JP2003088760A - Ethylene trimerization catalyst and ethylene trimerization method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce 1-hexene efficiently and highly selectively from ethylene. SOLUTION: The trimerization catalyst consists of either an organic metal complex coordinated with a neutral multi-dentate ligand and having a tripod- type structure defined as AMBn (1) (in the formula, n is an integer of 1-3; A denotes a neutral multi-dentate ligand having a tripod-type structure; M denotes a transition metal atom belonging to group III to group X of a periodic table; B denotes one or more substances selected from hydrogen atom, a halogen atom, and linear or branched alkyl groups), a halogenated inorganic compound, and an alkyl aluminoxamine or an organic metal complex as described above, a halogenated inorganic compound, an alkyl aluminoxamine, and an alkyl- containing compound. The catalyst is used for the production.

Description

Detailed Description of the Invention

[0001]

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

[0002]

It is known to use chromium compounds as catalysts in the process of trimerizing ethylene to give 1-hexene. For example, JP-A-62-265237 discloses a catalyst system comprising a chromium compound, polyhydrocarbyl aluminum oxide and a donor ligand. JP-A-6-239920 discloses a catalyst system comprising a chromium compound, a pyrrole-containing compound, a metal alkyl compound and a halide, and JP-A-8-59732.
Japanese Patent Publication discloses a catalyst system comprising a chromium compound, a metal alkyl compound and an acid amide or imide compound.

Further, JP-A-6-298673 discloses a catalyst comprising a coordination complex with phosphine, arsine and / or stibine, which are polydentate ligands of chromium salt, and aluminoxane. Furthermore, JP-A-1
No. 0-7712 discloses a catalyst composed of an aluminum compound and a chlorine complex or an alkyl complex of chromium coordinated with a specific nitrogen ligand, and JP-A No. 10-231317 discloses a cyclic polyamine or hydrotris (pyrazolyl).
A catalyst composed of an organometallic complex in which a borate is coordinated and an alkylaluminum compound is disclosed.

[0004]

However, Japanese Patent Laid-Open No. 62-62
The method described in Japanese Patent No. 265237 has a drawback that polyethylene is produced as a large amount together with 1-hexene. The method described in Japanese Patent Application Laid-Open No. 6-239920 has little by-product of polyethylene, and is considerably improved in this respect. However, the pyrrole-containing compound, which is a constituent component of the catalyst, is a substance that is extremely unstable to air, and therefore tends to be colored and deteriorate. Therefore, it is not sufficient as an industrial catalyst because it is difficult to handle and requires a treatment or a new device for removing the coloring component after the reaction. Further, in the method described in JP-A-8-59732, it is necessary to use a specific imide compound (that is, maleimide) in order to obtain activity in the compound group of acid amide or imide compound which is a constituent component of the catalyst. There is.
Since maleimide has low solubility, catalyst preparation is complicated,
Not only difficult to obtain but also expensive, there is a problem in terms of economy.

On the other hand, the method described in JP-A-6-298673 has poor reproducibility of experimental data. Further, the method described in JP-A-10-7712 has a problem that the catalytic activity is low. Furthermore, Japanese Patent Laid-Open No. 10-2313
The method described in Japanese Patent No. 17 has a drawback that not only a large amount of polyethylene is produced, but also the 1-hexene selectivity in the oligomer is low.

The present invention has been made in view of the above problems, and an object thereof is to efficiently and highly selectively produce 1-hexene, which is useful as a raw material comonomer for LLDPE, from ethylene and is easy to handle. An ethylene trimerization catalyst and an ethylene trimerization method using the catalyst are provided.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that periodic table 3 in which a halogenated inorganic compound and a specific polydentate ligand are coordinated.
Organometallic complex having a transition metal of Group 10 to Group 10 and an alkylaluminoxane, or ethylene comprising a halogenated inorganic compound, an organometallic complex having a transition metal of Group 3 to Group 10 of the periodic table, an alkylaluminoxane, and an alkyl group-containing compound It was found that the trimerization catalyst (1) is stable and easy to handle, and that when it is used, the trimerization reaction of ethylene proceeds with high activity and 1-hexene is highly selectively produced, and the present invention is completed. Came to.

That is, the present invention relates to an organometallic complex having a transition metal of Group 3 to Group 10 of the periodic table, in which a halogenated inorganic compound and a neutral polydentate ligand having a tripod structure are coordinated, and an alkylaluminoxane. Or an ethylene trimerization catalyst comprising a halogenated inorganic compound, the organometallic complex, an alkylaluminoxane and an alkyl group-containing compound, and an ethylene trimerization method using the same.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail.

In the present invention, one component constituting the ethylene trimerization catalyst is represented by the following general formula (1) AMB _n (1) (wherein A is a neutral polydentate ligand having a tripod type structure). And M is a transition metal atom of Group 3 to Group 10 of the periodic table, B is a hydrogen atom, a halogen atom, and one or more selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms. , N is an integer equal to the valence of M), and an organometallic complex in which a neutral polydentate ligand having a tripod structure is coordinated is used.

Here, the neutral polydentate ligand having a tripod type structure coordinated to the organometallic complex is not particularly limited, but for example, the following general formula (2) can be used.

