JPH02167305A - Production of benzene-insoluble organic aluminumoxy compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound insoluble in hydrocarbon solvents such as benzene, useful as a component of an olefin-polymerization catalyst having excellent polymerization activity and giving a polymer having narrow molecular weight distribution by contacting a solution of an alumino-oxane with water. CONSTITUTION:The objective compound containing <=10% (in terms of Al atom) of Al component soluble in benzene at 60 deg.C is produced by contacting a solution of an alumino-oxane with water. The water to be contacted with the alumino-oxane solution may be a solution or dispersion in a solvent (e.g. benzene, toluene, THF or triethylamine) or used in the state of steam or ice. Furthermore, crystallization water of a salt such as magnesium chloride or water adsorbed to silica, etc., can be used as the above water.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing organoaluminumoxy compounds that are insoluble in hydrocarbon solvents such as benzene. The present invention relates to a method for producing organoaluminumoxy compounds that are insoluble in hydrocarbon solvents.

Technical background of the invention and its problems Conventionally, titanium-based catalysts consisting of titanium compounds and organic aluminum or vanadium have been used as catalysts for producing α-olefin polymers, such as ethylene polymers or ethylene/α-olefin copolymers. Vanadium-based catalysts comprising a compound and an organoaluminium compound are known.

Generally, ethylene/α-olefin copolymers obtained using titanium-based catalysts have a wide molecular weight distribution and a wide indium distribution, and have problems in that they are poor in transparency, surface non-adhesion, and mechanical properties. Furthermore, ethylene/α-olefin copolymers obtained using vanadium-based catalysts have narrower molecular weight and composition distributions, and are less transparent than ethylene/α-olefin copolymers obtained using titanium-based catalysts. Although the surface non-adhesion and mechanical properties were considerably improved, the polymerization activity was low and demineralization was required. Therefore, there is a desire for a catalyst system with further improved performance.

On the other hand, as a new Ziegler type olefin polymerization catalyst,
Recently, a method for producing an ethylene/α-olefin copolymer using a catalyst consisting of a zirconium compound and an aluminoxane has been proposed.

For example, in JP-A-58-19309, the following formula % formula % [where R is cyclopentadienyl, C1 to C6 alkyl or halogen, Me is a transition metal,
Hag is a halogen] and a transition metal-containing compound represented by the following formula %)) [where R is methyl or ethyl and n is 4 to 2
In the presence of a catalyst consisting of a linear aluminoxane represented by the number 0] or a cyclic aluminoxane represented by the following formula [where R and n are defined as above, ethylene and A method for producing an ethylene/α-olefin copolymer is described in which one or more C3 to C12 α-olefins are polymerized at a temperature of 150°C to 200°C. The same publication teaches that in order 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 long-chain α-olefins or mixtures. There is.

JP-A-59-95292 describes a linear aluminoxane represented by the following formula, [where n is 2 to 40, and R is C-C6] and a linear aluminoxane represented by the following formula [where n and R
The definition is the same as above] An invention relating to a method for producing a cyclic aluminoxane represented by The publication states that when olefin is polymerized by mixing, for example, methylaluminoxane and a titanium or zirconium bis(cyclopentagenyl) compound produced by the same production method, per hour,
It is stated that more than 25 million g of polyethylene can be obtained.

JP-A-60-35005 discloses that an aluminoxane compound represented by the following formula R is R1 or combines to represent 10-] is first reacted with a magnesium compound, and then the reaction product is chlorinated. and further Ti V
A method for producing an olefin polymerization catalyst by treatment with a SZr or Cr compound is disclosed. The same publication states that the above catalyst is particularly suitable for copolymerizing a mixture of ethylene and a C3 to C12 α-olefin.

JP-A-60-35006 discloses that two or more different transition metal mono- or tricyclopentadienyl or derivatives thereof (a) and aluminoxane (b) are used as a catalyst system for producing a reactor blend polymer. ) is disclosed.

