JPH0278687A - Method for producing benzene-insoluble organoaluminumoxy compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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.

Conventionally, as catalysts for producing α-olefin polymers such as ethylene polymers or ethylene/α-olefin copolymers, titanium-based catalysts made of a titanium compound and organoaluminium, or vanadium compounds made of a vanadium compound and an organoaluminium compound have been used as catalysts. catalysts are known.

Generally, ethylene/α-olefin copolymers obtained using titanium-based catalysts have a wide molecular weight distribution and composition 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 cyclopentagenyl, alkyl of 01 to CB, or halogen, Me is a transition metal,
HaJ7 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 the same as above], ethylene and A method for producing an ethylene/α-olefin copolymer is described in which one or more C-C12 α-refines 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 No. 59-95292 describes a linear aluminoxane represented by the following formula, [where n is 2 to 40, and R is 01 to 6°C], and a linear aluminoxane represented by the following formula [where n and The invention relates to a method for producing a cyclic aluminoxane represented by [the definition of R is the same as above]. The publication describes, for example, methylaluminoxane and titanium or zirconium bis(
It is stated that when olefins are polymerized by mixing with cyclopentadienyl) compounds, 25 million g or more of polyethylene can be obtained per 1 g of transition metal and per hour.

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 Tl 1V
The publication discloses a method for producing a polymerization catalyst for olefins by treatment with a compound of SZr or C. It is described as being particularly suitable.

JP-A No. 60-35006 discloses that two or more different transition metals of hepnotic, di- or tricyclopentadienyl or its derivative (a) and aluminoxane ( A combination with b) 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 with 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 dichloride, bis(methylcyclopentadienyl)zirconium dichloride, and aluminoxane. , a toluene soluble portion containing a propylene component with a number average molecular weight of 2.200, a weight average molecular weight of 11,900 and 30 mol%, and a propylene component with a number average molecular weight of 3,000, a weight average molecular weight of 7.400 and 4.8 mol%. A number average molecular weight of 2.0 consisting of a toluene-insoluble portion containing
00, 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, Example 3 contained LLDPE consisting of a soluble portion with a molecular weight distribution (My/Mn) of 4.57 and a propylene component of 20.6 mol%, and an insoluble portion with a molecular weight distribution of 3.04 and a propylene component of 2.9 mol%. Blends of ethylene-propylene copolymers are described.

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 polymerization is carried out in the presence of a catalyst system containing 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 about 1.5 to 4.0.

JP-A No. 60-35008 discloses that by using a catalyst system containing at least two types of metallocene and aluminoxane, polyethylene or ethylene having a wide molecular weight distribution and α-olefin of C3 to C1° can be combined. 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.

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; No. 148491 discloses an organic aluminum compound, a magnesium compound,
It is taught that aluminoxane can be obtained by reacting a compound containing water of crystallization selected from the group consisting of nickel compounds and lanthanide compounds;
No. 3-56508 discloses 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. It has been taught that.

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 determined by the freezing point depression method by 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 an active hydrogen-containing compound, and the resulting benzene-insoluble organoaluminumoxy compound is The Al component dissolved in benzene at 60° C. is 10% or less in terms of Al 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.

DETAILED DESCRIPTION OF THE INVENTION 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 an active hydrogen-containing compound.

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, sulfuric acid hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to a suspension in a hydrocarbon medium, causing a reaction, and recovering 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. After removing the solvent and unreacted organoaluminum compound by distillation from the recovered aluminoxane solution, it may be redissolved in the solvent.

Specifically, the organoaluminum compounds used in producing such an aluminoxane solution include trimethylaluminum, triethylaluminum,
Tripropylaluminium, triisopropylaluminium, tri-n-butylaluminum, triisobutylaluminum, tri-5ee-butylaluminum, tri-t
trialkylaluminum such as ert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, diethylaluminum chloride, diethylaluminum chloride, diethylaluminium bromide, diisobutylaluminum Dialkyl aluminum halides such as chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride, diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide,
Examples include dialkyl aluminum alkoxides such as diethylaluminium phenoxide.

Among these, trialkylaluminum is particularly preferred.