[0012]

[Chemical 5] (In the formula, j, k, and m are each independently an integer of 0 to 6. D ¹ is each independently a divalent hydrocarbon group which may have a substituent, and L ¹ is each independently. Then periodic table 1
It represents a substituent containing a group 4, group 15, group 16 or group 17 element. G ¹ is carbon or silicon, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms.
Represents an aryl group. ) Or the following general formula (3)

[0013]

[Chemical 6] (In the formula, a, b and c are each independently an integer of 0 to 6 and u is an integer of 0 or 1. D ² is each independently a divalent group which may have a substituent. Hydrocarbon group of L
Each ² independently represents a substituent containing an element of Group 14, Group 15, Group 16 or Group 17 of the periodic table. G ² represents a nitrogen atom or a phosphorus atom, and R ² represents an oxygen atom or a sulfur atom. The tridentate ligand represented by) is mentioned as a suitable thing.

In the above general formulas (2) and (3),
D ¹ and D ² are not particularly limited,
Examples thereof include an alkylene group, a cycloalkylene group, a phenylene group, a tolylene group and a xylylene group. Further, examples of the substituent include alkyl groups such as methyl group and ethyl group, and alkoxy groups such as methoxy group and ethoxy group.

In the general formulas (2) and (3), L ¹
And the substituent containing an element of group 14, group 15, group 16 or group 17 of the periodic table represented by L ² is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Aryloxy groups such as alkoxy groups, phenoxy group and 2,6-dimethylphenoxy group, methylthio group, ethylthio group, propylthio group,
Alkylthio groups such as butylthio group, phenylthio group,
Arylthio groups such as tolylthio groups, dimethylamino groups, diethylamino groups, dialkylamino groups such as bis (trimethylsilyl) amino groups, diarylamino groups such as diphenylamino groups, alkylarylamino groups such as methylphenyl groups, dimethyl Examples include dialkylphosphino groups such as phosphino group and diethylphosphino group, diarylphosphino groups such as diphenylphosphino group and ditolylphosphino group, and alkylarylphosphino groups such as methylphenylphosphino group. .

Furyl group, benzofuryl group, thienyl group, benzothienyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group, imidazolyl group, benzimidazolyl group, indazolyl group, quinolyl group, isoquinolyl group, oxazolyl group, thiazole group. And heterocyclic groups containing an element of group 14, group 15, group 16 or group 17 of the periodic table. Examples of the substituent on the ring of these heterocyclic groups include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and a phenyl group.

R ¹ in the general formula (2) is not particularly limited, but for example, hydrogen atom, methyl group, ethyl group, propyl group, butyl group, benzyl group, hydroxymethyl group, cyanoethyl group, allyl group. , An alkyl group having 1 to 10 carbon atoms such as a trifluoropropyl group, or an aryl group having 6 to 10 carbon atoms such as a phenyl group, a p-methylphenyl group, and a p-chlorophenyl group.

The neutral tridentate ligand having the tripod type structure represented by the above general formulas (2) and (3) is not particularly limited, but for example, the periodic table groups 14, 15 and 16
Examples of the polydentate ligand having a substituent containing a group III or group 17 element include tris (methoxymethyl) methane, 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)
Oxygen-containing tridentate ligands such as ethane, 1,1,1-tris (methylthiomethyl) ethane, 1,1,1-tris (butylthiomethyl) ethane, 1,1,1-tris (phenylthiomethyl) ) Sulfur-containing tridentate ligands such as ethane, 1,
1,1-tris (dimethylaminomethyl) ethane, 1,
Nitrogen-containing tridentate ligands such as 1,1-tris (diphenylaminomethyl) ethane, 1,1,1-tris (diphenylphosphinomethyl) ethane, 1,1,1-tris (dimethylphosphinomethyl) Examples thereof include phosphorus-containing tridentate ligands such as ethane and 1,1,1-tris (diethylphosphinomethyl) ethane.

Further, as a polydentate ligand having a heterocyclic group containing an element of Group 14, 15, 16 or 17 of the periodic table, trifurylmethane, tris (5-methyl-2-)
Furyl) methane, tris (5-ethyl-2-furyl) methane, tris (5-butyl-2-furyl) methane, 1,
Oxygen-containing tridentate ligands such as 1,1-trifurylethane, trifurylamine, trifurylphosphine and trifurylphosphine oxide, sulfur-containing tridentate ligands such as tris (thienyl) methane, and tri ( 1-pyrazolyl) methane, tris (3,5-dimethyl-1-pyrazolyl) methane, tris (3,5-diisopropyl-1-pyrazolyl) methane, tris (3,5-diphenyl-1-pyrazolyl) methane, 1, 1,1-tris (3,5-dimethyl-1-pyrazolyl) ethane, 1,1,1-tris (3,3
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 , Tris (2
-Pyridyl) phosphine oxide, tris (2-pyridyl) hydroxymethane, tris (1-imidazolyl) methane, tris (3,5-dimethyl-1-pyrazolyl) methane, tris (3,5-diethyl-1-pyrazolyl) methane , Tris (3,4,5-trimethyl-1-pyrazolyl) methane, tris (3,5-dimethyl-4-n-butyl-1-pyrazolyl) methane, tris (3-phenyl-
5-methyl-1-pyrazolyl) methane, tris (3-
(4-Tolyl) -5-methyl-1-pyrazolyl) methane, tris (3- (4-anisyl) -5-methyl-1-
Pyrazolyl) methane, tris (3- (2-pyridyl)-
5-methyl-1-pyrazolyl) methane, tris (3-
(3-pyridyl) -5-methyl-1-pyrazolyl) methane, tris (3- (4-pyridyl) -5-methyl-1-
Pyrazolyl) methane, tris (3-phenyl-1-pyrazolyl) methane, 1-methyl-tris (3-phenyl-
1-pyrazolyl) methane, methyl-tris (3-ethyl-1-pyrazolyl) methane, methyl-tris (3-phenyl-1-pyrazolyl) methane, methyl-tris (3,3
5-dimethyl-1-pyrazolyl) methane, tris (3-
(4-tolyl) -1-pyrazolyl) methane, tris (3
-(4-anisyl) -1-pyrazolyl) methane, tris (3-propyl-1-pyrazolyl) methane, tris (3
Examples of the nitrogen-containing tridentate ligands include -ethyl-1-pyrazolyl) methane, tris (3-methyl-1-pyrazolyl) methane, and tris (3-t-butyl-1-pyrazolyl) methane.

