JP2000219704A - Catalyst for olefin polymerization and preparation of polyolefin by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which can efficiently prepare an industrially valuable polyolefin by using an organic transition metal compound and an alkylaluminoxane. SOLUTION: An organic transition metal compound of formula I or formula II and an alkylaluminoxane of formula VI and/or formula VII are used. In the formulas, M is a transition metal of the group 3-10; R1 and R2 are each H, a 1-20C hydrocarbon group, an alkylsilyl or a hydrocarbon group containing an atom of the group 15 or 16; X is H, a 1-20C hydrocarbon group, a hydrocarbon group containing an atom of the group 15 or 16, or a halogen; Y is a group of formula III, formula IV or formula V (wherein R2 means the same as R1; and Q is an atom of the group 15 or 16); n is the same as the oxidation number of M; R3 is H or a 1-20C hydrocarbon group; and q is 2-60. In addition, an organometallic compound may be used, an example being a compound represented by (R7)3Z (wherein Z is a metal atom of the group 1, 2 or 13, Sn or Zn; and R7 is H, amido, an alkoxy or a 1-20C hydrocarbon group provided at least one R7 is a hydrocarbon group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization catalyst using an organic transition metal compound having a specific structure, and a method for producing a polyolefin using the same. More specifically, the present invention relates to a method for efficiently producing an industrially valuable polyolefin by using an organic transition metal compound having a specific structure as a catalyst component.

[0002]

2. Description of the Related Art In recent years, metallocene catalysts obtained by combining an aluminoxane with a complex having a cyclopentadienyl ring as a ligand have been attracting attention as olefin polymerization catalysts because of their high activity, narrow molecular weight distribution, and possible structure control. Have been. For example, there is JP-A-58-19309.

Recently, by using a bidentate-type diimine chelate type nickel complex as a catalyst component, a multi-branched structure having a structure different from that of a polyolefin which can be produced by a conventional metallocene catalyst has been obtained. It has been reported that a polyolefin having the same can be produced. For example, there is WO96 / 23010.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin polymerization catalyst capable of efficiently producing an industrially valuable polyolefin, and a method for producing a polyolefin using the same. To provide.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and as a result, used an organic transition metal compound having a specific structure as a component of a catalyst for olefin polymerization, and used this as an alkylaluminoxane. Or by combining with a specific activation co-catalyst, organometallic compound,
It has been found that polyolefins of industrial value can be produced efficiently, and the present invention has been completed.

That is, the present invention provides the following general formula (1) or (1 ′)

[0007]

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(Where M is a transition metal atom selected from Groups 3 to 10 of the periodic table, R ¹ may be the same or different, and is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) , An alkylsilyl group or group 15 of the periodic table, 1
It represents a hydrocarbon group containing a Group 6 atom. Xs may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing an atom of Groups 15 and 16, or a halogen atom. Y is the following general formula (2), (3) or (4)

[0009]

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(Wherein R ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group or a hydrocarbon containing an atom belonging to Group 15 or 16 of the periodic table) Q represents group 15 of the periodic table, 1
Shows Group 6 atoms. ) Is shown. n is equal to the oxidation number of the transition metal atom M. An organic transition metal compound represented by the following general formula (5) and / or (6):

[0011]

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(Wherein R ³ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and q is an integer of 2 to 60). An olefin polymerization catalyst comprising an alkylaluminoxane, an olefin polymerization catalyst further comprising an organometallic compound, or an organic transition metal compound represented by the general formula (1) or (1 '), an activation co-catalyst, and an organometallic compound An object of the present invention is to provide an olefin polymerization catalyst. Further, the present invention provides a method for producing a polyolefin, comprising polymerizing an olefin using the olefin polymerization catalyst.

Hereinafter, the present invention will be described in detail.

As shown in the general formula (1) or (1 '), the organic transition metal compound used as the main catalyst of the olefin polymerization catalyst of the present invention is such that the transition metal M has two nitrogen atoms and one periodic table 15 It is characterized by having a tridentate structure chelated at three points of group 13 or group 16 atoms.