Moreover, isoprenyl aluminum represented by the general formula %) can also be used as an organoaluminum 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 cyclopenkune, cyclohexane, cyclooctane, cyclodecane, and cyclododecane, petroleum fractions such as gasoline, kerosene, and light oil, or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Examples include hydrocarbon solvents such as chlorides, bromides, etc., among others. 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 bringing the above aluminoxane solution into contact with an active hydrogen-containing compound.

The active hydrogen-containing compounds used in the present invention include alcohols such as methanol, ethanol, ■-propanol, and isoprobal, diols such as ethylene glycol and hydroquinone, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, acetic acid, Organic acids such as propionic acid are used. Among these, alcohols and diols are preferred, and alcohols are particularly preferred.

The active hydrogen-containing compound to be contacted with the aluminoxane solution may be 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 in a vapor state. It can be used in Further, as the active hydrogen-containing compound, active hydrogen-containing compounds adsorbed on inorganic compounds such as magnesium chloride, aluminum sulfate, copper sulfate, nickel sulfate, silica, alumina, or polymers can also be used.

The contact reaction between the aluminoxane solution and the active hydrogen-containing compound is usually carried out in a solvent, such as a hydrocarbon solvent. Hydrocarbon solvents used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, cyclodecane, and cyclododecane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene, and light oil; or the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. It is also possible to use halogenated hydrocarbons, especially halogenated hydrocarbons such as chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran. Among these media, aromatic hydrocarbons are particularly preferred.

The active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, per Al atom in the aluminoxane solution. The concentration in the reaction system is usually lXl0- in terms of aluminum atoms.
It is desirable that the range is 3 to 5 gram atoms/g, preferably 1 x 10-2 to 3 gram atoms/I, and the concentration of the active hydrogen-containing compound in the reaction system is usually 2 x 10-' to 5
Mol/g preferably 2X10-3 to 3 mol/j! It is desirable that the concentration is .

Specifically, the aluminoxane solution and the active hydrogen-containing compound may be brought into contact as follows.

(1) A method of bringing a solution of aluminoxane into contact with a hydrocarbon solvent containing an active hydrogen-containing compound.

(2) A method of bringing the aluminoxane and the vapor of the active hydrogen-containing compound into contact by, for example, blowing the vapor of the active hydrogen-containing compound into the aluminoxane solution.

(3) A method in which an aluminoxane solution and an active hydrogen-containing compound are brought into direct contact.

(4) A method of mixing a solution of aluminoxane and a hydrocarbon suspension of a compound to which an active hydrogen-containing compound has been adsorbed, and bringing the aluminoxane and the active hydrogen-containing compound into contact.

Note that the aluminoxane solution as described above may contain other components as long as they do not adversely affect the reaction between the aluminoxane and the active hydrogen-containing compound.

The contact reaction between the aluminoxane solution and the active hydrogen-containing compound as described above is usually carried out at a temperature of -50 to 200°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 0.5 to 300 hours, preferably 1 to 1 hour.
It takes about 50 hours.

This benzene-insoluble organic a[formula,
R1 is a hydrocarbon group having 1 to 12 carbon atoms] is estimated to have an alkyl oxydialuminum unit,
Moreover, the l component that dissolves in benzene at 60° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, and is insoluble or poorly soluble in benzene.

The solubility of the organoaluminumoxy compound according to the present invention is determined by suspending the organoaluminumoxy compound equivalent to 1 in 100 milligram atoms in 100ml of benzene, mixing at 60°C for 6 hours with stirring, and then adding a jacketed suspension. After performing hot filtration at 60°C using a G5 glass filter and washing the solid portion separated on the filter four times with 50ml of benzene at 60°C, the amount of All atoms present in the filtrate was determined. (X%) is determined by measuring (x mmol).

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.

