JP2002201209A - Olefin polymerization catalyst and process for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce industrially useful poly-olefins. SOLUTION: This process for polymerizing olefins comprises polymerizing olefins in the presence of a catalyst having, as the constituting components, (A) a specific group 3 to 11 in the periodical table transition-metal compound, (B) an activation cocatalyst and, if necessary, (C) an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyolefin, which comprises using a catalyst comprising a transition metal compound having a specific structure and an activating cocatalyst in the presence of an olefin.

[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. Also, recently, by using bidentate diimine chelate-type palladium and nickel complexes as catalyst components, they have many branched structures that are different from polyolefins that can be produced with conventional metallocene catalysts. It has been reported that polyolefins can be produced. For example, there is WO96 / 23010. Further, a polymerization method using a product obtained by mixing various coordinating compounds, an acid and a zero-valent nickel compound as a polymerization catalyst for olefin is disclosed in JP-T-11-5086.
No. 35.

[0003]

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

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and have found that a transition metal complex obtained by reacting a compound having a specific structure with a transition metal compound is used as a catalyst for olefin polymerization. It has been found that by using this as a component and combining it with a specific activating cocatalyst, an industrially valuable polyolefin can be efficiently produced, and the present invention has been completed.

That is, the present invention relates to (A) the following general formula (1)

[0006]

Embedded image (M is the periodic table Group 3 to 11 transition metal atom, R ¹
To R ⁴ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group or a substituent containing an atom of Groups 15 and 16 of the periodic table, and R ^{1 to} R ⁴ are the same or different. Is also good. X represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituent containing an atom belonging to Groups 15 and 16 of the Periodic Table, or halogen; L represents a π electron;
1 shows a coordination bonding compound having a group atom as a coordination atom. X
And L may have a bond. a represents an integer of 1 to 6, and when a is 2 or more, Xs may be the same or different. b represents an integer of 0 to 6, and when b is 2 or more, L
May be the same or different. And (B) a catalyst for olefin polymerization containing (B) an activation co-catalyst as a component, and (A) a periodic table represented by the general formula (1). Third
Olefin polymerization is carried out in the presence of an olefin polymerization catalyst comprising a Group III to 11 transition metal compound, (B) an activating co-catalyst and (C) an organometallic compound, and furthermore, olefin polymerization in the presence of the olefin polymerization catalyst. The present invention relates to a method for polymerizing an olefin.

Hereinafter, the present invention will be described in detail. However,
Specific examples will be given in the description, but the present invention is not limited to these.

The transition metal compound (A) used as a component of the olefin polymerization catalyst of the present invention is characterized by having a structure represented by the following general formula (1).

[0009]

Embedded image In the general formula (1), M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table. Specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold And the like. Preferred are nickel and palladium.

R ^{1 to} R ⁴ of the compound represented by the general formula (1), which is the catalyst for olefin polymerization of the present invention, may be the same or different, and may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. , A substituted silyl group or a substituent containing an atom of Groups 15 and 16 of the periodic table. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a butyl group,
Isobutyl group, tert-butyl group, allyl group, prenyl group, benzyl group, cyclohexyl group, phenyl group,
-Methylphenyl group, 2-isopropylphenyl group, 2
-Tert-butylphenyl group, 2- (2-norbornyl) phenyl group, 2-biphenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, 2-
Trimethylsilylphenyl group, 1-naphthyl group, 9-anthracenyl group, 2-trifluoromethylphenyl group,
Examples thereof include a 2,6-dibromophenyl group and a 2,6-dichlorophenyl group. Specific examples of the substituted silyl group include a trimethylsilyl group, a dimethylphenylsilyl group, a dimethyl-tert-butylsilyl group, a diphenylmethylsilyl group, And a triphenylsilyl group. Examples of the substituents containing atoms of groups 15 and 16 of the periodic table include a dimethylamino group, a diethylamino group,
Diisopropylamino group, diphenylamino group, dibenzylamino group, dimethylphosphino group, 2-dimethylaminophenyl group, 2-dimethylphosphinophenyl group,
Examples include a methoxy group, an ethoxy group, an isopropoxy group, a phenoxy group, a thiomethyl group, a 2-methoxyphenyl group, a 2-thiomethylphenyl, and a p-toluenesulfonylmethyl group. Particularly preferably, it has 1 to 2 carbon atoms.
0 hydrocarbon group.