[0015]

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In the general formula (1) or (1 '), M is a transition metal atom selected from Groups 3 to 10 of the periodic table, preferably a transition metal atom of Groups 4, 8, 9 and 10 And more preferably a titanium atom, a zirconium atom,
Examples include a hafnium atom, an iron atom, a ruthenium atom, a cobalt atom, a rhodium atom, a nickel atom, a palladium atom, and a platinum atom. R ¹ may be the same or different and each represents a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group or a hydrocarbon group containing an atom belonging to Group 15 or 16 of the periodic table; To form a ring. Specifically, hydrocarbon groups such as methyl group, ethyl group, butyl group, isobutyl group, benzyl group and phenyl group, alkylsilyl groups such as trimethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group, methoxy group, ethoxy group Groups, an alkoxy group such as an isopropoxy group, an alkylamino group such as a phenoxy group, a dimethylamino group, a diethylamino group, and a diisopropylamino group, a diphenylamino group, a dibenzylamino group, and the like. X may be the same as or different from each other, and represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing an atom of Group 15 or 16 of the periodic table, or a halogen atom.
Hydrogen atom, methyl group, ethyl group, isobutyl group, ter
Examples thereof include hydrocarbon groups such as t-butyl group and phenyl group, alkoxy groups such as methoxy group, alkylamino groups such as dimethylamino group, and halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. . Y
Is the general formula (2), (3) or (4)

[0017]

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Wherein R ² may be the same as or different from each other, and may be a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, or a group 15 or 1 group of the periodic table.
A hydrocarbon group containing a group 6 atom, specifically, a methyl group, an ethyl group, a butyl group, an isobutyl group, a tert-
Hydrocarbon groups such as butyl group and phenyl group; alkylsilyl groups such as trimethylsilyl group; alkoxy groups such as dimethylphenylsilyl group, triphenylsilyl group and methoxy group; alkylamino groups such as phenoxy group, dimethylamino group and diisobutylamino group. And a diphenylamino group. Q represents an atom of Group 15 or 16 of the periodic table, specifically, a nitrogen atom, an oxygen atom,
Examples thereof include a sulfur atom. Q can form a coordination bond with the transition metal atom M. n is equal to the oxidation number of M and is an integer of 1 to 6. N indicates the number of X.

The organic transition metal compound represented by the general formula (1) or (1 '), which is the catalyst component of the present invention, is a method often used as a synthesis technique of this kind of organic transition metal compound. It can be synthesized by reacting the ligand to be reacted with the corresponding transition metal compound or the corresponding transition metal precursor in a solution state or a suspension state, but is not limited to this method.

