JP2002212214A - Process for producing olefin polymer, and polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polymerization catalyst, and a process for producing an olefin polymer by using it. SOLUTION: The catalyst for olefin polymerization is made by using a component (A) comprising a mixture of a transition metal compound represented by the formula: (1) MXlLm and a silylated diimine compound represented by general formula (2), and a compound (B) comprising (B1) an organoaluminum compound represented by the formula: (E1)aAlZ(3-a), (B2) a cyclic aluminoxane having a structure represented by the formula: -Al(E2)-O-)b, or (B3) a linear aluminoxane having a structure represented by the formula: E3 -Al(E3)-O-)cAl(E 3)2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerization catalyst comprising a mixture of a silicon-substituted diimine compound and a Group 5 or 6 transition metal compound, and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art Hitherto, a polymerization catalyst using a component obtained by mixing a silicon-substituted diimine compound (2) represented by the following general formula (2) and a transition metal compound of Group 5 or 6 has not been known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polymerization catalyst and a method for producing an olefin polymer using the same.

[0004]

That is, the present invention provides a catalyst for olefin polymerization using the following component (A) and compound (B), and a catalyst for olefin polymerization using compound (C). Component (A): general formula (1) in MX _l L _m (wherein, M represents a transition metal of Group 5, 6, X represents a halogen atom, L is an organic ligand, l and m Each represents an integer of 0 to 6.) and a general formula (2) (Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted having 6 to 20 carbon atoms, and R ₂ , R ₃ , and R ₄ are the same or different. Alternatively, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a substituted aralkyl group having 6 to 20 carbon atoms may be used. A compound obtained by mixing a silicon-substituted diimine compound represented by the following formula (II): Compound (B): Any of the following compounds (B1) to (B3), or a mixture of two or three of them (B1 ): Organoaluminum compound represented by the general formula (E1) a Al Z (3-a) (B2): Cyclic aluminoxane having a structure represented by the general formula {-Al (E2) -O-} b (B3) : General formula E3 ｛-Al (E3) -O-｝ c Al
(E3) A linear aluminoxane having the structure represented by 2 (wherein E1 to E3 are the same or different and have 1 to 1 carbon atoms)
8, Z is the same or different and represents a hydrogen atom or a halogen atom, a is an integer of 1-3, b
Represents an integer of 2 or more, and c represents an integer of 1 or more. Compound (C): Any of the following compounds (C1) to (C3) (C1): a boron compound represented by the general formula BQ1 Q2 Q3, (C2): a general formula Z ⁺ (BQ1 Q2 Q3 Q4) ^- A boron compound represented by the formula (C3): general formula (LH) ⁺ (BQ1 Q2 Q3 Q4)
^- the boron compound represented (wherein, Z ⁺ is an inorganic or organic cation, (L-H)
⁺ Is a Bronsted acid, B is a trivalent boron atom, Q1 to Q4 are the same or different, and are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1 to 2 carbon atoms.
It represents a halogenated hydrocarbon group having 0, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a disubstituted amino group having 2 to 20 carbon atoms. ). Further, the present invention provides a method for producing an olefin polymer in which an olefin is polymerized using the catalyst.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the olefin polymerization catalyst of the present invention will be described. In the transition metal compound represented by the general formula (1), M represents a Group 5 or 6 transition metal.

Examples of the halogen atom in the substituent X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The organic ligands L include olefin ligands, acetylene ligands, aromatic compound ligands, organic oxygen-containing compound ligands, and organic compounds in addition to CO, NO, NH2, and NH3. Examples thereof include a sulfur-containing compound ligand and an organic nitrogen-containing compound ligand.

The transition metal compound in the present invention includes:
Halogen compounds of transition metals of groups 5 and 6 include, for example, vanadium trichloride, vanadium trichloride tetrahydrofuran adduct, niobium pentachloride, tantalum pentachloride, chromium dichloride, chromium trichloride, chromium trichloride tetrahydrofuran adduct , Molybdenum trichloride, molybdenum pentachloride, tungsten tetrachloride, tungsten hexachloride, and compounds obtained by changing chlorine to fluorine, bromine, and iodine.

