KR20130092300A - Catalysts for preparing 1-hexene and method for preparing 1-hexene using the same - Google Patents

Abstract

PURPOSE: A catalyst for manufacturing 1-hexene and a manufacturing method of 1-hexene are provided to increase the selectivity of 1-hexene in ethylene trimerization and manufacture 1-hexene from ethylene with high selectivity by using a new, eco-friendly, and chrome-free catalyst and the said catalyst. CONSTITUTION: A transition metal compound is expressed by either chemical formula 1 or chemical formula 3. A catalyst for manufacturing 1-hexene comprises: the catalyst of the transition metal compound, alkylaluminum or weakly coordinating Lewis acid cocatalyst which activates the transition metal compound by reacting with the transition metal compound. The ethylene trimerization is the unique characteristic of the manufacturing method of 1-hexene in the presence of the catalyst for manufacturing 1-hexene as claimed in Claim 6. The reaction temperature ranges from 0°C to 200°C, and the reaction pressure ranges from 1 bar to100 bar.

Description

Catalyst for producing 1-hexene and method for producing 1-hexene {CATALYSTS FOR PREPARING 1-HEXENE AND METHOD FOR PREPARING 1-HEXENE USING THE SAME}

The present invention relates to a novel catalyst for preparing 1-hexene and a method for preparing 1-hexene using the same, more particularly, a novel catalyst for increasing the selectivity of 1-hexene in an ethylene trimerization reaction, and the catalyst. The present invention relates to a novel process for producing 1-hexene from ethylene with high selectivity.

1-hexene is used as an important petrochemical industry raw material as a copolymerization monomer for producing linear low density polyethylene.

To date, 1-hexene is mainly manufactured by oligomerizing ethylene to prepare various 1-olefin mixtures, and then separating and purifying 1-hexene from the mixture, or from coal. A method of extracting and separating 1-hexene from the prepared 1-olefin mixture using the prepared syngas was used. However, according to the aforementioned method, since various olefins are simultaneously included in addition to commercially useful 1-hexene and 1-octene, the separation cost is high.

Accordingly, ethylene trimerization technology capable of selectively preparing 1-hexene has been developed, and various studies are still in progress. However, ethylene trimerization catalysts commercialized to date are mainly chromium (Cr) -based compounds, which are likely to cause environmental problems due to the toxicity of these chromium-based compounds. Moreover, since the performance of a catalyst is expressed at high temperature and high pressure, it can be said to be an energy consumption type process.

Therefore, there is an urgent need for a technique for developing a new catalyst having high selectivity in 1-hexene while replacing the conventional chromium-based catalyst.

The present invention has been made to solve the above problems, and an object thereof is to provide a catalyst for producing a non-chromium (Cr) 1-hexene having increased selectivity of 1-hexene.

In addition, another object of the present invention is to provide a low energy consumption type 1-hexene production method using the catalyst for producing non-chromium 1-hexene.

The present invention provides a transition metal compound, preferably a main catalyst for producing 1-hexene, which is represented by any one of the following Chemical Formulas 1 to 3.

Where

M is selected from the group consisting of Group 3 to Group 10 elements on the periodic table,

Cp is a ligand having a substituted or unsubstituted cyclopentadienyl skeleton,

B is a bridging group containing elements of Groups 13-16 on the periodic table, where the linking group may contain one or more heteroatoms or form a ring with adjacent groups,

n is an integer from 1 to 10,

m is an integer from 0 to 5, and when m is 0, all substituents bound to the ligand having a cyclopentadienyl skeleton are hydrogen,

Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms,

O and N are oxygen atoms and nitrogen atoms, respectively

Q1, Q2 and Q3 are a linking group connecting an oxygen atom and a nitrogen atom, and are represented by the following Chemical Formula 4,

R, R ¹ and R ² are the same as or different from each other, and each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, substituted Or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 aryl Groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6 ˜20 silylaryl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C1-C20 alkylsiloxy groups, substituted or unsubstituted C6-C20 aryloxy groups, and substituted Or an unsubstituted amino group It is selected from the group, wherein the alkyl moiety constituting the substituent can be chain (chain), branch (branch) type, and if there are two or more substituents of substituents, the ring between the substituents to form a ring (ring) or non-formation ,

