JP2000212212A - Ethylene trimerization catalyst and trimerization of ethylene in the presence of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene trimerization catalyst used to produce 1-hexene from ethylene in high selectivity at good efficiency by using at least three components of a chromium complex coordinated with neutral polydentate ligands, an alkyl metal compound, and a modified clay mineral. SOLUTION: The chromium complex used is desirably a complex represented by the formula: ACrBn (wherein A is a neutral polydentate ligand; (n) is 1-3; and B is desirably a carbonyl, a 1-10C hydrocarbon group, a halogen, an amino, or a thioalkoxide. The neutral polydentate ligand is desirably the one having a tripod structure. The modified clay compound is desirably the reaction product of a clay mineral with at least one salt selected from among a protonate of an amine compound, a protonate of a phosphine compound, a phosphonium salt, an oxonium salt, a sulfonium salt, a carbonium salt, a silver salt, and a ferrocenium salt.

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 a modified clay having a neutral polydentate ligand coordinated thereto. It has been found that when an ethylene trimerization catalyst comprising at least three components of a compound is used, the ethylene trimerization reaction proceeds with high activity, and 1-hexene is produced with high selectivity, thereby completing the present invention.

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 modified clay compound, and ethylene trimerization using the catalyst. About the method.

[0007]

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

[0008] In the present invention, a modified clay compound is used as one component constituting the ethylene trimerization catalyst. The modified clay compound is at least one salt selected from the group consisting of a protic acid salt of a clay compound and an amine compound and a protic acid salt of a phosphine compound, a phosphonium salt, an oxonium salt, a sulfonium salt, a carbonium salt, a silver salt or a ferrocenium salt. The reaction product with is preferred.

Here, the clay compound is generally a tetrahedron formed by coordinating oxygen ions with silicon ions and an octahedron formed by coordinating oxygen or hydroxide ions with ions of aluminum, magnesium or iron. It is an inorganic polymer compound composed of The skeletal structure of many clay compounds is not electrically neutral and has a positive or negative charge on the surface. Cations are provided between the layers to compensate for this negative charge, and the interlayer cations can be ion-exchanged with other cations. For this reason, the amount of interlayer cations is called cation exchange capacity (CEC) and is represented by the number of milliequivalents per 100 g of clay (meq). The CEC varies depending on the clay, but according to the second edition of the Clay Handbook (edited by The Clay Society of Japan, published by Gihodo Shuppan Co., Ltd.), kaolinite: 3 to 15 meq / 100 g, halloysite: 5 to 4
0 meq / 100 g, montmorillonite: 80 to 150
meq / 100g, illite: 10-40 meq / 10
0 g, vermiculite: 100 to 150 meq / 10
0 g, chlorite: 10 to 40 meq / 100 g, sepiolite and attapulgite: 20 to 30 meq / 100
g.

The clay compound used in the present invention is:
A clay compound having a negative charge on the surface of the clay compound and having a cation exchange ability. Specifically, although not particularly limited, for example, kaolinites, dickite, kaolin compounds such as halloysite, montmorillonite, hectorite, beidellite, saponite, teniolite, smectites such as sauconite, muscovite, paragonite , Illites and the like, micalites, margarites, brittle mica such as clintite, chlorites such as donbasite, coucheite, clinochlore, sepiolite and palygorskite. These clay compounds exist naturally, but can be obtained with less impurities by artificial synthesis. In the present invention, the clay compound means the natural clay compound shown here and the clay compound obtained by artificial synthesis, and these can be used.

In the present invention, examples of the salt to be reacted with the clay compound include a protonic acid salt of an amine compound and a protonic acid salt of a phosphine compound, a phosphonium salt, an oxonium salt, a sulfonium salt, a carbonium salt, a silver salt or a ferrocenium salt. Can be