Although the specific examples of the organometallic complex represented by the above general formula (1) are not particularly limited,
For example, when M of the organometallic complex is a chromium element of Group 6 of the periodic table, tris (methoxymethyl) methanechromium trichloride (III), tris (methoxymethyl) methanechromium (benzyl) dichloride (II
I), 1,1,1-tris (methoxymethyl) ethane chromium trichloride (III), 1,1,1-tris (ethoxymethyl) ethane chromium trichloride (II)
I), 1,1,1-tris (butoxymethyl) ethane chromium trichloride (III), 1,1,1-tris (phenoxymethyl) ethane chromium trichloride (I)
II), trifurylmethanechromium trichloride (II
I), 1,1,1-tris (methylthiomethyl) ethane chromium trichloride (III), 1,1,1-tris (dimethylaminomethyl) ethane chromium trichloride (III), tris (pyrazolyl) methane chromium trichloride (III), tris (3,5-dimethyl-1-)
Pyrazolyl) methanchrome trichloride (III),
Tris (3,5-diethyl-1-pyrazolyl) methanechromium trichloride (III), tris (3,5-dimethyl-1-pyrazolyl) -methyl-methanechromium trichloride (III), tris (3-phenyl-5) -Methyl-1-pyrazolyl) methanechromium trichloride (I
II), tris (3- (2-pyridyl) -5-methyl-
1-pyrazolyl) methanechromium trichloride (II
I), tris (3- (3-pyridyl) -5-methyl-1
-Pyrazolyl) methanchrome trichloride (II
I), tris (3- (4-pyridyl) -5-methyl-1
-Pyrazolyl) methanchrome trichloride (II
I), tris (3-phenyl-1-pyrazolyl) methanechromium trichloride (III), tris (3- (3-
Tolyl) -5-methyl-1-pyrazolyl) methanechromium trichloride (III), tris (3- (3-anisyl) -5-methyl-1-pyrazolyl) methanechromium trichloride (III), tris (3,5) -Dimethyl-1
-Pyrazolyl) methanechromium (hydride) dichloride (III), tris (3,5-dimethyl-1-pyrazolyl) methanechromium (benzyl) dichloride (II)
I), tris (3,5-dimethyl-1-pyrazolyl) methanechromium (ethyl) dichloride (III), tris (3,5-dimethyl-1-pyrazolyl) methanechromiumtribenzyl (III), 1,1,1 -Tris (3,5-
Dimethyl-1-pyrazolyl) ethane chromium trichloride (III), tris (3,5-diisopropyl-1-)
Pyrazolyl) methanchrome trichloride (III),
Tris (3-isopropyl-1-pyrazolyl) methanechromium trichloride (III), tris (3-ethyl-
1-pyrazolyl) methanechromium trichloride (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methanechrome trichloride (III), tris (2-
Pyridyl) methane chromium trichloride (III), tris (6-methyl-2-pyridyl) methane chromium trichloride (III), tris (2-pyridyl) amine chromium trichloride (III), tris (1-imidazolyl) methane chromium Trichloride (III), 1,
1,1-Tris (dimethylphosphinomethyl) ethane chromium trichloride (III), 1,1,1-Tris (diphenylphosphinomethyl) ethane chromium trichloride (III), 1,1,1-Tris (diethylphos) Finomethyl) ethane chromium trichloride (III)
Etc. Examples of M other than chromium in the organometallic complex include, but are not particularly limited to, M is scandium, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium. , Nickel, palladium, platinum and the like.