In the silicon-substituted diimine compound represented by the general formula (2), R ₁ , R ₂ , R ₃ and R ₄ have 1 to 20 carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, s-
Examples thereof include a butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group and the like. In addition, R _1,
Examples of the optionally substituted aryl group having 6 to 20 carbon atoms of R ₂ , R ₃ and R ₄ include, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3- Xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,
6-xylyl group, 2,4,6-trimethylphenyl group,
Examples include a 2,3-diisopropylphenyl group, a 2,4-diisopropylphenyl group, a 2,5-diisopropylphenyl group, a 2,6-diisopropylphenyl group, an α-naphthyl group, and a β-naphthyl group. Each of these aryl groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a substituted silyl group such as a trimethylsilyl group and a triphenylsilyl group, a methoxy group, an ethoxy group, an n-propoxy group and an i-propoxy group. Group, an alkoxy group such as a phenoxy group or an aryloxy group,
Substituted with alkylthio or arylthio group such as methylthio group and phenylthio group, dialkylamino group such as dimethylamino group, diarylamino group such as diphenylamino group, diarylphosphino group such as diphenylphosphino group, cyano group, nitro group, etc. It may be. Examples of the alkenyl group having 2 to 20 carbon atoms for R ₂ , R ₃ , and R ₄ include a vinyl group, a propenyl group, and a butenyl group. Examples of the optionally substituted aralkyl group having 7 to 20 carbon atoms of R ₂ , R ₃ and R ₄ include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group,
5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, naphthylmethyl group and the like. Each of these aralkyl groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a substituted silyl group such as a trimethylsilyl group and a triphenylsilyl group, a methoxy group, an ethoxy group, an n-propoxy group and an i-propoxy group. Groups, alkoxy groups such as phenoxy groups, aryloxy groups, alkylthio groups such as methylthio groups and phenylthio groups, disubstituted amino groups such as arylthio groups, dimethylamino groups and diphenylamino groups, and diarylphosphino groups such as diphenylphosphino groups , A cyano group, a nitro group or the like.

Specific examples of the silicon-substituted diimine compound represented by the general formula (2) include, for example, N, N'-bis (trimethylsilyl) -2,3-butanediimine, N, N'-
Bis (triethylsilyl) -2,3-butanediimine,
N, N'-bis (triisopropylsilyl) -2,3-
Butanediimine, N, N'-bis (t-butyldimethylsilyl) -2,3-butanediimine, N, N'-bis (trivinylsilyl) -2,3-butanediimine, N,
N'-bis (tripropenylsilyl) -2,3-butanediimine, N, N'-bis (tribenzylsilyl)-
2,3-butanediimine, N, N'-bis (tri-4-
Chlorobenzylsilyl) -2,3-butanediimine,
N, N'-bis (tri-4-methoxybenzylsilyl)
−2,3-butanediimine, N, N′-bis (tri-4
-Methylthiobenzylsilyl) -2,3-butanediimine, N, N′-bis (tri-4-dimethylaminobenzylsilyl) -2,3-butanediimine, N, N′-bis (tri-4-diphenylphosphino) Benzylsilyl)-
2,3-butanediimine, N, N'-bis (tri-4-
Nitrobenzylsilyl) -2,3-butanediimine,
N, N'-bis (tri-4-cyanobenzylsilyl)-
2,3-butanediimine, N, N'-bis (triphenylsilyl) -2,3-butanediimine, N, N'-bis (tri-2,6-xylylsilyl) -2,3-butanediimine, N, N ' -Bis (tri-2,4,6-trimethylphenylsilyl) -2,3-butanediimine, N,
N′-bis (tri-2,6-diisopropylphenylsilyl) -2,3-butanediimine, N, N′-bis (tri-1-naphthylsilyl) -2,3-butanediimine,
N, N'-bis (tri-2-naphthylsilyl) -2,3
-Butanediimine, N, N'-bis (tri-4-chlorophenylsilyl) -2,3-butanediimine, N, N '
-Bis (tri-4-methoxyphenylsilyl) -2,3
-Butanediimine, N, N'-bis (tri-4-methylthiophenylsilyl) -2,3-butanediimine, N,
N'-bis (tri-4-dimethylaminophenylsilyl) -2,3-butanediimine, N, N'-bis (tri-4-diphenylphosphinophenylsilyl) -2,3
-Butanediimine, N, N'-bis (tri-4-nitrophenylsilyl) -2,3-butanediimine, N, N '
-Bis (tri-4-cyanophenylsilyl) -2,3-
Butanediimine, and aralkyl groups and aryl groups in which the position of a substituent is changed are exemplified. In addition, those in which these methyl groups are replaced with hydrogen atoms, ethyl groups, n-propyl groups, isopropyl groups, phenyl groups, naphthyl groups, and the like can be mentioned.