Here, the amine salt used as a protonic acid salt of the amine compound is not particularly limited. For example, methylamine hydrochloride, ethylamine hydrochloride, butylamine hydrochloride, s-butylamine hydrochloride, t
-Butylamine hydrochloride, hexylamine hydrochloride, 2-aminoheptane hydrochloride, 3-aminoheptane hydrochloride, heptylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, octylamine hydrochloride Salts, t-octylamine hydrochloride, nonylamine hydrochloride, decylamine hydrochloride, undecylamine hydrochloride,
Dodecylamine hydrochloride, tridecylamine hydrochloride, 1-
Tetradecylamine hydrochloride, pentadecylamine hydrochloride, 1-hexadecylamine hydrochloride, octadecylamine hydrochloride, oleylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, cyclohexanemethylamine hydrochloride, 2-methylcyclohexyl Amine hydrochloride, 4-methylcyclohexylamine hydrochloride,
2,3-dimethylcyclohexylamine hydrochloride, cyclododecylamine hydrochloride, 2- (1-cyclohexenyl)
Proton acid salts of aliphatic primary amines such as ethylamine hydrochloride and geranylamine hydrochloride, dimethylamine hydrochloride,
Diethylamine hydrochloride, dibutylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride,
Bis (2-ethylhexyl) amine hydrochloride, dioctylamine hydrochloride, didecylamine hydrochloride, didodecylamine hydrochloride, ditetradecylamine hydrochloride, dihexadecylamine hydrochloride, dioctadecylamine hydrochloride, dioleylamine hydrochloride, Protons of aliphatic secondary amines such as N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, Nt-butylcyclohexylamine hydrochloride, N-allylcyclohexylamine hydrochloride Acid salts, N, N-dimethylbutylamine hydrochloride, N, N-dimethylhexylamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine Hydrochloride, N, N
-Dimethyltetradecylamine hydrochloride, N, N-dimethylhexadecylamine hydrochloride, N, N-dimethyloctadecylamine hydrochloride, N, N-dioctylmethylamine hydrochloride, N, N-diundecylmethylamine hydrochloride,
N, N-didodecylmethylamine hydrochloride, N, N-ditetradecylmethylamine hydrochloride, N, N-dihexadecylmethylamine hydrochloride, N, N-dioctadecylmethylamine hydrochloride, N, N- Dioleylmethylamine hydrochloride, triethylamine hydrochloride, tributylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecylamine hydrochloride, N, Proton acid salts of aliphatic tertiary amines such as N-dimethylcyclohexylamine hydrochloride and N, N-diethylcyclohexylamine hydrochloride are exemplified.

Also, pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3-methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride Salt, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine hydrochloride, 2,2,6,6-tetramethylpiperidine hydrochloride,
Aliphatic heterocyclic such as 1-methylpyrrolidine hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpiperidine hydrochloride, 1,2,2,6,6-pentamethylpiperidine hydrochloride Proton acid salts of amines are mentioned.