X in the general formula (1) is a hydrogen atom, and has 1 carbon atom.
A hydrocarbon group, a substituent containing an atom of Groups 15 and 16 of the Periodic Table, or halogen. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, butyl, isobutyl, tert-butyl, benzyl, allyl, phenyl, substituted phenyl, 1-naphthyl, and the like. Suitable examples of the substituent containing an atom belonging to Groups 15 and 16 of the periodic table include a dimethylamide group, a diethylamide group, a diphenylamide group, a methoxy group, an ethoxy group, and a phenoxy group. Can be mentioned. Examples of halogen include fluorine,
Chlorine, bromine and iodine.

L in the general formula (1) is a π electron,
It shows a coordination bonding compound having atoms of groups 4, 15, and 16 as coordination atoms. Specifically, ethylene, propylene,
Monoenes such as butene and styrene; butenes such as butadiene, isoprene and 1,5-cyclooctadiene; phenyl isocyanide; (2,6-dimethylphenyl) isocyanide; (2,6-diisopropylphenyl) isocyanide; Methylphenyl) isocyanide, (2-
Isopropylphenyl) isocyanide, (2-ethyl-
6-isopropylphenyl) isocyanide, {2- (2
-Norbornyl) phenyl} isocyanide, (2-biphenyl) isocyanide, (2,4-terphenyl) isocyanide, {2,4-di- (1-naphthyl)} isocyanide, (9-anthracenyl) isocyanide, (2-trimethylsilyl) (Phenyl) isocyanide, (4-methylphenyl) isocyanide, (2,6-dichlorophenyl) isocyanide, (2,6-dibromophenyl) isocyanide, (2,6-dinitrophenyl) isocyanide, (2-trifluoromethylphenyl) isocyanide Isocyanides having an aryl group such as tert-butyl isocyanide, isopropyl isocyanide, isocyanide having an aliphatic group such as butyl isocyanide, trimethylsilyl isocyanide, triphenylsilyl isocyanide, tert- Isocyanides having silyl group such as chill dimethylsilyl isocyanide, trimethylamine, triethylamine, N, N-dimethylaniline,
Examples thereof include amines such as pyridine, nitriles such as acetonitrile and benzonitrile, phosphines such as trimethylphosphine and triphenylphosphine, triethylphosphite, triphenylphosphine oxide, diethyl ether, tetrahydrofuran, and dimethylsulfide. In particular, isocyanides having an aryl group are preferable from the viewpoint of improving polymerization activity.

X and L may have a bond, for example, a π-allyl group.

In the general formula (1), a represents an integer of 1 to 6; b represents an integer of 0 to 6;
In the above case, X and L may be the same or different from each other. When X is a halogen and b is 0, the compound represented by the general formula (1) may have a dimer structure in which the halogen is a crosslink.

Among the compounds represented by the general formula (1), which are constituents of the catalyst for olefin polymerization of the present invention, those in which M is nickel, for example, the corresponding nickel / isocyanide complex is replaced by the presence of an alkyl halide. under,
It can be synthesized by reacting. Further, a method used in an existing complex synthesis reaction can be used as it is. For example, J. Am. Chem. Soc. 1
969, 91, 7196. Can be used. It goes without saying that the compound represented by the general formula (1) produced by the reaction can be used as a polymerization catalyst after purification and isolation, but it can also be subjected to a polymerization reaction in-situ without isolation.