In Example 1 of the same publication, ethylene and propylene were polymerized using a catalyst consisting of bis(pentamethylcyclopentadienyl)zirconium dimethyl and aluminoxane, and the number average molecular weight was 15.300, the weight average It is disclosed that a polyethylene having a molecular weight of 36,400 and a propylene content of 3.4% was obtained. In addition, in Example 2, ethylene and propylene were polymerized using a catalyst consisting of bis(pentamethylcyclopentadienyl)zirconium dichlorite, bis(methylcyclopentadienyl)zirconium dichloride, and aluminoxane. and number average molecular weight 2.200. A number consisting of a toluene soluble portion containing a weight average molecular weight of 11,900 and a propylene component of 30 mol% and a toluene insoluble portion containing a number average molecular weight ff of 13,000, a weight average molecular weight of 7.400 and a propylene component of 4.8 mol%. Average molecular weight 2
．． 000, a weight average molecular weight of 8,300, and a blend of polyethylene and ethylene-propylene copolymer containing a propylene component of 7.1 mol%. Similarly, in Example 3, molecular weight distribution (Viw /Mn) 4.
A blend of LLDPE and an ethylene-propylene copolymer is described, consisting of a soluble portion with a molecular weight distribution of 3.04 and an insoluble portion with a molecular weight distribution of 3.04 and a propylene component of 20.6 mol % and a propylene component of 2.9 mol %.

JP-A-60-35007 discloses that ethylene alone or ethylene and an α-olefin having 3 or more carbon atoms are combined with metallocene and the following formula [where R is an alkyl group having 1 to 5 carbon atoms] , n is an integer from 1 to about 20] or the following formula % [Here, R is an alkyl group having 1 to 5 carbon atoms, and the definition of n is the same as above. A method is described in which the polymerization is carried out in the presence of a catalyst system comprising a linear aluminoxane represented by the following formula. According to the description in 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.

JP-A-60-35008 discloses that polyethylene or ethylene having a wide molecular weight distribution and α-olefin of 08 to C1° are combined by using a catalyst system containing at least two metallocenes and an aluminoxane. It is described that copolymers are prepared. The publication also states that the above copolymer has a molecular weight distribution (My/Mn) of 2 to 50.
It is described that it has.

A method of polymerizing olefins using a catalyst formed from a mixed organoaluminum compound consisting of a transition metal compound, an aluminoxane, and an organoaluminum compound is disclosed in JP-A-60-260602 and JP-A-60-130.
It is proposed in Japanese Patent No. 604, and it is stated that the polymerization activity per unit transition metal is improved by adding an organoaluminum compound.

Furthermore, JP-A No. 62-36390 teaches that aluminoxane can be obtained by reacting an organoaluminum compound with an iron compound containing water of crystallization, and JP-A No. 62-148491 The publication teaches that aluminoxane can be obtained by reacting an organoaluminum compound with a crystal water-containing compound selected from the group consisting of magnesium compounds, nickel compounds, and lanthanide compounds,
Furthermore, JP-A-63-56507 and JP-A-63
Publication No. 56508 states that aluminoxane can be obtained by directly reacting water and an organoaluminum compound in an inert hydrocarbon solvent using a high-speed shear force-inducing impeller or ultrasonic waves. taught.

When producing α-olefin (co)polymers in this way, using an aluminoxane compound as a component of the catalyst can produce α-olefin (co)polymers with excellent polymerization activity and narrow molecular weight and composition distributions. can be manufactured.

However, there is a strong desire for the emergence of aluminoxane-based organoaluminum compounds that have even better polymerization activity toward α-olefins and can yield olefin (co)polymers with narrow molecular weight and composition distributions. ing.

By the way, the aluminoxane compounds that have been used in the known olefin polymerization mentioned above, whether they themselves are liquid or solid, are all soluble in hydrocarbon solvents such as benzene or toluene. Furthermore, its molecular weight was measured by the 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 its freezing point.

In view of the above points, the present inventors conducted further intensive research and found that a novel organoaluminum oxy, which is insoluble or sparingly soluble in benzene and toluene, was obtained from a solution of aluminoxane and was completely unknown in the past. The present invention was completed based on the discovery that the compound has excellent catalytic activity for olefin polymerization.

Purpose of the Invention The present invention was completed in view of the prior art as described above, and is capable of providing an olefin (co)polymer having excellent catalytic activity and having a narrow molecular weight distribution and composition distribution. The purpose of the present invention is to provide a method for producing a novel catalyst component for olefin polymerization.

