JP2000202299A - Catalyst for trimerizing ethylene and method for trimerizing ethylene using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce 1-hexene from ethylene with high selectivity by preparing an ethylene trimerization catalyst from a chromium complex with a coordinated neutral multidentate ligand, a metal alkyl compound and a topotactic reduction product accompanied with electron transfer. SOLUTION: The ethylene trimerization catalyst for the production of 1- hexene useful as a comonomer of linear low density polyethylene from ethylene is prepared using at least a chromium complex with a coordinated neutral multidentate ligand, a metal alkyl compound and a topotactic reduction product accompanied with electron transfer. The topotactic reduction product has been subjected to salt treatment, acid treatment or other treatments). The chromium complex is represented by the formula ACrBn A is a neutral multidentate ligand, (n) is an integer of 1-3 and B is H, halogen, amido, alkoxide or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for trimerizing ethylene and a method for trimerizing ethylene using the catalyst.
More specifically, linear low density polyethylene (LLDP)
The present invention relates to an ethylene trimerization catalyst for producing 1-hexene useful as a raw material comonomer of E) efficiently and highly selectively from ethylene, and a method for trimerizing ethylene using the catalyst.

[0002]

2. Description of the Related Art It is known to use a catalyst comprising a chromium complex coordinated with a specific polydentate ligand and an alkylaluminum compound in a process for obtaining 1-hexene by trimerizing ethylene. For example, JP-A-10-7712 discloses a catalyst comprising a chromium chloride complex or an alkyl complex coordinated with a specific nitrogen ligand and an aluminum compound,
JP-A-10-231317 discloses a catalyst comprising a chromium complex coordinated with a cyclic polyamine or hydrotris (pyrazolyl) borate and an alkylaluminum compound.

[0003]

However, Japanese Patent Application Laid-Open No.
The method described in JP 7712 has a problem that the catalytic activity is low. Further, the 1-hexene selectivity in the oligomer was low, and was not sufficient from an industrial viewpoint.
Also, the method described in JP-A-10-231317 has a low catalytic activity. Further, with respect to the selectivity, not only the production of polyethylene than 1-hexene was increased, but also the selectivity of 1-hexene in the oligomer was low.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a 1-hexene useful as a raw material comonomer for LLDPE from ethylene which can be efficiently and highly selectively produced from ethylene. An object of the present invention is to provide a trimerization catalyst and a method for trimerizing ethylene using the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a chromium complex, an alkyl metal compound and an electron transfer compound coordinated with a neutral polydentate ligand. With the use of an ethylene trimerization catalyst consisting of at least three components of a topotactic reduction reaction product with the following, it has been found that the ethylene trimerization reaction proceeds with high activity, and 1-hexene is generated with high selectivity, The present invention has been completed.

That is, the present invention provides an ethylene trimerization catalyst comprising at least three components of a chromium complex coordinated with a neutral polydentate ligand, an alkyl metal compound, and a topotactic reduction reaction product involving electron transfer. And a method for trimerizing ethylene using the same.

[0007]

Next, the present invention will be described in more detail.

According to the present invention, as a component constituting the ethylene trimerization catalyst, a topotactic reduction reaction product accompanied by electron transfer is used.

The topotactic reduction reaction involving electron transfer in the present invention is described in Schollhorn,
Angew. Chem. Int. Ed. Engl. 1
9,983-3003 (1980) is a reaction in which a host compound obtains an electron and is reduced, and a guest cation is incorporated into an empty lattice site in the host compound in order to balance charge. In addition, the reaction does not change the structure and composition of the host compound before and after the reaction. In this reaction, the general formula (3) xE ⁺ + xe ⁻ + □ [Q] → (E ⁺ ) _x [Q] ^x− (3) [wherein [Q] is a host compound and □ is [Q ], E ⁻ is an electron, x is a reduction amount, and E ⁺ is a monovalent guest cation.

The topotactic reduction reaction product involving electron transfer in the present invention is a product of the above-described topotactic reduction reaction involving electron transfer, and is represented by the general formula (4) (E ⁺ _a + E ^2+). _{b / 2} + E3 ⁺ _{c / 3} + ^{E4 +} _{d / 4} + ^E5 + _{e / 5} + ^E6 + _{f / 6} + ^E7 + _{g / 7} + ^{E8 +} _{h / 8} + ^{E9 +} _{i / 9} + ^E10 + _{j / 10} ) (L ² ) _h [Q] ^k- (4) [wherein [Q] is a host compound and k is a reduction amount. E is a guest cation, and a + b + c + d +
e + f + g + h + i + j = k. L ² is a Lewis base and h is the amount of Lewis base].

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.

The host compound having a three-dimensional structure is not particularly limited. Examples include triniobium tetrasulfide, hexavana octasulfide, hexavanapentapentasulfide, pentavanadium pentaoxide, divanadium pentoxide, tungsten trioxide, titanium dioxide, vanadium dioxide, chromium dioxide, manganese dioxide, tungsten dioxide, ruthenium dioxide, osmium dioxide, and iridium dioxide. can do.

The host compound having a two-dimensional structure is not particularly limited, and examples thereof include titanium disulfide, zirconium disulfide, hafnium disulfide, vanadium disulfide, niobium disulfide, tantalum disulfide, and tantalum disulfide. Chromium, molybdenum disulfide, tungsten disulfide, rhenium disulfide, platinum disulfide, tin disulfide, lead disulfide, titanium diselenide, zirconium diselenide, hafnium diselenide, vanadium diselenide, niobium diselenide , Tantalum diselenide, chromium diselenide, molybdenum selenide, tungsten diselenide, rhenium diselenide, platinum diselenide, tin diselenide, lead diselenide,
Titanium ditelluride, zirconium ditelluride, hafnium ditelluride, vanadium ditelluride, niobium ditelluride, tantalum ditelluride, chromium ditelluride, molybdenum ditelluride, tungsten ditelluride, rhenium ditelluride, Platinum ditelluride, tin ditelluride, lead ditelluride, phosphorus magnesium trisulfide, calcium phosphate trisulfide,
Phosphorus vanadium trisulfide, phosphorus manganese trisulfide, phosphorus iron trisulfide, phosphorus cobalt trisulfide, phosphorus nickel trisulfide, phosphorus palladium trisulfide, phosphorus zinc trisulfide, phosphorus cadmium trisulfide, phosphorus mercury trisulfide, phosphorus tin trisulfide, tritin Magnesium phosphorus selenide, calcium calcium triselenide, phosphorus vanadium triselenide, phosphorous manganese triselenide, iron triphosphate selenide, phosphorous cobalt triselenide, phosphorus nickel triselenide, phosphorus palladium triselenide, triselenide Phosphorus zinc, phosphorus cadmium triselenide, phosphorus mercury triselenide,
Phosphorus tin triselenide, phosphorus chromium tetrasulfide, tantalum sulfide carbide, molybdenum trioxide, fifty-eighteen molybdenum molybdenum, vanadium pentoxide gel, iron oxychloride, titanium oxychloride, vanadium oxychloride, chromium oxychloride, oxychloride Aluminum, bismuth oxychloride,
α-zirconium nitride chloride, β-zirconium chloride nitride, α-zirconium nitride bromide, β-zirconium nitride bromide, zirconium nitride iodide, titanium nitride chloride, titanium nitride bromide, titanium nitride iodide, graphite, polyacene can do.

The host compound having a one-dimensional structure is not particularly limited. For example, titanium trisulfide, niobium triselenide, potassium iron disulfide, polyacetylene, polyaniline, polypyrrole, polythiophene, poly (p- Phenylene), poly (triphenylene), polyazulene, polyfluorene, polynaphthalene, polyanthracene, polyfuran, polycarbazole, tetrathiofulvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbazole-substituted polyethylene,
Polyoxyphenazine can be exemplified.

As the host compound which is a molecular solid,
Although not particularly limited, for example, tetracyanoquinodimethane and tetrathiofulvalene can be exemplified.

Further, as [Q], a plurality of the above-mentioned host compounds may be mixed and used.

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

In the following, E ⁺ of the above general formula (4)
From E ¹⁰⁺ to E ^{n +} for convenience. Here, n is an integer of 1 to 10.

