JP2001149788A - Trimerizing catalyst for ethylene and trimerizing method for ethylene using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture 1-hexene from ethylene efficiently and at high selectively. SOLUTION: The catalyst composed of a transition metal complex in which a ligand consisting of a benzene ring substituted with an amino group is coordinated and an alkyl metal compound is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 from E) with high selectivity from ethylene, and a method for ethylene trimerization using the same.

[0002]

2. Description of the Related Art In a process for obtaining 1-hexene by trimerizing ethylene, for example, JP-A-62-265237 discloses a catalyst system comprising a chromium compound, polyhydrocarbyl aluminum oxide and a donor ligand. Have been. JP-A-6-239920 discloses a catalyst system comprising a chromium compound, a pyrrole-containing compound, a metal alkyl compound and a halide.
Japanese Patent Application Publication No. JP-A-2003-115139 discloses a catalyst system comprising a chromium compound, a metal alkyl compound and an acid amide or imide compound.

JP-A-6-298673 discloses a catalyst comprising an aluminoxane and a coordination complex of chromium salt with phosphine, arsine and / or stibine which is a polydentate ligand. Further, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. Hei 10-231317 discloses a catalyst comprising an aluminum compound and a chlorine complex or an alkyl complex of chromium coordinated with a specific nitrogen ligand.
A catalyst comprising a chromium complex coordinated with a cyclic polyamine or hydrotris (pyrazolyl) borate and an alkylaluminum compound is disclosed.

[0004]

However, Japanese Patent Application Laid-Open No. Sho 62-62
The method described in Japanese Patent Publication No. 265237 has a disadvantage that a large amount of polyethylene is by-produced simultaneously with 1-hexene. Also,
Since polyhydrocarbyl aluminum oxide (also referred to as aluminoxane), which is a component of the catalyst, is a polymer obtained by reacting alkyl aluminum with water, it is difficult to synthesize polyhydrocarbyl aluminum oxide having a certain quality. Therefore, there is a problem that a reaction with good reproducibility cannot be performed even in the ethylene trimerization reaction.

[0005] The method described in Japanese Patent Application Laid-Open No. 6-239920 has little polyethylene by-product and is considerably improved in this respect. However, the pyrrole-containing compound, which is a component of the catalyst, is a substance that is extremely unstable with respect to air, and is liable to be colored and deteriorated. Therefore, not only is it difficult to handle, but it is not sufficient as an industrial catalyst because it requires a treatment for removing coloring components or a new device after completion of the reaction. Also, Japanese Patent Application Laid-Open No. 8-597
In the method described in Japanese Patent Publication No. 32, it is necessary to use a specific imide compound, that is, maleimide, in order to obtain activity among acid amide or imide compounds which are constituent components of the catalyst. Since maleimide has low solubility, preparation of the catalyst is complicated, and maleimide is not only difficult to obtain but also expensive, and has a problem in terms of economy.

On the other hand, the method described in Japanese Patent Application Laid-Open No. 6-298673 has a problem that an aluminoxane which cannot be synthesized with good reproducibility must be used. Further, the method described in JP-A-10-7712 has a problem that the catalytic activity is low. Further, the method described in JP-A-10-231317 has the disadvantage that not only 1-hexene is produced more than polyethylene but also the selectivity of 1-hexene in the oligomer is low.

The present invention has been made in view of the above problems, and an object of the present invention is to produce 1-hexene useful as a raw material comonomer of LLDPE from ethylene in a highly selective manner.
Moreover, it is an object of the present invention to provide an ethylene trimerization catalyst which is easy to handle and a method for ethylene trimerization using the catalyst.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the ethylene trimerization catalyst comprising a specific transition metal complex and an alkyl metal compound is stable and can be handled. It was found that 1-hexene was produced with high selectivity by using this, and the present invention was completed.

That is, the present invention relates to an ethylene trimerization catalyst comprising a transition metal complex coordinated with a ligand comprising a benzene ring substituted with an amino group and an alkyl metal compound, and a method for trimerizing ethylene using the same. .

[0010]

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

In the present invention, a transition metal complex in which a ligand comprising a benzene ring substituted with an amino group is coordinated is used as one component constituting the ethylene trimerization catalyst. Specific examples include the following general formula (1): AM (CO) _n B _3-n (1) (where A is a ligand comprising a benzene ring substituted with an amino group. A group 10 transition metal, n is an integer of 0 to 3, B is hydrogen, a halogen atom, an arene ligand, an alkene ligand, an alkyne ligand, an amine ligand, an imine ligand, Amide group, imide group, nitrile ligand, isonitrile ligand, nitrosyl ligand, phosphine ligand, phosphite ligand, phosphine oxide ligand, ether ligand, sulfide ligand, sulfone ligand And a transition metal complex having a structure consisting of a benzene ring substituted with an amino group and having a structure represented by the following formula: Can be

The ligand comprising a benzene ring substituted with an amino group, which is coordinated to the transition metal complex, is not particularly limited. For example, the ligand represented by the following general formula (2)

[0013]

Embedded image

(Wherein, NR ₂ represents an amino group, wherein R is the same or independently hydrogen, C 1-10)
An alkyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a halogen atom, an aryl group having 6 to 10 carbon atoms, and
When R is other than hydrogen or a halogen atom, R is linked to each other;
A ring may be formed. Z _{1 to} Z ₅ are the same or independently represent one or more selected from the group consisting of hydrogen, amino group, alkyl group, hydroxyl group and alkoxy group. Here, when any of Z _{1 to} Z ₅ is an amino group (NR ₂ ), R
Is selected from the group of amino groups described above. ) Are mentioned as suitable ligands. The alkyl group in which R has 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. The alkenyl group having 1 to 10 carbon atoms is not particularly limited, and includes, for example, an ethenyl group, a 1-propenyl group, and a 2-propenyl group. The alkynyl group having 1 to 10 carbon atoms is not particularly limited, and includes, for example, an ethynyl group, a 1-propynyl group, and a 2-propynyl 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 aryl group having 6 to 10 carbon atoms is not particularly limited, and examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the case where Rs are connected to each other to form a ring include a pyrrolidino group and a piperidino group.