Examples of the organic transition metal compound represented by formula (1) or (1 ') of the present invention include (2,6-bis (N-methyl-2-imidazolinyl) pyridine) iron chloride (II) ), (2,6-bis (N-methyl-4-methyl-2-imidazolinyl) pyridine) iron (II) chloride,
(2,6-bis (N-methyl-4,4-dimethyl-2-
Imidazolinyl) pyridine) iron (II) chloride, (2,6
-Bis (N-methyl-4,5-dimethyl-2-imidazolinyl) pyridine) iron (II) chloride, (2,5-bis (N-methyl-2-imidazolinyl) thiophene) iron (II) chloride, (2 , 5-bis (N-methyl-4-methyl-2-imidazolinyl) thiophene) iron (II) chloride,
(2,5-bis (N-methyl-4,4-dimethyl-2-
Imidazolinyl) thiophene) iron (II) chloride, (2,
5-bis (N-methyl-4,5-dimethyl-2-imidazolinyl) thiophene) iron (II) chloride, (2,5-bis (N-methyl-2-imidazolinyl) furan) iron (II) chloride, 2,5-bis (N-methyl-4-methyl-
2-imidazolinyl) furan) iron (II) chloride, (2
5-bis (N-methyl-4,4-dimethyl-2-imidazolinyl) furan) iron (II) chloride, (2,5-bis (N-methyl-4,5-dimethyl-2-imidazolinyl) furan) chloride Iron (II), (2,2′-bis (N-
Methyl-2-imidazolinyl) -4,5-dibenzofuran) iron (II) chloride, (2,2′-bis (N-methyl-
4-methyl-2-imidazolinyl) -4,5-dibenzofuran) iron (II) chloride, (2,2′-bis (N-methyl-4,4-dimethyl-2-imidazolinyl) -4,5
-Dibenzofuran) iron (II) chloride, (2,2′-bis (N-methyl-4,5-dimethyl-2-imidazolinyl) -4,5-dibenzofuran) iron (II) chloride,
(2,6-bis (N-methyl-2-imidazolyl) pyridine) iron (II) chloride, (2,6-bis (N-methyl-
4,4-dimethyl-2-imidazolyl) pyridine) iron (II) chloride, (2,6-bis (N-methyl-4,5-dimethyl-2-imidazolyl) pyridine) iron (I) chloride
I), (2,5-bis (N-methyl-2-imidazolyl) thiophene) iron (II) chloride, (2,5-bis (N
-Methyl-4,4-dimethyl-2-imidazolyl) thiophene) iron (II) chloride, (2,5-bis (N-methyl-4,5-dimethyl-2-imidazolyl) thiophene)
Iron (II) chloride, (2,5-bis (N-methyl-2-imidazolyl) furan) iron (II) chloride, (2,5-bis (N-methyl-4,4-dimethyl-2-imidazolyl)
(Furan) iron (II) chloride, (2,5-bis (N-methyl-4,5-dimethyl-2-imidazolyl) furan) iron (II) chloride, (2,2′-bis (N-methyl-2) -Imidazolyl) -4,5-dibenzofuran) iron chloride (I
I), (2,2'-bis (N-methyl-4,4-dimethyl-2-imidazolyl) -4,5-dibenzofuran) iron (II) chloride, (2,2'-bis (N-methyl- 4,5
-Dimethyl-2-imidazolyl) -4,5-dibenzofuran) iron (II) chloride, (2,6-bis (N-methyl-
2-benzimidazolyl) pyridine) iron (II) chloride;
(2,6-bis (N-isopropyl-2-benzimidazolyl) pyridine) iron (II) chloride, (2,6-bis (N-phenyl-2-benzimidazolyl) pyridine)
Iron (II) chloride, (2,6-bis (N-benzyl-2-
Benzimidazolyl) pyridine) iron (II) chloride,
(2,5-bis (N-methyl-2-benzimidazolyl) thiophene) iron (II) chloride, (2,5-bis (N
-Isopropyl-2-benzimidazolyl) thiophene) iron (II) chloride, (2,5-bis (N-phenyl-
2-benzimidazolyl) thiophene) iron chloride (I
I), (2,5-bis (N-benzyl-2-benzimidazolyl) thiophene) iron (II) chloride, (2,5-bis (N-methyl-2-benzimidazolyl) furan) iron (II) chloride , (2,5-bis (N-isopropyl-2)
-Benzimidazolyl) furan) iron (II) chloride,
(2,5-bis (N-phenyl-2-benzimidazolyl) furan) iron (II) chloride, (2,5-bis (N-benzyl-2-benzimidazolyl) furan) iron (I) chloride
I), (2,2'-bis (N-methyl-2-benzimidazolyl) -4,6-dibenzofuran) iron chloride (I
I), (2,2′-bis (N-isopropyl-2-benzimidazolyl) -4,6-dibenzofuran) iron (II) chloride, (2,2′-bis (N-phenyl-2-benzimidazolyl) -4,6-dibenzofuran) iron (II) chloride, (2,2′-bis (N-benzyl-2-benzimidazolyl) -4,6-dibenzofuran) iron (II) chloride, and iron atoms of these compounds Is replaced by a nickel atom, palladium atom, platinum atom, titanium atom, zirconium atom, hafnium atom, ruthenium atom, cobalt atom, organic transition metal compound replaced by rhodium atom, etc., chlorine atom becomes bromine atom, methyl group, phenyl group etc. Examples of the substituted organic transition metal compound include, but are not limited to, these.

The following general formulas (5) and / or (6), which are one of the components of the catalyst for olefin polymerization of the present invention:

[0022]

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Wherein R ³ may be the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and q is an integer of 2 to 60. (B) Alkyl aluminoxane is an aluminum oxy compound having a bond between aluminum and oxygen. In the general formulas (5) and (6), R ³ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a tert-butyl group.
20 hydrocarbon groups. Q is an integer of 2 to 60.

The (C) activating co-catalyst, which is one of the components of the olefin polymerization catalyst of the present invention, refers to the organic transition metal compound (1) or (1 ') which is the main catalyst of the catalyst system of the present invention. Or a compound capable of forming an active species capable of polymerizing an olefin by acting or reacting with a reaction mixture of an organotransition metal compound (1) or (1 ′) and an organometallic compound; or It shows a compound having a role of reactivating an inactivated polymerization active species during polymerization. Furthermore, these compounds, after forming a polymerization active species of the organic transition metal compound,
A compound that provides a compound that weakly coordinates or interacts with the generated active species, but does not react with the active species.