Specific examples of the transition metal compound represented by the general formula (1), which is a component of the catalyst for olefin polymerization of the present invention, include the following transition metal complexes. It is not limited.

[0017]

Embedded image

Embedded image

Embedded image In the present invention, (B) the activating co-catalyst is capable of polymerizing an olefin by acting or reacting with a transition metal compound of Groups 3 to 11 of the periodic table (A) represented by the general formula (1). Shows compounds that can form possible polymerization active species. An activation co-catalyst is a compound that forms a polymerization active species, then provides a compound that weakly coordinates or interacts with the generated polymerization active species, but does not directly react with the active species.

The activation cocatalyst (B) can be classified into a type used by dissolving it in a hydrocarbon solvent and a type used by suspending it. Either of them can be used in the present invention. Examples of the activating cocatalyst (B) used by dissolving in the hydrocarbon solvent used in the present invention include alkylaluminoxane, a non-coordinating anion, which has recently been frequently used as a cocatalyst component of a homogeneous olefin polymerization catalyst system Carboxylic acid compounds described in JP-A-8-198908, phenol compounds described in JP-A-8-198909, JP-A-9-11091
No. 8 dicarboxylic acid compounds.

When the activating cocatalyst (B) used in the present invention is an aluminoxane, its structure is represented by the following general formula (2) and / or (3)

[0020]

Embedded image (In the formula, R ⁵ may be the same or different, and is a hydrocarbon group having 1 to 20 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a tert-butyl group. Is an integer of 2 to 60). The aluminoxane may contain a small amount of an organometallic compound.

When the activating co-catalyst (B) used in the present invention is an ionized ionic compound having a non-coordinating anion, its structure is a protonic acid represented by the following general formula (4), It is desirable to be a compound having a structure of any of the ionized ionic compound represented by (5), the Lewis acid represented by the general formula (6) or the Lewis acidic compound represented by the general formula (7).

[HL ¹ ] [B (Ar) ₄ ] (4) [AL ² _m ] [B (Ar) ₄ ] (5) [D] [B (Ar) ₄ ] (6) B (Ar) ₃ (7) (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 lithium, sodium, iron Or a cation of a metal selected from silver, D is a carbonium cation or a tropylium cation, Ar is a halogen-substituted aryl group having 6 to 20 carbon atoms, and m is an integer of 0 to 2.) Specific examples of the protonic acid represented by the general formula (4) include diethyloxonium tetrakis {3,5-bis (trifluoromethyl) phenyl} borate, diethyloxonium tetrakis (pentafluorophenyl) Borate,
Dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) borate, hydronium tetrakis (pentafluorophenyl) borate, N,
N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-N-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetra Methyleneoxonium tetrakis (pentafluorophenyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri-n-butylammonium tetrakis (pentafluorophenyl) ) Aluminates and the like,
It is not limited to these.

Specific examples of the ionizable ionic compound represented by the general formula (5) include sodium tetrakis {3,5-bis (trifluoromethyl) phenyl} borate and lithium tetrakis (pentafluorophenyl).
Borate, lithium salt such as lithium tetrakis (pentafluorophenyl) aluminate, or an ether complex thereof, ferrocenium salt such as ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) aluminate,
Examples thereof include silver salts such as silver tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) aluminate, but are not limited thereto.

As the Lewis acid represented by the general formula (6), specifically, trityl tetrakis {3,5-bis (trifluoromethyl) phenyl} borate, trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis ( Pentafluorophenyl) aluminate,
Examples include, but are not limited to, tropylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) aluminate, and the like.

As specific examples of the Lewis acidic compound represented by the general formula (7), tris {3,5-bis (trifluoromethyl) phenyl} borane, 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 thereto.