Further, aniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5-dimethyl Aniline hydrochloride,
2,6-dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-
Ethyl aniline hydrochloride, 3-ethyl aniline hydrochloride, 4
-Ethylaniline hydrochloride, 6-ethyl-o-toluidine hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-t-butylaniline hydrochloride, 4-butylaniline hydrochloride, 4-s- Butylaniline hydrochloride, 4-t-butylaniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl-6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, Chloroaniline hydrochloride, 2-bromoaniline hydrochloride, 3-bromoaniline hydrochloride, 4-
Bromoaniline hydrochloride, o-anisidine hydrochloride, m-anisidine hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2- Aminonaphthalene hydrochloride, 1-aminofluorene hydrochloride, 2-aminofluorene hydrochloride, 3-aminofluorene hydrochloride,
4-aminofluorene hydrochloride, 5-aminoindane hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N-methyl-o-toluidine hydrochloride, N-methyl-m-toluidine hydrochloride, N- Methyl-p-toluidine hydrochloride, N-ethyl-o-toluidine hydrochloride, N-
Ethyl-m-toluidine hydrochloride, N-ethyl-p-toluidine hydrochloride, N-allyl-o-toluidine hydrochloride, N
-Allyl-m-toluidine hydrochloride, N-allyl-p-toluidine hydrochloride, N-propyl-o-toluidine hydrochloride, N-propyl-m-toluidine hydrochloride, N-propyl-p-toluidine hydrochloride, N , 2,3-Trimethylaniline hydrochloride, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trimethylaniline hydrochloride, N, 2
6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride, N, 3,5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N-methyl-3-ethylaniline hydrochloride N-methyl-4-ethylaniline hydrochloride, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4-isopropylaniline hydrochloride, N- Methyl-2-t-butylaniline hydrochloride, N-
Methyl-4-butylaniline hydrochloride, N-methyl-4-
s-butylaniline hydrochloride, N-methyl-4-t-butylaniline hydrochloride, N-methyl-2,6-diethylaniline hydrochloride, N-methyl-2-isopropyl-6-methylaniline hydrochloride, N- Methyl-p-anisidine hydrochloride, N-ethyl-p-anisidine hydrochloride, N, N-dimethylaniline hydrochloride, N, N-diethylaniline hydrochloride, N, N-dibutylaniline hydrochloride, diphenylmethylamine hydrochloride , Triphenylamine hydrochloride, N, N-
Dimethyl-o-toluidine hydrochloride, N, N-dimethyl-
m-toluidine hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, N, N, 2,3-tetramethylaniline hydrochloride, N, N, 2,4-tetramethylaniline hydrochloride,
N, N, 2,5-tetramethylaniline hydrochloride, N,
N, 2,6-tetramethylaniline hydrochloride, N, N,
3,4-tetramethylaniline hydrochloride, N, N, 3,5
-Tetramethylaniline hydrochloride, N, N-dimethyl-2
-Ethylaniline hydrochloride, N, N-dimethyl-3-ethylaniline hydrochloride, N, N-dimethyl-4-ethylaniline hydrochloride, N, N-dimethyl-6-ethyl-o-toluidine hydrochloride, N-dimethyl-2-isopropylaniline hydrochloride, N, N-dimethyl-4-isopropylaniline hydrochloride, N, N-dimethyl-2-t-butylaniline hydrochloride, N, N-dimethyl-4-s-butyl Aniline hydrochloride, N, N-dimethyl-4-t-butylaniline hydrochloride, N, N-dimethyl-2,6-diethylaniline hydrochloride, N, N-dimethyl-2-isopropyl-6-methylaniline hydrochloride , N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl-4-chloroaniline hydrochloride, N, N-dimethyl 2-bromoaniline hydrochloride,
N, N-dimethyl-3-bromoaniline hydrochloride, N, N
-Dimethyl-4-bromoaniline hydrochloride, N, N-dimethyl-o-anisidine hydrochloride, N, N-dimethyl-m-
Anisidine hydrochloride, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-phenetidine hydrochloride,
N, N-dimethyl-m-phenetidine hydrochloride, N, N-
Dimethyl-p-phenetidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2
-Aminonaphthalene hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl-2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl -4-aminofluorene hydrochloride, N, N-dimethyl-5-aminoindan hydrochloride, N, N-dimethyl-2-aminobiphenyl hydrochloride,
N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N
Proton acid salts of aromatic amines such as N-dimethyl-p-trimethylsilylaniline hydrochloride, pyridine hydrochloride, 2-methylpyridine hydrochloride, 3-methylpyridine hydrochloride, 4-methylpyridine hydrochloride, quinoline hydrochloride, Examples include protonic acid salts of heterocyclic aromatic amines such as isoquinoline hydrochloride.

Further, the one usually used as a protonic acid salt of a phosphine compound is not particularly limited, and examples thereof include triphenylphosphine hydrobromide. What is usually used as the phosphonium salt is not particularly limited, and examples thereof include tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and tetraphenylphosphonium iodide. The oxonium salt is not particularly limited, but includes, for example, triethyloxonium chloride and the like. The sulfonium salts are not particularly limited,
For example, trimethylsulfonium iodide and the like can be mentioned. The carbonium salt is not particularly limited, for example, triphenylmethyl chloride,
Triphenylmethyl bromide and the like. Although it does not specifically limit as a silver salt, For example, silver chloride, silver bromide, silver iodide, etc. are mentioned. The ferrocenium salt is not particularly limited, for example,
Ferrocenium chloride, decamethylferrocenium chloride and the like can be mentioned. Of these, a protonic acid salt of an amine compound is preferably used from the viewpoints of activity and availability.

The modified clay compound used in the present invention can be prepared by contacting the above-mentioned clay compound with a salt in a solvent. The reaction conditions for preparing the modified clay compound are not particularly limited.

The reaction amount ratio between the clay compound and the salt is not particularly limited, but it is preferable to react a cation present in the clay compound with an equivalent or more of the salt. One of the above clay compounds may be used alone, or a plurality of them may be mixed. One of the salts may be used alone, or a plurality of salts may be mixed. Water or a polar organic solvent is used as a reaction solvent used in the preparation. The polar organic solvent is not particularly limited, but includes, for example, alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, N, N
Amides such as dimethylformamide, sulfoxides such as dimethylsulfoxide, and halogenated hydrocarbons such as methylene chloride. Of these, water and alcohols are preferably used.