As L ^{2 in the} general formula (4), a Lewis base which coordinates to En ⁺ can be used. Lewis bases are
Although not particularly limited, for example, water, an amine compound, a heterocyclic compound containing nitrogen, ethers such as ethyl ether or n-butyl ether, formamide,
Amides such as N-methylformamide, N, N-dimethylformamide or N-methylacetamide, alcohols such as methyl alcohol or ethyl alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diols such as diol or 2,3-butanediol, glycerin, poly (ethylene glycol), diglyme, 1,2-dimethoxyethane,
Trimethyl phosphate, hexamethylphosphoramide, tri-n-butyl phosphor oxide, 1,4-dioxane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide or propylene carbonate can be exemplified,
These two or more kinds can be used as a mixture.

H can be in the range of 0 ≦ h ≦ 10.

In the general formula (4), E ^{n +} is at least one selected from the group consisting of atoms of groups 1 to 14 of the periodic table.
Cations containing species atoms can be used. For the purpose of performing the trimerization of ethylene at high catalytic activity, preferably the general formula (5), (6), (7) or _{^{(8) R 1 2 R 2}} NH + (5) [ wherein, R ¹ ₂ R ² N is an amine compound, R ¹ is each independently an aliphatic hydrocarbon group hydrogen atom or C1-30, R ² is a hydrogen atom, an aliphatic having 1 to 30 carbon atoms carbide A hydrogen group or an aromatic hydrocarbon group having 1 to 50 carbon atoms] T ¹ H ⁺ (6) [wherein T ¹ is a heterocyclic compound containing nitrogen] (R ³ ) ⁺ (7) [formula Wherein (R ³ ) ⁺ is a carbonium cation or a tropylium cation having 1 to 50 carbon atoms] G ^{n +} (8) wherein G is at least selected from the group consisting of atoms of groups 1 to 14 of the periodic table. a one atom metal atom or a cyclopentadienyl group is substituted, represented by G n ⁺ is an n-valent cation] Cation is used. These cations can be used alone or in combination of two or more.

[0022] amine compound represented by R ^{1 ₂} R ₂ N is not particularly limited but, for example, methylamine,
Ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, allylamine, cyclopentylamine, dimethylamine, diethylamine, diallylamine, trimethylamine, tri-n-butylamine, triallylamine, hexylamine, 2-amino Heptane, 3-aminoheptane, n-heptylamine, 1,5-dimethylhexylamine, 1-methylheptylamine, n-octylamine, t-octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine , Tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, cyclohexylamine, cycloheptylamine Cyclohexane methylamine, 2
-Methylcyclohexylamine, 4-methylcyclohexylamine, 2,3-dimethylcyclohexylamine,
Cyclododecylamine, 2- (1-cyclohexenyl)
Ethylamine, geranylamine, N-methylhexylamine, dihexylamine, bis (2-ethylhexyl)
Amine, dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexylamine, Nt-butylcyclohexylamine , N-allylcyclohexylamine, N,
N-dimethyloctylamine, N, N-dimethylundecylamine, N, N-dimethyldodecylamine, N, N
-Dimethyloctadecylamine, N, N-dioctadecylmethylamine, N, N-dioleylmethylamine, trihexylamine, triisooctylamine, trioctylamine, triisodecylamine, tridodecylamine, N, N-dimethyl Cyclohexylamine, N, N-
Aliphatic amines such as diethylcyclohexylamine, aniline, N-methylaniline, N-ethylaniline, N
-Allylaniline, o-toluidine, m-toluidine,
p-toluidine, N, N-dimethylaniline, N-methyl-o-toluidine, N-methyl-m-toluidine, N
-Methyl-p-toluidine, N-ethyl-o-toluidine, N-ethyl-m-toluidine, N-ethyl-p-toluidine, N-allyl-o-toluidine, N-allyl-
m-toluidine, N-allyl-p-toluidine, N-propyl-o-toluidine, N-propyl-m-toluidine, N-propyl-p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline,
N, N-diethylaniline, 2-isopropylaniline, 4-isopropylaniline, 2-t-butylaniline, 4-n-butylaniline, 4-s-butylaniline, 4-t-butylaniline, 2,6-diethyl Aniline, 2-isopropyl-6-methylaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, o-anisidine, m-anisidine, p −
Anisidine, o-phenetidine, m-phenetidine, p
-Phenetidine, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminofluorene, 2-aminofluorene, 3-aminofluorene, 4-aminofluorene, 5
-Aminoindene, 2-aminobiphenyl, 4-aminobiphenyl, N, 2,3-trimethylaniline, N,
2,4-trimethylaniline, N, 2,5-trimethylaniline, N, 2,6-trimethylaniline, N, 3
4-trimethylaniline, N, 3,5-trimethylaniline, N-methyl-2-ethylaniline, N-methyl-
3-ethylaniline, N-methyl-4-ethylaniline, N-methyl-6-ethyl-o-toluidine, N-methyl-2-isopropylaniline, N-methyl-4-isopropylaniline, N-methyl-2- t-butylaniline, N-methyl-4-n-butylaniline, N-methyl-4-s-butylaniline, N-methyl-4-t. −
Butylaniline, N-methyl-2,6-diethylaniline, N-methyl-2-isopropyl-6-methylaniline, N-methyl-p-anisidine, N-ethyl-2,3
-Anisidine, N, N-dimethyl-o-toluidine,
N, N-dimethyl-m-toluidine, N, N-dimethyl-p-toluidine, N, N, 2,3-tetramethylaniline, N, N, 2,4-tetramethylaniline, N, N
N, 2,5-tetramethylaniline, N, N, 2,6-
Tetramethylaniline, N, N, 3,4-tetramethylaniline, N, N, 3,5-tetramethylaniline,
N, N-dimethyl-2-ethylaniline, N, N-dimethyl-3-ethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-6-ethyl-o-toluidine, N, N -Dimethyl-2-isopropylaniline, N, N-dimethyl-4-isopropylaniline,
N, N-dimethyl-2-t-butylaniline, N, N-
Dimethyl-4-n-butylaniline, N, N-dimethyl-4-s-butylaniline, N, N-dimethyl-4-t
-Butylaniline, N, N-dimethyl-2,6-diethylaniline, N, N-dimethyl-2-isopropyl-6
-Methylaniline, N, N-dimethyl-2-chloroaniline, N, N-dimethyl-3-chloroaniline, N, N
-Dimethyl-4-chloroaniline, N, N-dimethyl-
2-bromoaniline, N, N-dimethyl-3-bromoaniline, N, N-dimethyl-4-bromoaniline, N,
N-dimethyl-o-anisidine, N, N-dimethyl-m
-Anisidine, N, N-dimethyl-p-anisidine,
N, N-dimethyl-o-phenetidine, N, N-dimethyl-m-phenetidine, N, N-dimethyl-p-phenetidine, N, N-dimethyl-1-aminonaphthalene,
N, N-dimethyl-2-aminonaphthalene, N, N-dimethyl-1-aminofluorene, N, N-dimethyl-2
-Aminofluorene, N, N-dimethyl-3-aminofluorene, N, N-dimethyl-4-aminofluorene,
N, N-dimethyl-5-aminoindene, N, N-dimethyl-2-aminobiphenyl, N, N-dimethyl-4-
Aromatic amines such as aminobiphenyl and N, N-dimethyl-p-trimethylsilylaniline can be exemplified.

The nitrogen-containing heterocyclic compound represented by T ¹ is not particularly restricted but includes, for example, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, pyridine,
Pyridazine, pyrimidine, pyrazine, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, picoline, collidine, indole, isoindole, indazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine Pteridine, carbazole, phenanthridine, acridine, phenazine, phenanthroline, indoline, isoindoline, 2,5-dimethylpyrrolidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine,
2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 2,2,6,6-tetramethylpiperidine, 1-
Methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine, 1-butylpyrrolidine, 1,2,2,6
6-pentamethylpiperidine can be exemplified.

The cation represented by the general formula (7) is not particularly limited, and examples thereof include a triphenylmethyl cation and a tropylium cation.