In the present invention, the activating cocatalyst (B) used by suspending it in a hydrocarbon solvent is described in JP-A-5-30.
1917, JP-A-7-224106, JP-A-10-
139807, JP-A-10-204114, JP-A-10-231313, JP-A-10-231313,
Clay compounds described in JP-A-10-182715 and JP-A-11-1509, and Japanese Patent Application No. 10-5658.
No. 5, Topotactic reduction reaction product with electron transfer, sulfonate compound described in JP-A-8-48713, JP-A-8-157518
Compound described in JP-A-8-291
Examples include solid components obtained by chemically fixing general formulas (4), (5), and (6) to an inorganic oxide, an ion-exchange resin, and the like described in No. 202, but are not limited thereto. It is not something to be done.

When the activating cocatalyst (B) used in the present invention is a clay compound, a clay compound having a cation exchange ability is used. Further, the clay compound used in the present invention is previously treated with an acid and an alkali,
It is preferable to perform chemical treatment such as complex formation by salt treatment and organic compound or inorganic compound treatment.

Examples of the clay compound include naturally occurring kaolinites such as 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, coucheite, clinochlore; sepiolite and palygorskite; and artificially synthesized clay compounds.
It is not limited to these.

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 sodium phosphate, potassium phosphate, aluminum phosphate, and ammonium phosphate; and sodium acetate, potassium acetate, potassium oxalate; Organic acid salts such as sodium citrate and sodium tartrate can be exemplified.

Examples of the organic compound used to form the organic complex of the clay compound include compounds that generate carbon cations such as onium salts, trityl chloride and tropylium bromide, and complex compounds that generate metal complex cations such as ferrocenium salts. Is exemplified. 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 compounds used in the present invention, a modified clay compound which is a clay compound-organic ion complex in which a metal ion which is an exchangeable cation present in the clay compound 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 methyl ammonium, ethyl ammonium, butyl ammonium, hexyl ammonium, decyl ammonium, dodecyl ammonium, diamyl ammonium, tributyl ammonium, N, N-
Aliphatic ammonium cations such as dimethyldodecylammonium, N, N-dimethyloctadecylammonium, N, N-dioctadecylmethylammonium, N, N-dioleylmethylammonium, anilinium, N-
Methylanilinium, N, N-dimethylanilinium,
N-ethylanilinium, N, N-diethylanilinium, benzylammonium, toluidinium, dibenzylammonium, tribenzylammonium, N, N,
Examples include ammonium ions such as aromatic ammonium cations such as 2,4,6-pentamethylanilinium, and oxonium ions such as dimethyloxonium and diethyloxonium, but are not limited thereto.

When the activation cocatalyst (B) used in the present invention is a topotactic reduction reaction product accompanied by electron transfer, the reaction product is represented by the general formula (8) E ^{r +} _{(k / r)} ( L ³ ) _h [Q] ^k− (8) [wherein [Q] is a host compound, k is a reduction amount, ^{Er +} is an r-valent guest cation, and L ³ is a Lewis base. , H is the amount of Lewis base. ] Can be exemplified.

Here, [Q] is a host compound having a three-dimensional structure, a host compound having a two-dimensional structure,
A host compound having a one-dimensional structure and a host compound which is a molecular solid can be exemplified.

Examples of the host compound having a three-dimensional structure include hexamolybdenum octasulfide, vanadium pentoxide, tungsten trioxide, titanium dioxide, vanadium dioxide, chromium dioxide, manganese dioxide, tungsten dioxide, ruthenium dioxide, osmium dioxide, and iridium dioxide. Can be exemplified.

Examples of the host compound having a two-dimensional structure include titanium disulfide, zirconium disulfide, hafnium disulfide, vanadium disulfide, niobium disulfide, tantalum disulfide, chromium disulfide, molybdenum disulfide, tungsten disulfide, and tungsten disulfide. Rhenium sulfide, platinum disulfide, tin disulfide, lead disulfide, phosphorus magnesium trisulfide, phosphorus manganese trisulfide,
Examples include tantalum sulfide carbide, molybdenum trioxide, vanadium pentoxide gel, graphite, and polyacene.

Examples of the host compound having a one-dimensional structure include titanium trisulfide and niobium triselenide.