Among these, from the viewpoint of catalytic activity, as the neutral polydentate ligand having a tripod type structure represented by the general formula (1), there are nitrogen-containing tridentate ligands having a heterocyclic group. It is preferably used, more preferably tris (3- (4-tolyl) -1-pyrazolyl) methane, tris (3-phenyl-1-pyrazolyl) methane, tris (3,5-dimethyl-1-pyrazolyl) methane, tris. (3-phenyl-5
-Methyl-1-pyrazolyl) methane, tris (3- (2
-Pyridyl) -5-methyl-1-pyrazolyl) methane,
Tris (3- (3-pyridyl) -5-methyl-1-pyrazolyl) methane, Tris (3- (4-pyridyl) -5-
Methyl-1-pyrazolyl) methane is used. Also,
A halogen atom is preferably used as B. More preferable organometallic complexes having neutral polydentate ligands having a tripod structure are 3- (4-tolyl) -1-pyrazolyl) methanechromium trichloride (III) and tris (3-phenyl). -1-Pyrazolyl) methanechromium trichloride (III), tris (3-phenyl-1-)
Pyrazolyl) methane titanium trichloride (III),
Tris (3-phenyl-1-pyrazolyl) methane scandium trichloride (III), tris (3-phenyl-1-pyrazolyl) methane molybdenum trichloride (III), tris (3-phenyl-1-pyrazolyl)
Methanetungsten trichloride (III), tris (3-phenyl-1-pyrazolyl) methane iron trichloride (III), tris (3-phenyl-1-pyrazolyl) methane iron dichloride (II), tris (3,5-
Dimethyl-1-pyrazolyl) methane chromium trichloride (III), tris (3,5-dimethyl-1-pyrazolyl) methane molybdenum trichloride (III), tris (3,5-dimethyl-1-pyrazolyl) methane tungsten trichloride (III), Tris (3,5-
Dimethyl-1-pyrazolyl) methane titanium trichloride (III), tris (3,5-dimethyl-1-pyrazolyl) methane scandium trichloride (III),
Tris (3,5-dimethyl-1-pyrazolyl) methane iron dichloride (II), tris (3,5-dimethyl-1)
-Pyrazolyl) methane iron trichloride (III), tris (3,5-dimethyl-1-pyrazolyl) methane nickel dichloride (I tris (3,5-dimethyl-1-
Pyrazolyl) methane palladium dichloride (II),
Tris (3,5-dimethyl-1-pyrazolyl) methane platinum dichloride (II), tris (3-phenyl-
5-methyl-1-pyrazolyl) methanechromium trichloride (III), tris (3-phenyl-5-methyl-)
1-pyrazolyl) methane scandium trichloride (III), tris (3-phenyl-5-methyl-1-)
Pyrazolyl) methane titanium trichloride (III),
Tris (3-phenyl-5-methyl-1-pyrazolyl)
Methane iron trichloride (III), tris (3-phenyl-5-methyl-1-pyrazolyl) methane iron dichloride (II), tris (3-phenyl-5-methyl-1)
-Pyrazolyl) methane nickel dichloride (II),
Tris (3-phenyl-5-methyl-1-pyrazolyl)
Methane nickel trichloride (III), tris (3
-(2-Pyridyl) -5-methyl-1-pyrazolyl) methanechromium trichloride (III), tris (3-
(3-pyridyl) -5-methyl-1-pyrazolyl) methanechromium trichloride (III), tris (3- (4
-Pyridyl) -5-methyl-1-pyrazolyl) methanechromium trichloride (III) and the like are used.

In the present invention, the method for synthesizing the organometallic complex having the above-mentioned neutral polydentate ligand having a tripod structure is not particularly limited.
Chem. , 25, 1080 (1986) and the like. In this case, the metal compound that can be used is not particularly limited, for example,
Tris (tetrahydrofuran) scandium chloride (II
I), tris (tetrahydrofuran) titanium chloride (II
I), tris (tetrahydrofuran) molybdenum (II
I), tris (tetrahydrofuran) tungsten (III) chloride, chromium (II) chloride, chromium bromide (II)
I), chromium (II) bromide, chromium (III) iodide,
Chromium (II) iodide, Chromium (III) fluoride, Chromium (II) fluoride, Tris (tetrahydrofuran) chromium trichloride (III), Tris (1,4-dioxane) chromium trichloride (III), Tris (diethyl) Ether) chrome trichloride (III), tris (pyridine) chrome trichloride (III), tris (acetonitrile) chrome trichloride (II)
I), iron (II) chloride, iron (III) chloride, nickel (II) chloride, nickel (III) chloride, palladium (II) chloride, platinum (II) chloride and the like.

The concentration of the transition metal in preparing the organometallic complex having the polydentate ligand 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, trimethylbenzene, diethyl ether,
Examples thereof include ethers such as tetrahydrofuran and halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. Further, the above solvents can be used not only individually but also as a mixture of two or more kinds.

The complex formation reaction is carried out at any temperature from -80 ° C to the boiling point of the reaction solvent used, preferably 20 to 200 ° C. When the complex formation reaction is carried out at a temperature above the boiling point of the reaction solvent, it can be carried out under pressure. The reaction time is not particularly limited and is usually 1 minute to 48 hours,
It is preferably 5 minutes to 24 hours. In addition, it is desirable that all the 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.

Further, as another synthesis method, a halogen complex of a transition metal coordinated with a neutral polydentate ligand having a tripod structure synthesized by the above method is used as a raw material, and an alkylaluminoxane or a metal hydride compound is used in a solvent. To react with
You may synthesize | combine the organometallic complex of this invention which coordinated the neutral polydentate ligand which has a tripod type structure.

Since the organometallic complex coordinated with the polydentate ligand usually precipitates as a solid, it can be separated from the reaction solvent by filtration. Further, if necessary, the above solvent is used for washing and then dried to synthesize an organometallic complex which is one of the constituents of the ethylene trimerization catalyst. In addition, when it does not precipitate, it can be precipitated by distilling off the solvent, adding a poor solvent, cooling treatment, or the like.