Specific examples of the ligand comprising a benzene ring substituted with an amino group represented by the general formula (1) are not particularly limited, but R has 1 to 10 carbon atoms. Examples of the alkyl group include 1,3,5-tris (dimethylamino) benzene, 1,3,5-tris (diethylamino) benzene, and 1,3,5-tris (dipropylamino) -4-hydroxybenzene. Can be The alkenyl group in which R has 1 to 10 carbon atoms is not particularly limited, but 1,3,5-tris (diethenylamino) benzene, 1,3,5-tris (di-2-propenylamino) benzene , 1,3,5-tris (di-2
-Butenylamino) -4-hydroxybenzene and the like. The alkynyl group in which R has 1 to 10 carbon atoms is not particularly limited, but includes 1,3,5-tris (diethynylamino) benzene, 1,3,5-tris (di-2-propynylamino) ) Benzene, 1,3,5-
Tris (di-2-butenylamino) -4-hydroxybenzene and the like can be mentioned. R is a halogen atom such as 1,3,5-tris (dichloroamino) benzene,
3,5-tris (dibromoamino) benzene, 1,3
5-tris (difluoroamino) -4-hydroxybenzene and the like. The aryl group in which R has 6 to 10 carbon atoms is not particularly limited.
3,5-tris (diphenylamino) benzene, 1,
3,5-tris (di-4-tolylamino) benzene,
1,3,5-tris (di-4-tolylamino) benzene and the like. Further, when Rs are connected to each other to form a ring, 1,3,5-tripyrrolidinobenzene,
Examples thereof include 1,3,5-tripiperidinobenzene and 1,3-dipiperidino-5-pyrrolidinobenzene.

Here, in M of the general formula (1), 3
The transition metals of Groups 10 to 10 are not particularly limited, but preferably, scandium, yttrium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel And the like. Among them, particularly preferred are titanium, vanadium, chromium, iron, cobalt and nickel.

Here, in B of the above general formula (1), the halogen atom is not particularly limited,
For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be given. The arene ligand is not particularly limited, and examples thereof include benzene, toluene, xylene, trimethylbenzene, hexamethylbenzene, and naphthalene. The alkene ligand is not particularly limited, but examples include ethylene, propylene, butene, hexene, and decene. The alkyne ligand is not particularly limited, but includes, for example, acetylene, phenylacetylene, diphenylacetylene and the like. Although the amine ligand is not particularly limited, for example, triethylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-
Examples thereof include dibutylaniline, diphenylmethylamine, triphenylamine, pyridine and quinoline.
The imine ligand is not particularly limited,
For example, benzophenone imine, methyl ethyl ketone imine and the like can be mentioned. The amide group is not particularly limited, and includes, for example, a dimethylamide group, a diethylamide group, a diisopropylamide group, a dioctylamide group, a didecylamide group, a didodecylamide group, a bis (trimethylsilyl) amide group, a diphenylamide group,
Examples thereof include N-methylanilide and an anilide group.
The imide group is not particularly limited, but examples include benzophenone imide. The nitrile ligand is not particularly limited, for example,
Acetonitrile or benzonitrile is exemplified.
The isonitrile ligand is not particularly limited, and examples thereof include t-butyl isonitrile and phenyl isonitrile. Although it does not specifically limit as a phosphine ligand, For example, triphenyl phosphine, tolyl phosphine, tricyclohexyl phosphine, tributyl phosphine, etc. are mentioned. Although it does not specifically limit as a phosphite ligand, For example, triphenyl phosphite, tolyl phosphite, tributyl phosphite, triethyl phosphite, etc. are mentioned. The phosphine oxide ligand is not particularly limited, and examples thereof include tributylphosphine oxide and triphenylphosphine oxide. The ether ligand is not particularly limited, but includes, for example, dimethyl ether, diethyl ether, tetrahydrofuran and the like. The sulfide ligand is not particularly limited, but examples include ethyl sulfide and butyl sulfide. The sulfone ligand is not particularly limited, but examples include dimethyl sulfone and dibutyl sulfone.
The sulfoxide ligand is not particularly limited, but includes, for example, dimethyl sulfoxide or dibutyl sulfoxide.

Specific examples of the transition metal complex represented by the above general formula (1) are not particularly limited.
When M is chromium, R is an alkyl group having 1 to 10 carbon atoms such as 1,3,5-tris (dimethylamino) benzenechromium tricarbonyl (0), 1,3,5-tris (dimethylamino) benzene Chromium (hydrido) (ethylene) carbonyl (0), 1,3,5-tris (dimethylamino) benzene chromium (hydrido) bis (benzophenone imide) (II), 1, 3, 5-tris (dimethylamino) benzene chromium (Hydrido) (benzophenoneimide) dimethylamide (II), 1,3,5-tris (dimethylamino) benzenechromium tris (dimethylamide) (III), 1,3,5-tris (dimethylamino) benzenechromium (hydride ) (Benzophenone imide) triphenylphosphine (I), 1,3,5-
Tris (dimethylamino) benzenechromium (benzophenoneimide) bis (ethylsulfide) (0), 1,
3,5-tris (dimethylamino) benzenechromium tris (ethylsulfide) (0), 1,3,5-tris (dimethylamino) benzenechromium (benzophenoneimide) (ethylsulfide) (triphenylphosphine) (I) , 1,3,5-tris (dimethylamino) benzenechromium tris (benzophenoneimide) (II
I) 1,3,5-tris (dimethylamino) benzenechromium tris (triphenylphosphine) (0),
1,3,5-tris (dimethylamino) benzenechromium trichloride (III), 1,3,5-tris (diethylamino) benzenechromium tricarbonyl (0),
1,3,5-tris (diethylamino) benzenechromium (hydride) (ethylene) carbonyl (0), 1,3
5-tris (diethylamino) benzenechromium (hydrido) bis (benzophenoneimide) (II), 1,3
5-tris (diethylamino) benzenechromium (hydrido) (benzophenonimide) dimethylamide (I
I), 1,3,5-tris (diethylamino) benzenechromium tris (dimethylamide) (III), 1,3,
5-tris (diethylamino) benzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1,3,5-tris (diethylamino) benzenechromium (benzophenoneimide) bis (ethylsulfide) (0), 1, 3,5-tris (diethylamino) benzenechromium tris (ethyl sulfide)
(0), 1,3,5-tris (diethylamino) benzenechromium (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), 1,3,5-tris (diethylamino) benzenechrometris (benzophenoneimide) ( III), 1,3,5-tris (diethylamino) benzenechrome tris (triphenylphosphine) (0), 1,3,5-tris (diethylamino) benzenechrome trichloride (III) and the like.