Summary of the Invention The method for producing a benzene-insoluble organoaluminumoxy compound according to the present invention is characterized by bringing a solution of aluminoxane into contact with water, and the resulting benzene-insoluble organoaluminumoxy compound is heated at 60°C. The AJ acid component dissolved in benzene is 10% or less in terms of AN atoms.

When the benzene-insoluble organoaluminumoxy compound obtained in 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 composition distribution.
Polymers can be provided.

The method for producing a benzene-insoluble organoaluminumoxy compound according to the present invention will be specifically described below.

The benzene-insoluble organoaluminumoxy compound according to the present invention can be obtained by bringing a solution of aluminoxane into contact with water.

The aluminoxane solution used in the present invention can be produced, for example, by the following method.

(1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminium to a hydrocarbon medium and reacting it to recover a hydrocarbon solution.

(2) A method in which water, ice, or steam is directly applied to an organoaluminum compound such as trialkylaluminium in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a hydrocarbon solution.

Note that the aluminoxane may contain a small amount of organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent.

Specifically, the organoaluminum compounds used in producing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-5ec. - trialkylaluminum such as butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum Dialkyl aluminum halides such as bromide and diisobutyl aluminum chloride; dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum alkoxides such as diethyl aluminum phenoxide. Can be mentioned.

Among these, trialkylaluminum is particularly preferred.

Furthermore, isoprenylaluminum represented by the general formula % can also be used as the organic aluminum compound.

The organoaluminum compounds described above may be used alone or in combination.

Solvents used for aluminoxane solutions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, and aliphatic carbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane. Hydrogen, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, cyclodecane, and cyclododecane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Mention may be made of halides, especially hydrocarbon solvents such as chlorides and bromides. 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 organoaluminumoxy compound is obtained by contacting the aluminoxane solution as described above with water.

The water contacted with the aluminoxane solution contains benzene,
It can be used by dissolving or dispersing it in a hydrocarbon solvent such as toluene or hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of water vapor or ice. In addition, as water, crystallized water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or adsorbed 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 aluminoxane solution and water is usually carried out in a solvent, such as a hydrocarbon solvent.

Solvents used at this time include benzene, toluene,
Aromatic hydrocarbons such as xylene, cumene, cymene, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, cyclodecane, cyclododecane, etc. Hydrocarbon solvents such as alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated and brominated compounds. Ethers such as halogenated hydrocarbons, ethyl ether, and tetrahydrofuran can also be used. Among these media, aromatic hydrocarbons are particularly preferred.

The amount of water used in the catalytic reaction is 0.1 to 5 mol, preferably 0.2 mol per AI atom in the aluminoxane solution.
It is used in an amount of ~3 mol. The concentration in the reaction system is usually in the range of 1 x 10-3 to 5 gram atoms/D, preferably 1 x 10-2 to 3 gram atoms/D, in terms of aluminum atoms. The concentration of water is
Usually 2 x 10-4 to 5 mol/g preferably 2 x 10-3
A concentration of ~3 mol/g is desirable.

Specifically, the aluminoxane solution and water may be brought into contact as follows.

(1) A method of bringing a solution of aluminoxane into contact with a hydrocarbon solvent containing water.

(2) A method of bringing aluminoxane and water vapor into contact by, for example, blowing water vapor into a solution of aluminoxane.

(3) A method in which a solution of aluminoxane is brought into direct contact with water or ice.

(4) mixing a solution of aluminoxane and a hydrocarbon suspension of an adsorbed water-containing compound or a crystalline water-containing compound;
A method of bringing aluminoxane into contact with adsorbed water or water of crystallization.

Note that the aluminoxane solution as described above may contain other components as long as they do not adversely affect the reaction between aluminoxane and water.

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

The organoaluminumoxy compound obtained as described above dissolves in benzene at 60°C in an amount of 10% or less, preferably 5% or less, particularly preferably 2%, calculated as one atom of the Ap acid component.
It is insoluble or poorly soluble in benzene.

The solubility of the organoaluminumoxy compound in benzene is determined by suspending the organoaluminumoxy compound corresponding to 100 milligram atoms of AN in 100 ml of benzene, and then mixing at 60°C for 6 hours with stirring. Using a jacketed G-5 glass filter, 60
After performing hot filtration at ℃ and washing the solid part separated on the filter 4 times with 50 ml of benzene at 60℃, the presence ff1 (x mmol) of AJ7 atoms present in the total atom was measured. (X%).

