hexane was removed by heating the system, the temperature was raised to 95 ° C. and the mixture was stirred for 24 hours.

[Polymerization] The polymerization was carried out in the same manner as in Example 13, except that the aluminoxane prepared above was used.
Thus, 48.5 g of an ethylene / propylene copolymer having an intrinsic viscosity [η] of 2.69 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.

Claims (1)

(57) [Claims] An aluminum component dissolved in benzene at 60 ° C. is not more than 10% in terms of Al atom, characterized by contacting a solution of aluminoxane with water. A method for producing a benzene-insoluble organoaluminum oxy compound having an alkyloxyaluminum unit represented by the formula: