JP2837720B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst. More specifically, the present invention relates to an olefin having excellent polymerization activity and a wide molecular weight distribution (copolymer). The present invention relates to a novel catalyst for olefin polymerization capable of providing a polymer and a method for olefin polymerization using the catalyst.

BACKGROUND 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 an organic aluminum, generally a titanium catalyst The olefin polymer obtained in (1) had a wide molecular weight distribution and a wide composition distribution, and particularly had a wide composition distribution, and thus had poor surface non-adhesiveness and transparency.

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.

In addition, Japanese Patent Publication No. 1-501950 and Japanese Patent Publication No. 1-502036
The publication discloses a method for producing a transition metal compound catalyst containing a ligand having a cycloalkadienyl skeleton and containing an anion containing a boron element, and this catalyst exhibits activity in olefin polymerization. Is taught.

The olefin polymer obtained by using the above-mentioned new Ziegler-type olefin polymerization catalyst usually has a narrow molecular weight distribution and a narrow composition distribution. Therefore, depending on the application, an olefin polymer having a wide molecular weight distribution and excellent moldability has been desired.

Also, when an olefin is polymerized or copolymerized in the presence of a transition metal compound catalyst containing a ligand having a cycloalkadienyl skeleton, it is difficult to obtain an olefin polymer having a high molecular weight, and thus an olefin polymer having a high molecular weight is obtained. There has been a demand for the appearance of a transition metal compound catalyst containing a ligand having a cycloalkadienyl skeleton so as to obtain the compound (1).

Object of the Invention The present invention has been made in view of the prior art as described above, and has a good balance of having excellent polymerization activity, wide molecular weight distribution, excellent moldability, and narrow composition distribution. An object of the present invention is to provide an olefin polymerization catalyst capable of obtaining an olefin polymer and a method for polymerizing an olefin using the catalyst.

SUMMARY OF THE INVENTION An olefin polymerization catalyst according to the present invention comprises: [A] a titanium catalyst component containing titanium, magnesium and halogen as essential components; [B] a ligand having a cycloalkadienyl skeleton; And a transition metal compound containing a transition metal selected from the group consisting of titanium, zirconium and hafnium, and [C] an organic aluminum compound and / or an organic aluminum oxy compound. And

The olefin polymerization catalyst and the olefin according to the present invention may be preliminarily polymerized.

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

The olefin polymerization catalyst according to the present invention has excellent polymerization activity and can provide a high molecular weight olefin polymer having a wide molecular weight distribution and excellent moldability.

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

FIG. 1 shows an explanatory diagram of the olefin polymerization catalyst according to the present invention.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. Sometimes used in

The olefin polymerization catalyst according to the present invention comprises: [A] a titanium catalyst component having titanium, magnesium and halogen as essential components, and [B] a ligand having a cycloalkadienyl skeleton and containing a boron element. A transition metal compound containing an anion and containing a transition metal selected from the group consisting of titanium, zirconium and hafnium; and [C] an organic aluminum compound and / or an organic aluminum oxy compound.

First, [A] a titanium catalyst component containing titanium, magnesium and halogen as essential components will be described. This titanium catalyst component [A] contains titanium, magnesium and halogen as essential components and further contains an electron donor as necessary. And preferably in the form of a solid.

Such a titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound and, if necessary, an electron donor.

In the present invention, the titanium compound used for preparing the titanium catalyst component [A] includes, for example, Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4). More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (Oiso C ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti _{(On-C 4 H 9)} 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti ( Mono-halogenated trialkoxy titanium such as On-C ₄ H ₉ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ Examples thereof include tetraalkoxy titanium such as H ₉ ) ₄ Ti (Oiso-C ₄ H ₉ ) ₄ Ti (O-2-ethylhexyl) ₄ .

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a reducing magnesium compound include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, butylmagnesium chloride. Examples include magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butylethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium halide, and the like. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound include: magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxychloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyloximers such as phenoxymagnesium and dimethylphenoxymagnesium Neshiumu; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

In the present invention, the magnesium compound, in addition to the magnesium compound having a reducing property and the magnesium compound having no reducing property, a complex compound of the magnesium compound and another metal, a double compound or another metal compound. May be used. Further, a mixture of two or more of the above compounds may be used.

In the present invention, among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

In the present invention, in preparing the titanium catalyst component [A], it is preferable to use an electron donor. As the electron donor, alcohols, amines, amides, ethers, ketones, esters, nitriles, Examples thereof include phosphines, stippins, arsines, phosphoramides, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, and organic acids. Of these, alcohols, amines, ethers, esters, acid anhydrides, alkoxy (aryloxy) silanes, and organic acids are preferably used.

In the present invention, the titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium) into contact with a titanium compound and, if necessary, an electron donor. To produce the titanium catalyst component, a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and, if necessary, an electron donor can be employed.
The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The production method of these titanium catalyst components will be briefly described below with several examples.

In the method for producing the titanium catalyst component [A] described below, an example in which an electron donor is used will be described. However, the electron donor is not necessarily used.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing property;
A method of reacting a liquid titanium compound in the presence of an electron donor to precipitate a solid magnesium-titanium composite.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A solid obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. In this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(9) magnesium compound and alkoxycitane and / or
Or a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as an alcohol or an ether is reacted with a halogen-containing compound such as a titanium compound and / or a halogen-containing silicon compound.

(10) A method in which a liquid magnesium compound having no reducibility is reacted with an organoaluminum compound to precipitate a solid magnesium-aluminum composite, and then a titanium compound is reacted.

Among the methods for preparing the titanium catalyst component [A] described in the above (1) to (10), the methods (1) to (4) and (10) are preferably used.

The amount of each of the above components used in preparing the titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally.
Per mole, the electron donor is about 0.01 to 20 moles, preferably 0.1 to 20 moles.
In the amount of 05 to 10 mol, the titanium compound is used in an amount of about 0.01 to 500 mol, preferably 0.05 to 300 mol.

The titanium catalyst component thus obtained contains magnesium, titanium and halogen and, if necessary, an electron donor as essential components.

In this titanium catalyst component [A], halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100, and the electron donor / titanium (molar ratio) is about 0.1 to 50,
Preferably, it is about 0.2 to about 25, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.

When the titanium catalyst component [A] is in a solid state, it contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 10 m ² / g or more, preferably about 30 to 30 m ² / g. 1000 m ² / g, more preferably from about 50 to 800 m ² / g. The titanium catalyst component [A] does not substantially change its composition due to the hessian washing because the above components are combined to form a catalyst component.

The method for preparing such a highly active titanium catalyst component [A] is described in, for example, JP-A-50-108385 and JP-A-50-108385.
No. 126590, No. 51-20297, No. 51-28189, No. 51-64586, No. 51-2885, No. 51-136
No. 625, No. 52-87489, No. 52-100596,
No. 52-147688, No. 52-104593, No. 532580, No. 53-40093, No. 53-40094, No. 53-
No. 43094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-119
No. 08, No. 56-18606, No. 58-83006,
JP-A-58-138705, JP-A-58-138706, JP-A-58-138707
JP-A-58-138708, JP-A-58-138709,
Nos. 58-138710, 58-138715, 60-23404
No. 60-195108, No. 61-21109, No. 6
These are disclosed in, for example, JP-A-37802 and JP-A-61-37803.

[B] A transition metal compound containing a ligand having a cycloalkadienyl skeleton and containing an anion containing a boron element and containing a transition metal selected from the group consisting of titanium, zirconium and hafnium used in the present invention Is a transition metal compound containing a ligand having a [Ba] cycloalkadienyl skeleton, containing an anion containing a boron element, and containing a transition metal selected from the group consisting of titanium, zirconium and hafnium; Ba] a transition metal compound containing a ligand having a cycloalkadienyl skeleton, including a transition metal selected from the group consisting of titanium, zirconium and hafnium, [Bb] Bronsted acid or proton, and [Bc] boron It is a reaction product with an anion containing an element.

The transition metal compound containing a ligand having a [Ba] cycloalkadienyl skeleton and containing a transition metal selected from the group consisting of titanium, zirconium and hafnium used in the present invention is represented by the following formula: ML _x Is a transition metal, L is a ligand coordinated to the transition metal, at least one L is a ligand having a cycloalkadienyl skeleton, and a ligand having a cycloalkadienyl skeleton is When containing at least two or more, the ligand having at least two cycloalkadienyl skeletons may be bonded via a cross-linking group such as an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. L other than a ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms 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, and particularly preferably zirconium and hafnium.

As the ligand having a cycloalkadienyl skeleton,
For example, alkyl-substituted cyclopentane such as cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-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 cross-linking group such as an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms 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.

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) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) ) Neopentyl zirconium hydride, bis (methylcyclopentadienyl) dimethyl zirconium, bis (n-butylcyclopentadienyl) dimethyl zirconium, bis (indenyl) dimethyl zirconium, (pentamethylcyclopentadienyl) (cyclopentadienyl ) Dimethyl zirconium, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) dimethyl zirconium, Bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dihydride, bis (fluorenyl) dimethyl zirconium, ethylenebis (indenyl) dimethyldicornium, ethylene Bis (indenyl) diethyl zirconium, ethylenebis (indenyl) zirconium dihydride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4-methyl-1-indenyl) dimethylzirconium, Ethylene bis (5-methyl-1-indenyl) dimethyl zirconium, ethylene bis (6-methyl-1-indenyl) dimethyl zirconium, ethylene bis (7-methyl-1-indenyl) Dimethyl zirconium, ethylene bis (5-methoxy-1-indenyl) dimethyl zirconium, ethylene bis (2,3-dimethyl-1-indenyl) dimethyl zirconium, ethylene bis (4,7-dimethyl-1-indenyl) dimethyl zirconium, ethylene Bis (4,7-dimethoxy-1-indenyl)
Dimethylzirconium, methylenebis (cyclopentadienyl) zirconium dihydride, methylenebis (cyclopentadienyl) dimethylzirconium, isopropylidenebis (cyclopentadienyl) zirconium dihydride, isopropylidenebis (cyclopentadienyl) dimethylzirconium, isopropylidene Lidene (cyclopentadienyl-fluorenyl) zirconium dihydride, isopropylidene (cyclopentadienyl-fluorenyl) dimethyl zirconium, silylene bis (cyclopentadienyl) zirconium dihydride, silylene bis (cyclopentadienyl) dimethyl zirconium, dimethyl silylene bis (Cyclopentadienyl) zirconium dihydride, dimethylsilylenebis Lopentadienyl) dimethyl zirconium.

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

The [Bb] Bronsted acid used in the present invention has a formula [M ² R ₄ ] ⁺ (where M ² is nitrogen or phosphorus, R is a hydrogen or hydrocarbon group, and at least one R Is hydrogen.)
Indicated by

In the above formula, as the hydrocarbon group, an alkyl group,
Examples thereof include a cycloalkyl group, an aryl group, and an aralkyl group.Specifically, as the alkyl group,
Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.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 and a neophyl group.

As the above-mentioned [Bb] Bronsted acid, specifically, the following compounds are used.

 Trimethylammonium, triethylammonium, tripropylammonium, tri (n-butyl) ammonium, N, N-dimethylanilinium N, N-diethylanilinium, N, N-2,4,5-pentamethylanilinium, di ( i-propyl) ammonium, dicyclohexylammonium, triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium.

The [Bc] boron-containing anion used in the present invention has the formula [BR ¹ R ² R ³ R ⁴ ] (wherein B is boron and R ¹ and R ² are aromatic or aromatic carbonized). A hydrogen group, and R ³ and R ⁴ are hydrogen, a halogen, a hydrocarbon and a substituted hydrocarbon group, or an organic metalloid group.) Or a formula [(CR ⁵ ) x ₁ (BR ⁶ ) x ₂ R ⁷ x ₃ ] ^a- (wherein C and B are carbon and boron, respectively, R ⁵ , R ⁶ , and R ⁷ are hydrogen, a hydrocarbon group or an organic metalloid group, and x ₁ and x ₃ are integers of ≧ 0 Where a is an integer ≧ 1, x ₁ + x ₃ + a is an even number from 2 to about 8, and x ₂ is an integer from 5 to about 22.) or the formula [[[CR ⁸ ) x ₁ (BR ⁹ ) x ₂ (R ¹⁰ ) x ₃ ] ^a- ] ₂ M ⁿ ] ^b- (where C, B and M are carbon, boron and a transition metal, respectively, and R ⁸ , R ⁹ and R ¹⁰ Is hydrogen, ha Gen,
A hydrocarbon group or an organic metalloid group, x ₁ and x ₃
Is an integer of ≧ 0, a is an integer of ≧ 2, x ₁ + x ₃ + a = an even number from 4 to about 8, x ₂ is an integer from 6 to about 12, and n is 2a−n = b Where b is ≧ 1
Is an integer. Or the formula [(CH) x ₁ (BH) x ₂ ] ^a- (where C, B and H are carbon, boron and hydrogen respectively, x ₁ is 0 or 1 and a is 2 1 and x ₁
+ A = a 2, x ₂ is an integer from 10 to 12. ).

As the anion containing the [Bc] boron element as described above, specifically, the following compounds are used.

Tetraphenylborate, tetra (p-tolyl) borate, tetra (o-tolyl) borate, tetra (m, m-dimethylphenyl) borate, tetra (o, m-dimethylphenyl) borate, tetra (pentafluorophenyl) borate, 7,8-dicarbaundecaborate, tridecahydride-7-carbaundecaborate, octadecaborate, bis (undecahydride-7,8-dicarbaoundecaborate) cobaltate (III), bis (7,8- (Dicarboundecaborate) nickelate (III), bis (7,8-dicarboundecaborate) ferrate (III), dodecaborate, 1-carboundecaborate, 1-carbadodecaborate.

The [C] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane,
Further, it may be a benzene-insoluble organic aluminum oxy compound found by the present inventors.

The aluminoxane as described above can be produced, for example, by the following method.

(1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as trialkylaluminum is directly allowed to act on water, ice or steam in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover as a hydrocarbon solution.

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

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

Of these, trialkyl aluminum is particularly preferred.

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

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

Solvents used in the solution of aluminoxane include:
Aromatic hydrocarbons such as benzene, tolene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane Petroleum fractions such as alicyclic hydrocarbons, gasoline, kerosene and light oil, or hydrocarbon solvents such as the above aromatic hydrocarbons, aliphatic hydrocarbons and halides of alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. No. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of not more than 10%, preferably not more than 5%, particularly preferably not more than 2% in terms of Al atom. Insoluble or poorly soluble.

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

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

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

First, in a nitrogen box, the organoaluminum oxy compound and nujol are ground in an agate 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.

Of the organoaluminum oxy compound used in the present invention
The IR spectrum is shown in FIG.

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

(B) 1280 cm ^-1 bear maximum point in the vicinity of and around 1240 cm ^-1, which is the baseline L _1.

(B) the transmittance (T%) at the absorption minimum point near 1260 cm ^-1 ,
A vertical line with wavenumber axis (horizontal axis) from the minimum point, reads the transmittance of intersection of the perpendicular line and the baseline _{L 1 (T 0%),} 1260cm -1 vicinity of absorbance (D ₁₂₆₀ = log T _o Calculate / T.

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

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

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

FIG. 3 shows the IR spectrum of a conventionally known benzene-soluble organic aluminum oxy compound. As can be seen from FIG. 3, the benzene-soluble organoaluminum oxy compound has a D ₁₂₆₀ / D ₁₂₂₀ value of about 0.10 to 0.13.
The benzene-insoluble organoaluminum oxy compound used in the present invention is clearly different from the conventionally known benzene-soluble organoaluminum oxy compound in the D ₁₂₆₀ / D ₁₂₂₀ value.

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

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

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

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

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

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

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

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

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

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

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

(2) A method in which water or an active hydrogen-containing compound vapor is blown into a solution of aluminoxane to bring the aluminoxane into contact with the vapor.

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

(4) A solution of aluminoxane and a hydrocarbon suspension of a compound containing adsorbed water or a compound of water of crystallization or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound is adsorbed are mixed with each other to form aluminoxane. A method of contacting adsorbed water or water of crystallization.

The aluminoxane solution as described above may contain other components as long as the reaction between the aluminoxane and water or the active hydrogen-containing compound is not adversely affected.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out at -50 to 150 ° C, preferably at 0 to 1 ° C.
The reaction is carried out at a temperature of 20 ° C, more preferably 20 to 100 ° C.
The reaction time varies greatly depending on the reaction temperature,
Usually, it is about 0.5 to 300 hours, preferably about 1 to 150 hours.

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

Water to be brought into contact with the organoaluminum compound can be used by dissolving or dispersing it in a hydrocarbon solvent such as benzene, toluene, and hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of steam or ice. . As water, it was adsorbed on water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or on inorganic compounds or polymers such as silica, alumina and aluminum hydroxide. Adsorbed water or the like can also be used.

The contact reaction between the organoaluminum compound and water is usually
Performed in a hydrocarbon solvent. Examples of the hydrocarbon solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclohexane, petroleum fractions such as gasoline, kerosene, and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether tetrahydrofuran can be used. Of these media, aromatic hydrocarbons are particularly preferred.

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

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

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

(3) A method in which a hydrocarbon solution of an organic aluminum is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and the organic aluminum is brought into contact with the adsorbed water or the water of crystallization.

(4) A method in which ice is brought into contact with a hydrocarbon solution of an organic aluminum.

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

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

Examples of the [C] organoaluminum compound used in the present invention include, for example, R _n ⁶ AlX _3-n (wherein R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, and 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, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

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

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

Alkenyl aluminum such as isoprenyl aluminum.

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

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

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

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

As the organoaluminum ^{_{compound, R 6 n AlY 3-n}} ( wherein R ⁶ is as defined above, Y is -OR ⁷ group, -OSiR ⁸ ₃ group,
-OAlR ⁹ ₂ group, -NR ¹⁰ ₂ group, -SiR ¹¹ ₃ group or 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,
R ¹⁰ is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc .; and R ¹¹ and R ¹² are methyl, ethyl, etc. ) 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 AlNEt Et ₂ AlN (Me ₃ Si) ₂ (iso-Bu) ₂ AlN (Me ₃ Si) ₂ etc., (v) R ⁶ _n Al (SiR ¹¹ ₃ ) _3-n (iso-Bu) ₂ AlSiMe ₃ etc. Organoaluminum compounds mentioned above, R ⁶ ₃ A
_{^{l, R 6 n Al (OR}} 7) 3-n, can be mentioned organoaluminum compounds represented by ^{_{R 6 n Al (OAlR 9 2}} ) 3-n Suitable examples include those of n = 2 is preferable. These organoaluminum compounds can be used as a mixture of two or more kinds.

The olefin polymerization catalyst according to the present invention contains the above-mentioned [A] titanium catalyst component and [B] a ligand having a cycloalkadienyl skeleton, and further contains an anion containing a boron element, and comprises titanium, zirconium. The olefin is prepolymerized in a suspension containing a transition metal compound containing a transition metal selected from the group consisting of and a hafnium and, if necessary, [C] an organoaluminum compound and / or an organoaluminum oxy compound. May be formed. At this time, the prepolymerization is carried out by prepolymerizing the α-olefin in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g per 1 g of the olefin polymerization catalyst.

 Usually, the prepolymerization is carried out as follows.

In a hydrocarbon solvent, it contains [A] a titanium catalyst component and [B] a ligand having a cycloalkadienyl skeleton, contains a boron element-containing anion, and is selected from the group consisting of titanium, zirconium and hafnium. After the transition metal compound containing a transition metal and the [C] organoaluminum oxy compound and / or the organoaluminum compound are mixed and contacted as necessary, an olefin is introduced and prepolymerization is performed. At this time, [A], [B] and [C] may be mixed simultaneously or sequentially.

The temperature at which each component is mixed and contacted is usually -50 to 100 ° C.
Preferably in the range of −20 to 50 ° C., the mixing contact time is:
Depending on the reaction temperature and the order of mixing, it is usually 0.2
For about 50 to 50 hours, preferably about 0.5 to 20 hours.