Furthermore, when the above-mentioned benzene-insoluble organoaluminumoxy compound is analyzed by infrared spectroscopy (IR),
Absorbance (D) near 1220cm'',
The ratio (D/D) to the absorbance near 1260 cm-' (D/D) is desirably 0.09 or less, preferably 0.08 or less, particularly preferably in the range of 0.04 to 0.07.

In this specification, infrared spectroscopic analysis of organoaluminumoxy compounds is performed as follows.

First, in a nitrogen box, the organoaluminumoxy compound and Nujol are ground into a paste using an agate needle.

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

The IR spectrum of the organoaluminumoxy compound thus obtained is shown in FIG.

From this IR spectrum, D /D is determined, and the D /D value is determined as follows.

(a) Connect the maximum points near 1280 cm-1 and 1240 cm-1, and define this as the baseline L1.

(b) Transmittance of absorption minimum point near 1260(7)-1 (
T%), draw a perpendicular line from this minimum point to the wave number axis (horizontal axis), read the transmittance (78%) at the intersection of this perpendicular line and baseline L1, and calculate the absorbance (D -1ogT / 12 [i.o.
.

Calculate T).

(c) Similarly, around 1280cm-' and 1180cm-L
Connect nearby maximum points and use this as the baseline L2.

(d) Transmittance of absorption minimum point near 1220 cm-1 (T
' %), a perpendicular line is drawn from this minimum point to the wave number axis (horizontal axis), and this perpendicular line and the baseline L2/T') are calculated.

(e) Calculate D/D from these values.

Incidentally, the IR spectrum of a conventionally known benzene-soluble organoaluminumoxy compound is shown in FIG. As can be seen from Figure 2, benzene-soluble organoaluminumoxy compounds have a D1260/D value of approximately 0,
10-0. Tomorrow, during Step 3, the benzene-insoluble organoaluminumoxy compound obtained by the present invention will be combined with a conventionally known benzene-soluble organoaluminumoxy compound and D.
/D values are clearly different.

It is presumed to have an alkyl oxydialuminum unit represented by the above-mentioned benzene-insoluble organic aluminium.

In the above alkyl oxydialuminum unit, R1
Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, cyclooctyl group, etc. can. Among these, methyl group and ethyl group are preferred, and methyl group is particularly preferred.

In addition to the benzene-insoluble organoaluminum oxydialuminum unit described above, the formula [where R1 is the same as above, and R2 has a carbon number of 1]
~12 hydrocarbon group, alkoxy group having 1 to 12 carbon atoms,
an aryloxy group, a hydroxyl group, a halogen, or hydrogen having 6 to 20 carbon atoms, and R1 and R2 represent mutually different groups. In that case, the alkyloxyaluminum content is 50% by mole or more, particularly preferably 70% by mole.
An organoaluminumoxy compound having an alkyloxydialuminum unit in a proportion of mol % or more is preferred.

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

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

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

In the above formula, M is a transition metal, specifically,
Zirconium, titanium, hafnium, chromium, and vanadium are preferred, and among these, zirconium and hafnium are particularly preferred.

Examples of the ligand having a cycloalkagenyl skeleton include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, a dimethylcyclopentagenyl group, Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

Two or more of the above-mentioned ligands having a cycloalkagenyl skeleton may be coordinated to a transition metal, and in this case, the ligand having at least two cycloalkagenyl skeletons is It may be bonded via a lower alkylene group.

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

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group; aryl groups include phenyl group, tolyl group, etc.; aralkyl groups include benzyl group, Examples include a neophyll group.

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

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

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be exemplified.