The protonic acid salt of an amine compound used in the present invention is synthesized by reacting an amine compound with a protonic acid. The protonic acid used in synthesizing the protonic acid salt is not particularly limited, and examples thereof include hydrogen chloride, hydrogen fluoride, hydrogen bromide, hydrogen iodide, and sulfuric acid. Examples of the amine compound include, but are not limited to, methylamine, ethylamine, butylamine, s-butylamine, t-butylamine, hexylamine, 2-aminoheptane, 3-aminoheptane, heptylamine, and the like. , 5
-Dimethylhexylamine, 1-methylheptylamine, octylamine, t-octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, 1-tetradecylamine, pentadecylamine, 1-hexadecylamine, Octadecylamine, oleylamine, cyclohexylamine, cycloheptylamine, cyclohexanemethylamine, 2
-Methylcyclohexylamine, 4-methylcyclohexylamine, 2,3-dimethylcyclohexylamine,
Cyclododecylamine, 2- (1-cyclohexenyl)
Aliphatic primary amines such as ethylamine and geranylamine, dimethylamine, diethylamine, dibutylamine, N-methylhexylamine, dihexylamine, bis (2-ethylhexyl) amine, dioctylamine;
Didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine,
Dioleylamine, N-methylcyclohexylamine,
Aliphatic secondary amines such as N-ethylcyclohexylamine, N-isopropylcyclohexylamine, Nt-butylcyclohexylamine, N-allylcyclohexylamine, N, N-dimethylbutylamine, N, N-dimethylhexylamine, N , N-dimethyloctylamine, N, N-dimethylundecylamine, N, N-dimethyldodecylamine, N, N-dimethyltetradecylamine, N, N-dimethylhexadecylamine, N, N-
Dimethyloctadecylamine, N, N-dioctylmethylamine, N, N-diundecylmethylamine, N, N
-Didodecylmethylamine, N, N-ditetradecylmethylamine, N, N-dihexadecylmethylamine,
N, N-dioctadecylmethylamine, N, N-dioleylmethylamine, triethylamine, tributylamine, trihexylamine, triisooctylamine, trioctylamine, triisodecylamine, tridodecylamine, N, N-dimethyl Cyclohexylamine, N,
And aliphatic tertiary amines such as N-diethylcyclohexylamine.

Further, pyrrolidine, piperidine, 2,5-
Dimethylpyrrolidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-
Dimethyl piperidine, 2-ethylpiperidine, 2,2
6,6-tetramethylpiperidine, 1-methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine, 1
And aliphatic heterocyclic amines such as -butylpiperidine and 1,2,2,6,6-pentamethylpiperidine.

Further, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline,
4-dimethylaniline, 2,5-dimethylaniline,
2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-ethylaniline,
3-ethylaniline, 4-ethylaniline, 6-ethyl-o-toluidine, 2-isopropylaniline, 4-isopropylaniline, 2-t-butylaniline, 4-butylaniline, 4-s-butylaniline, 4-t -Butylaniline, 2,6-diethylaniline, 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-aminoindane,
2-aminobiphenyl, 4-aminobiphenyl, 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, 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-butylaniline, N-methyl-4-s-butyl Aniline, N-
Methyl-4-t-butylaniline, N-methyl-2,6
-Diethylaniline, N-methyl-2-isopropyl-
6-methylaniline, N-methyl-p-anisidine, N
-Ethyl-p-anisidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dibutylaniline, diphenylmethylamine, triphenylamine,
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, 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
N-dimethyl-2-isopropylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-2-t-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-amino Fluorene, N, N
-Dimethyl-5-aminoindan, N, N-dimethyl-
Aromatic amines such as 2-aminobiphenyl, N, N-dimethyl-4-aminobiphenyl, N, N-dimethyl-p-trimethylsilylaniline, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine And heterocyclic aromatic amines such as quinoline and isoquinoline. In addition, the protonic acid salt of the amine compound to be reacted with the clay compound may be one isolated by reacting the amine compound and the protonic acid in advance, or may be formed in a reaction solvent when reacting with the clay compound. Is also good.