The cation represented by the general formula (8) is not particularly limited. Examples thereof include a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, a rubidium atom, a cesium atom, a beryllium atom, a magnesium atom, Calcium, strontium, barium, titanium, zirconium, hafnium,
Examples include cations of niobium atom, tantalum atom, chromium atom, iron atom, nickel atom, copper atom, silver atom, zinc atom, aluminum atom, and tin atom. The metal atom substituted by the cyclopentadienyl group is not particularly limited, and examples thereof include ferrocenium and decamethylferrocenium.

The specific method for preparing the topotactic reduction reaction product involving electron transfer in the present invention is not particularly limited. [Equation (9)],

[0027]

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(B) A method of reacting an atom to be a guest cation with a host compound at 100 to 1500 ° C. [formula (1)
0)],

[0029]

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(C) reacting a halide of a guest cation with a host compound at 100 to 1500 ° C. [formula (11)]

[0031]

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[Wherein X ⁴ is a halogen atom] (d) A method of immersing a host compound in a non-aqueous solvent solution of a reducing reagent [formula (12)]

[0033]

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[Wherein Red ¹ is a reducing agent containing G ^{n +} and Solv ¹ is a non-aqueous solvent]

[0035]

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[In the formula, Red ² is a reducing reagent containing G ^{n +} ] (f) A method of electrochemical reduction in an electrolyte solution containing a guest cation using a host compound as a cathode [Formula (14)] ,

[0037]

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Wherein Solv ² is water or a non-aqueous solvent. (G) A method of electrochemical reduction using a host compound as a cathode and an anode containing a guest cation [formula (14)] (H) a method of electrochemically reducing using a host compound as a cathode and an anode containing an atom to be a guest cation [formula (15)];

[0039]

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(I) An amine compound and a host compound are
A method of reacting at 0 to 1500 ° C. [formula (16)],

[0041]

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[Wherein T ² is an amine compound] (j) a nitrogen-containing heterocyclic compound and a host compound
A method of reacting at ~ 1500C [formula (17)],

[0043]

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Can be exemplified.

The non-aqueous solvent used in the methods (d), (f), (g) and (h) is not particularly limited. Aliphatic hydrocarbons such as cyclopentane or cyclohexane, aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as ethyl ether or n-butyl ether, halogenated hydrocarbons such as methylene chloride or chloroform, formamide, Amides such as N-methylformamide, N, N-dimethylformamide or N-methylacetamide, alcohols such as methyl alcohol or ethyl alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diol or a few
-Diols such as butanediol, glycerin, poly (ethylene glycol), diglyme, 1,2-dimethoxyethane, trimethyl phosphate, hexamethylphosphoramide, tri-n-butylphosphine oxide, 1,4-dioxane, acetonitrile , Tetrahydrofuran, dimethyl sulfoxide or propylene carbonate.

Regarding the method (c), the halide of the guest cation is not particularly limited, but
For example, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, and cesium chloride can be exemplified.

Regarding the method (d), as the reducing reagent,
Although not particularly limited, for example, n-butyl lithium, naphthalene lithium, naphthalene sodium,
Lithium benzophenone, sodium benzophenone,
Lithium iodide can be exemplified, from 0.001 to 1
At a concentration of 0 mol / l, 0.001 to 10 mol can be used per 1 mol of the host compound. Although the reaction temperature is not particularly limited, -100 to 100 ° C can be used, and there is no particular limitation on the reaction time, but 1 minute to 1 minute.
60 days can be used.

Regarding the method (e), the reducing reagent is not particularly restricted but includes, for example, sodium dithionite, sodium borohydride and sodium sulfide. At a concentration of
0.001 to 10 mol per 1 mol of host compound
Can be used. The reaction temperature is not particularly limited.
To 100 ° C, and the reaction time is not particularly limited, but 1 minute to 60 days can be used.

With respect to the method (f), the electrolyte is not particularly limited.
Formate, acetate, propionate, oxalate, malonate, succinate, citrate, tetrafluoroborate and hexafluorophosphate can be exemplified,
It can be used at a concentration of 0.001 to 10 mol / l.

Regarding the method (g), the anode is not particularly limited, and examples thereof include alkali metal salts of graphite.

Regarding the method (h), the anode is not particularly limited. For example, lithium can be exemplified.

[0052] with respect to the method (i), the amine compound is not particularly limited, for example, ammonia, may be exemplified the R ¹ ₂ amine compound represented by R ² N.

Further, the topotactic reduction reaction product accompanied by electron transfer in the present invention can be used after being subjected to salt treatment, acid treatment and / or Lewis base treatment as required.

The salts used in the salt treatment are as shown in the periodic table 1
A compound comprising at least one cation containing at least one atom selected from the group consisting of Group 14 atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids and organic acid anions, preferably Is at least one cation selected from the group consisting of cations represented by general formulas (5), (6), (7) and (8);
Fluorine, chlorine, bromine, iodine, phosphoric, sulfuric, nitric, carbonic, perchloric, formic, acetic, propionic, oxalic, malonic, succinic, citric, acetylacetone, tetrafluoroboric And at least one anion selected from the group consisting of hexafluorophosphate anions.

[0055] and a cation represented by the general formula (5), the salts comprising the anions of chlorine, but are not particularly limited, for example, represented by R ^{1 ₂} R ₂ N Examples thereof include a hydrochloride of an amine compound.

[0056] complex and the cation represented by the general formula (6), the salts comprising the anions of chlorine, but are not particularly limited, including, for example, a nitrogen represented by T ¹ The hydrochloride of a ring compound can be exemplified.

The salt comprising the cation represented by the general formula (7) and the anion of a halogen atom is not particularly limited, but examples thereof include triphenylmethyl chloride and tropylium bromide. be able to.

The salts containing a cation represented by the general formula (8) are not particularly limited.
Lithium chloride, sodium chloride, sodium phosphate, sodium sulfate, sodium nitrate, sodium formate, sodium acetate, sodium oxalate, sodium citrate, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride, magnesium phosphate, sulfuric acid Magnesium, magnesium nitrate, magnesium perchlorate, magnesium acetate, magnesium oxalate, magnesium succinate, calcium chloride, strontium chloride, barium chloride, titanium chloride, zirconium chloride, hafnium chloride, niobium chloride, tantalum chloride, chromium chloride, iron chloride , Nickel chloride, copper chloride, silver chloride, silver bromide, zinc chloride, aluminum chloride, aluminum phosphate, aluminum sulfate, aluminum nitrate, aluminum oxalate, tin chloride, It can be exemplified Eroseniumu sulfate.

The acid used for the acid treatment is not particularly limited, but for example, hydrochloric acid, phosphoric acid, sulfuric acid,
Examples include nitric acid, carbonic acid, perchloric acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, and citric acid, but they can also be used in combination of two or more.

The Lewis base used in the Lewis base treatment is not particularly limited.
NH _3, wherein the amine compound represented by R ^{1 ₂} R ₂ N, wherein T
A nitrogen-containing heterocyclic compound represented by ¹ , an ether such as ethyl ether or n-butyl ether, an amide such as formamide, N-methylformamide, N, N-dimethylformamide or N-methylacetamide, methyl alcohol or ethyl Alcohols such as alcohol, diols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol or 2,3-butanediol, glycerin, poly (ethylene glycol), diglyme, 2-dimethoxyethane, trimethyl phosphate, hexamethylphosphoramide, tri-n-butyl phosphor oxide, 1,4-dioxane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide or propylene carbonate can be exemplified. Mix over Can also be used.

The salt treatment, acid treatment and / or Lewis base treatment may be carried out by adding a salt, an acid and / or a Lewis base,
Or a method of immersing at least one type of reduction reaction product selected from the group consisting of products obtained by the reduction reactions of methods (a) to (j) in a solution in which salts, acids and / or Lewis bases are dissolved. Can be exemplified.