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monobromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis( cyclopentadienyl) phenylzirconium hydride, bis(cyclopentadienyl)benzylzirconium hydride, bis(cyclopentadienyl)neopentylzirconium hydride, bis(methylcyclopentadienylnozirconium monochloride hydride, bis(indenyl)zirconium Monochloride Monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dibromide, Bis(cyclopentagenyl)methylzirconium monochloride, Bis(cyclopentagenyl)ethylzirconium monochloride, Bis(cyclopentagenyl)cyclohexylzirconium monochloride, Bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, Bis(methylcyclopentagenyl)zirconium dichloride, Bis(t) -butylcyclopentagenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium diphenyl, bis(cyclopentagenyl)zirconium diphenyl ) zirconium dibenzyl, bis(fluorenyl)zirconium dichloride, bis(
cyclopentagenyl)zirconium methoxychloride, bis(cyclopentagenyl)zirconium ethoxychloride, bis(methylcyclopentagenyl)zirconium ethoxychloride, bis(cyclopentagenyl)zirconium phenoxychloride, ethylenebis(indenyl)dimethylzirconium , Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis(indenyl)methylzirconium monochloride, Ethylenebis(indenyl)ethylzirconium monochloride, Ethylenebis(indenyl)methylzirconium monopromide, Ethylenebis(indenyl)methylzirconium monopromide (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dimethyl, ethylene bis (4,5,8,7-tetra7-drow(-indenyl) dimethyl zirconium, ethylene bis (4,5,6,7-titrahydro- 1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-l-indenyl)zirconium dibromide, Ethylenebis(4-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5-methyl-1-indenyl)zirconium dichloride, Ethylenebis(6-methyl-(-indenyl)zirconium dichloride, Ethylenebis(7-methyl-1) -indenyl) zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-l-indenyl)zirconium Dichloride, ethylenebis(4,7-dimethoxy-l-indenyl)
Zirconium dichloride.

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

Furthermore, the benzene-insoluble organoaluminumoxy compound obtained in the present invention can be used together with other organoaluminum compounds as a catalyst component for olefin polymerization. At this time, the organoaluminum compound used is, for example, RAf1X (wherein R6 is a hydrocarbon-n group having 1 to 12 carbon atoms,
).

In the above formula, R6 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. , pentyl group,
These include hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specifically, the following compounds are used as such organoaluminum compounds.

Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride 1, dimethylaluminum bromide.

Alkylaluminium sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide.

Alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dichloride.

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

In addition, as other organoaluminum compounds, Y is 10R group, -0SI R group, R7R8R and R13 are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc. , RlO is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc.;
1 and R12 are a methyl group, an ethyl group, etc. ) can also be used.

Specifically, the following compounds are used as such organoaluminum compounds.

(i) RAll (OR7) n 3-n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc., (i) RAll (O3iR) n 3 3-n E t AD (OS I Me s ) (l5
o-Bu)2Aρ (OS i Me a ) (Is
o-Bu)2AN (O3I Et 3) etc., (I
ii) RA1 (OAIR) n 2 3-n E t 2 A fI OA fl E t 2 (Is
o-Bu)2Aff OAR(iso-Bu)2, etc.
(1 ■) Me t Me t Ap AR 2A, 17 AD i.

A11) (NR) Et2 HMe HEt N (M e a S 1) 2 -n (iso-Bu) 2 AflS I Me 3, etc., as the above organoaluminum compounds, is an isoalkyl group, and n-2 is preferred. Two or more of these organoaluminum compounds can also be used in combination.

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

Olefins that can be polymerized with such olefin polymerization catalysts include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, ↓-
Butene, l-hexene, 4-methyl-1-pentene, l
-octene, i-decene, [-dodecene, l-tetradecene, l-hexadecene, l-octadecene, i-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.

Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

In the present invention, polymerization can be carried out by either liquid phase polymerization methods such as solution polymerization or suspension polymerization, or gas phase polymerization methods.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually -50 to 200°C, preferably 0 to 200°C.
The temperature range is 150°C. Polymerization pressure is usually normal pressure to 10
0kg/cd, preferably normal pressure ~ 50kg/c+
The polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous systems. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The molecular weight of the resulting olefin polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

When polymerizing olefins using the above catalyst for olefin polymerization, the benzene-insoluble organoaluminumoxy compound usually has a molecular weight of 10-6 to 0.1 gram atom -AN/D, preferably 10 to 10-2 gram atom-1/I), and the transition metal compound having a cycloalkagenyl skeleton is usually 10 to 10-3 mol/ρ
Preferably, the amount is 10 to 10-4 mol/g, and the organic aluminum compound is preferably used in an amount of usually 0 to 0.1 mol/g, preferably 10 to 10-2 mol/g. Further, the ratio of the benzene-insoluble organoaluminum compound (in terms of Ill atoms) to the organoaluminum compound is preferably used in the range of 0.01 to 5, preferably 0.02 to 2.