The benzene-insoluble organoaluminumoxy compound according to the present invention includes, in addition to the alkyloxyaluminum unit represented by the formula -←0Afi+, the oxydialuminum unit represented by the formula →OA, Q+ [where R is the same as above; , R2 is a hydrocarbon group having 1 to 12 carbon atoms;
12 alkoxy group, aryloxy group having 6 to 20 carbon atoms, hydroxyl group, halogen or hydrogen; R1 and R2
represent mutually different groups]. In that case, an organoaluminumoxy compound having an alkyloxyaluminum unit containing alkyloxyaluminum in a proportion of 50 mol% or more, particularly preferably 70 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 a catalyst for olefin polymerization together with the benzene-insoluble organoaluminumoxy compound obtained in the present invention has the formula MLx (wherein M is a transition metal, L is a ligand that coordinates to a transition metal, at least one of which is a ligand having a cycloalkagenyl skeleton, and when L contains at least two or more ligands having a cycloalkagenyl skeleton; The ligands having at least two cycloalkagenyl skeletons may be bonded via a lower alkylene group, and the ligands other than those having cycloalkagenyl skeletons have 1 to 12 carbon atoms. is a hydrocarbon group, alkoxy group, aryloxy group, 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 monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl) neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis(indenyl) Zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dichloride, 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(cyclopentagenyl)zirconium methoxychloride, Bis(cyclopentagenyl)zirconium ethoxychloride, Bis(methylcyclopentagenyl)zirconium ethoxychloride, Bis(cyclopentagenyl)zirconium phenoxychloride , Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)dimethylzirconium, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis(indenyl)methylzirconium monochloride, Ethylenebis(indenyl)ethylzirconium monochloride Chloride, Ethylenebis(indenyl)methylzirconium monopromide, Ethylenebis(indenyl)zirconium dichloride, Ethylenebis(indenyl)zirconium dibromide, Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, Ethylenebis(4,5,8 ,7-tetrahydro-l-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-■-indenyl)zirconium dichloride, ethylenebis(6-methyl-1- indenyl) zirconium dichloride, ethylenebis(7-methyl-■-indenyl)zirconium dichloride, ethylenebis(5-methoxytoindenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis (4,7-dimethyl-l-indenyl)zirconium dichloride, ethylenebis(4,7-simethoxy-1-indenyl)
Zirconium dichloride and transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, or vanadium metal in the above-mentioned zirconium compounds can also be used.

Furthermore, the benzene-insoluble organoaluminumoxy compound obtained in the present invention can also be used as a catalyst component for olefin polymerization together with other organoaluminum compounds. The organoaluminum compound used in this case is, for example, RlBAgX (wherein R8 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.

Alkylaluminum sesquino 1lides 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 diisobutyl aluminum hydride.

In addition, as other organoaluminum compounds, for example, R6n1 Y (wherein R6 is -n as above, Y is 10R group, OS I R8a group, -O
AgR9210□ group, -5IR''3 group, -NR, R, R, R and R13 are methyl group, ethyl group,
They are isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., RlO is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R11 and R12 are methyl group, ethyl group, etc.:) Compounds represented by can also be used.

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

(i) RAff (OR7) n 3-n dimethylaluminum methoxide, diethylaluminium ethoxide, diisobutylaluminum methoxide, etc. (i) R1? (OSiR) n 3 t1E t
All (OS I Me a) (iso-
Bu) Al (O8IMe3)Cl5o-B
u) All (OS I E t a ) etc., (i
)RAg (OAp R) R23-n Et 2Al 01! Et 2 (Iso-Bu) All OAR (lso-Bu)
2 etc., 6 lO (+V) Rp, I (NR> n 2 3-nMe 2A
D NEt 2 E t 2 A j! N HM e M e 2 A fl N HE t E t A M N (Me a S i) 2 (Is
o-Bu) AlN(Me3Sl)2, etc., 6
kl(ν)R1(SI
R) n 3 3-n(1so
-Bu) A, l! 51 Me 3 etc., Et 2
Ag〒1! Et 2 Me (iso-Bu) AD NAI! (1so-B
u) 2 etc.

Et As an organoaluminum compound as described above, 1(OA
gR) is preferred, and in particular, R823-n is an isoalkyl group, and n-2 is preferred, and two or more of these two organoaluminum compounds can also be used as a mixture.