The method of mixing the transition metal compound represented by the general formula (1) and the silicon-substituted diimine compound represented by the general formula (2) is not particularly limited, but the solvent may be mixed in an inert atmosphere such as nitrogen or argon. It can be preferably carried out by mixing the transition metal compound represented by the general formula (1) and the silicon-substituted diimine compound represented by the general formula (2) in the presence or absence.

The molar ratio of the silicon-substituted diimine compound represented by the general formula (2) to the transition metal compound represented by the general formula (1) is usually 0.1 to 10 times, preferably 0.5 to 10 times. It is about 3 mole times.

When a solvent is used, the solvent is not particularly limited, but aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, toluene, xylene,
Aromatic hydrocarbons such as mesitylene, aliphatic halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, aromatic halogenated hydrocarbons such as monochlorobenzene and dichlorobenzene, diethyl ether, dibutyl ether, methyl t-butyl ether, tetrahydrofuran and the like And alcohols such as methyl alcohol, ethyl alcohol and n-butyl alcohol, and mixtures thereof. The amount used is usually 1 to 200 times by weight, preferably about 3 to 30 times by weight of the transition metal compound represented by the general formula (1).

The reaction is carried out usually at a temperature in the range of -100 ° C to the boiling point of the solvent, preferably about -20 to 80 ° C.

After the reaction, for example, it can be used as it is as a solution or slurry, or it can be used after the solvent is distilled off.

[Organic aluminum compound (B)] As the compound (B) used in the present invention, the following (B1) to (B1)
It is a known organoaluminum compound of (B3), and includes any of them or a mixture thereof. (B1): an organoaluminum compound represented by the general formula (E1) a AlZ (3-a), (B2): a cyclic aluminoxane having a structure represented by the general formula ｛-Al (E2) -O-｝ b, And (B3): General formula E33-Al (E3) -O-｝ c A
linear aluminoxane having a structure represented by l (E3) 2 (wherein E1, E2 and E3 are hydrocarbon groups having 1 to 8 carbon atoms, and all E1, all E2 and all E3 are Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is an integer of 1 to 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.)

Specific examples of the organoaluminum compound (B1) represented by the general formula (E1) a AlZ (3-a) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum. Trialkylaluminum; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum halide, dihexylaluminum chloride; methylaluminum dichloride;
Examples thereof include alkyl aluminum dichlorides such as ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, and hexyl aluminum dichloride; and dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, and dihexyl aluminum hydride. be able to. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum and triisobutylaluminum.

A cyclic aluminoxane (B2) having a structure represented by the general formula ｛-Al (E2) -O-｝ b; a general formula E3 ｛-Al (E3) -O-｝ cAl (E3) 2
Linear aluminoxane (B3) having a structure represented by the formula:
In the above, specific examples of E2 and E3 include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. b
Is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E2 and E3 are a methyl group or an isobutyl group, b is an integer of 2 to 40, and c is an integer of 1 to 40.

The above aluminoxane is made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

[Compound C] In the present invention, compound (C)
(C1) a boron compound represented by the general formula BQ1 Q2 Q3; (C2) a boron compound represented by the general formula Z ⁺ (BQ1 Q2 Q3 Q4
) ^- a boron compound represented by, (C3) the general formula (L-
^{H) + (BQ1 Q2 Q3 Q4} ) - one of boron compound represented by the used.

In the boron compound (C1) represented by the general formula BQ1 Q2 Q3, B is a trivalent boron atom, Q1 to Q3 are halogen atoms, and carbon atoms containing 1 to 20 carbon atoms. A hydrogen group, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, or 2 to 20 carbon atoms And may be the same or different. Preferred Q1 to Q3 are a halogen atom and 1-2.
Examples thereof include a hydrocarbon group containing 0 carbon atoms and a halogenated hydrocarbon group containing 1 to 20 carbon atoms.

Specific examples of the boron compound (C1) include:
Tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane,
Tris (2,3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) ) Borane and the like, more preferably tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula Z ⁺ (BQ 1 Q 2 Q 3 Q 4) ^- , Z ⁺ is an inorganic or organic cation, B is a trivalent boron atom, Q1 to Q4 are Q in the above (C1).
Same as 1 to Q3.