In the present invention, among the organometallic complexes having a neutral polydentate ligand having a tripod structure, the organometallic complex having the polydentate ligand coordinated with facial is preferably used. preferable. By using the organometallic complex in which the multidentate ligand is coordinated to the facial, the effect of suppressing the by-product of polyethylene is recognized. Here, a complex in which a polydentate ligand is coordinated to a facial is one of the isomers of a hexacoordinate octahedral complex in which three coordination dents are occupied by the polydentate ligand [Chemical Selection Organometallic Chemistry-Basics and Applications-, p. 143 (Sokabo)]. That is, in a hexacoordinated octahedral complex in which three coordination sites are occupied by a multidentate ligand, the polydentate ligands are coordinated in a cis position with respect to each other. It means doing.

The alkylaluminoxane used in the present invention is not particularly limited, but may be represented by the following general formulas (4) and / or (5).

[0029]

[Chemical 7]

[Chemical 8] (Here, R ³ may be the same or different from each other,
A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
q is an integer of 2 to 60. ) Is an aluminum oxy compound having a bond between aluminum and oxygen. In formulas (4) and (5), R ³ may be the same or different. R ³ is, for example, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which can be represented by a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a tert-butyl group or the like. Also,
q is an integer of 2 to 60. The amount of the alkylaluminoxane used is 0.1 to 10000 equivalents of aluminum, preferably 0.5 to 8000 equivalents, and more preferably 1 to 5000 equivalents, relative to 1 mol of the organometallic complex.

The alkyl group-containing compound used in the present invention is not particularly limited. For example, the following general formula (6) R _p EY _q (6) (where p is 0 <p ≦ 3) And q is 0 ≦ q <3, and p + q is 1 to 3. E is a periodic table group 1 to 3
Represents an atom of Group III or an atom of Group 11 to Group 13 of the periodic table, and R
Represents one or more selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, and Y represents a hydrogen atom, an alkoxide group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a halogen atom. Represents one or more selected. The compound represented by the formula () is mentioned as a preferable example.

In the above general formula (6), the number of carbon atoms is 1 to 1.
The alkyl group of 0 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and an octyl group. The alkoxide group is not particularly limited, and examples thereof include a methoxide group, an ethoxide group, a butoxide group, and a phenoxide group. The aryl group is not particularly limited, and examples thereof include a phenyl group. The halogen atom is not particularly limited, but examples thereof include fluorine, chlorine, bromine and iodine.

In the general formula (6), E is A
l and p and q are 1.5, respectively, AlR _1.5 Y _1.5
Becomes Although such a compound does not theoretically exist, it is usually represented as a sesqui-form of Al ₂ R ₃ Y ₃ and these compounds are also included in the present invention.

Examples of the alkyl group-containing compound represented by the above general formula (6) include methyllithium, ethyllithium, propyllithium, n-butyllithium and se.
c-Butyl lithium, tert-butyl lithium, diethyl magnesium, ethyl butyl magnesium, ethyl chloro magnesium, ethyl bromo magnesium, dimethyl zinc, diethyl zinc, dibutyl zinc, trimethyl borane, triethyl borane, trimethyl aluminum, triethyl aluminum, tri-n- Butyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tricyclohexyl aluminum, dimethyl ethyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dicyclohexyl phenyl aluminum, Ethyl aluminum ethoxy chloride, diethyl Rumi chloride, diethylaluminum bromide, diisobutylaluminum chloride, dicyclohexyl aluminum chloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride and the like. Of these, a trialkylaluminum compound is preferably used from the viewpoint of easy availability and activity, and more preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-aluminum.
Hexyl aluminum or tri-n-octyl aluminum is used. These alkyl group-containing compounds can be used not only alone but also as a mixture of two or more kinds. The amount of the alkyl group-containing compound used is 0.1 to 10 with respect to 1 mol of the organometallic complex.
000 equivalents, preferably 3-3000 equivalents, more preferably 5-2000 equivalents.

The halogenated inorganic compound used in the present invention is not particularly limited, but is represented by the following general formula (7) ZX _h (7) (wherein Z is a group 1 or 2 of the periodic table). Atom or periodic table 13
Represents a group-15 atom, and X represents a halogen atom. X
The number h of represents a natural number equal to the valence of Z. The compound represented by () is mentioned as a suitable example. Specifically, but not limited to, hydrogen fluoride, hydrochloric acid, hydrogen bromide, hydrogen iodide, sodium fluoride, sodium chloride, sodium bromide, potassium chloride, magnesium dichloride, boron trifluoride. , Boron trichloride, thallium trichloride,
Indium trichloride, gallium trichloride, germanium tetraiodide, germanium tetrachloride, germanium tetrabromide, silicon tetrachloride, silicon tetraiodide, silicon tetrabromide, silicon tetrafluoride, lead tetrachloride, lead tetrafluoride, Aluminum trichloride, boron trichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, phosphorus trifluoride, phosphorus tribromide, phosphorus triiodide, antimony trichloride, arsenic pentachloride, antimony pentachloride, bismuth pentachloride Etc. The amount of the halogenated inorganic compound used is 0.000 with respect to 1 mol of the organometallic complex.
0001 to 1000 equivalents, preferably 0.000
001 to 500 equivalents, more preferably 0.00001 to
It is 100 equivalents.