As these compounds, the following general formula (7)
A proton acid represented by the general formula (8), an ionic compound represented by the general formula (8), a Lewis acid represented by the general formula (9) and a Lewis acidic compound represented by the general formula (10), [HL ¹ ] [ B (Ar) ₄ ] (7) [AL ² _m ] [B (Ar) ₄ ] (8) [D] [B (Ar) ₄ ] (9) B (Ar) ₃ (10) (where H Is a proton, B is a boron atom or an aluminum atom, L ¹ is a Lewis base, L ² is a Lewis base or a cyclopentadienyl group, A is a cation of a metal selected from lithium, iron or silver. Yes,
D is a carbonium cation or a tropylium cation. Ar is a halogen-substituted aryl group having 6 to 20 carbon atoms. m is an integer of 0 to 2. ) Clay mineral, the following general formula (11)

[0026]

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(Where E is an atom selected from Groups 1 to 16 of the periodic table, and R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a halogen atom, or a halogen atom. And G is a hydrogen atom, having 1 to 20 carbon atoms
Or a halogen atom. m is 1 to 7
Where l is 1 ≦ l ≦ 7. A sulfonate represented by the following general formula (12)

[0028]

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(Where R ⁵ is a halogen atom-containing hydrocarbon group), a solid component obtained by reacting a halogenated hydrocarbon derivative with the surface of a carboxylic acid, an inorganic oxide or an inorganic halide, or A solid component in which the carrier surface is a cationic component and an anionic component of an ionic compound is coordinated can be shown.

When the activating cocatalyst (C) which is the catalyst component of the present invention is a compound represented by the general formula (7), (8), (9) or (10), Specific examples of the protonic acid represented include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) borate, and hydronium tetrakis (pentafluorophenyl) Phenyl) borate, N, N-dimethylammoniumtetrakis (pentafluorophenyl)
Borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) ) Aluminates, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) aluminate, etc. Can be.

Specific examples of the ionic compound represented by the general formula (8) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, and ether complexes thereof. Ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) borate and ferrocenium tetrakis (pentafluorophenyl) aluminate; silver salts such as silver tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorphenyl) aluminate And the like, but are not limited thereto.

Specific examples of the Lewis acid represented by the general formula (9) include trityltetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, Examples include, but are not limited to, tropylium tetrakis (pentafluorophenyl) aluminate.

Specific examples of the Lewis acidic compound represented by the general formula (10) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2 3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like But are not limited to these.

When the activating polymerization catalyst (C), which is a component of the catalyst for olefin polymerization of the present invention, is a clay mineral, the clay mineral having cation exchange ability is used.
The clay mineral used in the present invention is an acid,
It is preferable to perform chemical treatment such as treatment with an alkali, salt treatment, and complex formation by treatment with an organic compound or an inorganic compound.

Examples of the clay mineral include kaolinites such as naturally occurring kaolinite, dickite and halloysite; montmorillonite, hectorite, beidellite,
Smectites such as saponite, teniolite and sauconite; mica such as muscovite, paragonite and illite;
Vermiculite group; brittle mica group such as margarite and clintonite; curbstone group such as dombasite, cocoaite, clinochlore; sepiolite / palygorskite; and artificially synthesized clay minerals, but are not limited thereto. Not something.

Examples of the acid used for the chemical treatment include Bronsted acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid. As the alkali, sodium hydroxide, potassium hydroxide and calcium hydroxide are preferably used. Compounds used in the salt treatment include ionic halides such as sodium chloride, potassium chloride, lithium chloride, magnesium chloride, aluminum chloride, iron chloride, and ammonium chloride; sulfates such as sodium sulfate, potassium sulfate, aluminum sulfate, and ammonium sulfate; Carbonates such as potassium carbonate, sodium carbonate and calcium carbonate; inorganic salts such as phosphates such as sodium phosphate, potassium phosphate, aluminum phosphate and ammonium phosphate; and sodium acetate, potassium acetate, potassium oxalate and citric acid Organic acid salts such as sodium acid salt and sodium tartrate can be exemplified.

The organic compounds used to form the organic complex of the clay mineral include onium salts, trityl chloride,
Examples thereof include compounds that generate carbon cations such as tropylium bromide and complex compounds that generate metal complex cations such as ferrocenium salts. Examples of the inorganic compound used for forming the inorganic composite include metal hydroxides that generate hydroxide cations such as aluminum hydroxide, zirconium hydroxide, and chromium hydroxide.

Among the clay minerals used in the present invention, a modified clay compound which is a clay mineral-organic ion complex in which a metal ion which is an exchangeable cation present in the clay mineral is exchanged for a specific organic cation component is particularly preferable. It is. Specific examples of the organic cation to be introduced into the modified clay compound include butylammonium, hexylammonium, decylammonium, dodecylammonium, diamylammonium, tributylammonium, N, N
Aliphatic ammonium cations such as dimethyldecyl ammonium, anilinium, N-methylanilinium,
N, N-dimethylanilinium, N-ethylanilinium, N, N-diethylanilinium, benzylammonium, toluidinium, dibenzylammonium, tribenzylammonium, N, N, 2,4,6-pentamethylanilinium, etc. Ammonium ions such as aromatic ammonium cations, or dimethyloxonium,
Examples include oxonium ions such as diethyloxonium, but are not limited thereto.