Y ¹ and Y ² are the same as or different from each other, and each independently a hydrogen atom, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 cycloalkyl group, a substituted or unsubstituted carbon number 1-20 alkylsilyl groups, substituted or unsubstituted C1-C20 silylalkyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted It is selected from the group consisting of a substituted C7-20 alkylaryl group, a substituted or unsubstituted C6-C20 arylsilyl group, and a substituted or unsubstituted C6-C20 silylaryl group,

X ¹ and X ² are the same as or different from each other, and each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted A substituted C1-C20 alkylsilyl group, a substituted or unsubstituted C1-C20 silylalkyl group, a substituted or unsubstituted C1-C20 haloalkyl group, a substituted or unsubstituted C6-C20 aryl group, Substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 alkylaryl group, substituted or unsubstituted C6-20 arylsilyl group, substituted or unsubstituted C6-20 Silylaryl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C1-C20 alkylsiloxy groups, substituted or unsubstituted C6-C20 aryloxy groups, and tetrahydroborate Tetrahydroborate group It is selected from the group consisting.

Here, M is preferably selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V) and tantalum (Ta).

In addition, B is a substituted or unsubstituted C 1-20 alkylene group; A substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms; Substituted or unsubstituted C1-C20 alkylsilylene group; A substituted or unsubstituted haloalkylene group having 6 to 20 carbon atoms; Substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms; Substituted or unsubstituted arylsilylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylene group having 5 to 40 carbon atoms; And substituted or unsubstituted C1-C20 alkylene group, substituted or unsubstituted C3-C20 cycloalkylene group, substituted or unsubstituted C1-C20 alkylsilylene group between two arylene groups, substituted or Unsubstituted C6-C20 haloalkylene group, substituted or unsubstituted C6-C20 arylalkylene group, substituted or unsubstituted C6-C20 arylsilylene group, and substituted or unsubstituted C7-C20 It is selected from the group consisting of functional groups containing three alkyl arylene groups. In this case, when two or more kinds of substituents are bonded to carbon and silicon, these substituents may be selected from the group consisting of functional groups capable of being linked to each other to form a ring.

In addition, the present invention (A) the above-described transition metal compound-based main catalyst; And (B) a catalyst for preparing 1-hexene comprising an alkylaluminum-based or weakly coordinated Lewis acid-based promoter compound which reacts with the transition metal compound to activate the transition metal compound.

In addition, the present invention provides a method for producing 1-hexene, characterized in that the ethylene trimerization reaction in the presence of the catalyst for producing 1-hexene described above.

The non-chromium (Cr) transition metal-based novel catalyst according to the present invention can be applied to the trimerization reaction of ethylene, which is not only useful for selectively preparing 1-hexene, but also is environmentally friendly and can improve the economics of the manufacturing process.

Hereinafter, the present invention will be described in detail.

The present invention uses a non-chromium (Cr) -based transition metal compound catalyst satisfying any one of Formulas 1 to 3 as a main catalyst for producing 1-hexene from ethylene and the catalyst as a main catalyst. It provides a method for preparing 1-hexene.

More specifically, in the present invention, by applying a combination of a non-Cr-based transition metal compound having an catalytic activity and an alcohol amine ligand to the ethylene trimerization reaction, the ligand coordination form and the electronic properties around the transition metal where the trimerization reaction occurs In order to control the characteristics of the catalyst involved in the ethylene trimerization reaction by inducing a slight change in the ethylene trimerization reaction.

That is, by introducing a Bn-Ar group into the Cp group represented by Formulas 1 to 3, the ligand coordination form is changed to selectively generate only 1-hexene, and the main catalyst is activated by introducing an electron-rich multidentate alcohol amine group. When the cation is stabilized to provide a catalyst having a high activity in 1-hexene.

<Transition metal compound catalyst>

The main catalyst for preparing 1-hexene according to the present invention may be represented by any one of Formulas 1 to 3.

In Formulas 1 to 3, the alcohol amine ligand may be composed of O, N, Q ¹ , Q ² , Q ³ , Y ¹ , and Y ² described in the above-described formula.