When the salt treatment, the acid treatment, and the Lewis base treatment are combined, a method of performing the salt treatment and then performing the acid treatment, a method of performing the salt treatment and then performing the Lewis base treatment, and the acid treatment are performed. After, a method of performing a salt treatment, a method of performing a Lewis base treatment after performing an acid treatment, a method of performing a salt treatment after performing the Lewis base treatment, a method of performing an acid treatment after performing the Lewis base treatment, A method of simultaneously performing salt treatment and acid treatment, a method of simultaneously performing salt treatment and Lewis base treatment, a method of simultaneously performing acid treatment and Lewis base treatment, a method of simultaneously performing acid treatment and Lewis base treatment after performing salt treatment, After performing the acid treatment, a method of simultaneously performing the salt treatment and the Lewis base treatment, a method of simultaneously performing the salt treatment and the acid treatment after performing the Lewis base treatment, a method of simultaneously performing the salt treatment and the acid treatment, A method of performing a base treatment, a method of performing an acid treatment after simultaneously performing a salt treatment and a Lewis base treatment, a method of performing a salt treatment after simultaneously performing an acid treatment and a Lewis base treatment, and a method of performing a salt treatment, an acid treatment and Lewis A method of simultaneously performing the base treatment can be used.

The conditions for treatment with salts, acids and Lewis bases are not particularly limited.
At a concentration of 01 to 10 mol / l, 0.001 to 1000 m per 1 mol of guest cation in the reduction reaction product
ol, the processing temperature is preferably from -100 to 150 ° C., and the processing time is preferably from 1 minute to 60 days. Further, these processes may be repeatedly performed as necessary.

Solvents used for salt treatment, acid treatment and / or Lewis base treatment include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane.
Aromatic hydrocarbons such as benzene, toluene or xylene; alcohols such as methyl alcohol or ethyl alcohol; ethers such as ethyl ether or n-butyl ether; halogenated hydrocarbons such as methylene chloride or chloroform; Examples thereof include dioxane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, propylene carbonate, and aqueous ammonia, and a plurality of these solvents may be used as a mixture.

In the present invention, the amount of the topotactic reduction reaction product accompanied by electron transfer is not particularly limited, but may be 0.0 to 1 mol of the chromium complex described below.
1 to 10,000 kg, preferably 0.1 to 100
0 kg, more preferably 1 to 500 kg.

In the present invention, a chromium complex to which a neutral polydentate ligand is coordinated is used as one component constituting the ethylene trimerization catalyst. The chromium complex coordinated by the neutral polydentate ligand is represented by the following general formula (1): ACrB _n (1) (where A is a neutral polydentate ligand. B is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxylate group or a diketonate group, a halogen atom, an amide, an imide, an alkoxide, a thioalkoxide, a carbonyl, an arene, an alkene, an alkyne,
A complex represented by at least one selected from the group consisting of amine, imine, nitrile, isonitrile, phosphine, phosphine oxide, phosphite, ether, sulfone, sulfoxide and sulfide).

The neutral polydentate ligand to be coordinated with the chromium complex is not particularly limited. For example, the following general formula (18)

[0068]

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(Where a, b, and c are each independently 0
6 to an integer. D ¹ represents a divalent hydrocarbon group which may have a substituent independently, and L ¹ represents a hetero element group or a heterocyclic compound which may have a substituent independently. G represents a hydrocarbon, silicon, nitrogen or phosphorus), a polydentate ligand having a tripod-type structure represented by the following general formula (19)

[0070]

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(Where d, e, and f are independent 1
6 to an integer. D ² represents a divalent hydrocarbon group which may have a substituent independently, and L ² represents a hetero element group which may have a substituent independently.) Polydentate ligand having a structure and the following general formula (20)

[0072]

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(Wherein g and h are independently 0-6
Is an integer. D ³ represents a divalent hydrocarbon group which may have a substituent independently, and L ³ represents a hetero element group or a heterocyclic compound which may have a substituent independently.) And a polydentate ligand having a bridge-type structure.

The above general formulas (18), (19) and (2)
In 0), D ¹ , D ² and D ³ are not particularly restricted but include, for example, alkylene, cycloalkylene, phenylene, tolylene, xylylene and the like. Examples of the substituent include alkyl groups such as a methyl group and an ethyl group, and alkoxy groups such as a methoxy group and an ethoxy group.

In the general formulas (18), (19) and (20), the hetero element groups represented by L ¹ , L ² and L ³ are
Although not particularly limited, for example, a methoxy group,
Alkoxy groups such as ethoxy group, propoxy group and butoxy group, phenoxy group, aryloxy groups such as 2,6-dimethylphenoxy group, methylthio group, ethylthio group,
Alkylthio groups such as propylthio group and butylthio group,
Arylthio groups such as phenylthio group and tolylthio group,
Dialkylamino groups such as dimethylamino group, diethylamino group and bis (trimethylsilyl) amino group; diarylamino groups such as diphenylamino group; alkylarylamino groups such as methylphenyl group; dimethylphosphino group; diethylphosphino group And diarylphosphino groups such as diphenylphosphino group and ditolylphosphino group, and alkylarylphosphino groups such as methylphenylphosphino group.

In the general formulas (18) and (20), the heterocyclic compounds represented by L ¹ and L ³ are not particularly restricted but include, for example, furyl, benzofuryl, thienyl, Benzothienyl group, pyrazolyl group,
Examples include triazolyl, tetrazolyl, pyridyl, imidazolyl, benzimidazolyl, indazolyl, quinolyl, isoquinolyl, oxazolyl, and thiazole groups. Examples of the substituents of the hetero element group and the heterocyclic compound include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a phenyl group and the like.

In the above general formula (18), G is
Although not particularly limited, examples include methane, ethane, propane, butane, hydroxymethane, methylsilane, phenylsilane, amine, amine oxide, phosphine, phosphine oxide, and the like.

Examples of the polydentate ligand having a tripod-type structure represented by the general formula (18) which are generally used include, but are not particularly limited to, tris (methoxymethyl) methane, 1,1 1,1-tris (methoxymethyl) ethane, 1,1,1-tris (methoxymethyl) propane, 1,1,1-tris (methoxymethyl) butane, 1,1,1-tris (ethoxymethyl) ethane,
1,1,1-tris (propoxymethyl) ethane, 1,
1,1-tris (butoxymethyl) ethane, 1,1,1
-Tris (phenoxymethyl) ethane, trifurylmethane, tris (5-methyl-2-furyl) methane, tris (5-ethyl-2-furyl) methane, tris (5-butyl-2-furyl) methane, 1, Oxygen-containing polydentate ligands such as 1,1-trifurylethane, trifurylamine, trifurylphosphine, and trifurylphosphine oxide;
1,1-tris (methylthiomethyl) ethane, 1,1,
1-tris (butylthiomethyl) ethane, 1,1,1-
Sulfur-containing polydentate ligands such as tris (phenylthiomethyl) ethane and tris (thienyl) methane, 1,1,1-tris (dimethylaminomethyl) ethane, 1,1,1-tris (diphenylaminomethyl) Ethane, tris (pyrazolyl) methane, tris (3,5-dimethyl-1-pyrazolyl) methane, tris (3,5-diisopropyl-1)
-Pyrazolyl) methane, 1,1,1-tris (3,5-
Dimethyl-1-pyrazolyl) ethane, 1,1,1-tris (3,5-dimethyl-1-pyrazolyl) propane,
1,1,1-tris (3,5-dimethyl-1-pyrazolyl) butane, tris (2-pyridyl) methane, tris (6-methyl-2-pyridyl) methane, tris (2-pyridyl) amine, tris ( 2-pyridyl) phosphine,
Nitrogen-containing polydentate ligands such as tris (2-pyridyl) phosphine oxide, tris (2-pyridyl) hydroxymethane, and tris (1-imidazolyl) methane; 1,1,1
-Tris (diphenylphosphinomethyl) ethane, 1,
1,1-tris (dimethylphosphinomethyl) ethane,
Phosphorus-containing polydentate ligands such as 1,1,1-tris (diethylphosphinomethyl) ethane;

The polydentate ligand having a cyclic structure is not particularly limited.
3,5-trimethyl-1,3,5-triazacyclohexane, 1,3,5-triethyl-1,3,5-triazacyclohexane, 1,3,5-tri-i-propyl-
1,3,5-triazacyclohexane, 1,3,5-tri-t-butyl-1,3,5-triazacyclohexane, 1,3,5-tri-n-butyl-1,3,5- Triazacyclohexane, 1,3,5-tricyclohexyl-1,3,5-triazacyclohexane, 1,3,5-
Tribenzyl-1,3,5-triazacyclohexane,
1,3,5-triphenyl-1,3,5-triazacyclohexane, 2,4,6-trimethyl-1,3,5-triazacyclohexane, 1,4,7-triazacyclononane, 1, 4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7-triethyl-1,4,7-
Triazacyclononane, 1,4,7-tri-i-propyl-1,4,7-triazacyclononane, 1,4,7-
Tri-t-butyl-1,4,7-triazacyclononane, 1,4,7-tricyclohexyl-1,4,7-triazacyclononane, 1,4,7-triphenyl-1,
Nitrogen-containing polydentate ligands such as 4,7-triazacyclononane, 1,3,5-trithiacyclohexane, 1,4,7
Sulfur-containing polydentate ligands such as -trithiacyclononane, 1,4,7,10-tetrathiacyclododecane, 1,5,9,13-tetrathiahexadecane, 1,3,5-trioxacyclohexane , 1,4,7-trioxacyclononane, 12-crown-4, 15-crown-5,1
And oxygen-containing polydentate ligands such as 8-crown-6.