Note that the above [A] organoaluminumoxy compound may be supported on solid inorganic compounds such as silica, alumina, magnesium oxide, and magnesium chloride, or solid organic compounds such as polyethylene, polypropylene, and polystyrene. can.

An olefin polymerization catalyst formed from a benzene-insoluble organoaluminumoxy compound, a transition metal compound having a cycloalkagenyl skeleton, and an organoaluminum compound as described above has excellent polymerization activity.

That is, the olefin polymerization catalyst containing a benzene-insoluble organoaluminum oxy compound according to the present invention has a higher unit organic aluminum Approximately 1 per weight of oxy compound
．． 2 to 20 times more olefin polymer can be obtained.

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

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

Effects of the Invention When the benzene-insoluble organoaluminumoxy 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 also produces olefin copolymers with narrow molecular weight and composition distributions. Obtainable.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 [Preparation of aluminoxane] Add AN to a 400 ml flask that had been sufficiently purged with nitrogen.
(SO) ・14 H2037g and toluene 125m
After cooling to 0℃, add 125 m of toluene.
500 mmol of trimethylaluminum diluted with 1 ml was added dropwise. Next, the temperature was raised to 40°C, and the reaction was continued at that temperature for 10 hours. After the reaction was completed, solid-liquid separation was performed by filtration, and toluene was further removed from the filtrate to obtain white solid aluminoxane 12K.

Example 1 A 400 ml glass flask that was sufficiently purged with nitrogen was charged with 100 ml of toluene and 4 g of /1 (So) 14 H203-4 remaining on the sieve, which was separated using a 32-mesh sieve and suspended. It was made into a shape. There, at room temperature, a toluene solution of aluminoxane prepared in Reference Example 1 (2.14 mol-A
N/n) 93 ml was added.

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 dividing the mixture using an 80-mesh sieve in a nitrogen atmosphere, and a suspension consisting of fine particle solids and toluene that had passed through the sieve was recovered. Further, this suspension was filtered using a 04 glass filter, the toluene solution portion was removed, and the solid portion was recovered, and then resuspended in toluene. From the measurement results of sulfate groups in the resuspension, the amount of sulfate AII in the resuspension could be considered to be 0.1 mol% or less based on the total AN atoms.

In addition, a portion of the solid was recovered without being resuspended in toluene.
A dry solid (organoaluminumoxy compound) obtained by drying under reduced pressure at room temperature was added to a 200 ml reactor equipped with a stirrer in an amount of 100 mmol in terms of AII atoms, and an additional 100 mmol was added.
ml of benzene was added, and the mixture was stirred and mixed at 60° C. for 6 hours. This suspension was filtered while hot using a jacketed G5 glass filter while keeping the silicone oil poured into the jacket at 60°C.
Washed 4 times using 0ml. When the filtrate was collected and the amount of Al in the filtrate was measured, Afi equivalent to 0.4 mmol was found.
was detected, it was considered that the amount of AfI component dissolved in benzene at 60° C. in the solid organoaluminumoxy compound was 0.4% in terms of AJ) atoms. others,
When the above-mentioned solid organoaluminumoxy compound was subjected to IR measurement, the IR spectrum showed 600 to 8
Absorption in the Aj)-0-Ap atomic group is seen at 00 cm-1, and the absorbance (D) at 1220 cm
and the absorbance (D ) at 1260(7) (D
/D122o) was 0.068. Generation of methane was observed due to decomposition with water, and the specific surface area was 30 g/bo.

A polymerization activity test of the benzene-insoluble organoaluminumoxy compound prepared above was conducted as follows.