The general formula ^{Z + (BQ1 Q2 Q3 Q4)} - Examples of compound represented by, the Z ⁺ is an inorganic cation, ferrocenium cation, alkyl-substituted ferrocenium cation, silver cation And Z ⁺ which is an organic cation include triphenylmethyl cation. (BQ1 Q2 Q3 Q4) ^-, the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) Borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

Further, the general formula (LH) ⁺ (BQ1 Q2Q
In the boron compound (C3) represented by 3Q4) ^- , L is a neutral Lewis base, (LH) ⁺ is a Bronsted acid, and B is a boron atom in a trivalent valence state. And Q1 to Q4 correspond to Q1 to Q in the above (C1).
Same as 3.

The general formula (LH) ⁺ (BQ1 Q2 Q3 Q4
) ^- Specific examples of the compound represented by a Bronsted acid (L-H) ^+, the trialkyl-substituted ammonium, N, N-dialkyl anilinium, dialkyl ammonium, triarylphosphonium mentioned , (BQ1 Q2 Q3 Q4) ^- to include the same as described above.

Specific examples of these combinations include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal) Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5
-Bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl)
Examples thereof include borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (normal butyl) ammonium tetrakis (pentane) Fluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the present invention, the component (A) comprising a mixture of a transition metal compound represented by the general formula (1) and a silicon-substituted diimine compound represented by the general formula (2), (B) The compound (C) can be charged and used in an arbitrary order during the polymerization, if necessary, and a reaction product obtained by previously contacting a combination of these arbitrary compounds may be used. .

The amount of each catalyst component used is such that the molar ratio of the transition metal compound represented by the general formula (1) / the silicon-substituted diimine compound represented by the general formula (2) is about 0.1 to 10, preferably 0.1 to 10. About 5 to 3 and a molar ratio of compound (B) / transition metal compound of 0.1 to 10000, preferably 5 to 20
00, the molar ratio of compound (C) / transition metal compound is 0.0
It is desirable to use each component so that it is in the range of 1 to 100, preferably about 0.5 to 10.

Next, a method for polymerizing a monomer using the polymerization catalyst obtained above will be described. Monomers used for polymerization are olefins having 2 to 20 carbon atoms,
Any of diolefins and olefins having polar substituents such as carboxylic acids, esters, amino groups and the like can be used, and two or more monomers can be used at the same time. Such monomers are exemplified below, but are not limited to the following compounds. Specific examples of such olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-
1, nonene-1, decene-1, 5-methyl-2-pentene-1, vinylcyclohexene, and the like, and diolefin compounds include conjugated dienes and non-conjugated dienes of hydrocarbon compounds. Specific examples of the non-conjugated diene compound include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene,
9-decadiene, 4-methyl-1,4-hexadiene,
5-methyl-1,4-hexadiene, 7-methyl-1,
6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, and 1,3-cyclooctadiene. , 1,3-cyclohexadiene and the like. Specific examples of the olefin having a polar substituent include acrylic acid, methyl acrylate, methacrylic acid,
Examples include methyl methacrylate and vinyl acetate. Preferably, it is ethylene. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, and the like. However, the present invention is limited to the above compounds. Not something.

The polymerization method is not particularly limited either. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, and methylene dichloride and the like can be used. Solvent polymerization using a halogenated hydrocarbon as a solvent, slurry polymerization, gas phase polymerization in a gaseous monomer, and the like are possible, and both continuous polymerization and batch polymerization are possible.

The polymerization temperature can usually be in the range of about -50 ° C to 200 ° C, and particularly preferably in the range of about -20 ° C to 100 ° C, and the polymerization pressure is normal pressure to 60 kg / cm
About 2 G (6 MPa) is preferable. The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can range from about 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

The silicon-substituted diimine compound used in the present invention is Heteroatom Chemistry V
ol. 10, No. 5, 1999, p 423 and the like. For example, it can be obtained by reacting a diketone compound with a bissilyl-substituted amide lithium compound and then reacting with a chlorotrialkylsilane compound. Further, if necessary, it can be purified by a usual method such as recrystallization or distillation.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 Preparation of N, N'-bis (trimethylsilyl) -1,2-diphenylethanediimine / chromium trichloride tetrahydrofuran adduct N, N'-bis (trimethylsilyl)-under a nitrogen atmosphere
119 mg of 1,2-diphenylethanediimine was dissolved in 5 ml of dichloromethane, followed by addition of 126 mg of a chromium trichloride tetrahydrofuran adduct. This mixture is
Stirred at 5 ° C for 4 hours. Thereafter, the mixture was filtered to remove insolubles, and the obtained solution was concentrated under reduced pressure to obtain a dark green solid (224 mg).