When the activating polymerization catalyst (C) which is a component of the catalyst for olefin polymerization of the present invention is a sulfonate represented by the general formula (11), the sulfonate used as the catalyst component includes: For example, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate,
Bis (trifluoromethanesulfonate) calcium,
Bis (trifluoromethanesulfonate) barium, tris (trifluoromethanesulfonate) titanium,
Tetrakis (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate)
Zirconium, tetrakis (trifluoromethanesulfonate) hafnium, pentakis (trifluoromethanesulfonate) niobium, pentakis (trifluoromethanesulfonate) tantalum, tris (trifluoromethanesulfonate) iron, trifluoromethanesulfonate silver, tris (trifluoromethanesulfonate) ) Boron, tris (trifluoromethanesulfonate) aluminum, tris (trifluoromethanesulfonate) gallium, tetrakis (trifluoromethanesulfonate) tin, lithium pentafluorobenzenesulfonate, sodium pentafluorobenzenesulfonate,
Potassium pentafluorobenzenesulfonate, bis (pentafluorobenzenesulfonate) magnesium, bis (pentafluorobenzenesulfonate) calcium, bis (pentafluorobenzenesulfonate)
Barium, tris (pentafluorobenzenesulfonate) titanium, tetrakis (pentafluorobenzenesulfonate) zirconium, tetrakis (pentafluorobenzenesulfonate) hafnium, pentakis (pentafluorobenzenesulfonate) niobium, pentakis (pentafluorobenzenesulfonate) Tantalum, tris (pentafluorobenzenesulfonate)
Iron, silver pentafluorobenzenesulfonate, tris (pentafluorobenzenesulfonate) boron, tris (pentafluorobenzenesulfonate) aluminum, tris (pentafluorobenzenesulfonate) gallium, tetrakis (pentafluorobenzenesulfonate) tin, etc. Mention may be made of bis (trifluoromethanesulfonate) magnesium, pentakis (trifluoromethanesulfonate) niobium, bis (pentafluorobenzenesulfonate) magnesium, tetrakis (pentafluorobenzenesulfonate) titanium and pentakis (pentafluorobenzenesulfonate) Nart) niobium is preferred.

When the (C) activating co-catalyst, which is a component of the catalyst for olefin polymerization of the present invention, is a carboxylic acid represented by the general formula (12), the carboxylic acid used as the catalyst component is, for example, tricarboxylic acid. Fluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluorobenzoic acid,
Examples thereof include tetrafluorotoluic acid, 2,4- (trifluoromethyl) benzoic acid, and pentafluorophenylacetic acid, and pentafluorobenzoic acid is preferred.

When the (C) activating co-catalyst, which is a component of the catalyst for olefin polymerization of the present invention, is a solid component obtained by reacting a halogenated hydrocarbon derivative on the surface of an inorganic oxide or an inorganic halide, Specific examples of the product include oxides of typical elements such as alumina and silica, oxides of transition metal elements such as titania and zirconia, and composite oxides such as silica-alumina and silica-magnesia. Examples of the inorganic halide include a halide of an alkaline earth metal such as magnesium chloride, and a halide of a Group 13 element of the periodic table such as aluminum chloride. The halogenated hydrocarbon derivative used in the present invention has a general formula (13) WR ⁶ _{s Yt} (13) (where W is a metal atom belonging to Group 1, 2, or 13 of the periodic table,
An atom selected from a Zn atom or a Sn atom;
Reference numeral ⁶ is a group in which part or all of the hydrogen atoms of a hydrocarbon group having 1 to 30 carbon atoms have been replaced with fluorine. Y is a halogen, a hydroxyl group, or a hydrocarbon group having 1 to 30 carbon atoms. s ≧ t
And s + t is equal to the oxidation number of the transition metal atom M. )
Is a metal salt represented by Examples of the hydrocarbon group having 1 to 30 carbon atoms include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aromatic hydrocarbon group is preferably a phenyl group, a substituted phenyl group such as a tolyl group, or a naphthyl group. The aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decanyl group. All must be halogenated. Particularly, those which are fluorinated are preferable.

The method for reacting the halogenated hydrocarbon derivative on the surface of the inorganic oxide or inorganic halide is not particularly limited.