In addition, the arrows indicated in Formulas 1 to 3 mean transannular interactions in the form of coordination bonds, and may or may not be generated according to the lengths of Q ¹ , Q ² , and Q ³ .

In Chemical Formulas 1 to 3 according to the present invention, the metal which can be used as M is preferably a Group 4 to 5 element on the periodic table having high activity. More specifically, it may be selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V) and tantalum (Ta) so as to produce 1-hexene at a lower temperature and pressure than chromium-based catalysts. .

In addition, in Chemical Formulas 1 to 3, non-limiting examples of the ligand (Cp) having a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, and a fluorenyl group. have.

In Formulas 1 to 3, the linking groups included in B include boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P), and sulfur (S). A linking group including at least one member selected from the group consisting of: is more preferably a linking group including carbon (C) and / or silicon (Si). B may optionally have heteroatoms and form a ring.

Preferred examples of B that can be used include substituted or unsubstituted C1-20 alkylene (Alkylene) groups; Substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms; Substituted or unsubstituted C1-C20 alkylsilylene group; Substituted or unsubstituted Haloalkylene group having 6 to 20 carbon atoms; Substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms; Substituted or unsubstituted arylsilylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylene group having 5 to 40 carbon atoms; And a substituted or unsubstituted C1-20 alkylene (Alkylene) group between the two arylene groups, a substituted or unsubstituted C3-20 C20 cycloalkylene group, a substituted or unsubstituted C1 ~ 20 alkylsilylene groups, substituted or unsubstituted C6-C20 haloalkylene groups, substituted or unsubstituted C6-C20 arylalkylene groups, substituted or unsubstituted A arylsilylene group having 6 to 20 ring carbon atoms, or a functional group including a substituted or unsubstituted Alkylarylene group having 7 to 20 carbon atoms, and may be selected from carbon and silicon. When two or more kinds of substituents are bonded, these substituents may be selected from the group consisting of functional groups capable of being linked to each other to form a ring. For example, since both carbon and silicon are Group 14 elements, when two methyl groups are substituted, the two methyl groups may be linked to form a cyclopropyl-like ring.

In Chemical Formulas 1 to 3, the aryl group (Ar) may be used without limitation, an ordinary aryl group having 6 to 30 carbon atoms in the art that π-electrons are delocalized, or nitrogen (N), oxygen ( A heteroaryl group having 5 to 30 carbon atoms containing a hetero atom such as O) may be used. Preferred examples include phenyl group, biphenyl group, terphenyl group naphthalyl group, anthracyl, phenanthryl, pyridinyl, pyridinyl, Pyrazinyl), quinolinyl group and the like. In this case, the aryl group may or may not include a substituent, and the substituent is the same as the substituent (R) substituted in the Cp group.

In the above R, R ¹ , R ² , Q ¹ , Q ² , Q ³ , Y ¹ , Y ² , X ¹ and X ² , the substituents having the term “substituted or unsubstituted” are each independently halogen, It may be substituted with one or more substituents selected from the group consisting of C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, and C ₆ ~ C ₆₀ aryl group.

As used herein, the term "alkyl group" means a saturated functional group containing only carbon and hydrogen atoms. The term "alkyl group" may also mean a linear, branched or cyclic alkyl group. Examples of linear alkyl groups include, but are not limited to, methyl groups, ethyl groups, propyl groups, butyl groups and the like. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of the cyclic alkyl group include, but are not limited to, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like.

In addition, when m is not 0 (eg, 1 to 5) in R _m of Chemical Formulas 1 to 3, R may be the same as or different from each other, and may be independently selected.