Example 2 (Polymerization) In a jacketed separable flask, 100 ml of toluene was charged under nitrogen and stabilized at 25 ° C., and then ethylene was bubbled under normal pressure. Here, a hexane solution of triisobutylaluminum (2.0 m
1, 1.0 M, Kanto Chemical), 2.6 m solid obtained above
g and triphenylcarbenium tetrakispentafluorophenyl borate (13.8 mg) were added, and 1
Stirred for 0 minutes. Thereafter, ethylene was stopped, and a 5% aqueous hydrochloric acid solution was added to stop the polymerization. Methanol was added to the obtained mixture, and the insoluble matter was filtered and dried under reduced pressure.
0.68 g of polymer was obtained.

Example 3 (Polymerization) In Example 2, a hexane solution of triisobutylaluminum and triphenylcarbenium tetrakispentafluorophenylborate were replaced by M
MAO hexane solution (5.4 wt%, Al concentration)
The same operation as above was carried out except that the amount of the solid obtained above was changed to 1.0 mg using 3 ml, and the polymer 0.30 was used.
g was obtained. * MMAO: A type of aluminoxane (trade name of Tosoh Akzo)

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[Procedure amendment]

[Submission date] March 1, 2001 (2001.3.1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

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[Claims]

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[Document name to be amended] Statement

[Correction target item name] 0001

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[0001]

The present invention relates to the reaction of a silicon-substituted diimine compound with a Group 5 or 6 transition metal compound.
The present invention relates to a polymerization catalyst and a method for producing an olefin polymer using the catalyst.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art Hitherto, a polymerization catalyst using a component obtained by reacting a silicon-substituted diimine compound (2) represented by the following general formula (2) with a Group 5 or 6 transition metal compound has not been known.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

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[0004]

That is, the present invention provides a catalyst for olefin polymerization comprising a combination of the following component (A) and compound (B), and a compound (C). A catalyst for olefin polymerization characterized by the following. Component (A): general formula (1) in MX _l L _m (wherein, M represents a transition metal of Group 5, 6, X represents a halogen atom, L is an organic ligand, l and m Each represents an integer of 0 to 6.) and a general formula (2) (Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted having 6 to 20 carbon atoms, and R ₂ , R ₃ , and R ₄ are the same or different. Alternatively, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a substituted aralkyl group having 6 to 20 carbon atoms may be used. A compound obtained by mixing a silicon-substituted diimine compound represented by the following formula (II): Compound (B): Any of the following compounds (B1) to (B3), or a mixture of two or three of them (B1 ): Organoaluminum compound represented by the general formula (E1) a Al Z (3-a) (B2): Cyclic aluminoxane having a structure represented by the general formula {-Al (E2) -O-} b (B3) : General formula E3 ｛-Al (E3) -O-｝ c Al
(E3) A linear aluminoxane having the structure represented by 2 (wherein E1 to E3 are the same or different and have 1 to 1 carbon atoms)
8, Z is the same or different and represents a hydrogen atom or a halogen atom, a is an integer of 1-3, b
Represents an integer of 2 or more, and c represents an integer of 1 or more. Compound (C): Any of the following compounds (C1) to (C3) (C1): a boron compound represented by the general formula BQ1 Q2 Q3, (C2): a general formula Z ⁺ (BQ1 Q2 Q3 Q4) ^- A boron compound represented by the formula (C3): general formula (LH) ⁺ (BQ1 Q2 Q3 Q4)
^- the boron compound represented (wherein, Z ⁺ is an inorganic or organic cation, (L-H)
⁺ Is a Bronsted acid, B is a trivalent boron atom, Q1 to Q4 are the same or different, and are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1 to 2 carbon atoms.
It represents a halogenated hydrocarbon group having 0, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a disubstituted amino group having 2 to 20 carbon atoms. ). Further, the present invention provides a method for producing an olefin polymer in which an olefin is polymerized using the catalyst.