The polydentate ligand having a bridge-type structure is not particularly limited, and examples thereof include phosphorus-containing compounds such as bis (dimethylphosphinoethyl) methylphosphine and bis (diphenylphosphinoethyl) phenylphosphine. Polydentate ligands, diethylenetriamine, bis (dimethylaminoethyl) methylamine, bis (diethylaminoethyl) ethylamine, bis (phenylaminoethyl) amine, α, α ′, α ″ -tripyridine, 2,6-
Nitrogen-containing polydentate ligands such as bis (2-phenyl-2-azaethenyl) pyridine and bis [3- (2-pyridylethylimino) -2-butanone oxime], diethylene glycol methyl ether, bis (methoxyethyl) ether , Bis (ethoxyethyl) ether, bis (butoxyethyl) ether, (t-butoxyethyl) (methoxyethyl) ether and the like.

In B of the above general formula (1), the hydrocarbon group having 1 to 10 carbon atoms is not particularly limited. Examples thereof include a cyclohexyl group, a benzyl group and a phenyl group. Examples of the carboxylate group having 1 to 10 carbon atoms include, but are not particularly limited to, an acetate group, a naphthenate group, and a 2-ethylhexanoate group. The diketonate group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include an acetylacetonate group. Examples of the halogen atom include, but are not particularly limited to, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The amide group is not particularly limited, for example, dimethylamide group, diethylamide group, diisopropylamide group, dioctylamide group,
Examples include a didecylamide group, a didodecylamide group, a bis (trimethylsilyl) amide group, a diphenylamide group, N-methylanilide, and an anilide group. The imide group is not particularly limited, but examples include benzophenone imide. The alkoxide group is not particularly limited, but includes, for example, a methoxide group, an ethoxide group, a propoxide group, a butoxide group, a phenoxide group and the like. The thioalkoxide group is not particularly limited, for example,
Examples thereof include a thiomethoxide group, a thioethoxide group, a thiopropoxide group, a thiobutoxide group and a thiophenoxide group. The arene is not particularly limited, and examples thereof include benzene, toluene, xylene, trimethylbenzene, hexamethylbenzene, and naphthalene. The alkene is not particularly restricted but includes, for example, ethylene, propylene, butene, hexene or decene. The alkyne is not particularly restricted but includes, for example, acetylene, phenylacetylene, diphenylacetylene and the like. Examples of the amine include, but are not particularly limited to, triethylamine and tributylamine. Examples of the imine include, but are not particularly limited to, benzophenone imine and methyl ethyl ketone imine. The nitrile is not particularly limited, but includes, for example, acetonitrile or benzonitrile. The isonitrile is not particularly limited, and examples thereof include t-butyl isonitrile and phenyl isonitrile. Although it does not specifically limit as a phosphine, For example, triphenyl phosphine, tolyl phosphine, tricyclohexyl phosphine, tributyl phosphine, etc. are mentioned. Although it does not specifically limit as a phosphine oxide, For example, a tributyl phosphine oxide, a triphenyl phosphine oxide, etc. are mentioned. Although it does not specifically limit as a phosphite, For example, a triphenyl phosphite, a tolyl phosphite, a tributyl phosphite, a triethyl phosphite, etc. are mentioned. Examples of the ether include, but are not particularly limited to, diethyl ether and tetrahydrofuran. The sulfone is not particularly limited, and examples thereof include dimethyl sulfone and dibutyl sulfone. The sulfoxide is not particularly limited, but includes, for example, dimethyl sulfoxide or dibutyl sulfoxide. Although it does not specifically limit as a sulfide, For example, ethyl sulfide, butyl sulfide, etc. are mentioned.

Specific examples of the chromium complex to which the neutral polydentate ligand represented by the above general formula (1) is coordinated are not particularly limited. For example, tris (methoxymethyl) Methane chromium trichloride (III), 1,
1,1-tris (methoxymethyl) ethanechrome tricarbonyl (0), 1,1,1-tris (methoxymethyl) ethanechrome trichloride (III), 1,1,
1-tris (methoxymethyl) ethane-tris (diisopropylamido) chromium (III), 1,1,1-tris (methoxymethyl) ethane-tris (dimethylamido) chromium (III), 1,1,1-tris ( Methoxymethyl) ethane-tris [bis (trimethylsilyl) amide] chromium (III), 1,1,1-tris (methoxymethyl) ethanechrome triethoxide (III),
1,1,1-tris (methoxymethyl) ethanechrome trithiobutoxide (III), 1,1,1-tris (ethoxymethyl) ethanechrome trichloride (II)
I), 1,1,1-tris (butoxymethyl) ethanechrome trichloride (III), 1,1,1-tris (phenoxymethyl) ethanechrome trichloride (I)
II), trifuryl methane chromium tricarbonyl (0), tris (5-methyl-2-furyl) methane chromium tricarbonyl (0), tris (5-butyl-2-furyl) methane chromium tricarbonyl (0), tris Furylamine chromium tricarbonyl (0), trifurylphosphine chromium tricarbonyl (0), trifurylphosphine oxide chromium tricarbonyl (0), 1,1,1-
Tris (methylthiomethyl) ethanechrome tricarbonyl (0), tris (thienyl) methanechrometricarbonyl (0), 1,1,1-tris (dimethylaminomethyl) ethanechrometricarbonyl (0), tris (pyrazolyl) methane Chromium tricarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechromium tricarbonyl (0), tris (3,5-dimethyl-1-)
Pyrazolyl) methanechrome trichloride (III),
Tris (3,5-dimethyl-1-pyrazolyl) methane-
Tris (diethylamido) chromium (III), tris (3,5-dimethyl-1-pyrazolyl) methane-tris (diisopropylamido) chromium (III), tris (3,5-dimethyl-1-pyrazolyl) methane-tris [bis (Trimethylsilyl) amide] chromium (II
I), tris (3,5-dimethyl-1-pyrazolyl) methane-tris (benzophenoneimido) chromium (II)
I), tris (3,5-dimethyl-1-pyrazolyl) methanechromium triethoxide (III), tris (3,5
-Dimethyl-1-pyrazolyl) methanechromium trithiobutoxide (III), tris (3,5-dimethyl-1-)
Pyrazolyl) methane-toluenechromium (0), tris (3,5-dimethyl-1-pyrazolyl) methanechrome (ethylene) dicarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechrome (phenylacetylene) ) Dicarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechromium (dimethylaniline) dicarbonyl (0), tris (3,5-dimethyl-)
1-pyrazolyl) methanechromium (benzophenoneimine) dicarbonyl (0), tris (3,5-dimethyl-
1-pyrazolyl) methanechrome (acetonitrile) dicarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechrome (t-butylisonitrile) dicarbonyl (0), tris (3,5-dimethyl-1) -Pyrazolyl) methanechromium (tributylphosphine) dicarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechrome (tributylphosphine oxide)
Dicarbonyl (0), tris (3,5-dimethyl-1-
Pyrazolyl) methanechromium (triphenylphosphite) dicarbonyl (0), tris (3,5-dimethyl-
1-pyrazolyl) methanechrome (tetrahydrofuran)
Dicarbonyl (0), tris (3,5-dimethyl-1-
Pyrazolyl) methanechromium (dimethylsulfone) dicarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechrome (dimethylsulfoxide) dicarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) Methane chromium (dibutyl sulfide) dicarbonyl (0), tris (3,5-diisopropyl-1-pyrazolyl) methane chromium tricarbonyl (0), 1,1,1
-Tris (3,5-dimethyl-1-pyrazolyl) ethanechrome tricarbonyl (0), 1,1,1-tris (3,5-dimethyl-1-pyrazolyl) propanechrometricarbonyl (0), 1,1 , 1-tris (3,5-
Dimethyl-1-pyrazolyl) butanechrometricarbonyl (0), tris (2-pyridyl) methanechrometricarbonyl (0), tris (6-methyl-2-pyridyl)
Methane chromium tricarbonyl (0), tris (2-pyridyl) amine chromium tricarbonyl (0), tris (2
-Pyridyl) phosphine chromium tricarbonyl (0),
Tris (2-pyridyl) phosphine oxide chromium tricarbonyl (0), tris (1-imidazolyl) methane chromium tricarbonyl (0), 1,1,1-tris (diphenylphosphinomethyl) ethanechrome tricarbonyl (0), 1,1,1-tris (diphenylphosphinomethyl) ethanechrome trichloride (III),
1,1-tris (dimethylphosphinomethyl) ethanechrome tricarbonyl (0), 1,1,1-tris (diethylphosphinomethyl) ethanechrometricarbonyl (0), 1,1,1-tris (diethylphosphinomethyl) (Finomethyl) ethanechrome trichloride (III), 1,1,
A chromium complex coordinated by a polydentate ligand having a tripod-type structure such as 1-tris (diethylphosphinomethyl) ethane-tris (diisopropylamido) chromium (III) is exemplified.