Examples of the alkenyl group in which R has 1 to 10 carbon atoms include 1,3,5-tris (diethenylamino) benzenechromium tricarbonyl (0) and 1,3,5-tris (diethenylamino) benzenechromium (hydrido) ( Ethylene) carbonyl (0), 1,3,5-tris (diethenylamino) benzenechromium (hydrido) bis (benzophenoneimide) (II), 1,3,5-tris (diethenylamino) benzenechromium (hydrido) (benzophenoneimide) Dimethylamide (II), 1,3,5
-Tris (diethenylamino) benzenechromium tris (dimethylamide) (III), 1,3,5-tris (diethenylamino) benzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1,3,5-tris (Diethenylamino) benzenechromium (benzophenoneimide) bis (ethylsulfide) (0), 1,3,5-tris (diethenylamino) benzenechrometris (ethylsulfide)
(0), 1,3,5-tris (diethenylamino) benzenechrome (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), 1,3,5-tris (diethenylamino) benzenechrometris (benzophenoneimide) ( III), 1,3,5-tris (diethenylamino) benzenechrome tris (triphenylphosphine) (0), 1,3,5-tris (diethenylamino) benzenechrome trichloride (II)
I), 1,3,5-tris (di-2-propenylamino) benzenechromium tricarbonyl (0), 1,3,5
-Tris (di-2-propenylamino) benzenechromium (hydrido) (ethylene) carbonyl (0), 1,3,
5-tris (di-2-propenylamino) benzenechromium (hydrido) bis (benzophenoneimide) (I
I), 1,3,5-tris (di-2-propenylamino) benzenechromium (hydrido) (benzophenoneimide) dimethylamide (II), 1,3,5-tris (di-2-propenylamino) benzenechromium Tris (dimethylamide) (III), 1,3,5-tris (di-2
-Propenylamino) benzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1,3,5-tris (di-2-propenylamino) benzenechromium (benzophenoneimide) bis (ethylsulfide) (0) , 1,3,5-tris (di-2
-Propenylamino) benzenechromium tris (ethylsulfide) (0), 1,3,5-tris (di-2-propenylamino) benzenechromium (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), 1, 3,5-tris (di-2-propenylamino) benzenechromium tris (benzophenone imide)
(III) 1,3,5-tris (di-2-propenylamino) benzenechromium tris (triphenylphosphine) (0), 1,3,5-tris (di-2-propenylamino) benzenechromium Chloride (III) and the like.

Examples of the alkynyl group in which R has 1 to 10 carbon atoms include 1,3,5-tris (diethynylamino) benzenechrome tricarbonyl (0) and 1,3,5-tris (diethynylamino) benzenechrome (Hydrido) (ethylene) carbonyl (0), 1,3,5-tris (diethynylamino) benzenechromium (hydrido) bis (benzophenoneimide) (II), 1,3,5-tris (diethynylamino) benzene Chromium (hydride) (benzophenone imide) dimethylamide (II), 1,3,5
Tris (diethynylamino) benzenechromium tris (dimethylamide) (III), 1,3,5-tris (diethynylamino) benzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1,3 , 5-Tris (diethynylamino) benzenechromium (benzophenoneimide) bis (ethylsulfide) (0), 1,3,5-tris (diethynylamino) benzenechromium tris (ethylsulfide)
(0), 1,3,5-tris (diethynylamino) benzenechromium (benzophenonimide) (ethylsulfide) triphenylphosphine (I), 1,3,5-tris (diethynylamino) benzenechromium tris ( Benzophenone imide) (III), 1,3,5-tris (diethynylamino) benzenechromium tris (triphenylphosphine) (0), 1,3,5-tris (diethynylamino) benzenechrome trichloride (II)
I), 1,3,5-tris (di-2-propynylamino) benzenechromium tricarbonyl (0), 1,3,5
-Tris (di-2-propynylamino) benzenechromium (hydride) (ethylene) carbonyl (0), 1,3,
5-tris (di-2-propynylamino) benzenechromium (hydrido) bis (benzophenoneimide) (I
I), 1,3,5-tris (di-2-propynylamino) benzenechromium (hydrido) (benzophenoneimide) dimethylamide (II), 1,3,5-tris (di-2-propynylamino) benzenechromium Tris (dimethylamide) (III), 1,3,5-tris (di-2
-Propynylamino) benzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1,3,5-tris (di-2-propynylamino) benzenechromium (benzophenoneimide) bis (ethylsulfide) (0) , 1,3,5-tris (di-2
-Propynylamino) benzenechromium tris (ethyl sulfide) (0), 1,3,5-tris (di-2-propynylamino) benzenechromium (benzophenonimide) (ethyl sulfide) triphenylphosphine (I), 1, 3,5-tris (di-2-propynylamino) benzenechromium tris (benzophenone imide)
(III) 1,3,5-tris (di-2-propynylamino) benzenechromium tris (triphenylphosphine) (0), 1,3,5-tris (di-2-propynylamino) benzenechromium Chloride (III) and the like.