The prepolymerization temperature is usually -20 to 60 ° C, preferably 0 to 50 ° C.
° C and the pre-polymerization time varies depending on the pre-polymerization amount and temperature, but is usually 0.5 to 100 hours, preferably 1 to 100 hours.
About 50 hours.

In the prepolymerization, a catalyst having a considerably higher concentration than the catalyst concentration in the system in the main polymerization can be used.

In the prepolymerization, [A] the titanium catalyst component is converted into titanium atoms per inert hydrocarbon medium described below,
Usually about 0.01-200 milligram atoms, preferably about 0.1-10
It is desirable to use a concentration of 0 milligram atoms, particularly preferably 1 to 50 milligram atoms.

In the prepolymerization, a transition metal containing a ligand having a [B] cycloalkadienyl skeleton, containing a boron element-containing anion, and containing a transition metal selected from the group consisting of titanium, zirconium and hafnium The compound is desirably used in an amount of 0.02 to 10 mol, preferably 0.05 to 5 mol, per gram atom of titanium atom.

If necessary, the [C] organoaluminum oxy compound may be used in an amount of 10 to 500 g atoms, preferably 20 to 200 g atoms per mole of the transition metal atom of the component [B] in terms of aluminum atoms.
Preferably, it is used in an amount of gram atoms.

Furthermore, [C] the organoaluminum compound, when used, is used per mole of the transition metal atom of the component [B].
It is desirable to use it in an amount of 1 to 200 mol, preferably 2 to 100 mol.

The prepolymerization is preferably carried out under a mild condition in a suspended state by adding an olefin and the above catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. The prepolymerization can be performed using the olefin itself as a solvent, or the prepolymerization can be performed in a substantially solvent-free state.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below, and specifically, ethylene is preferable.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer in an amount such that the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135 ° C. is about 0.2 dl / g or more, preferably about 0.5 to 10 dl / g.

The prepolymerization is carried out at about 0.1 to 5 per gram of the solid catalyst as described above.
00 g, preferably about 0.3 to 300 g, particularly preferably 1 to 100 g
It is desirable to carry out the reaction so as to produce a polymer of If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

In the thus obtained prepolymerized solid catalyst, 0.05 to 20 g atoms, preferably 0.1 to 10 g atoms, of the titanium atom based on the component [A] per 1 g of the transition metal atom based on the component [B]. 0.2 to more than atomic
The sum of aluminum atoms based on [C] and [D] components is 15-500 gram atoms,
Preferably it is 20 to 200 gram atoms.

The solid catalyst for olefin polymerization prepared as described above exhibits excellent polymerization activity for olefin itself.

When performing olefin polymerization using the olefin polymerization catalyst composed of the component [A], the component [B] and the component [C] as described above, the [A] titanium catalyst component includes:
Usually, about 10 ^-8 to 10
Desirably, it is used in an amount of ^-3 gram atoms, preferably about ^10-7 to ^10-4 gram atoms.

[B] A transition metal compound containing a ligand having a cycloalkadienyl skeleton, containing an anion containing a boron element, and containing a transition metal selected from the group consisting of titanium, zirconium and hafnium is usually 10%. ^-8 to
It is desirable to use it in an amount of 10 ^-3 mol / preferably 10 ^-7 to 10 ^-4 mol /.

The transition metal compound (B) is preferably used in an amount of 0.02 to 10 mol, preferably 0.05 to 5 mol, per gram atom of titanium atom.

Further, [C] the organoaluminum compound and / or the organoaluminum oxy compound is usually 10 ^-5 to 10 ^-2 gram atom-Al / preferably 10 ^{-4 to} 5 × 10 ^-3 gram atom in terms of aluminum atom. It is desirable to use Al /.

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-methyl1 , 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.
Range. The polymerization pressure is usually from normal pressure to 100 kg / cm ² ,
It is preferably under 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.

The olefin polymerization catalyst formed from component [A], component [B] and component [C] as described above has excellent polymerization activity, a wide molecular weight distribution, and excellent moldability. Coalescence 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.