When the activating polymerization catalyst (C) which is a component of the catalyst for olefin polymerization of the present invention is a solid component in which the surface of the carrier is a cationic component and the anionic component of the ionic compound is coordinated, the ionic compound is represented by (14), - the general formula ^{(14) [C +] [} a] [a -] is an anion sites of the ionic compound is a stable anion component reacts with the organic transition metal compound, an organic Examples thereof include a boron compound anion, an organic aluminum compound anion, an organic phosphorus compound anion, and an organic antimony compound anion. In particular,
Tetrakis (pentafluorophenyl) boron, tetrakisphenylboron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (pentafluorophenyl) aluminum, tetrakisphenylaluminum, tetrakis (3,5-di (trifluoro) Methyl) phenyl) aluminum and the like.

[C ⁺ ] is a cationic component of the ionic compound, and is characterized by making the surface of the carrier cationic. The carrier having a cationic surface is, for example, a component composed of a cationic group such as an aluminum cation, an oxonium cation, a sulfonium cation, a phosphonium cation, a carbonium cation, a tropylium cation, and a metal cation. Solid components whose parts or all are chemically bonded to the surface of the carrier may be mentioned. Specific examples of the cationic group constituting the carrier having cationic properties include tripropylammonium, tributylammonium, N, N-dimethylanilinium, N, N-2,4,5-pentamethylanilinium, pyridinium , Diethyloxonium, triphenylsulfonium, trimethylsulfonium, triphenylphosphonium, tri (o-tolyl) phosphonium, triphenylcarbenium, cycloheptatrienium, ferrocenium and the like, but are not limited thereto. Not something. These cationic groups may be a part of components constituting the carrier, or may be those immobilized on the surface of the carrier by chemical modification.

The organometallic compound (D) which is a component of the olefin polymerization catalyst of the present invention and is used together with the component (A), the component (B) and the component (C) is represented by the following general formula (15). Compounds to be used can be mentioned.

(R ⁷ ) ₃ Z (15) (where Z is a metal atom belonging to Group 1, 2 or 13 of the periodic table;
Indicates a Sn atom or a Zn atom. R ⁷ may be the same or different and each represents a hydrogen atom, an amide group, an alkoxy group, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, at least one of which is a hydrocarbon group. ) Such compounds include trimethylaluminum,
Triethylaluminum, organoaluminum compounds such as triisobutylaluminum, organolithium compounds such as n-butyllithium, organomagnesium compounds such as methylmagnesium chloride, dimethyltin, diethylzinc and the like, but are not limited thereto. Absent.

The ratio of (A) the organic transition metal compound to (B) the alkylaluminoxane represented by the general formula (5) and / or (6) in the preparation of the catalyst is not particularly limited, but is preferably (A) The molar ratio of the organic transition metal compound to the (B) alkylaluminoxane is (A) :( B) = 10
0: 1 to 1: 1,000,000, particularly preferably 1: 1 to 1: 1
The range is 1: 100,000. The ratio of the (B) alkylaluminoxane to the (D) organometallic compound is not particularly limited, but is preferably from an amount of the organometallic compound contained as a small amount of impurities in the alkylaluminoxane to an excess amount of the organometallic compound relative to the alkylaluminoxane. May be used.

The ratio of (A) the organic transition metal compound to the (C) activating cocatalyst and the ratio of (A) the organic transition metal compound to the (D) organometallic compound are not limited. Is a compound represented by the general formula (7), (8), (9) or (10), a sulfonic acid salt represented by the general formula (11) or a carboxylic acid represented by the general formula (12) In this case, preferably, the molar ratio of (A) the organic transition metal compound to (C) the activating co-catalyst is such that the component (A): the component (C) = 10: 1 to 1:
1000, particularly preferably in the range from 3: 1 to 1: 100. Preferably, the molar ratio of the (A) organic transition metal compound to the (D) organometallic compound per metal atom is (A) component: (D) component = 100: 1 to 1: 10000.
0, particularly preferably in the range of 1: 1 to 1: 10000.

When the (C) activating co-catalyst is a clay mineral, the molar ratio of (A) the organic transition metal compound to (C) the activating co-catalyst is sufficient if the organic transition metal compound reacts. There is no particular limitation, but the amount of cations in the clay mineral relative to the organic transition metal compound is preferably from 1 to 10,000 times mol. If the amount is less than 1 mol, sufficient activity cannot be obtained.
When the molar ratio exceeds 00 times, the activity per catalyst becomes low, and it becomes necessary to remove ash from the polymer. The amount ratio of the (A) organic transition metal compound to the (D) organic metal compound is not particularly limited, but is preferably 100000 times or less the molar amount of the organic transition metal compound. It is necessary to consider the process. In view of the stability of the catalyst and the elimination of catalyst poisons, it is particularly desirable to use the organometallic compound in a range of 1 to 1000 times mol.