Also, 1,3,5-triethyl-1,3,
5-triazacyclohexanechromium tricarbonyl (0), 1,3,5-tri-i-propyl-1,3,5
-Triazacyclohexanechromium tricarbonyl (0), 1,3,5-tri-i-propyl-1,3,5
-Triazacyclohexanechromium trichloride (II
I), 1,3,5-tri-i-propyl-1,3,5-
Triazacyclohexanechromium dichloride (II),
Dichlorophenylchrome-1,3,5-trimethyl-
1,3,5-triazacyclohexanechromium (II
I), dichlorophenylchrom-1,3,5-tri-i
-Propyl-1,3,5-triazacyclohexanechromium (III), 1,3,5-tri-t-butyl-1,
3,5-triazacyclohexanechromium tricarbonyl (0), 1,3,5-tri-t-butyl-1,3,5-
Triazacyclohexanechromium trichloride (II
I), 1,3,5-tri-t-butyl-1,3,5-triazacyclohexane-tris (diisopropylamide) chromium (III), 1,3,5-tricyclohexyl-1,3,5- Triazacyclohexanechromium tricarbonyl (0), 2,4,6-trimethyl-1,3,5
-Triazacyclohexanechromium tricarbonyl (0), 1,4,7-trimethyl-1,4,7-triazacyclononanechromium trichloride (III), 1,
4,7-tri-t-butyl-1,4,7-triazacyclononanechromium tricarbonyl (0), 1,3,5-trithiacyclohexanechromium tricarbonyl (0),
Cyclic rings such as 1,4,7-trithiacyclononanechromium tricarbonyl (0), 1,3,5-trioxacyclohexanechromium tricarbonyl (0), and 1,4,7-trioxacyclononanechromium tricarbonyl (0) A chromium complex coordinated by a polydentate ligand having a type structure is exemplified.

Further, bis (dimethylphosphinoethyl) methylphosphinechromium trichloride (II
I), bis (diphenylphosphinoethyl) phenylphosphinechromium tricarbonyl (0), bis (diphenylphosphinoethyl) phenylphosphinechromium trichloride (III), diethylenetriaminechromiumtricarbonyl (0), bis (dimethylaminoethyl) methyl Amine chromium trichloride (III), α, α ',
α "-tripyridinechromium trichloride (III),
2,6-bis (2-phenyl-2-azaethenyl) pyridinechromium trichloride (III), bis [3- (2
-Pyridylethylimino) -2-butanone oxime] chromium trichloride (III), bis (methoxyethyl) ether chromium trichloride (III), bis (ethoxyethyl) ether chromium trichloride (I
A chromium complex coordinated by a polydentate ligand having a bridge-type structure such as II).

Among these, from the viewpoint of 1-hexene selectivity and catalytic activity, a polydentate ligand having a tripod structure is preferably used as the neutral polydentate ligand of the general formula (1). As B, carbonyl, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, an amide and a thioalkoxide are preferably used. More preferably, a carbonyl complex, a halogen complex and an amide complex of chromium coordinated by a polydentate ligand having a tripod structure are used. More preferably, tris (3,5-dimethyl-1-pyrazolyl) methanechrome tricarbonyl (0), tris (3,5-dimethyl-1-pyrazolyl) methanechrome trichloride (III), tris (3,5- Dimethyl-1-pyrazolyl) methanechrome tris (diisopropyl) amide (I
II), 1,1,1-tris (methoxymethyl) ethanechrome tricarbonyl (0) and the like are used.

In the present invention, the method of synthesizing the chromium complex having the neutral polydentate ligand coordinated thereto is not particularly limited. And a known complex formation method [for example, J. Amer. Ch
em. Soc. , 92, 5118 (1970) and An
gew. Chem. Int. Ed. Engl. , 33,
1877 (1994)]. In this case, as a chromium compound that can be used,
Although not particularly limited, for example, chromium hexacarbonyl (0), pentacarbonyl (triphenylphosphine) chromium (0), tetracarbonylbis (ethylene) chromium (0), tricarbonyl (benzene) chromium (0) , Tricarbonyl (toluene) chromium (0),
Tricarbonyl (trimethylbenzene) chromium (0),
Tricarbonyl (hexamethylbenzene) chromium (0), tricarbonyl (naphthalene) chromium (0),
Tricarbonyl (cycloheptatriene) chromium (0), tricarbonyltris (acetonitrile) chromium (0), tricarbonyltris (triphenylphosphite) chromium (0), (ethylene) dicarbonyl (trimethylbenzene) chromium (0) , Cyclohexylisonitriledicarbonyl (trimethylbenzene) chromium (0), tributylphosphinedicarbonyl (trimethylbenzene) chromium (0), tricarbonyl (cyclopentadienyl) chromium (I) dimer, hydridetricarbonyl (cyclopentadienyl) Chromium carbonyl compounds such as chromium (II), chromium (III) chloride, chromium (II) chloride, chromium (III) bromide, chromium (II) bromide, chromium (III) iodide, chromium (I)
I), chromium fluoride (III), chromium fluoride (I
I), tris (tetrahydrofuran) chromium chloride (III), tris (1,4-dioxane) chromium chloride (III), tris (diethyl ether) chromium chloride (III), tris (pyridine) chromium chloride (III), tris ( Chromium halides such as acetonitrile) chromium chloride (III), chromamides such as tris (tetrahydrofuran) chromium tris (diisopropylamide) (III), tris (tetrahydrofuran) chromium tris (diethylamide) (III), and chromium (IV) t-butoxide Chrome alkoxides such as chromium (III) acetylacetonate and the like, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) naphthene It includes chromic acid salts over bets like.

The concentration of chromium metal in forming a chromium complex by reacting a neutral polydentate ligand with a chromium compound is not particularly limited. The solvent used here is not particularly limited, but an organic solvent is preferably used. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, decalin, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and trimethylbenzene; ethers such as diethyl ether and tetrahydrofuran And halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. Further, the solvent is
Not only can each be used alone, but also two or more can be used as a mixture.

The complex formation reaction is carried out at any temperature from 0 ° C. to the boiling point of the reaction solvent used, preferably at 20 to 200 ° C. The reaction time is not particularly limited, and is usually 1 minute to 48 hours, preferably 5 minutes to 24 hours.
It is desirable that all operations during the reaction be performed while avoiding air and moisture. Further, it is preferable that the raw materials and the solvent are sufficiently dried.

The chromium complex to which a neutral polydentate ligand is coordinated usually precipitates as a solid, and can be separated from the reaction solvent by filtration. Further, if necessary, washing is carried out using the above-mentioned solvent, followed by drying to synthesize a chromium complex which is one of the components of the ethylene trimerization catalyst. still,
When precipitation does not occur, precipitation can be performed by evaporating the solvent, adding a poor solvent, or cooling.