Meanwhile, the transition metal compound represented by Chemical Formulas 1 to 3 according to the present invention includes an alcoholamine ligand having a plurality of binding sites centered on the transition metal (M). Non-limiting examples of alcohol amine based ligands that can be used include N- (2-hydroxyethyl) amine ( N- (2-Hydroxyethyl) amine), N, N- bis- (2-hydroxyethyl) amine ( N , N- Bis- (2-hydroxyethyl) amine), N, N, N- tris- (2-hydroxyethyl) amine ( N, N, N- Tris- (2-hydroxyethyl) amine), ( N- ( 3-hydroxypropyl) amine ( N- (3-hydroxypropyl) amine), N, N - bis- (3-hydroxypropyl) amine ( N, N - Bis- (3-hydroxypropyl) amine), N, N , N- tris- (3-hydroxypropyl) amine ( N, N, N- Tris- (3-hydroxypropyl) amine), N- (4-hydroxybutyl) amine ( N- (4-Hydroxybutyl) amine) , N, N - bis- (4-hydroxybutyl) amine ( N, N - Bis- (4-hydroxybutyl) amine), N, N, N- tris- (4-hydroxybutyl) amine ( N, N , N- Tris- (4-hydroxybutyl) amine), N- (5-hydroxypentyl) amine ( N- (5-Hydroxypentyl) amine), N, N- bis- (5-hydroxypentyl) amine ( N , N- Bis- (5-hydroxypentyl) amine), N, N, N- tris- (5-hydroxypentyl) amine (N, N, N- tris- ( 5-hydroxypentyl) amine), N- (6 -Hydroxyhexyl) amine ( N - (6-Hydroxyhexyl) amine) , N, N- bis (6-hydroxyhexyl) amine (N, N- Bis- (6- Hydroxyhexyl) amine), N, N, N- tris- (6-hydroxy Hydroxyhexyl) amine ( N, N, N- Tris- (6-Hydroxyhexyl) amine), ( N- 2 hydroxyethyl) methylamine ( N- (2-Hydroxyethyl) methylamine), ( N- 2 hydroxy Ethyl) ethylamine ( N- (2-Hydroxyethyl) ethylamine), N, N - bis- (2-hydroxyethyl) methylamine ( N, N- Bis- (2-hydroxyethyl) methylamine), N, N- bis - (2-hydroxyethyl) amine (N, N- Bis- (2- hydroxyethyl) ethylamine), (N- 3- hydroxypropyl) methylamine (N- (3-hydroxypropyl) methylamine ), (N- 3-hydroxypropyl) ethylamine ( N- (3-Hydroxypropyl) ethylamine), N, N - bis- (3-hydroxypropyl) methylamine ( N, N - Bis- (3-hydroxypropyl) methylamine), N , N - bis- (3-hydroxypropyl) ethylamine ( N , N- Bis- (3-hydroxypropyl) ethylamine), ( N- 2-hydroxyethyl) dimethylamine ( N- (2-Hydroxyethyl) dimethylamine) , (N- 2- hydroxyethyl) amine, diethyl (N- (2-hydroxyethyl) diethylamine ), (N- 3- De-hydroxypropyl) dimethylamine (N- (3-Hydroxypropyl) dimethylamine ), (N- 3- hydroxypropyl) amine, diethyl (N- (3-Hydroxypropyl) diethylamine ),

N- (2-methyl-2-hydroxyethyl) amine ( N- (2-Methyl-2-hydroxyethyl) amine), N- (1-methyl-2-hydroxyethyl) amine ( N- (1-Methyl -2-hydroxyethyl) amine), N- (1,2-dimethyl-2-hydroxyethyl) amine ( N- (1.2-Dimethyl-2-hydroxyethyl) amine), N, N- bis- (2-methyl- 2-hydroxyethyl) amine ( N, N - Bis- (2-methyl-2-hydroxyethyl) amine), N, N -bis- (1-methyl-2-hydroxyethyl) amine ( N, N- Bis -(1-methyl-2-hydroxyethyl) amine), N, N - bis- (1,2-dimethyl-2-hydroxyethyl) amine ( N, N - Bis- (1,2-Dimethyl-2-hydroxyethyl ) amine), N, N, N- tris- (2-methyl-2-hydroxyethyl) amine ( N, N, N- Tris- (2-methyl-2-hydroxyethyl) amine), N, N, N - tris - (1-methyl-2-hydroxyethyl) amine (N, N, N- tris- ( 1-methyl-2-hydroxyethyl) amine),