Effects of the Invention The olefin polymerization catalyst according to the present invention exhibits excellent polymerization activity for olefin polymerization, has a wide molecular weight distribution, and can provide an olefin (co) polymer excellent in moldability.

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

The molecular weight distribution (w / n) and the composition distribution (the amount of n-decane soluble part) in Examples of the present invention were determined as follows.

The measurement of the w / n value is performed as follows according to "Gelper Emission Chromatography" by Takeuchi and published by Maruzen.

(1) The molecular weight M and its GPC (Gel Permeation Chromato-graph) count were measured using standard polystyrene of known molecular weight (Toyo Soda Co., Ltd. monodisperse polystyrene), and the correlation between molecular weight M and EV (Elution Volume) was measured. Create a diagram calibration curve. The concentration at this time is 0.02% by weight.

(2) GPC chromatograph of the sample by GPC measurement,
According to the above (1), the number average molecular weight n and the weight average molecular weight w in terms of polystyrene are calculated, and the w / n value is obtained. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample Preparation] (a) A sample is dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to be 0.1% by weight.

(B) Heat the Erlenmeyer flask to 140 ° C, stir for about 30 minutes, and dissolve.

(C) Apply the filtrate to GPC.

[GPC Measurement Conditions] The measurement was performed under the following conditions.

(B) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda Co., Ltd. (GMH type) (c) Sample amount 400μ (d) Temperature 140 ° C (e) Flow rate 1ml / The amount of n-decane soluble part in the copolymer was measured (the smaller the soluble part, the narrower the composition distribution).
Add to 450 ml of decane, dissolve at 145 ° C, cool to 23 ° C,
This was carried out by removing the n-decane-insoluble portion by filtration, removing the n-decane-insoluble portion by the filtrate, and collecting the n-decane-soluble portion from the filtrate.

 The MFP was measured at 190 ° C. under a load of 2.16 kg.

Example 1 (Preparation of [A] solid titanium catalyst component) 5.1 g of commercially available anhydrous magnesium chloride and 194 ml of decane were mixed with 400 g of
into a 1 ml glass flask and stir ethanol 1
8.8 ml was added dropwise over 10 minutes. After the addition, the mixture was stirred at room temperature for 1 hour. Thereafter, 17.5 ml of diethylaluminum chloride diluted with 20 ml of decane was added dropwise over 1 hour. At this time, the temperature in the system was maintained at 35 to 40 ° C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour. Continuously, titanium tetrachloride 70.6 ml
Was added dropwise over 30 minutes, then the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours. The reaction product was filtered through a jacketed glass filter kept at 80 ° C, and washed several times with decane to obtain 4.8% by weight of titanium and 14% of magnesium.
Weight%, chlorine 57% by weight, aluminum 2.2% by weight,
A solid titanium catalyst component having 9.7% by weight of ethoxy groups was obtained.

(Preparation of [B] zirconium catalyst component) 0.65 g of tri (n-butyl) ammonium tetra (p-tolyl) borate was suspended in 50 ml of toluene, and 0.50 g of bis (pentamethylcyclopentadienyl) dimethylzirconium was added thereto. In addition, stirring was continued at room temperature for 1 hour. Then, after a part of toluene was distilled off, a solid was obtained by filtration. The solid was washed with pentane and dried under reduced pressure to obtain a zirconium catalyst component [B].

(Preparation of [C] organoaluminum oxy compound) Al ₂ (SO ₄ ) ₃ was placed in a 400 ml flask sufficiently purged with nitrogen.
・ 37.1 g of 14H ₂ O and 133 ml of toluene were charged, and after cooling to −5 ° C., 47.9 ml of trimethylaluminum diluted with 152 ml of toluene was added dropwise over 1 hour. After reacting at 0-5 ° C for 1 hour, the temperature was raised to 40 ° C over 3 hours,
The reaction was further carried out at 72 ° C for 72 hours. After the reaction, solid-liquid separation was performed by filtration, and further, toluene was removed from the filtrate to obtain an organic aluminum oxy compound as a white solid.