In the present invention, among the chromium complexes coordinated by a neutral polydentate ligand, the polydentate ligand is facia
It is preferable to use a chromium complex coordinated to l. By using a chromium complex in which a polydentate ligand is coordinated with a factor, effects such as suppression of by-product of polyethylene are recognized. Here, the complex in which the polydentate ligand is coordinated to facial is one of the isomers of a six-coordinate octahedral complex in which three ligands are coordinated [Chemical Selection Organometallic Chemistry-Basic and Application-, p. 143 (Shokabo). That is, in a six-coordinate octahedral complex in which three ligands are coordinated, this means that all three ligands are coordinated in an arrangement such that they are in the cis position.

The alkyl metal compound used in the present invention is not particularly limited. For example, the following general formula (2) R _p MX _q (2) (where p is 0 <p ≦ 3) And q is 0 ≦ q <3, and p + q is 1 to 3. M represents lithium, magnesium, zinc, boron or aluminum, and R represents a group consisting of an alkyl group having 1 to 10 carbon atoms. 1 to be chosen
Wherein X represents one or more selected from the group consisting of a hydrogen atom, an alkoxy group, an aryl group, and a halogen atom).

In the above general formula (2), the number of carbon atoms is 1 to 1.
The alkyl group of 0 is not particularly limited, but examples include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and an octyl group.
Although it does not specifically limit as an alkoxy group, For example, a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, etc. are mentioned. The aryl group is not particularly limited, but includes, for example, a phenyl group. Although it does not specifically limit as a halogen atom, For example, fluorine, chlorine, bromine, or iodine is mentioned.

In the general formula (2), M is A
l, when p and q are each 1.5, AlR _1.5 X _1.5
Becomes Although such compounds do not exist in theory, they are usually conventionally expressed as sesqui-forms of Al ₂ R ₃ X ₃ , and these compounds are also included in the present invention.

Examples of the alkyl metal compound represented by the general formula (2) include methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, diethyl magnesium, and ethyl butyl magnesium. , Ethyl chloro magnesium, ethyl bromo magnesium, dimethyl zinc, diethyl zinc, dibutyl zinc, trimethyl borane, triethyl borane, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tricyclohexyl Aluminum, dimethylethylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethyl Rumi bromide phenoxide, dicyclohexyl phenyl aluminum, ethyl aluminum ethoxy chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, dicyclohexyl aluminum chloride,
Examples include methylaluminum sesquichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like.

Of these, alkyl aluminum compounds are preferably used in terms of availability and activity.
More preferably, triethylaluminum or triisobutylaluminum is used. These alkyl metal compounds can be used alone or in combination of two or more.

The amount of the alkyl metal compound to be used is 0.1 to 10000 equivalents, preferably 3 to 3000 equivalents, more preferably 5 to 2000 equivalents, per 1 mol of the chromium complex.
Is equivalent.

The catalyst for trimerizing ethylene comprising a chromium complex coordinated with a neutral polydentate ligand, an alkyl metal compound and a topotactic reduction reaction product involving electron transfer according to the present invention is a chromium complex as defined above. , An alkyl metal compound and a topotactic reduction reaction product involving electron transfer are brought into contact with a raw material in a solvent. The contact method is not particularly limited.

The concentration of the chromium complex in preparing the catalyst is not particularly limited, but is usually 0.001 per liter of the solvent.
1 micromole to 100 mmol, preferably 0.01
Used at micromolar to 10 mM concentrations. If the catalyst concentration is lower than this, sufficient activity cannot be obtained. Conversely, if the catalyst concentration is higher than this, catalyst activity does not increase and it is not economical. Further, as the solvent used here, for example, butane, pentane, hexane, heptane, octane, isooctane, nonane, decane, cyclopentane,
Aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane, and decalin; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, trimethylbenzene, chlorobenzene, and dichlorobenzene; methylene chloride, chloroform, and carbon tetrachloride And chlorinated hydrocarbons such as dichloroethane. Further, a reaction product, that is, 1-hexene, can be used as a solvent. These solvents can be used alone or in combination of two or more. Here, for the purpose of controlling the chromium complex concentration at the time of the ethylene trimerization reaction, the chromium complex may be concentrated or diluted as necessary.

The temperature at which the above-mentioned chromium complex, alkyl metal compound and topotactic reduction reaction product involving electron transfer are brought into contact is -100 to 250 ° C, preferably 0 to 200 ° C. The contact time is not particularly limited, and is 1 minute to 24 hours, preferably 2 minutes to 12 hours. It is desirable that all operations during contact be performed while avoiding air and moisture. Further, it is preferable that the raw materials and the solvent are sufficiently dried.

The ethylene trimerization reaction of the present invention can be carried out by bringing ethylene into contact with a catalyst comprising the chromium complex, an alkyl metal compound and a topotactic reduction reaction product accompanied by electron transfer. The contacting method is not particularly limited. A method of initiating a quantification reaction or a method of bringing a chromium complex, an alkyl metal compound and a topotactic reduction reaction product involving electron transfer into contact in advance, and then contacting with ethylene to carry out a trimerization reaction is employed.

Specifically, in the former case, (1) a chromium complex, an alkyl metal compound, a topotactic reduction reaction product involving electron transfer, and ethylene are simultaneously and independently introduced into the reaction system. ) Introducing a chromium complex, a topotactic reduction reaction product with electron transfer and ethylene into a solution containing an alkyl metal compound; and (3) a chromium complex, containing a topotactic reduction reaction product with electron transfer. (4) introducing an alkyl metal compound and ethylene into a suspension; (4) introducing a chromium complex and ethylene into a suspension containing an alkyl metal compound and a topotactic reduction reaction product accompanied by electron transfer; (5) a chromium complex Introducing a metal compound, a topotactic reduction reaction product involving electron transfer, and ethylene into a solution containing ethylene. It is possible to carry out the trimerization reaction.
In the latter case, (1) an alkyl metal compound is introduced into a suspension containing a chromium complex and a topotactic reduction reaction product accompanied by electron transfer; Introducing a chromium complex into a suspension containing a tactic reduction reaction product, (3) introducing a chromium complex and a topotactic reduction reaction product accompanied by electron transfer into a solution containing an alkyl metal compound,
(4) A catalyst is prepared by a method of introducing a topotactic reduction reaction product accompanied by electron transfer and an alkyl metal compound into a solution containing a chromium complex, and the trimerization reaction can be performed by bringing the catalyst into contact with ethylene. . The order of mixing these raw materials is not particularly limited.

In the present invention, if necessary, a catalyst comprising a chromium complex coordinated with a neutral polydentate ligand, an alkyl metal compound, and a topotactic reduction reaction product involving electron transfer is irradiated with light. Irradiation may be performed to perform a trimerization reaction of ethylene. Effects such as a significant improvement in catalytic activity by light irradiation are recognized.

The light used in the present invention is not particularly limited, and includes, for example, ultraviolet light, visible light and infrared light.
m, preferably 200 to 700 nm
Of light is used. The illuminance of light is not particularly limited.

Either sunlight or an artificial light source may be used as the light source. However, an artificial light source is desirable because sunlight has low illuminance, is affected by the weather, and cannot be used at night. The artificial light source is not particularly limited, but includes, for example, a deuterium lamp, a xenon lamp, a tungsten lamp, an incandescent lamp, a halogen lamp, a low-pressure mercury lamp, a hollow cathode lamp, a metal vapor discharge tube, a metal halide lamp, and a high-pressure lamp. Examples thereof include a sodium lamp, a thallium lamp, a mercury-thallium lamp, a mercury-lead lamp, an H-type discharge tube, a xenon-mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a flash lamp.

The timing of light irradiation is not particularly limited, and the catalyst may be irradiated with the chromium complex, the alkyl metal compound, and a catalyst comprising a topotactic reduction reaction product accompanied by electron transfer. Further, the reaction may be directly applied to the ethylene trimerization reaction system. Note that the light irradiation time is not particularly limited.