As the host compound which is a molecular solid,
Examples thereof include tetracyanoquinodimethane and tetrathiofulvalene.

Further, as [Q], a plurality of the above host compounds may be used as a mixture.

Although k is not particularly limited, it is preferably 0 for the purpose of producing an olefin polymer with high catalytic activity.
A range of <k ≦ 3 can be used. More preferably, the range of 0 <k ≦ 2 can be used.

As L ³ , a Lewis base or cyclopentadienyl group capable of coordinating to ^{Er +} can be used.
Examples of the Lewis base include water, amine compounds, heterocyclic compounds containing nitrogen, ethers such as ethyl ether or n-butyl ether, amides such as formamide, N-methylformamide or N-methylacetamide, methyl alcohol or ethyl alcohol, and the like. But diols such as 1,2-butanediol and 1,3-butanediol can be exemplified, but the present invention is not limited thereto. These two or more kinds can be used as a mixture.

H can be in the range of 0 ≦ h ≦ 10.

As E ^{r +} , a cation containing at least one atom selected from the group consisting of atoms of groups 1 to 14 of the periodic table can be used, and r is in the range of 0 <r ≦ 10. but it is high for the purpose of the catalytic activity for producing an olefin polymer, in preferably, the formula (9) or _{^{(10) (R 6) 2}} R 7 NH + (9) [ wherein, (R ⁶ ₂ ) R ⁷ N is an amine compound, R ⁶ is each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 30 carbon atoms, and R ⁷ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 30 carbon atoms. It is a hydrogen group or an aromatic hydrocarbon group having 6 to 50 carbon atoms. (R ⁸ ) ⁺ (10) wherein (R ⁸ ) ⁺ is a carbonium cation or a tropylium cation having 1 to 50 carbon atoms. At least one cation selected from the group consisting of the cations represented by

Examples of the amine compound represented by (R ⁶ ) ₂ R ⁷ N include methylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, allylamine, N-methylcyclohexylamine,
N, N-dimethyloctylamine, N, N-dimethyldodecylamine, N, N-dimethyloctadecylamine,
N, N-dioctadecylmethylamine, trihexylamine, triisooctylamine, tridodecylamine,
Aliphatic amines such as N, N-dimethylcyclohexylamine, aniline, N-methylaniline, N-ethylaniline, N-allylaniline, o-toluidine, p-toluidine, N, N-dimethylaniline, N-methyl-o -Toluidine, N-methyl-m-toluidine, N-ethyl-
Aromatic amines such as o-toluidine can be exemplified.

Examples of the cation represented by the general formula (10) include a triphenylmethyl cation and a tropylium cation.

The organometallic compound (C) which is a component of the olefin polymerization catalyst of the present invention and is used together with the transition metal compound and the activating cocatalyst is, specifically, an alkyllithium such as methyllithium or n-butyllithium. Compound, methyl magnesium chloride, ethyl magnesium chloride, isopropyl magnesium chloride,
Grignard reagents such as benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium bromide and benzylmagnesium bromide; dialkylmagnesium such as dimethylmagnesium; dialkylzinc such as dimethylzinc and diethylzinc; and alkylboranes such as trimethylborane and triethylborane And alkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum. Preferred organometallic compounds include organoaluminum compounds represented by the following general formula (11).

(R ⁹ ) ₃ Al (11) (wherein R ⁹ may be the same or different and represents a hydrogen atom, an amide group, an alkoxy group, a hydrocarbon group,
At least one of them is a hydrocarbon group. Particularly preferred compounds include trialkylaluminums such as triethylaluminum and triisobutylaluminum.