N- (3-methyl-3-hydroxypropyl) amine ( N- (3-Methyl-3-hydroxypropyl) amine), N- (2-methyl-3-hydroxypropyl) amine ( N- (2-Methyl -3-hydroxypropyl) amine), N- (1-methyl-3-hydroxypropyl) amine ( N- (1-Methyl-3-hydroxypropyl) amine), N- (2,3-dimethyl-3-hydroxy Propyl) amine ( N- (2,3-Dimethyl-3-hydroxypropyl) amine), N- (1,3-dimethyl-3-hydroxypropyl) amine ( N- (1,3-Dimethyl-3-hydroxypropyl) amine amine), N- (1,2-dimethyl-3-hydroxypropyl) amine ( N- (1,2-dimethyl-3-hydroxypropyl) amine), N- (1,2,3-trimethyl-3-hydride Oxypropyl) amine ( N- (1,2,3-Triimethyl-3-hydroxypropyl) amine),

N, N - bis- (3-methyl-3-hydroxypropyl) amine ( N, N- Bis- (3-methyl-3-hydroxypropyl) amine), N, N- bis- (2-methyl-3- hydroxypropyl) amine (N, N- bis- (2- methyl-3-hydroxypropyl) amine), N, N- bis- (1-methyl-3-hydroxypropyl) amine (N, N- bis- ( 1-methyl-3-hydroxypropyl) amine), N, N - bis- (2,3-dimethyl-3-hydroxypropyl) amine ( N, N - Bis- (2,3-dimethyl-3-hydroxypropyl) amine ), N, N - bis- (1,3-dimethyl-3-hydroxypropyl) amine ( N, N- Bis- (1,3-dimethyl-3-hydroxypropyl) amine), N, N- bis- ( 1,2-dimethyl-3-hydroxypropyl) amine (N, N- bis- (1,2- dimethyl-3-hydroxypropyl) amine), N, N- bis (1,2,3-trimethyl -3 -Hydroxypropyl) amine ( N, N- Bis- (1,2,3-trimethyl-3-hydroxypropyl) amine),

N, N, N- tris- (3-methyl-3-hydroxypropyl) amine ( N, N, N- Tris- (3-methyl-3-hydroxypropyl) amine), N, N, N- tris- ( 2-methyl-3-hydroxypropyl) amine ( N, N, N- Tis- (2-methyl-3-hydroxypropyl) amine), N, N, N- tris- (1-methyl-3-hydroxypropyl Amine ( N, N, N- Tris- (1-methyl-3-hydroxypropyl) amine), N, N, N- tris- (2,3-dimethyl-3-hydroxypropyl) amine ( N, N, N- Tris- (2,3-dimethyl-3-hydroxypropyl) amine), N, N, N- tris- (1,3-dimethyl-3-hydroxypropyl) amine ( N, N, N- Tris- ( 1,3-dimethyl-3-hydroxypropyl) amine), N, N, N- tris- (1,2-dimethyl-3-hydroxypropyl) amine ( N, N, N- Tris- (1,2-dimethyl -3-hydroxypropyl) amine), N, N, N- tris- (1,2,3-trimethyl-3-hydroxypropyl) amine ( N, N, N- Tris- (1,2,3-trimethyl- 3-hydroxypropyl) amine),

N- (2-methyl-2-hydroxyethyl) methylamine ( N- (2-Methyl-2-hyroxyethyl) methylamine), N- (1-methyl-2-hydroxyethyl) methylamine ( N- (1 -Methyl-2-hyroxyethyl) methylamine), N- (1,2-dimethyl-2-hydroxyethyl) methylamine ( N- (1,2-Dimethyl-2-hyroxyethyl) methylamine), N, N- bis- (2-Methyl-2-hydroxyethyl) methylamine ( N, N -Bis- (2-methyl-2-hyroxyethyl) methylamine), N, N- bis- (1-methyl-2-hydroxyethyl) methyl amine (N, N- bis- (1- methyl-2-hyroxyethyl) methylamine), N, N- bis - (1,2-dimethyl-2-hydroxyethyl) methyl amine (N, N- bis- (1 , 2-dimethyl-2-hyroxyethyl) methylamine),