The temperature of the ethylene trimerization reaction in the present invention is from -100 to 250 ° C., preferably from 0 to 2 ° C.
00 ° C. The reaction pressure is not particularly limited as long as the reaction system is in an ethylene atmosphere.
3000 kg / cm ² , preferably 0.1 to 30
It is 0 kg / cm ² . The reaction time depends on the temperature and the pressure and cannot be determined unconditionally, but is usually 5 seconds to 6 hours. Ethylene may be continuously supplied so as to maintain the above-mentioned pressure, or may be sealed at the above-mentioned pressure at the start of the reaction to cause a reaction. Ethylene as a raw material gas may contain a gas inert to the reaction, for example, nitrogen, argon, helium, or the like. It is desirable that all operations of the ethylene trimerization reaction be performed while avoiding air and moisture. Further, it is preferable that ethylene is sufficiently dried.

This reaction can be carried out in any of a batch system, a semi-batch system and a continuous system. After completion of the ethylene trimerization reaction, a polymerization deactivator such as water, alcohol, or an aqueous sodium hydroxide solution is added to the reaction solution to stop the reaction. After the deactivated waste chromium catalyst is removed by a known deashing method, for example, extraction with water or an aqueous alkaline solution, the generated 1-hexene is separated from the reaction solution by a known extraction method or a distillation method. . In addition, polyethylene as a by-product is separated and removed at a reaction solution outlet as a residue in a known centrifugation method or distillation separation of 1-hexene.

[0108]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are only for illustrating the outline of the present invention and the present invention is not limited to these Examples. .

Reference Example 1 A Schlenk tube was manufactured according to J. Amer. Chem. Soc. ,
92, 5118 (1970), 238 mg of tris (3,5-dimethyl-1-pyrazolyl) methane having a tripod structure, 176 mg of chromium hexacarbonyl, 40 ml of mesitylene and 10 ml of toluene
And heated to reflux while stirring under a nitrogen atmosphere for 1 hour. The precipitated crystals were filtered to obtain tris (3,5-dimethyl-1-pyrazolyl) methanechromium tricarbonyl (0) (hereinafter, referred to as complex A). As a result of an IR analysis of this complex A, two peaks based on CO absorption were observed at 1896 cm ^-1 and 1759 cm ^-1 , and tris (3,5-dimethyl-1-pyrazolyl) methane was distributed to chromium in a factal manner. It showed that it was ranked.

Reference Example 2 After adding 100 ml of n-hexane to 7.0 g (44 mmol) of molybdenum disulfide, n-butyllithium
-Hexane solution (1.54 M) 57 ml (88 mmol
l) was added dropwise. The suspension was stirred at room temperature for 3 days to remove the supernatant, and then washed with n-hexane. afterwards,
Dry at room temperature, 10 ^-3 Torr, then at 75-85 ° C.
Drying at 10 ⁻³ Torr gave a black solid. As a result of elemental analysis of the obtained product, the composition was (Li ⁺ ) _1.20 [Mo
S _2] was ^1.20-.

130 ml of 25% aqueous ammonia was added to 7.0 g of the above reduction reaction product. This suspension is -30 ° C
, And the supernatant was removed, followed by washing with water.

7.1 g of dimethylaniline hydrochloride (45 m
mol) was dissolved in 500 ml of water, and 7.0 g of the above Lewis base-treated product was added to the aqueous solution. The suspension was stirred at room temperature for 24 hours to remove the supernatant, and then washed with water and ethanol. Then, at room temperature, 10 ^-3 Torr
For 24 hours to obtain a black solid (hereinafter, referred to as compound-1). As a result of elemental analysis of the obtained compound-1,
The composition was [Ph (Me) ₂ NH ⁺ ] _0.12 [MoS ₂ ] ^0.12- .

Example 1 In a Schlenk tube, 0.20 g of compound-1 was added in an amount of 0.154 g.
A mol / l triisobutylaluminum / cyclohexane solution (2.1 ml) and dried toluene (40 ml) were added and mixed and stirred to obtain a suspension (hereinafter referred to as suspension C).

Internal volume 150 equipped with thermometer and stirrer
6.9 mg of the complex A synthesized in Reference Example 1, 2.1 ml of a 0.154 mol / l triisobutylaluminum / cyclohexane solution, and 40 ml of dry toluene were placed in a ml pressure-resistant reaction vessel made of glass, and mixed and stirred. Light was irradiated from the outside for 30 minutes using an ultra-high pressure mercury lamp (500 W) manufactured by Ushio Electric Co., and then the suspension C was mixed.

The reaction vessel was heated to 80 ° C., and the stirring speed was 1
After adjusting to 400 rpm, ethylene was introduced into the reaction vessel to start the ethylene trimerization reaction. Ethylene gas was blown in so that the absolute pressure in the reaction vessel became 5 kg / cm ^2, and thereafter, introduction was continued so as to maintain the pressure,
The reaction was performed for 30 minutes while maintaining these reaction conditions. After 30 minutes, the catalyst was deactivated by forcing water into the reaction vessel with nitrogen and the reaction was stopped.

The reactor was cooled to room temperature and then depressurized. The products contained in the reaction solution and the recovered gas were analyzed by gas chromatography. The solid content contained in the reaction solution was separated by filtration using filter paper, air-dried, and then dried under reduced pressure (1 Torr, 100 ° C.), and its weight was measured. Further, the dried solid was fired at 700 ° C. in an electric furnace, and the ignition residue was measured. The weight obtained by subtracting the ignition residue from the dried solid was defined as the polymer weight. Table 1 shows the results.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 0.40 g of Compound-1 was used. Table 1 shows the results.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that Compound-1 was not used. Table 1 shows the results.

Comparative Example 2 Instead of complex A, (1,3,5-trimethylbenzene)
Chromium tricarbonyl (0) (hereinafter, referred to as complex B)
The reaction was carried out in the same manner as in Example 1, except that 4.1 mg of was used. Table 1 shows the results. The catalytic activity was low and the by-product of polyethylene increased.

[0120]

[Table 1]

[0121]

According to the present invention, at least three of a chromium complex coordinated with a neutral polydentate ligand, an alkyl metal compound, and a topotactic reduction reaction product accompanied by electron transfer.
By using the ethylene trimerization catalyst as a component, 1-hexene can be efficiently and highly selectively produced from ethylene.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA06 BA21A BA21B BA27A BA27B BC04A BC10A BC16A BC16B BC58A BC58B BD03A CB47 4H006 AA02 AC21 BA02 BA05 BA09 BA14 BA31 BA32.

Claims (7)

[Claims] (1) a chromium complex coordinated with a neutral polydentate ligand,
An ethylene trimerization catalyst comprising at least three components of an alkyl metal compound and a topotactic reduction reaction product involving electron transfer. 2. The ethylene trimerization according to claim 1, wherein the topotactic reduction reaction product accompanied by electron transfer has been subjected to salt treatment, acid treatment and / or Lewis base treatment. catalyst. 3. A chromium complex coordinated with a neutral polydentate ligand is represented by the following general formula (1): ACrB _n (1) (where A is a neutral polydentate ligand. N Is an integer of 1 to 3, and B is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxylate group or a diketonate group, a halogen atom, an amide, an imide, an alkoxide, a thioalkoxide, a carbonyl, an arene, an alkene, or an alkyne. ,
A complex represented by at least one selected from the group consisting of amines, imines, nitriles, isonitriles, phosphines, phosphine oxides, phosphites, ethers, sulfones, sulfoxides and sulfides). The catalyst for trimerizing ethylene according to claim 2. 4. The ethylene trimerization catalyst according to claim 1, wherein the neutral polydentate ligand has a tripod-type structure. 5. The ethylene trimerization catalyst according to claim 1, wherein a chromium complex in which a neutral polydentate ligand is coordinated with a factor is used. 6. An alkyl metal compound represented by the following general formula (2): R _p MX _q (2) (where p is 0 <p ≦ 3, q is 0 ≦ q <3, and p + q Is 1 to 3. M represents lithium, magnesium, zinc, boron or aluminum, and R represents 1 selected from the group consisting of alkyl groups having 1 to 10 carbon atoms.
At least one kind selected from the group consisting of a hydrogen atom, an alkoxy group, an aryl group, and a halogen atom). Of ethylene trimerization catalyst. 7. A process for trimerizing ethylene, wherein ethylene is trimerized in the presence of the catalyst for trimerizing ethylene according to any one of claims 1 to 6.