In the present invention, the amount of the modified clay compound used is not particularly limited.
0.01 to 10000 kg, preferably 0.1 to 1000 kg, more preferably 1 to 500 mol per mol.
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 (3)

[0024]

Embedded image

(Where a, b, and c are 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 (4)

[0026]

Embedded image

(Where d, e, and f are independent 1
6 to an integer. D ² is independently a divalent hydrocarbon group which may have a substituent, and L ² is independently a hetero element group which may have a substituent. Polydentate ligand having a structure and the following general formula (5)

[0028]

Embedded image

Wherein g and h are each 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.

In the above general formulas (3), (4) and (5), D ¹ , D ² and D ³ are not particularly restricted but include, for example, alkylene, cycloalkylene, phenylene, Examples include a tolylene group and a xylylene group. 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 (3), (4) and (5), the hetero element groups represented by L ¹ , L ² and L ³ are not particularly restricted but include, for example, a methoxy group and an ethoxy group. , Alkoxy groups such as propoxy group and butoxy group, aryloxy groups such as phenoxy group and 2,6-dimethylphenoxy group, alkylthio groups such as methylthio group, ethylthio group, propylthio group and butylthio group, phenylthio group and tolylthio. Arylthio groups such as a dimethylamino group, a diethylamino group, a dialkylamino group such as a bis (trimethylsilyl) amino group, a diarylamino group such as a diphenylamino group; an alkylarylamino group such as a methylphenyl group; Dialkyl phosphino groups such as a fino group and a diethyl phosphino group; Diaryl phosphino groups such as ino group and ditolyl phosphino group; and alkylaryl phosphino groups such as methylphenyl phosphino group.

In the general formulas (3) and (5),
The heterocyclic compounds represented by L ¹ and L ³ are not particularly limited, but include, for example, a furyl group, a benzofuryl group, a thienyl group, a benzothienyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, Examples include an imidazolyl group, a benzimidazolyl group, an indazolyl group, a quinolyl group, an isoquinolyl group, an oxazolyl group, and a thiazole group. 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.

G in the general formula (3) is not particularly limited, but may be, for example, methane, ethane, propane, butane, hydroxymethane, methylsilane, phenylsilane, amine, amine oxide, phosphine, phosphine oxide. And the like.

The generally used polydentate ligand having a tripod-type structure represented by the above general formula (3) is not particularly limited. Examples thereof include tris (methoxymethyl) methane and 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, 1,1,1-trifurylethane,
Oxygen-containing polydentate ligands such as triflylamine, trifurylphosphine, and trifurylphosphine oxide;
1-tris (methylthiomethyl) ethane, 1,1,1-
Tris (butylthiomethyl) ethane, 1,1,1-tris (phenylthiomethyl) ethane, tris (thienyl)
Sulfur-containing polydentate ligands such as methane, 1,1,1-tris (dimethylaminomethyl) ethane, 1,1,1-tris (diphenylaminomethyl) ethane, tris (pyrazolyl) methane, tris (3,3) 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, tris (2-pyridyl) phosphine oxide, tris (2-
Nitrogen-containing polydentate ligands such as pyridyl) hydroxymethane and tris (1-imidazolyl) methane, 1,1,1-tris (diphenylphosphinomethyl) ethane, 1,1,1
-Tris (dimethylphosphinomethyl) ethane, 1,
Phosphorus-containing polydentate ligands such as 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. For example, phosphorus-containing bis (dimethylphosphinoethyl) methylphosphine, bis (diphenylphosphinoethyl) phenylphosphine, etc. 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 formula (1), the hydrocarbon group having 1 to 10 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, 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) methylphosphine chromium 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 at the time of 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 the 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 view 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 10,000 equivalents, preferably 3 to 3000 equivalents, more preferably 5 to 2000 equivalents, per mol of the chromium complex.
Is equivalent.

The ethylene trimerization catalyst comprising a chromium complex, an alkyl metal compound and a modified clay compound coordinated with a neutral polydentate ligand according to the present invention comprises the above chromium complex, alkyl metal compound and modified clay compound. It can be prepared by contacting the raw materials in a solvent. The contact method is not particularly limited.