When R is a halogen atom, 1,3,5-tris (dichloroamino) benzenechrome tricarbonyl (0), 1,3,5-tris (dichloroamino) benzenechrome (hydride) (ethylene) carbonyl (0) ),
1,3,5-tris (dichloroamino) benzenechromium (hydrido) bis (benzophenoneimide) (II),
1,3,5-tris (dichloroamino) benzenechromium (hydrido) (benzophenoneimide) dimethylamide (II), 1,3,5-tris (dichloroamino) benzenechrome tris (dimethylamide) (III), 1,
3,5-tris (dichloroamino) benzenechromium (hydrido) (benzophenonimide) triphenylphosphine (I), 1,3,5-tris (dichloroamino)
Benzenechrome (benzophenone imide) bis (ethylsulfide) (0), 1,3,5-tris (dichloroamino) benzenechrome tris (ethylsulfide)
(0), 1,3,5-tris (dichloroamino) benzenechromium (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), 1,3,5-tris (dichloroamino) benzenechrometris (benzophenoneimide) ) (III), 1,3,5-tris (dichloroamino) benzenechrome tris (triphenylphosphine) (0), 1,3,5-tris (dichloroamino) benzenechrome trichloride (III), 1,
3,5-tris (dibromoamino) benzenechrome tricarbonyl (0), 1,3,5-tris (dibromoamino) benzenechrome (hydrido) (ethylene) carbonyl (0), 1,3,5-tris (dibromo Amino) benzenechromium (hydrido) bis (benzophenone imide)
(II), 1,3,5-tris (dibromoamino) benzenechromium (hydrido) (benzophenonimide) dimethylamide (II), 1,3,5-tris (dibromoamino) benzenechromium tris (dimethylamide) (II
I), 1,3,5-tris (dibromoamino) benzenechromium (hydride) (benzophenoneimide) triphenylphosphine (I), 1,3,5-tris (dibromoamino) benzenechrome (benzophenoneimide) bis ( Ethyl sulfide) (0), 1,3,5-tris (dibromoamino) benzenechrome Tris (ethyl sulfide) (0), 1,3,5-tris (dibromoamino) benzenechromium (benzophenone imide) (ethyl sulfide) Triphenylphosphine (I), 1,
3,5-tris (dibromoamino) benzenechromium tris (benzophenoneimide) (III), 1,3,5-
Tris (dibromoamino) benzenechrome tris (triphenylphosphine) (0), 1,3,5-tris (dibromoamino) benzenechrome trichloride (I
II) and the like.

Examples of the aryl group in which R has 6 to 10 carbon atoms include 1,3,5-tris (diphenylamino) benzenechrome tricarbonyl (0) and 1,3,5-tris (diphenylamino) benzenechrome (hydrido ) (Ethylene) carbonyl (0), 1,3,5-tris (diphenylamino) benzenechromium (hydrido) bis (benzophenoneimide) (II), 1,3,5-tris (diphenylamino) benzenechromium (hydride) (Benzophenone imide) dimethylamide (II), 1,3,5-tris (diphenylamino) benzenechromium tris (dimethylamide) (III), 1,3,5-tris (diphenylamino) benzenechromium (hydrido) (benzophenone Imido) triphenylphosphine (I), 1,
3,5-tris (diphenylamino) benzenechromium (benzophenone imide) bis (ethyl sulfide)
(0), 1,3,5-tris (diphenylamino) benzenechromium tris (ethylsulfide) (0), 1,
3,5-tris (diphenylamino) benzenechrome (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), 1,3,5-tris (diphenylamino) benzenechrometris (benzophenoneimide) (III), 1 1,3,5-tris (diphenylamino) benzenechrome tris (triphenylphosphine) (0), 1,3,5-tris (diphenylamino) benzenechrome trichloride (III),
3,5-tris (di-4-tolylamino) benzenechromium tricarbonyl (0), 1,3,5-tris (di-4
-Tolylamino) benzenechromium (hydride) (ethylene) carbonyl (0), 1,3,5-tris (di-4-
Tolylamino) benzenechromium (hydrido) bis (benzophenoneimide) (II), 1,3,5-tris (di-4-tolylamino) benzenechromium (hydrido) (benzophenoneimide) dimethylamide (II), 1,
3,5-tris (di-4-tolylamino) benzenechromium tris (dimethylamide) (III), 1,3,5-
Tris (di-4-tolylamino) benzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1,3,5-tris (di-4-tolylamino) benzenechrome (benzophenoneimide) bis (ethylsulfide) (0), 1,3,5-tris (di-4
-Tolylamino) benzenechromium tris (ethylsulfide) (0), 1,3,5-tris (di-4-tolylamino) benzenechromium (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), 1,
3,5-tris (di-4-tolylamino) benzenechromium tris (benzophenoneimide) (III), 1,
3,5-tris (di-4-tolylamino) benzenechromium tris (triphenylphosphine) (0), 1,
3,5-tris (di-4-tolylamino) benzenechromium trichloride (III) and the like.