N- (2-methyl-2-hydroxyethyl) ethylamine ( N- (2-Methyl-2-hyroxyethyl) ethylamine), N- (1-methyl-2-hydroxyethyl) ethylamine ( N- (1 -Methyl-2-hyroxyethyl) ethylamine), N- (1,2-dimethyl-2-hydroxyethyl) ethylamine ( N- (1,2-Dimethyl-2-hyroxyethyl) ethylamine), N, N- bis (2-Methyl-2-hydroxyethyl) ethylamine ( N, N -Bis- (2-methyl-2-hyroxyethyl) ethylamine), N, N- bis- (1-methyl-2-hydroxyethyl) ethyl amine (N, N- bis- (1- methyl-2-hyroxyethyl) ethylamine), N, N- bis - (1,2-dimethyl-2-hydroxyethyl) amine (N, N- bis- (1 , 2-dimethyl-2-hyroxyethyl) ethylamine),

N- (3-methyl-3-hydroxypropyl) methylamine ( N- (3-Methyl-3-hydroxypropyl) methylamine), N- (2-methyl-3-hydroxypropyl) methylamine ( N- (2 -Methyl-3-hydroxypropyl) methylamine), N- (1-methyl-3-hydroxypropyl) methylamine ( N- (1-Methyl-3-hydroxypropyl) methylamine), N- (2,3-dimethyl-3 -Hydroxypropyl) methylamine ( N- (2,3-Dimethyl-3-hydroxypropyl) methylamine), N- (1,3-dimethyl-3-hydroxypropyl) methylamine ( N- (1,3-Dimethyl -3-hydroxypropyl) methylamine), N- (1,2-dimethyl-3-hydroxypropyl) methylamine ( N- (1,2-Dimethyl-3-hydroxypropyl) methylamine), N- (1,2,3 -Trimethyl-3-hydroxypropyl) amine ( N- (1,2,3-Triimethyl-3-hydroxypropyl) methylamine),

N- (3-methyl-3-hydroxypropyl) ethylamine ( N- (3-Methyl-3-hydroxypropyl) ethylamine), N- (2-methyl-3-hydroxypropyl) ethylamine ( N- (2 -Methyl-3-hydroxypropyl) ethylamine), N- (1-methyl-3-hydroxypropyl) ethylamine ( N- (1-Methyl-3-hydroxypropyl) ethylamine), N- (2,3-dimethyl-3 -Hydroxypropyl) ethylamine ( N- (2,3-Dimethyl-3-hydroxypropyl) ethylamine), N- (1,3-dimethyl-3-hydroxypropyl) ethylamine ( N- (1,3-Dimethyl -3-hydroxypropyl) ethylamine), N- (1,2-dimethyl-3-hydroxypropyl) ethylamine ( N- (1,2-dimethyl-3-hydroxypropyl) ethylamine), N- (1,2,3 -Trimethyl-3-hydroxypropyl) ethylamine ( N- (1,2,3-Triimethyl-3-hydroxypropyl) ethylamine),

N, N - bis- (3-methyl-3-hydroxypropyl) methylamine ( N, N- Bis- (3-methyl-3-hydroxypropyl) methylamine), N, N- bis- (2-methyl-3 - hydroxypropyl) methyl amine (N, N- bis- (2- methyl-3-hydroxypropyl) methylamine), N, N- bis- (1-methyl-3-hydroxypropyl) methyl amine (N, N- Bis- (1-methyl-3-hydroxypropyl) methylamine), N, N - bis- (2,3-dimethyl-3-hydroxypropyl) methylamine ( N, N- Bis- (2,3-dimethyl-3 -hydroxypropyl) methylamine), N, N - bis- (1,3-dimethyl-3-hydroxypropyl) methylamine ( N, N - Bis- (1,3-dimethyl-3-hydroxypropyl) methylamine), N, N - bis- (1,2-dimethyl-3-hydroxypropyl) methylamine ( N, N- Bis- (1,2-dimethyl-3-hydroxypropyl) methylamine), N, N- bis- (1,2 , 3-trimethyl-3-hydroxypropyl) methylamine ( N, N- Bis- (1,2,3-trimethyl-3-hydroxypropyl) methylamine),