(Polymerization) 600 ml of cyclohexane and 4-methyl-1-pentene 3 were placed in a 2 stainless steel autoclave sufficiently purged with nitrogen.
Then, the system was heated to 70 ° C. Thereafter, the organoaluminum oxy compound [C] was converted to aluminum atom by 1 milligram atom, the titanium catalyst component [A] was converted to titanium atom by 1 × 10 ^-3 milligram atom, and the zirconium catalyst component [B] was converted to zirconium atom. Converted to 0.
The polymerization was initiated by injecting 1 milligram atom with ethylene. Total pressure 8kg / while continuously supplying ethylene
Polymerization was performed at 80 ° C. for 40 minutes at cm ² -G. As a result, MFR
Is 0.03 g / 10 min, the density is 0.913 g / cm ³ , w /
54.2 g of an ethylene-4-methyl-1-pentene copolymer having n of 9.8 and a decane-soluble portion of 0.31% by weight was obtained.

Example 2 (Preparation of [B] zirconium catalyst component) In the same manner as in Example 1, except that 0.32 g of bis (cyclopentadienyl) dimethylzirconium was used instead of bis (pentamethylcyclopentadienyl) dimethylzirconium. Thus, a zirconium catalyst component was obtained.

(Polymerization) In the polymerization of Example 1, the addition amount of the titanium catalyst component was changed to 5 × 10 ⁻⁴ milligram atom, and the zirconium catalyst component prepared in Example 2 was converted to 6 × 10 4 in terms of zirconium atom. Except for using ^-3 milligram atoms, the same was done, with an MFR of 0.59 g / 10 min and a density of 0.913 g / cm ³
, W / n is 10.9, and the decane soluble part amount is 1.0
48.9 g of an ethylene-4-methyl-1-pentene copolymer was obtained in an amount of 48.9% by weight.

Comparative Example 1 In the polymerization of Example 2, the same procedure was carried out except that the zirconium catalyst component was not used, the titanium catalyst component was 2 × 10 ⁻³ milligram atoms in terms of titanium atoms, and hydrogen was introduced at ² kg / cm ² , and the MFR was lower. 1.30 g / 10 min, the density is 0.914 g / cm ³ , the decane soluble part amount is 11.9% by weight, and w / n is
As a result, 61.5 g of an ethylene-4-methyl-1-pentene copolymer 7.3 was obtained.

Comparative Example 2 In the polymerization of Example 2, no titanium catalyst component was used.
The zirconium catalyst component is converted into 2 × 10 in terms of zirconium atoms.
MFR was the same except that ^-2 milligram atoms were used.
7.9 g / 10 min, a density of 0.912 g / cm ³ , a decane-soluble part amount of 2.0% by weight, and w / n of 3.5, an ethylene / 4-methyl-1-pentene copolymer 50.5 g was obtained.

[Brief description of the drawings]

FIG. 1 is an illustration of an olefin polymerization catalyst according to the present invention. FIG. 2 shows the benzene-insoluble aluminum oxy compound.
FIG. 3 shows the IR spectrum of the benzene-soluble aluminum oxy compound.
It is an IR spectrum.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-207703 (JP, A) JP-A-3-207704 (JP, A) 502036 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 4/64-4/658 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00 -210/18

Claims (2)

(57) [Claims] 1. A titanium catalyst comprising [A] a titanium catalyst component comprising titanium, magnesium and halogen as essential components, and [B] a titanium containing a ligand having a cycloalkadienyl skeleton and containing an anion containing a boron element. And a transition metal compound containing a transition metal selected from the group consisting of zirconium and hafnium, and [C] an organic aluminum compound and / or an organic aluminum oxy compound. 2. [A] a titanium catalyst component containing titanium, magnesium and halogen as essential components; and [B] a titanium catalyst containing a ligand having a cycloalkadienyl skeleton and containing an anion containing a boron element. An olefin in the presence of a catalyst formed from a transition metal compound containing a transition metal selected from the group consisting of, zirconium and hafnium, and [C] an organoaluminum compound and / or an organoaluminum oxy compound. A method for polymerizing an olefin, comprising polymerizing.