In the case where Rs are connected to each other to form a ring, 1,3,5-tripyrrolidinobenzenechromium tricarbonyl (0), 1,3,5-tripyrrolidinobenzenechromium (hydrido) (ethylene ) Carbonyl (0), 1,3,5-tripyrrolidinobenzene chromium (hydrido) bis (benzophenone imide) (II),
1,3,5-Tripyrrolidinobenzenechromium (hydrido) (benzophenone imide) dimethylamide (I
I), 1,3,5-Tripyrrolidinobenzenechromium tris (dimethylamide) (III), 1,3,5-Tripyrrolidinobenzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I), 1 , 3,5
-Tripyrrolidinobenzene chromium (benzophenone imide) bis (ethyl sulfide) (0), 1,3,5-tripyrrolidino benzene chrome tris (ethyl sulfide) (0), 1,3,5-tripyrrolidino benzene chrome (Benzophenone imide) (ethyl sulfide) triphenylphosphine (I), 1,3,5-tripyrrolidinobenzene chromium tris (benzophenone imide)
(III), 1,3,5-tripyrrolidinobenzenechromium tris (triphenylphosphine) (0), 1,
3,5-Tripyrrolidinobenzenechromium trichloride (III), 1,3,5-tripiperidinobenzenechromium tricarbonyl (0), 1,3,5-tripiperidinobenzenechromium (hydrido) (ethylene ) Carbonyl (0), 1,3,5-tripiperidinobenzene chromium (hydrido) bis (benzophenone imide) (II),
1,3,5-tripiperidinobenzene chromium (hydrido) (benzophenone imide) dimethylamide (I
I), 1,3,5-tripiperidinobenzenechromium tris (dimethylamide) (III), 1,3,5-tripiperidinobenzenechromium (hydrido) (benzophenoneimide) triphenylphosphine (I) , 1,3,5
-Tripiperidinobenzenechromium (benzophenone imide) bis (ethylsulfide) (0), 1,3,5-tripiperidinobenzenechromium tris (ethylsulfide) (0), 1,3,5-tripiperidi Nobenzenebenzene (benzophenone imide) (ethyl sulfide) triphenylphosphine (I), 1,3,5-tripiperidinobenzene chrome tris (benzophenone imide)
(III), 1,3,5-tripiperidinobenzenechromium tris (triphenylphosphine) (0), 1,
3,5-tripiperidinobenzene chromium trichloride (III) and the like.

The transition metal compound for forming a transition metal complex by reacting a ligand comprising a benzene ring substituted with an amino group with a transition metal compound is not particularly limited, but when the transition metal M is chromium, For example, chromium hexacarbonyl (0), chromium trichloride (II)
I), chromium dichloride (II), tris (tetrahydrofuran) benzene chromium tricarbonyl (0), tris (tetrahydrofuran) chromium (hydrido) (ethylene) carbonyl (0), tris (tetrahydrofuran) chromium (hydrido) bis (benzophenone imide)
(II), tris (tetrahydrofuran) chromium (hydride) (benzophenoneimide) dimethylamide (I
I), tris (tetrahydrofuran) chromium tris (dimethylamide) (III), tris (tetrahydrofuran) chromium (hydrido) (benzophenoneimide) triphenylphosphine (I), tris (tetrahydrofuran) chromium (benzophenoneimide) bis (ethylsulfide) (0), tris (tetrahydrofuran) chromium tris (ethylsulfide) (0), tris (tetrahydrofuran) chromium (benzophenoneimide) (ethylsulfide) triphenylphosphine (I), tris (tetrahydrofuran) chromium tris (benzophenoneimide) (III) , Tris (tetrahydrofuran)
Chromium tris (triphenylphosphine) (0), tris (tetrahydrofuran) chromium trichloride (I
II), tris (triethylphosphine) benzenechromium tricarbonyl (0), tris (triethylphosphine) chromium (hydrido) (ethylene) carbonyl (0), tris (triethylphosphine) chromium (hydrido) bis (benzophenoneimide) (I), tris (triethylphosphine) chromium (hydride) (benzophenonimide) dimethylamide (II), tris (triethylphosphine) chromium tris (dimethylamide) (III), tris (triethylphosphine)
Chromium (hydrido) (benzophenone imide) triphenylphosphine (I), tris (triethylphosphine) chromium (benzophenone imide) bis (ethylsulfide) (0), tris (triethylphosphine)
Chromium tris (ethyl sulfide) (0), tris (triethyl phosphine) chromium (benzophenone imide) (ethyl sulfide) triphenyl phosphine (I), tris (triethyl phosphine) chromium tris (benzophenone imide) (III), tris (triethyl) Phosphine) chromium tris (triphenyl phosphine) (0), tris (triethyl phosphine)
Chromium trichloride (III) and the like.

The solvent used when the ligand comprising the benzene ring substituted with an amino group is reacted with a transition metal compound to form a transition metal complex is not particularly limited, but an organic solvent is preferred. 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, tetrahydrofuran, dimethoxyethane And halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. Among these, aliphatic hydrocarbons, aromatic hydrocarbons, and ethers are more preferable from the viewpoint of easy handling. More preferably, decalin, trimethylbenzene, dimethoxyethane and toluene are used. In addition, each of the above solvents can be used alone, or two or more of them can be used as a mixture.

The complex formation reaction is carried out at any temperature from -80 ° C to the boiling point of the reaction solvent used, preferably from 0 to 200 ° C. When the complex formation reaction is performed at a temperature equal to or higher than the boiling point of the reaction solvent, it can be performed under pressure. The reaction time is not particularly limited, and is usually 1 minute to 120 hours, preferably 5 minutes to 72 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 transition metal complex to which a ligand comprising a benzene ring substituted by an amino group is coordinated usually precipitates as a solid, and can be separated from the reaction solvent by filtration. Further, if necessary, washing is performed using the above-mentioned solvent, followed by drying to synthesize a transition metal complex which is one of the components of the catalyst for trimerizing ethylene. If no precipitation occurs, precipitation can be performed by distilling off the solvent, adding a poor solvent, or cooling.

In the present invention, among transition metal complexes in which a ligand comprising a benzene ring substituted with an amino group is coordinated, it is preferable to use a transition metal complex in which the ligand is coordinated to a factor. By using a transition metal complex in which a ligand is coordinated to facial, effects such as suppression of polyethylene by-product are recognized. Here, the complex in which the ligand is coordinated with the factor is defined as 3 complex by the ligand.
Is one of the isomers of a six-coordinate octahedral complex occupied by two coordination sites [Chemical Selection Organometallic Chemistry-Basics and Applications-,
143 (Shokabo)]. That is, in a six-coordinate octahedral complex in which three coordination sites are occupied by ligands, the ligands are coordinated in an arrangement such that the three coordination sites are cis with respect to each other. Means

The alkyl metal compound used in the present invention is not particularly limited. For example, the following general formula (3) R ′ _p M′X _q (3) (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;
Represents one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, and X represents one or more selected from the group consisting of a hydrogen atom, an alkoxide group, an aryl group and a halogen atom. Compounds represented by the formula (1) are preferred.