The components (A) and (B) in the present invention,
There is no limitation on the ratio of component (C) and component (B), but when component (B) is a compound represented by general formula (2) and / or (3), metal atoms of component (A) and component (B) The molar ratio per component is (A component) :( B component) = 100: 1 to 1:10
00000, especially 1: 1 to 1: 10000
0, and the molar ratio of the component (A) to the component (C) per metal atom is (component (A)) :( component (C)).
= 100: 1 to 1: 100000, especially 1: 1 to 1
It is preferably in the range of 1: 10000. When the component (B) is a compound represented by the general formula (4), (5), (6) or (7), the molar ratio of the component (A) to the component (B) per metal atom is (A Component): (Component B) = 10:
In the range of 1-1: 1000, especially 3: 1 to 1:10
0, and the molar ratio of the component (A) to the component (C) per metal atom is (component (A)) :( component (C)).
= 100: 1 to 1: 100000, especially 1: 1 to 1
It is preferably in the range of 1: 10000. When the component (B) is a modified clay compound, the weight ratio of the component (A) to the component (B) is (A component) :( B component) = 10: 1 to 1:
In the range of 10,000, especially 3: 1 to 1: 10000
And the molar ratio of the component (A) to the component (C) per metal atom is (A component) :( C component) =
100: 1 to 1: 100000, especially 1: 1 to 1
It is preferably in the range of 1: 10000.

The method for preparing the olefin polymerization catalyst comprising the components (A), (B) and (C) is not limited, and the preparation may be carried out in an inert solvent for each component or in a monomer to be polymerized. Can be used as a solvent and a method of mixing. Further, there is no restriction on the order in which these components are reacted, and there is no restriction on the temperature or the processing time for performing this processing. In addition, each component is 2
It is also possible to prepare a catalyst for olefin polymerization using more than one kind.

In the present invention, an olefin polymerization catalyst comprising (A) the transition metal compound represented by the general formula (1) and (B) an activating co-catalyst can be used by being supported on fine solid particles. The fine particle solid used at this time is an inorganic carrier or an organic carrier, specifically, SiO ₂ , A
l ₂ O ₃ , ZrO, B ₂ O ₃ , CaO, ZnO, MgC
l ₂ , CaCl ₂ and combinations thereof, polyethylene, polypropylene, poly (1-butene), polyolefins such as polystyrene, and mixtures of these polyolefins with polar polymers such as polyethyl methacrylate, polyester, polyimide, or Those having a copolymer composition are exemplified. There is no limitation on the shape of the solid fine particles, but it is preferable that the particle size be 5 to 200 μm and the pore size be 20 to 100 Å.

The catalyst in the present invention can be prepared by a usual polymerization method,
That is, it can be used for any of slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization and bulk polymerization. In the present invention, the polymerization means not only homopolymerization but also copolymerization, and the polyolefin obtained by these polymerizations is used in a meaning including not only a homopolymer but also a copolymer.

The polymerization of 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, it is possible to efficiently and stably produce an olefin polymer having a uniform particle shape. it can. 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, cyclopentadiene, 4-methyl-1,4-hexadiene, 7- Conjugated and non-conjugated dienes such as methyl-1,6-octadiene, cyclic olefins such as cyclobutene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid,
Α, β-unsaturated carboxylic acids such as itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, and sodium, potassium, lithium, zinc and magnesium salts thereof Salts, metal salts such as calcium salts, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate Α, β-unsaturated carboxylic esters such as n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate , Vinyl stearate, trifluorovinegar Vinyl esters such as vinyl, glycidyl acrylate, include glycidyl methacrylate, glycidyl itaconate, unsaturated glycidyl such as such as itaconic acid monoglycidyl ester, further, ethylene and propylene, ethylene and 1-butene, and ethylene 1-
Mix two or more components such as hexene, ethylene and 1-octene, ethylene and vinyl acetate, ethylene and methyl methacrylate, ethylene and propylene and styrene, ethylene and 1-hexene and styrene, ethylene and propylene and ethylidene norbornene And then polymerize.

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.