(C) A solid component obtained by reacting the surface of an inorganic oxide or inorganic halide with a halogenated hydrocarbon derivative, or a carrier surface comprising a cation component and an anionic component of an ionic compound comprising an ionic compound. In the case of the solid component, the ratio of (A) the organic transition metal compound to (C) the activating co-catalyst is not particularly limited, but (A) the organic transition metal compound to (C) the activating co-catalyst (g). Is 0.0
It is desirably in the range of 1 to 1000 mol / g, and is highly active as an olefin polymerization catalyst. More preferably 0.1 to 500 mol / g, particularly preferably 1 to 30 mol / g.
When the content is in the range of 0 mol / g, the productivity of the olefin polymer is increased and the ash content of the obtained olefin polymer can be suppressed to a low level. The ratio of the (A) organic transition metal compound to the (D) organometallic compound is not particularly limited, but preferably the molar ratio of the (A) organic transition metal compound to the (D) organometallic compound per metal atom is ( A) Component:
The component (D) is in the range of 100: 1 to 1: 100000, particularly preferably 1: 1 to 1: 10000.

The method for preparing the catalyst from the compounds described above is not particularly limited, and examples of the preparation method include a method of mixing each of the components in an inert solvent or using a monomer to be polymerized as a solvent. it can. Also, there is no particular limitation on the order in which these components are reacted, and there is no particular limitation on the temperature and the processing time for this treatment.

The polymerization in the present invention is carried out by a usual polymerization method,
That is, any of slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, and bulk polymerization can be used.

In the present invention, the term "polymerization" means not only homopolymerization but also copolymerization, and the polyolefin obtained by these polymerizations is used to mean not only homopolymers but also copolymers.

The catalyst system obtained by the present invention can be used by being supported on solid fine particles. The fine particle solid used at this time is an inorganic carrier or an organic carrier.
iO ₂ , Al ₂ O ₃ , ZrO, B ₂ O ₃ , CaO, ZnO,
MgCl ₂ , CaCl ₂ and a combination thereof, a polyolefin such as polyethylene, polypropylene, poly 1-butene, and polystyrene, and a mixture or a mixture of these polyolefins and a polar polymer such as polyethyl methacrylate, polyester, and polyimide. Those having a polymerization composition are exemplified. The shape of the fine particle carrier is not limited, but the particle diameter is 5 to 200 μm.
m, and the pore diameter is preferably 20 to 100 Å.

When the organic transition metal compound in the present invention is used as a catalyst component, it is possible to carry out polymerization using two or more kinds of organic transition metal compounds.

The polymerization of the olefin in the present invention can be carried out in a gas phase or a liquid phase. In particular, when it is carried out in a gas phase, an olefin polymer having a uniform particle shape can be produced efficiently and stably. When the polymerization is performed in the liquid phase, the solvent used may be any organic solvent generally used, and specifically, benzene, toluene,
Xylene, pentane, hexane, heptane and the like can be mentioned, and olefin itself such as propylene, 1-butene, 1-octene and 1-hexene can be used as a solvent.

The olefin used for the polymerization in the present invention is ethylene, propylene, 1-butene, 4-methyl-
Α-olefins such as 1-pentene, 1-hexene and 1-octene, styrene, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7 Conjugated and non-conjugated dienes such as -methyl-1,6-octadiene; cyclic olefins such as cyclobutene; and ethylene and propylene and styrene;
-Three or more kinds of components such as hexene and styrene, ethylene, propylene and ethylidene norbornene can be mixed and polymerized.

In producing a polyolefin using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration are not particularly limited, but the polymerization temperature is -100 to 300 ° C. For 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. The polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system, and can be carried out in two or more stages by changing the polymerization conditions. Further, the polyolefin obtained after the completion of the polymerization can be separated and recovered from the polymerization solvent by a conventionally known method, and can be obtained by drying.

[0059]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. All reactions were performed under an inert gas atmosphere, and all solvents used for the reaction were previously purified, dried or deoxygenated by a known method. The ligand of the organic transition metal compound was identified by ¹ H-NMR (GPX-
400 type NMR measurement apparatus).