In the above general formula (3), 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, but examples include a methoxide group, an ethoxide group, a butoxide group, and a phenoxide group. The aryl group is not particularly limited, but includes, for example, a phenyl group. The halogen atom is not particularly limited, but includes, for example, fluorine, chlorine, bromine and iodine.

In the general formula (3), 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 (3) include methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, diethyl magnesium and ethyl butyl magnesium. , Ethylchloromagnesium, ethylbromomagnesium, dimethylzinc, diethylzinc, dibutylzinc, trimethylborane, triethylborane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, 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 10000 equivalents, preferably 3 to 3000 equivalents, more preferably 5 to 200 equivalents, per mol of the transition metal complex.
It is 0 equivalent.

In the present invention, a tertiary aromatic amine compound and / or a nitrogen-containing heterocyclic compound may be added as one component constituting the ethylene trimerization catalyst. The tertiary aromatic amine compound is not particularly limited. For example, N, N-dimethylaniline, N, N-diethylaniline, N, N-diisopropylaniline,
N, N-dibutylaniline, N, N-dibenzylaniline, diphenylmethylamine, triphenylamine, tris (p-methylphenyl) amine, tris (m-methylphenyl) amine, tris (o-methylphenyl) amine, N, N-dimethyl-o-toluidine, N, N-dimethyl-m-toluidine, N, N-dimethyl-p-toluidine, N, N, 2,3-tetramethylaniline,
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-2,
3,4-pentamethylaniline, N, N-2,3,5-
Pentamethylaniline, N, N-2,4,6-pentamethylaniline, N, N-3,4,5-pentamethylaniline, N, N-2,3,4,5,6-heptamethylaniline, N, N-dimethyl-2-ethylaniline, N, N
-Dimethyl-3-ethylaniline, N, N-dimethyl-
4-ethylaniline, N, N-dimethyl-6-ethyl-
o-toluidine, N, N-dimethyl-2-isopropylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-2-t-butylaniline,
N-dimethyl-4-s-butylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-
2,6-diethylaniline, N, N-dimethyl-6-isopropyl-o-toluidine, N, N-dimethyl-2-
Fluoroaniline, N, N-dimethyl-3-fluoroaniline, N, N-dimethyl-4-fluoroaniline,
N, N-dimethyl-2,3-difluoroaniline, N,
N-dimethyl-2,4-difluoroaniline, N, N-
Dimethyl-2,5-difluoroaniline, N, N-dimethyl-2,6-difluoroaniline, N, N-dimethyl-3,4-difluoroaniline, N, N-dimethyl-
3,5-difluoroaniline, N, N-dimethyl-2,
3,4-trifluoroaniline, N, N-dimethyl-
2,3,5-trifluoroaniline, N, N-dimethyl-2,4,6-trifluoroaniline, N, N-dimethyl-3,4,5-trifluoroaniline, N, N-dimethyl-2, 3,4,5,6-pentafluoroaniline,
N, N-dimethyl-3,5-bis (trifluoromethyl) aniline, 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-
2-Aminobiphenyl, N, N-dimethyl-4-aminobiphenyl, N, N-dimethyl-p-trimethylsilylaniline and the like can be mentioned.

The nitrogen-containing heterocyclic compound is not particularly limited.
Methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2,3,4-trimethylpyridine, 2,3
5-trimethylpyridine, 2,4,6-trimethylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-
Ethylpyridine, 2-isopropylpyridine, 4-isopropylpyridine, 2-t-butylpyridine, 4-t-
Butylpyridine, 2,6-diethylpyridine, 2,6-
Di-n-propylpyridine, 2,6-di-i-propylpyridine, 2,6-diphenylpyridine, 2,6-di-
t-butylpyridine, 2-methyl-6-ethylpyridine, 2-methyl-6-isopropylpyridine, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 2,3-difluoropyridine, 2,4-difluoro Pyridine, 2,5-difluoropyridine, 2,6-
Difluoropyridine, 2,3,4-trifluoropyridine, 2,3,5-trifluoropyridine, 2,4,6-
Trifluoropyridine, pentafluoropyridine, 2-
Chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-bromopyridine, 3-bromopyridine, 4-chloropyridine
Bromopyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, sinoline,
Examples include phthalazine, quinazoline, quinoxaline, and acylidine.

Of these, tertiary aromatic amine compounds are preferably used from the viewpoint of catalytic activity, and N, N-dimethylaniline, diphenylmethylamine and triphenylamine are more preferably used. In addition, the above tertiary aromatic amine compounds and / or nitrogen-containing heterocyclic compounds can be used alone or in combination of two or more.

The amount of the tertiary aromatic amine compound and / or nitrogen-containing heterocyclic compound to be used is preferably 0.01 to 10,000 equivalents, more preferably 0.1 to 1 mol, per mol of the transition metal complex. ~ 1000 equivalents.

The ethylene trimerization catalyst of the present invention comprising a transition metal complex to which a ligand comprising a benzene ring substituted by an amino group is coordinated and an alkyl metal compound is prepared by using the above transition metal complex and alkyl metal compound as raw materials. And in a solvent. The contact method is not particularly limited.

The concentration of the transition metal complex in preparing this catalyst is not particularly limited, but is usually used at a concentration of 0.001 to 100 mmol, preferably 0.01 to 10 mmol per liter of the solvent. Is done. If the catalyst concentration is lower than this, sufficient activity cannot be obtained. Conversely, if the catalyst concentration is higher than this, the 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, cyclohexane, methylcyclohexane, cyclooctane, aliphatic hydrocarbons such as decalin, benzene,
Examples 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, 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 transition metal complex concentration during the ethylene trimerization reaction, concentration and dilution may be performed as necessary.