[0054]

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. The polymerization was carried out in a 100 ml glass pressure vessel under stirring with a stirrer chip. The solvent used for the reaction was
All were previously purified, dried or deoxygenated by known methods. Polymer properties are measured by differential scanning calorimetry (DSC)
And the molecular weight distribution (Mw / Mn) was determined by gel permeation chromatography (GPC) measurement (column temperature: 140 ° C., solvent: 1,2,4-trichlorobenzene).

Example 1 (Preparation of complex solution)

[0056]

Embedded image Under a nitrogen atmosphere, 4.1 mg (5.6 μmol) of the complex represented by the above formula was collected in a 50 ml Schlenk tube, and dissolved in dry toluene (28 ml).

(Evaluation of Polymerization) In a nitrogen atmosphere, 45 ml of toluene and 5 ml (1 μmol of complex) of the above-mentioned catalyst solution were added to a 100 ml glass autoclave. Next, a toluene solution of methylaluminoxane (PMA-S, manufactured by Tosoh Finetech Co., Ltd., 2.85 mol /
0.35 ml (1 mmol) was added.
Stir for 1 hour. Next, ethylene was introduced into the autoclave, the partial pressure of ethylene was set to be 1 MPa, and polymerization was started at room temperature. Polymerization was carried out for 30 minutes, unreacted ethylene was depressurized and removed, and 5 ml of methanol was added to terminate the polymerization. The contents of the autoclave were added to 300 ml of a hydrochloric acid / methanol solution to precipitate a polymer. Thereafter, the polymer was separated by filtration, washed with methanol, and vacuum dried. The yield of the polymer was 0.85 g. Physical properties of the polymer were as follows: Tm = 128.0 ° C, Mw = 330000,
Mw / Mn = 4.3.

[0058]

Industrial Applicability The olefin polymerization catalyst comprising a transition metal compound as a main catalyst according to the present invention is extremely effective for olefin polymerization. By using this catalyst as an olefin polymerization catalyst, an industrially useful polyolefin is obtained. Can be manufactured efficiently.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J028 AA01A AB00A AB01A AC00A AC01A AC08A AC26A AC31A AC32A AC41A AC42A AC44A AC45A AC46A AC47A AC48A BA00A BA02B BB00A BB00B BB01B BB02B BC01 EB01 BC03B02 EB01 BC09B02 EB01 EB12 EB13 EB15 EB16 EB17 EB21 EB24 EB25 EC01 EC02 4J128 AA01 AB00 AB01 AC00 AC01 AC08 AC26 AC31 AC32 AC41 AC42 AC44 AC45 AC46 AC47 AC48 AD00 AE00 BA00A BA02B BB00A BB00B BB01B BB02B01B02B BCBC EB12 EB13 EB15 EB16 EB17 EB21 EB24 EB25 EC01 EC02

Claims (5)

[Claims] (A) The following general formula (1): (M is the periodic table Group 3 to 11 transition metal atom, R ¹
To R ⁴ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group or a substituent containing an atom of Groups 15 and 16 of the periodic table, and R ^{1 to} R ⁴ are the same or different. Is also good. X represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituent containing an atom belonging to Groups 15 and 16 of the Periodic Table, or halogen; L represents a π electron;
1 shows a coordination bonding compound having a group atom as a coordination atom. X
And L may have a bond. a represents an integer of 1 to 6, and when a is 2 or more, Xs may be the same or different. b represents an integer of 0 to 6, and when b is 2 or more, L
May be the same or different. A catalyst for olefin polymerization comprising, as constituents, a transition metal compound belonging to Groups 3 to 11 of the periodic table having a structure represented by the formula (1) and an activation promoter (B). 2. The olefin polymerization catalyst according to claim 1, wherein in the general formula (1), M is nickel. 3. The catalyst for olefin polymerization according to claim 1, wherein in the general formula (1), L is isocyanide. 4. An olefin polymerization catalyst comprising (A) the transition metal compound according to any one of claims 1 to 3, (B) an activation promoter and (C) an organometallic compound. 5. An olefin polymerization method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1.