The concentration of the chromium complex in preparing this 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 chromium complex, the alkyl metal compound and the modified clay compound are brought into contact is -10.
The temperature is 0 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 the above-mentioned catalyst comprising a chromium complex, an alkyl metal compound and a modified clay compound. Although the contacting method is not particularly limited, for example, in the presence of ethylene as a trimerization reaction raw material, a chromium complex,
Contacting an alkyl metal compound and a modified clay compound,
A method of initiating a trimerization reaction simultaneously with the contact, or a method of bringing a chromium complex, an alkyl metal compound and a modified clay compound 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 modified clay compound, and ethylene are simultaneously and independently introduced into the reaction system. Introducing a complex, a modified clay compound and ethylene, (3) introducing an alkyl metal compound and ethylene into a suspension containing a chromium complex and a modified clay compound, and (4) a suspension containing an alkyl metal compound and a modified clay compound. A trimerization reaction can be performed by a method of introducing a chromium complex and ethylene into the solution, and (5) introducing an alkyl metal compound, a modified clay compound and ethylene into a solution containing the chromium complex. In the latter case, (1) an alkyl metal compound is introduced into a suspension containing a chromium complex and a modified clay compound, and (2) a chromium complex is introduced into a suspension containing an alkyl metal compound and a modified clay compound. And (3) introducing a chromium complex and a modified clay compound into a solution containing an alkyl metal compound, and (4) introducing a modified clay compound and an alkyl metal compound into a solution containing a chromium complex. To effect a trimerization reaction. In addition,
The order of mixing these raw materials is not particularly limited.

In the present invention, if necessary, a catalyst comprising a chromium complex, an alkyl metal compound and a modified clay compound coordinated with a neutral polydentate ligand is irradiated with light to carry out ethylene trimerization. May go. 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, but 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 artificial light sources may be used as the light source. However, artificial light sources are 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 irradiation time of the light is not particularly limited, but it may be applied to the above-mentioned catalyst comprising a chromium complex, an alkyl metal compound and a modified clay compound, or directly to the ethylene trimerization reaction system. Irradiation may be performed. 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.

[0064]

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 is described in 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 6.3 g (40 mmol) of dimethylaniline hydrochloride was added to 5
This solution was dissolved in 0 ml of water, and 20 g of hectorite [trade name: Laponite RD, manufactured by Nippon Silica Industry Co., Ltd.] was used.
Was added to 150 ml of water containing. This suspension is added at room temperature for 2 hours.
After stirring for 4 hours and removing the supernatant, the mixture was washed with water and ethanol. Thereafter, the mixture was dried at room temperature at 10 ^-5 Torr for 24 hours, and was modified with a modified clay compound (hereinafter, referred to as modified clay B).
I got

Example 1 6.9 of the complex A synthesized in Reference Example 1 was placed in a 150-ml glass pressure-resistant reaction vessel equipped with a thermometer and a stirrer.
mg, 0.154 mol / l triisobutylaluminum / 2.1 ml of cyclohexane solution, 0.20 g of modified clay B synthesized in Reference Example 2, and 80 ml of dried toluene
was added and mixed and stirred.

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, and an ultra-high pressure mercury lamp (500 W) manufactured by Ushio Inc.
Was used to irradiate light from the outside to initiate a trimerization reaction of ethylene. 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, and a reaction was carried out 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 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 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 In a Schlenk tube, 0.20 g of modified clay B, 0.154 m
An ol / 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 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 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.

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

[0075]

[Table 1]

[0076]

According to the present invention, an ethylene trimerization catalyst comprising at least three components of a chromium complex to which a neutral polydentate ligand is coordinated, an alkyl metal compound and a modified clay compound is used. Can efficiently and highly selectively produce 1-hexene.

Continued on front page F-term (reference) 4J028 AA01A AB00A AC42A BA00A BA01B BB00A BB00B BB01B BC01B BC05B BC06B BC07B BC09B BC12B BC13B BC15B BC16B BC17B BC18B BC19B BC24B BC27B CA30C CB61C CB81CB01G

Claims (7)

[Claims] (1) a chromium complex coordinated with a neutral polydentate ligand,
At least 3 of an alkyl metal compound and a modified clay compound
An ethylene trimerization catalyst consisting of components. 2. The modified clay compound is selected from the group consisting of a protonic acid salt of a clay compound and an amine compound and a protonic acid salt of a phosphine compound, a phosphonium salt, an oxonium salt, a sulfonium salt, a carbonium salt, a silver salt or a ferrocenium salt. The ethylene trimerization catalyst according to claim 1, which is a reaction product with one or more salts. 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.