The halogenated inorganic compound of the present invention and an organometallic complex coordinated with a neutral polydentate ligand having a tripod structure and an alkylaluminoxane, or a halogenated inorganic compound and the organometallic complex. Ethylene trimerization catalyst consisting of alkylaluminoxane and alkyl group-containing compound can be prepared by contacting the above organometallic complex, alkylaluminoxane, alkyl group-containing compound, and halogenated inorganic compound as raw materials in a solvent. . The contact method is not particularly limited.

The concentration of the organometallic complex in preparing this catalyst is not particularly limited, but it is usually used in a concentration of 0.001 micromol to 100 millimol, preferably 0.01 micromol to 10 millimol per liter of solvent. To be done. When the catalyst concentration is less than 0.001 μmol, sufficient activity cannot be obtained, and conversely, when the catalyst concentration is more than 100 mmol, the catalyst activity does not increase, which is not economical. As the solvent used here, for example, butane, pentane, hexane, heptane, octane, isooctane, nonane, decane, cyclopentane, cyclohexane, methylcyclohexane, cyclooctane, aliphatic hydrocarbons such as decalin, benzene, Examples thereof include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, trimethylbenzene, chlorobenzene, and dichlorobenzene, and chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and dichloroethane. Further, the reaction product, that is, 1-hexene can also be used as a solvent. These solvents can be used not only individually but also as a mixture of two or more kinds. Here, for the purpose of controlling the concentration of the organometallic complex during the trimerization reaction of ethylene, it may be concentrated or diluted if necessary.

The temperature at which the halogenated inorganic compound is brought into contact with the organometallic complex and the alkylaluminoxane, or the halogenated inorganic compound is brought into contact with the organometallic complex, the alkylaluminoxane and the alkyl group-containing compound, -100 to 250 ° C, preferably 0
It is 200 ° C. The contact time is not particularly limited, and is 1 minute to 2
It is 4 hours, preferably 2 minutes to 2 hours. In addition, it is desirable that all operations at the time of 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 is carried out by the halogenated inorganic compound, the organometallic complex and the alkylaluminoxane, or the organometallic complex, the halogenated inorganic compound, the alkylaluminoxane and the alkyl group-containing compound. It can be carried out by contacting ethylene with a catalyst consisting of The contact method is not particularly limited, for example, in the presence of ethylene, which is a raw material for the trimerization reaction, a halogenated inorganic compound and the organometallic complex and an alkylaluminoxane, or a halogenated inorganic compound and the organometallic complex. And an alkylaluminoxane and an alkyl group-containing compound are contacted with each other to initiate a trimerization reaction at the same time, or a halogenated inorganic compound and the organometallic complex and alkylaluminoxane, or a halogenated inorganic compound and the organic compound. A method may be used in which the metal complex, the alkylaluminoxane, and the alkyl group-containing compound are brought into contact with each other in advance, and then brought into contact with ethylene to carry out the trimerization reaction. The order of mixing these is not particularly limited.

The temperature for the trimerization reaction of ethylene in the present invention is -100 to 250 ° C, preferably 0 to 2
It is 00 ° C. The reaction pressure is not particularly limited as long as the reaction system is an ethylene atmosphere, but is usually 0.01 to 100 absolute pressure.
3000 kg / cm ² , preferably 0.1-30
It is 0 kg / cm ² . The reaction time is 5 seconds to 6 hours. In addition, ethylene may be continuously supplied so as to maintain the above pressure, or may be sealed at the above pressure at the start of the reaction and reacted. There is no problem even if the material gas ethylene contains a gas inert to the reaction, such as nitrogen, argon, helium, or the like. In addition, it is desirable that all the operations of the ethylene trimerization reaction be performed while avoiding air and water. 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, the reaction can be stopped by adding a quenching agent such as water, alcohol, or sodium hydroxide aqueous solution to the reaction solution. The deactivated waste chromium catalyst can be removed by a known deashing treatment method, for example, extraction with water or an aqueous alkali solution. The produced 1-hexene is separated from the reaction solution by a known extraction method or distillation method. In addition, the by-produced polyethylene can be separated and removed as a residue at the time of a known centrifugal separation method or 1-hexene by distillation separation at the reaction solution outlet.

[0041]

The present invention will be described in more detail below with reference to examples, but these examples show an outline of the present invention, and the present invention is not limited to these examples.

IR measurement: IR was measured by Nujol method using an infrared spectrophotometer (FTIR-8100) manufactured by Shimadzu Corporation.

Analysis by Gas Chromatography: A product having 4 to 8 carbon atoms contained in the reaction solution was quantified using a Shimadzu gas chromatograph (GC-14A) equipped with a GL Science TC-1 column. Analyzed. The analysis conditions were such that a nitrogen carrier was used, the injection temperature was 280 ° C. and the detector temperature was 280 ° C., and n-heptane was used as an internal standard. The analysis was performed by injecting 1.2 μL of the reaction solution into this gas chromatograph and then raising the temperature of the column from 40 ° C. to 250 ° C.

The product having 10 or more carbon atoms was produced by GL Science, which was prepared separately from the gas chromatograph.
Analysis was performed using a Shimadzu gas chromatograph (GC-14A) equipped with a TC-1 column. The analysis conditions are a nitrogen carrier and an injection temperature of 300.
℃, the detector temperature is set to 300 ℃, n- as an internal standard
Heptane was used. The analysis was carried out by injecting 1.4 μL of the reaction solution into this gas chromatograph and then increasing the column temperature to 50 ° C.
To 300 ° C.