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

The ethylene trimerization reaction of the present invention can be carried out by bringing ethylene into contact with a catalyst comprising the above transition metal complex and an alkyl metal compound. The contacting method is not particularly limited.For example, a method in which a transition metal complex and an alkyl metal compound are brought into contact with each other in the presence of ethylene as a raw material for the trimerization reaction, and a trimerization reaction is started simultaneously with the contact, or a transition metal complex. And an alkyl metal compound in advance, followed by contact with ethylene to carry out a trimerization reaction. Specifically, in the former case,
(1) Introducing a transition metal complex, an alkyl metal compound and ethylene simultaneously and independently into a reaction system, (2) Introducing a transition metal complex and ethylene into a solution containing an alkyl metal compound, (3) Including a transition metal complex The ethylene trimerization reaction can be performed by a method of introducing an alkyl metal compound and ethylene into a solution. In the latter case, (1) an alkyl metal compound is introduced into a solution containing a transition metal complex and then brought into contact with ethylene; (2)
The trimerization reaction of ethylene can be performed by a method of introducing a transition metal complex into a solution containing an alkyl metal compound and then bringing the solution into contact with ethylene. The order of mixing these raw materials is not particularly limited. When a tertiary aromatic amine compound and / or a nitrogen-containing heterocyclic compound are used, the transition metal complex, an alkyl metal compound, and ethylene and a tertiary aromatic amine compound and / or a nitrogen-containing heterocyclic compound are added at any stage. You may make it contact.

In the present invention, if necessary, a catalyst comprising a transition metal complex to which a ligand comprising a benzene ring substituted by an amino group is coordinated and an alkyl metal compound is irradiated with light to trimmize ethylene. A reaction may be performed. Effects such as a significant improvement in catalytic activity by light irradiation are recognized.

At this time, the light used is not particularly limited, but includes, for example, ultraviolet light, visible light, and infrared light. The emission wavelength is preferably 0.2 to 2000 nm. More preferably, light of 200 to 700 nm is used. The illuminance of light is not particularly limited.

As a light source, either sunlight or an artificial light source may be used. However, an artificial light source is desirable because sunlight has low illuminance, is affected by the weather, and cannot be used at night. The artificial light source is not particularly limited. 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, a high-pressure sodium Lamps, thallium lamps, mercury-thallium lamps, mercury-lead lamps, H-type discharge tubes, xenon-mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, flash lamps, and the like.

The irradiation time of the light is not particularly limited, but the irradiation may be performed on the transition metal complex and the alkyl metal compound, or may be directly performed on the ethylene trimerization reaction system. Specifically, in the former case, (1) irradiating the solution containing the transition metal complex with light, then introducing an alkyl metal compound, and further bringing the solution into contact with ethylene to perform a trimerization reaction of ethylene; 2) Light can be irradiated by a method of irradiating a solution containing a transition metal complex and an alkyl metal compound with light, and then bringing the solution into contact with ethylene to perform a trimerization reaction of ethylene. In the latter case,
(1) In the presence of a transition metal complex and an alkyl metal compound,
Perform ethylene trimerization reaction while irradiating light. (2)
A solution containing a transition metal complex and an alkyl metal compound is irradiated with light, and then contacted with ethylene, and a trimerization reaction of ethylene is performed while irradiating the light. A compound is introduced, and then a trimerization reaction of ethylene is performed while irradiating light. (4) A transition metal complex, an alkyl metal compound and ethylene are simultaneously and independently introduced into the reaction system while irradiating light, and (5) irradiating the solution containing the transition metal complex with light, and introducing the transition metal complex, the alkyl metal compound, and ethylene simultaneously and independently into the reaction system. Light can be applied. 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. Further, 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 includes a gas inert to the reaction, for example, nitrogen, argon,
Helium or the like may be contained at all. In addition,
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, the reaction can be stopped by adding a deactivator such as water, alcohol, or an aqueous sodium hydroxide solution to the reaction solution. The deactivated waste transition metal catalyst is a known deashing method,
For example, it can be removed by extraction with water or an aqueous alkali solution. The generated 1-hexene is separated from the reaction solution by a known extraction method or distillation method. In addition, polyethylene as a by-product can be separated and removed at the reaction solution outlet as a residue when a known centrifugal separation method or 1-hexene is separated by distillation.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples show an outline of the present invention, and the present invention is not limited to these examples. Absent.

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

Analysis by Gas Chromatography: For quantification of the product having 4 to 8 carbon atoms contained in the reaction solution, a gas chromatograph (GC-14A) manufactured by Shimadzu Corporation equipped with a column of TC-1 manufactured by GL Science was used. And analyzed. The analysis conditions were set at an injection temperature of 280 ° C. and a detector temperature of 280 ° C. using a nitrogen carrier, and n-heptane was used as an internal standard. The analysis was performed by injecting 1.0 μl of the reaction solution into the 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 obtained from GL Science prepared separately from the gas chromatograph.
The analysis was performed using a gas chromatograph (GC-14A) manufactured by Shimadzu Corporation equipped with a TC-1 column. The analysis was performed using a nitrogen carrier at an injection temperature of 300.
℃, detector temperature 300 ℃, n- as internal standard
Heptane was used. In the analysis, after injecting 1.5 μl of the reaction solution into this gas chromatograph, the temperature of the column was raised to 50 ° C.
From 300 ° 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. Analysis conditions were as follows: using a nitrogen carrier, injection temperature 200 ° C., detector temperature 200 ° C., and column temperature 1
The temperature was set at 20 ° C., and the absolute calibration curve method was used. The analysis was performed by injecting 0.2 ml of the recovered gas into the gas chromatograph.