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[Document name to be amended] Statement

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[Correction method] Change

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The transition metal compound represented by the general formula (1) and the silicon-substituted diimine compound represented by the general formula (2) are
The reaction method is not particularly limited, but the reaction can be preferably carried out in an inert atmosphere such as nitrogen or argon in the presence or absence of a solvent.

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[Organic aluminum compound (B)] As the compound (B) used in the present invention, the following (B1) to (B1)
It is a known organoaluminum compound of (B3), and any of them or a combination thereof can be mentioned. (B1): an organoaluminum compound represented by the general formula (E1) a AlZ (3-a), (B2): a cyclic aluminoxane having a structure represented by the general formula ｛-Al (E2) -O-｝ b, And (B3): General formula E33-Al (E3) -O-｝ c A
linear aluminoxane having a structure represented by l (E3) 2 (wherein E1, E2 and E3 are hydrocarbon groups having 1 to 8 carbon atoms, and all E1, all E2 and all E3 are Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is an integer of 1 to 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.)

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In the present invention, the components (A) and (B) obtained by reacting the transition metal compound represented by the general formula (1) with the silicon-substituted diimine compound represented by the general formula (2) are required. The corresponding compound (C) can be charged and used in an arbitrary order during the polymerization, and a compound obtained by previously contacting a combination of these arbitrary compounds may be used.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoshi Kobayashi 2-10-1, Tsukahara, Takatsuki-shi, Osaka Sumitomo Kagaku Kogyo Co., Ltd. (72) Eiji Yoshikawa 2-1-1, Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Industries Co., Ltd. F-term (reference) 4J028 AA01A AB00A AC31A AC32A AC38A AC41A AC42A AC44A BA01A BA02B BB00A BB01B BC12B BC14B BC15B BC16B BC17B BC25B BC39A EB01 EB02 EB03 EB04 EB04 EB05 EB04 EB05 EB05 EB05 EB05 EB05 FA01 FA02 FA04 FA07 4J128 AA01 AB00 AC31 AC32 AC38 AC41 AC42 AC44 BA01A BA02B BB00A BB01B BC12B BC14B BC15B BC16B BC17B BC25B BC42A EB01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB11 FA14 EB13

Claims (4)

[Claims] 1. An olefin polymerization catalyst comprising the following component (A) and compound (B). Component (A): general formula (1) in MX _l L _m (wherein, M represents a transition metal of Group 5, 6, X represents a halogen atom, L is an organic ligand, l and m Each represents an integer of 0 to 6.) and a general formula (2) (Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted having 6 to 20 carbon atoms, and R ₂ , R ₃ , and R ₄ are the same or different. Alternatively, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a substituted aralkyl group having 6 to 20 carbon atoms may be used. A compound obtained by mixing a silicon-substituted diimine compound represented by the following formula (II): Compound (B): Any of the following compounds (B1) to (B3), or a mixture of two or three of them (B1 ): An organoaluminum compound represented by the general formula (E1) a Al Z (3-a); (B2): a cyclic aluminoxane having a structure represented by the general formula ｛-Al (E2) -O-｝ b; B3): General formula E3 ｛− Al (E3) -O-｝ c Al
(E3) A linear aluminoxane having the structure represented by 2 (wherein E1 to E3 are the same or different and have 1 to 1 carbon atoms)
8, Z is the same or different and represents a hydrogen atom or a halogen atom, a is an integer of 1-3, b
Represents an integer of 2 or more, and c represents an integer of 1 or more. ) 2. An olefin polymerization catalyst comprising the component (A), the compound (B) and the following compound (C) according to claim 1. Compound (C): Any of the following compounds (C1) to (C3) (C1): a boron compound represented by the general formula BQ1 Q2 Q3, (C2): a boron compound represented by the general formula Z ⁺ (BQ1 Q2 Q3 Q4) ^- (C3): General formula (LH) ⁺ (BQ1 Q2 Q3 Q4)
^- the boron compound represented (wherein, Z ⁺ is an inorganic or organic cation, (L-H)
⁺ Is a Bronsted acid, B is a trivalent boron atom, Q1 to Q4 are the same or different, and are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1 to 2 carbon atoms.
A halogenated hydrocarbon group of 0, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a disubstituted amino group having 2 to 20 carbon atoms; ). 3. The olefin polymerization catalyst according to claim 1, wherein M is Cr. 4. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1, 2 or 3.