The products contained in the gas were analyzed using a gas chromatograph (GC-9A) manufactured by Shimadzu Corporation equipped with a column of Al ₂ O ₃ / KCl manufactured by Chrompack. The analysis conditions were a nitrogen carrier, an injection temperature of 200 ° C., a detector temperature of 200 ° C. and a column temperature of 120 ° C., and an absolute calibration curve method. The analysis was performed by injecting 0.2 mL of the collected gas into this gas chromatograph.

Reference Example 1 In a Schlenk tube having an internal volume of 100 mL, Amer. C
hem. Soc. , 92, 5118 (1970), and tris (3) having a tripod structure.
-Phenyl-5-methyl-1-pyrazolyl) methane 3
46 mg, tris (tetrahydrofuran) chromium trichloride (III) 255 mg, tetrahydrofuran 5
mL and 20 mL of toluene were added, and the mixture was stirred at 95 ° C. for 24 hours under a nitrogen atmosphere. The generated crystals were separated by filtration to obtain tris (3-phenyl-5-methyl-1-pyrazolyl) methanechromium trichloride (III) (IR (KB
r): 1566 cm ^-1 ). Hereinafter, this complex is referred to as complex A.

Reference Example 2 A Schlenk tube having an internal volume of 100 mL was charged with J. Amer. C
hem. Soc. , 92, 5118 (1970), and tris (3) having a tripod structure.
-Phenyl-1-pyrazolyl) methane 120 mg, tris (tetrahydrofuran) chromium trichloride (I
II) 94 mg and toluene 18 mL were added, and the mixture was stirred at 100 ° C. for 12 hours under a nitrogen atmosphere. The generated crystals were separated by filtration to obtain tris (3-phenyl-1-pyrazolyl) methanechromium trichloride (III) (IR (KB
r): 1540 cm ^-1 ). Hereinafter this complex is referred to as complex B.

Reference Example 3 In a Schlenk tube having an internal volume of 100 mL, J. Amer. C
hem. Soc. , 92, 5118 (1970), and tris (3) having a tripod structure.
-(4-Tolyl) -1-pyrazolyl) methane 400 m
g, tris (tetrahydrofuran) chromium trichloride (III) 295 mg, and toluene 30 mL were added, and the mixture was stirred at 100 ° C. for 12 hours under a nitrogen atmosphere. The produced crystal was separated by filtration to obtain tris (3- (4-tolyl) -1-pyrazolyl) methanechromium trichloride (III) (IR (KBr): 1541 cm ^-1 ). Hereinafter this complex is referred to as complex C.

Comparative Example 1 A glass pressure resistant reactor having an internal volume of 150 mL equipped with a thermometer and a stirrer was charged with the complex A synthesized in Reference Example 1 and 60 mL of dry toluene under nitrogen and mixed and stirred. After adjusting the stirring speed to 1200 rpm, a toluene solution of methylaluminoxane was introduced with nitrogen, and mixed and stirred at 3
I went for 0 minutes.

Next, the reaction vessel was heated to 80 ° C., ethylene gas was blown into the reaction vessel so that the pressure in the reaction vessel became 5 kg / cm ^2, and the trimerization reaction of ethylene was started. Thereafter, the introduction was continued so as to maintain the above pressure, and the reaction was carried out for 30 minutes while maintaining these reaction conditions. afterwards,
The reaction was stopped by deactivating the catalyst by pouring water into the reaction vessel with nitrogen.

The reaction vessel 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 reaction conditions and results are shown in Tables 1 and 2.

Comparative Example 2 In a pressure resistant reaction vessel made of glass having an internal volume of 150 mL equipped with a thermometer and a stirrer, the complex A synthesized in Reference Example 1 and 60 mL of dry toluene were put under nitrogen and mixed and stirred. After adjusting the stirring speed to 1200 rpm, a solution obtained by mixing triisobutylaluminum and methylaluminoxane in toluene was introduced with nitrogen, and the mixture was stirred for 30 minutes.

Next, the reaction vessel was heated to 80 ° C., ethylene gas was blown into the reaction vessel so that the pressure in the reaction vessel became 5 kg / cm ^2, and the trimerization reaction of ethylene was started. Thereafter, the introduction was continued so as to maintain the above pressure, and the reaction was carried out for 30 minutes while maintaining these reaction conditions. afterwards,
The reaction was stopped by deactivating the catalyst by pouring water into the reaction vessel with nitrogen.

The reaction vessel 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 reaction conditions and results are shown in Tables 1 and 2.

Examples 1 to 4 In a glass pressure resistant reaction vessel having an internal volume of 150 mL equipped with a thermometer and a stirrer, under nitrogen, a predetermined amount of the organometallic complex shown in Table 1 (synthesized in Reference Examples 1 to 3) was used. Complex A, Complex B
Alternatively, the complex C), 60 mL of dried toluene, and alkylaluminoxane and germanium tetrachloride or alkylaluminoxane, an alkyl group-containing compound and germanium tetrachloride were added, and the mixture was stirred at 1200 rpm for 30 minutes.