Reference Example 1 In a Schlenk tube having an internal volume of 100 ml, 348 mg of 1,3,5-tris (diphenylamino) benzene, 143 mg of chromium hexacarbonyl, and 30 ml of dimethoxyethane were added.
Was added and heated to reflux with stirring under a nitrogen atmosphere for 72 hours. The solvent of the obtained reaction solution was distilled off, and as crystals,
Thus, 1,3,5-tris (diphenylamino) benzenechromium tricarbonyl (0) (hereinafter, referred to as complex A) was obtained. As a result of an IR analysis of this complex, two peaks based on CO absorption were observed at 1960 cm ^-1 and 1884 cm ^-1 , and 1,3,5-tris (diphenylamino) benzene was coaxially coordinated with chromium. Showed that.

Example 1 5.7 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, 3.9 ml of 0.247 mol / l triisobutylaluminum / toluene solution and dried toluene 8
0 ml was added and mixed and stirred.

The reaction vessel was heated to 80 ° C. and the stirring speed was 1
After adjusting to 100 rpm, ethylene was introduced into the reaction vessel, and an ultra-high pressure mercury lamp (500
Using W), light was radiated from outside to initiate the ethylene trimerization reaction. Absolute pressure in the reaction vessel is 5kg / cm
Ethylene gas was blown in so that the pressure became ^2. Thereafter, the introduction was continued so as to maintain the pressure, and the 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 filtered off using a filter paper, air-dried, and then dried under reduced pressure (1 mmHg, 100 ° C.), and its weight was measured. Table 1 shows the results.

Example 2 A reaction was carried out in the same manner as in Example 1 except that dimethylaniline was further added as one component of the trimerization catalyst. Table 1 shows the results.

Comparative Example 1 0.017 mol / l of chromium tris (2-ethylhexanoate) (hereinafter, referred to as complex B) was placed in a 150-ml glass pressure-resistant reaction vessel equipped with a thermometer and a stirrer. 0.96 ml of cyclohexane solution, 0.15
3.0 ml of 9 mol / l triethylaluminum / cyclohexane solution, 0.36 ml of 0.134 mol / l 2,5-dimethylpyrrole / cyclohexane solution,
1.26 ml of a 0.040 mol / l germanium chloride / cyclohexane solution and dried cyclohexane 80
Then, the mixture was mixed and stirred.

The reaction vessel was heated to 80 ° C., and the stirring speed was 1
After adjusting to 200 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 filtered off using a filter paper, air-dried, and then dried under reduced pressure (1 mmHg, 100 ° C.), and its weight was measured. Table 1 shows the results.

[0062]

[Table 1]

[0063]

According to the present invention, a transition metal complex coordinated with a ligand comprising a benzene ring substituted with an amino group and an ethylene trimerization catalyst comprising an alkyl metal compound are stable and easy to handle. Yes, and if it is used, 1-hexene can be produced from ethylene with high selectivity.

Continued on the front page F-term (reference) 4G069 AA02 AA08 BA21A BA21B BA27A BA27B BA48A BC04A BC10A BC15A BC16A BC16B BC35A BC38A BC49A BC53A BC57A BC58B BC61A BC65A BC69A BE01A BE42A BE42A BE14A BE37A BE14A BEA DA02 FA01 FB08 4H006 AA02 AC21 BA02 BA06 BA07 BA08 BA09 BA10 BA12 BA14 BA16 BA19 BA20 BA21 BA23 BA24 BA31 BA32 BA46 BA51 BA95 4H039 CA29 CF10 CL19 4J028 AA01A AB00A AB01A AC01A AC09A AC19A AC27A AC31AAC ACA ACA ACA ACA ACACA BB00B BB01B BC01B BC04B BC05B BC06B BC09B BC12B BC14B BC15B BC16B BC17B BC19B BC24B BC27B CB64C CB72C CB74C CB75C CB77C EB02 EC01 FA10 GA01

Claims (8)

[Claims] 1. A catalyst for trimerizing ethylene comprising an alkyl metal compound and a transition metal complex coordinated with a ligand comprising a benzene ring substituted with an amino group. 2. A catalyst according to claim 1, further comprising a tertiary aromatic amine compound and / or a nitrogen-containing heterocyclic compound. 3. A transition metal complex to which a ligand comprising a benzene ring substituted by an amino group is coordinated is represented by the following general formula (1): AM (CO) _n B _3-n (1) Is a ligand consisting of a benzene ring substituted with an amino group, M is a transition metal of Groups 3 to 10. n is an integer of 0 to 3, B is hydrogen, a halogen atom, or an arene ligand. , Alkene ligand, alkyne ligand, amine ligand, imine ligand, amide group, imide group, nitrile ligand, isonitrile ligand, nitrosyl ligand, phosphine ligand, phosphite ligand Or a phosphine oxide ligand, an ether ligand, a sulfide ligand, a sulfone ligand or a sulfone oxide ligand.) 3. The ethylene trimerization catalyst according to 1.). 4. A ligand comprising a benzene ring substituted with an amino group is represented by the following general formula (2): ## STR1 ## (Wherein, NR ₂ represents an amino group, wherein R is the same or independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
An alkynyl group having 10; a halogen atom;
When it consists of an aryl group having 0 and R is other than hydrogen or a halogen atom, Rs may be connected to each other to form a ring. Z _{1 to} Z ₅ are the same or independently hydrogen,
Represents one or more selected from the group consisting of an amino group, an alkyl group, a hydroxyl group, and an alkoxy group. Here, when any of Z _{1 to} Z ₅ is an amino group (NR ₂ ), R is selected from the group of the amino groups described above. Claims 1 to 1)
4. The catalyst for trimerizing ethylene according to any one of 3. 5. The catalyst for trimerizing ethylene according to claim 1, wherein the ligand comprising a benzene ring substituted with an amino group is a transition metal complex coordinated with a factor. . 6. An alkyl metal compound represented by the following general formula (3): R ′ _p M′X _q (3) (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;
R ′ represents one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, and X represents one or more selected from the group consisting of a hydrogen atom, an alkoxy group, an aryl group, and a halogen atom. The catalyst for trimerizing ethylene according to any one of claims 1 to 5, which is a compound represented by the formula: 7. A method 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. 8. The method according to claim 7, wherein ethylene is trimerized while irradiating light.