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 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 using such olefin polymerization catalysts include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene,
Butene, ■-hexene, 4-methyl-l-pentene, 1
-octene, ■-decene, ■-dodecene, ■-tetradecene, l-hexadecene, ■-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.

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
0 kg/cd, preferably normal pressure ~ 50 kg/cd
The polymerization reaction can be carried out in any of the batch, semi-continuous and continuous methods. 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 hydrogen and/or polymerization temperature.

When polymerizing olefins using the above catalyst for olefin polymerization, the benzene-insoluble organoaluminumoxy compound usually has a molecular weight of 10-8 to 0.1 gram atom-1'fj/fl, preferably 10-5 ~10-
In an amount of 2 gram atom-Aft/fl, transition metal compounds with a cycloalkagenyl backbone are usually
10-3 mol/g preferably 10-7 to 10-4 mol/g
In addition, the amount of the organoaluminum compound is usually 0 to
It is desirable to use it in an amount of 0.1 mol/fl, preferably 10 to 10-2 mol/g. Further, the ratio of the benzene-insoluble organoaluminum compound (in terms of 1 atom) 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.

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] Af was added to a 400 ml flask that had been sufficiently purged with nitrogen.
2037 g of I(So) 14 H and 125 ml of toluene were charged, and after cooling to 0° C., 500 mmol of trimethylaluminum diluted with 125 ml of toluene 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 12 g of white solid aluminoxane.

Example 1 In a 400 ml glass flask that was sufficiently purged with nitrogen,
60.3 ml of toluene and the toluene solution of aluminoxane prepared in Reference Example 1 (2.23 mol-Al/I
89.7 ml of I) was charged, and the temperature inside the system was set at 40°C. 80 mmol of methanol diluted with 50 ml of toluene was added dropwise thereto, and the mixture was reacted for 60 hours. Thereafter, solid-liquid separation was performed by filtration to obtain a solid component, that is, a benzene-insoluble organic aluminum oxy compound. (Yield per Aff 67.6%). In addition, when the concentration of aluminum dissolved in the filtrate was measured, it was found that the detection limit was 5 mmg-A.
It was less than 1/g.

100 milligrams of the benzene-insoluble organoaluminumoxy compound obtained as above was added to a 200 ml reactor equipped with a stirrer in terms of Afi atoms, and 1
00 ml of benzene was added and mixed with stirring at 60°C for 6 hours. This suspension was filtered using a jacketed G5 glass filter, and the silicone oil poured into the jacket was heated to 60°C.
Hot filtration was carried out while maintaining the temperature at 0.degree. C., and further washing was performed four times using 50 ml of benzene at 60.degree. When the filtrate was collected and the amount of 11 in the filtrate was measured, it was found that A equivalent to 0.4 mmol
l7 was detected. That is, the amount of the l component of the organoaluminumoxy compound dissolved in benzene at 60° C. was considered to be 0.4% in terms of Ag atoms. In addition, when the above solid organoaluminumoxy compound was subjected to IR measurement, the IR spectrum showed 600 to 800 cm.
Absorption in the Al-0-1 atomic group was observed at -', and generation of methane was observed due to decomposition by water.

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

After charging 900 ml of 4-methyl-1-pentene into a 2 g stainless steel autoclave that had been sufficiently purged with nitrogen,
The temperature was raised to 0°C, and a toluene suspension of the solid component obtained in Example 1, that is, a benzene-insoluble organoaluminumoxy compound (0.75 mol-Aj!/fl) 0.6
7 ml and (1-Bu) 2- A I 0- Al1
(1-Bu) 2 toluene solution (1 mol-AIl/
I) 1 ml was added. After further raising the temperature to 75°C, a toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (0,001 mol-Zr/N)
5 ml was injected together with ethylene to start polymerization. Total pressure 20 kg/c with continuous supply of ethylene
j-G, when polymerization was carried out at 80°C for 10 minutes,
[η] measured in decalin at 135°C is 3.3 dl/l
Ethylene/4-methyl-1-pentene copolymer 4
1 g was obtained.

Agent: Patent Attorney: Shunbetsu Suzuki

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 an active hydrogen-containing compound.