Example 1 (Synthesis of organic transition metal compound) Under a nitrogen atmosphere, 126.5 mg of anhydrous iron (II) chloride and 2,6-bis (N-methyl-2-benzimidazolyl) pyridine were placed in a Schlenk tube.
339 mg and tetrahydrofuran (THF) 10 m
and stirred overnight. The resulting purple solid was filtered and washed with 10 ml of hexane to obtain the desired complex (2,6-bis (N-methyl-2-benzimidazolyl) pyridine) iron (II) chloride.

(Preparation of catalyst) Under a nitrogen atmosphere, 4.3 mg (5 μm) of (2,6-bis (N-methyl-2-benzimidazolyl) pyridine) iron (II) chloride was placed in a Schlenk tube.
ol) It was separated. This was diluted with 10 ml of dry toluene, a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd., M-MAO, 1.78 mol / l toluene solution, 0.5 ml, 0.89 mmol) was added, and the mixture was stirred for 1 hour. did.

(Evaluation of Polymerization) Under a nitrogen atmosphere, 50 ml of dry toluene and the whole amount of the above-mentioned catalyst solution were introduced into a 100 ml stainless steel autoclave and stirred at room temperature. Next, ethylene was introduced into the autoclave, the ethylene partial pressure was set so as to be 0.6 MPa, and polymerization was started.
While maintaining the polymerization temperature at 80 ° C., polymerization was performed for 60 minutes, unreacted ethylene was depressurized and removed, and the polymerization was stopped.

As a result of collecting the contents of the autoclave,
Filamentous polyethylene was confirmed.

[0064]

The olefin polymerization catalyst comprising the organic transition metal compound of the present invention as a main catalyst is extremely effective for olefin polymerization. By using this catalyst as an olefin polymerization catalyst, it is industrially useful. It is possible to efficiently produce polyolefin.

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Claims (4)

[Claims] (A) The following general formula (1) or (1 ′): (Where M is a transition metal atom selected from Groups 3 to 10 of the periodic table, R ¹ may be the same or different, and may be a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, X represents a hydrocarbon group containing an atom of a group 15 or 16 of the periodic table, X may be the same or different, and represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, or a group of the group 15 or 16 of the periodic table. Y represents a hydrocarbon group or a halogen atom containing an atom represented by the following general formula (2):
(3) or (4) (Where R ² may be the same or different,
A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, or a hydrocarbon group containing an atom of Groups 15 and 16 of the periodic table is shown. Q represents an atom belonging to groups 15 and 16 of the periodic table. ) Is shown. n is a transition metal atom M
Equal to the oxidation number of ) Organic transition metal compound represented by
And (B) the following general formulas (5) and / or (6): (Where R ³ may be the same or different,
A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
q is an integer of 2 to 60. An olefin polymerization catalyst comprising an alkylaluminoxane represented by the formula: (A) The following general formula (1) or (1 ′): (Where M is a transition metal atom selected from Groups 3 to 10 of the periodic table, R ¹ may be the same or different, and may be a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, X represents a hydrocarbon group containing an atom of a group 15 or 16 of the periodic table, X may be the same or different, and represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, or a group of the group 15 or 16 of the periodic table. Y represents a hydrocarbon group or a halogen atom containing an atom represented by the following general formula (2):
(3) or (4) (Where R ² may be the same or different,
A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, or a hydrocarbon group containing an atom of Groups 15 and 16 of the periodic table is shown. Q represents an atom belonging to groups 15 and 16 of the periodic table. ) Is shown. n is a transition metal atom M
Equal to the oxidation number of ) Organic transition metal compound represented by
An olefin polymerization catalyst comprising (C) an activating co-catalyst and (D) an organometallic compound. (A) The following general formula (1) or (1 ′): (Where M is a transition metal atom selected from Groups 3 to 10 of the periodic table, R ¹ may be the same or different, and may be a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, X represents a hydrocarbon group containing an atom of a group 15 or 16 of the periodic table, X may be the same or different, and represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, or a group of the group 15 or 16 of the periodic table. Y represents a hydrocarbon group or a halogen atom containing an atom represented by the following general formula (2):
(3) or (4) (Where R ² may be the same or different,
A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group, or a hydrocarbon group containing an atom of Groups 15 and 16 of the periodic table is shown. Q represents an atom belonging to groups 15 and 16 of the periodic table. ) Is shown. n is a transition metal atom M
Equal to the oxidation number of ) Organic transition metal compound represented by
(B) The following general formulas (5) and / or (6) (Where R ³ may be the same or different,
A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
q is an integer of 2 to 60. An olefin polymerization catalyst comprising the alkylaluminoxane represented by the formula) and (D) an organometallic compound. 4. A method for producing a polyolefin, comprising polymerizing an olefin using the catalyst for olefin polymerization according to claim 1.