After charging 900ml of 4-methyl-1-pentene into a 2g stainless steel autoclave that had been sufficiently purged with nitrogen,
The temperature was raised to °C, and the solid component obtained in Example 1, that is, a toluene suspension of a benzene-insoluble organoaluminumoxy compound (0.44 ml -A (1/D) 0.2
2 ml and (1-Bu) 2-A N O-A D
(1-Bu) in toluene solution (1 mol-1/g
)1 ml was added. After further increasing the temperature to 75℃,
Toluene solution of bis(methylcyclopentadienyl)zirconium dichloride il&(0,001 mol-Z r
/1) 1 m! was injected together with ethylene to start polymerization. Total pressure of 8 kg while continuously supplying ethylene
/cE-G, when polymerized at 80℃ for 40 minutes, the MFR was 1.20g/10min, and the density was 0.18g/10min.
88 g/a+] and My/Mn was 2.2. 92.4 g of an ethylene/4-methyl-I-pentene copolymer was obtained.

Example 2 32.8 ml of toluene and 0.78 g of pulverized 6-Eiwa salt of magnesium chloride were charged into a 400 ml glass flask which was sufficiently purged with nitrogen to form a slurry. There, at room temperature, 25 toluene solution of aluminoxane prepared in Reference Example 1 (2.31 mol-All/U) was added.
ml was added.

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. When the concentration of aluminum dissolved in the filtrate was measured, it was found to be below the detection limit of 5.times.-1/I).

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 organoaluminumoxy compound prepared above was conducted as follows.

After charging 900 ml of 4-methylutopentene into a 2 g stainless steel autoclave that had been sufficiently purged with nitrogen,
The temperature was raised to 0.degree. C., and a toluene suspension of the solid component obtained in Example 2, that is, a benzene-insoluble organoaluminumoxy compound (0.44 ml -A I)/D ) 0. 2
2 ml and (i-Bu) 2-AN-0-A, l) (
1-f3u) Toluene solution of 2 (1 mol-Ag/D
) 1 ml was added. After further increasing the temperature to 75℃,
Toluene solution M of bis(methylcyclopentadienyl)zirconium dichloride (0,001 mol-Zr/, Q)
1 ml was injected together with ethylene to start polymerization. Total pressure 8 kg/c while continuously cofeeding ethylene
J-G, when polymerization was carried out at 80'C for 40 minutes, the MFR was 1.51 g/10 minutes, and the density was 0.88.
511-/- and My/Inn of 2.1, 95.4 g of ethylene/4-methyl-1-pentene copolymer was obtained.

Examples 3 to 11 A benzene-insoluble organoaluminumoxy compound was prepared in the same manner as in Example 2 under the conditions shown in Table 1. Manufactured.

Further, Table 2 shows the results of a polymerization activity test conducted in the same manner as in Example 2 and 11.

Example 12 Into a 400 ml glass flask that was sufficiently purged with nitrogen, 59.7 ml of toluene and a toluene solution of aluminoxane (AN 2.48) prepared in the same manner as in Reference Example 1 were added.
Mol-Aff/g) 40.3 ml, and a Teflon cylinder (φ21 IIX 1.2 mm) 25 f as a dispersant.
was loaded. Thereafter, it was cooled to -5°C and water 0. ,72m
1 was added gradually with a pipette. Continue to 40 at -5℃
The mixture was allowed to react for a minute, then the temperature was raised to 80° C. over 1 hour, and the reaction was continued at that temperature for an additional 3 hours. After 3 hours of reaction, the Teflon cylinder was removed using a sieve, and solid-liquid separation was performed by filtration to obtain a benzene-insoluble organoaluminumoxy compound. When the concentration of aluminum dissolved during filtration was measured, it was found to be below the detection limit of 5-Al171.

Further, the solubility in benzene at 60° C. was examined in the same manner as in Example 1, and it was found to be 0.7%.

(D /D) was 0.053.

The polymerization activity test of the benzene-insoluble organoaluminumoxy compound prepared above was conducted in the same manner as in Example 2.

The results are shown in Table 2.

Suishi Treasure (%) Rurayyu Heikku

[Brief explanation of the drawing]

FIG. 1 is an IR spectrum of the benzene-insoluble organoaluminumoxy compound used in the present invention, and the second
The figure shows an IR spectrum of a conventionally known benzene-soluble organoaluminum compound.

Claims (1)

[Claims] 1. A method for producing an organoaluminumoxy compound in which an Al component dissolved in benzene at 60° C. is 10% or less in terms of Al atoms, the method comprising bringing a solution of aluminoxane into contact with water.