Then, the reaction vessel was heated to 80 ° C., the stirring rate was kept at 1200 rpm, and the pressure in the reaction vessel was set to 5 k.
Ethylene gas was blown in so that the g / cm ² was obtained, and the trimerization reaction of ethylene was started. Thereafter, the introduction was continued so as to maintain the above pressure, and the reaction was carried out for 30 minutes while maintaining these reaction conditions. Then, the reaction was stopped by depressurizing water with nitrogen into the reaction vessel to deactivate the catalyst.

The reaction vessel 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 reaction conditions and results are shown in Tables 1 and 2.

[0058]

[Table 1]

[Table 2]

According to the present invention, a halogenated inorganic compound, an organometallic complex in which a neutral polydentate ligand having a tripod structure is coordinated, an alkylaluminoxane, or a halogenated inorganic compound is used. The ethylene trimerization catalyst comprising the organometallic complex, the alkylaluminoxane and the alkyl group-containing compound is stable and easy to handle, and when it is used, 1-hexene can be produced from ethylene efficiently and highly selectively. be able to.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 10/02 C08F 10/02 F term (reference) 4G069 AA06 AA08 BA21B BA27A BA27B BB08A BB08B BC16A BC16B BC23B BC57A BC58B BD02A BD02B BE01B BE13B BE46B CB47 4H039 CA20 CL19 4J028 AA01A AB00A AB01A AC01A AC09A AC27A AC38A AC41A AC42A AC44A AC45A AC46A AC47A AC48A AC49A AC50A BA01B BA02B BB01B BB02B BC01B BC05B BC06B BC09B BC15B BC19B BC24B BC25B CA13C CA14C CA16C CA17C CA19C CA20C CA52C EB02 FA06 FA07 GB01

Claims (8)

[Claims] 1. The following general formula (1) AMB _n (1) (wherein A is a neutral polydentate ligand having a tripod structure, and M is a transition metal of Groups 3 to 10 of the periodic table). Atom and B represent at least one selected from the group consisting of hydrogen atom, halogen atom, and linear or branched alkyl group having 1 to 10 carbon atoms, and n represents an integer equal to the valence of M.) An ethylene trimerization catalyst comprising an organometallic complex coordinated with a neutral polydentate ligand having a tripod structure, an alkylaluminoxane, and a halogenated inorganic compound. 2. The following general formula (1) AMB _n (1) (wherein A is a neutral polydentate ligand having a tripod structure, and M is a transition metal of Groups 3 to 10 of the periodic table). Atom and B represent at least one selected from the group consisting of hydrogen atom, halogen atom, and linear or branched alkyl group having 1 to 10 carbon atoms, and n represents an integer equal to the valence of M.) An ethylene trimerization catalyst comprising an organometallic complex coordinated with a neutral polydentate ligand having a tripod structure, an alkylaluminoxane, a compound containing an alkyl group, and a halogenated inorganic compound. 3. A neutral polydentate ligand having a tripod structure,
The following general formula (2): (In the formula, j, k, and m are each independently an integer of 0 to 6. D ¹ is each independently a divalent hydrocarbon group which may have a substituent, and L ¹ is each independently. Then periodic table 1
It represents a substituent containing a group 4, group 15, group 16 or group 17 element. G ¹ is carbon or silicon, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms.
Represents an aryl group. ) Or the following general formula (3): (In the formula, a, b and c are each independently an integer of 0 to 6 and u is an integer of 0 or 1. D ² is each independently a divalent group which may have a substituent. Hydrocarbon group of L
Each ² independently represents a substituent containing an element of Group 14, Group 15, Group 16 or Group 17 of the periodic table. G ² represents a nitrogen atom or a phosphorus atom, and R ² represents an oxygen atom or a sulfur atom. 3.) The ethylene trimerization catalyst according to claim 1 or 2, which is a tridentate ligand represented by the formula (1). 4. A neutral polydentate ligand having a tripod structure is f
The ethylene trimerization catalyst according to any one of claims 1 to 3, wherein an organometallic complex having a transition metal element of Group 3 to Group 10 of the periodic table coordinated with the axial is used. 5. An alkylaluminoxane represented by the following formula (4) and / or (5) [Chemical 4] (Here, R ³ may be the same or different from each other,
A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
q is an integer of 2 to 60. ) Claims 1-4 represented by
The ethylene trimerization catalyst described in 1. 6. An alkyl group-containing compound has the following general formula (6) R _p EY _q (6) (wherein p is 0 <p ≦ 3 and q is 0 ≦ q <3, and p + q is 1 to 3. E represents an atom of groups 1 to 3 of the periodic table excluding hydrogen or an atom of groups 11 to 13 of the periodic table, and R is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms. 1 or more types, Y is a hydrogen atom and has 1 to 1 carbon atoms.
It represents at least one selected from the group consisting of 10 alkoxide groups, aryl groups having 6 to 10 carbon atoms, and halogen atoms. 6. The ethylene trimerization catalyst according to claim 1, which is a compound represented by the formula (1). 7. A halogenated inorganic compound is represented by the following general formula (7) ZX _h (7) (wherein Z is an atom of Group 1 or 2 of the periodic table or 13 of the periodic table).
Represents a group-15 atom, and X represents a halogen atom. X
The number h of represents a natural number equal to the valence of Z. 7. The ethylene trimerization catalyst according to claim 1, which is a compound represented by the formula (1). 8. A method for trimerizing ethylene, which comprises trimerizing ethylene in the presence of the catalyst for trimerizing ethylene according to claim 1.