N, N - bis- (3-methyl-3-hydroxypropyl) ethylamine ( N, N- Bis- (3-methyl-3-hydroxypropyl) ethylamine), N, N- bis- (2-methyl-3 -hydroxypropyl) amine (N, N- bis- (2- methyl-3-hydroxypropyl) ethylamine), N, N- bis- (1-methyl-3-hydroxypropyl) amine (N, N- Bis- (1-methyl-3-hydroxypropyl) ethylamine), N, N - bis- (2,3-dimethyl-3-hydroxypropyl) ethylamine ( N, N- Bis- (2,3-dimethyl-3 -hydroxypropyl) ethylamine), N, N - bis- (1,3-dimethyl-3-hydroxypropyl) ethylamine ( N, N - Bis- (1,3-dimethyl-3-hydroxypropyl) ethylamine), N, N - bis- (1,2-dimethyl-3-hydroxypropyl) ethylamine ( N, N- Bis- (1,2-dimethyl-3-hydroxypropyl) ethylamine), N, N- bis- (1,2 , 3-trimethyl-3-hydroxypropyl) ethylamine ( N, N- Bis- (1,2,3-trimethyl-3-hydroxypropyl) ethylamine),

N- (2-methyl-2-hydroxyethyl) dimethylamine ( N- (2-Methyl-2-hyroxyethyl) dimethylamine), N- (1-methyl-2-hydroxyethyl) dimethylamine ( N- (1 -Methyl-2-hyroxyethyl) dimethylamine), N- (1,2-dimethyl-2-hydroxyethyl) dimethylamine ( N- (1,2-Dimethyl-2-hyroxyethyl) dimethylamine),

N- (2-methyl-2-hydroxyethyl) diethylamine ( N- (2-Methyl-2-hyroxyethyl) diethylamine), N- (1-methyl-2-hydroxyethyl) diethylamine ( N- (1-Methyl-2-hyroxyethyl) diethylamine), N- (1,2-dimethyl-2-hydroxyethyl) diethylamine ( N- (1,2-Dimethyl-2-hyroxyethyl) diethylamine),

N- (3-methyl-3-hydroxypropyl) dimethylamine ( N- (3-Methyl-3-hydroxypropyl) dimethylamine), N- (2-methyl-3-hydroxypropyl) dimethylamine ( N- (2 -Methyl-3-hydroxypropyl) dimethylamine), N- (1-methyl-3-hydroxypropyl) dimethylamine ( N- (1-Methyl-3-hydroxypropyl) dimethylamine), N- (2,3-dimethyl-3 -Hydroxypropyl) dimethylamine ( N- (2,3-Dimethyl-3-hydroxypropyl) dimethylamine), N- (1,3-dimethyl-3-hydroxypropyl) dimethylamine ( N- (1,3-Dimethyl -3-hydroxypropyl) dimethylamine), N- (1,2-dimethyl-3-hydroxypropyl) dimethylamine ( N- (1,2-Dimethyl-3-hydroxypropyl) dimethylamine), N- (1,2,3 -Trimethyl-3-hydroxypropyl) dimethylamine ( N- (1,2,3-Triimethyl-3-hydroxypropyl) dimethylamine),

N- (3-methyl-3-hydroxypropyl) diethylamine ( N- (3-Methyl-3-hydroxypropyl) diethylamine), N- (2-methyl-3-hydroxypropyl) diethylamine ( N- (2-methyl-3-hydroxypropyl ) diethylamine), N- (1- methyl-3-hydroxypropyl) amine, diethyl (N- (1-methyl-3 -hydroxypropyl) diethylamine), N- (2,3- Dimethyl-3-hydroxypropyl) diethylamine ( N- (2,3-Dimethyl-3-hydroxypropyl) diethylamine), N- (1,3-dimethyl-3-hydroxypropyl) diethylamine ( N- ( 1,3-Dimethyl-3-hydroxypropyl) diethylamine), N- (1,2-dimethyl-3-hydroxypropyl) diethylamine ( N- (1,2-dimethyl-3-hydroxypropyl) diethylamine), N- Hydrogen ion (Proton) of hydroxy group was removed from compound such as (1,2,3-trimethyl-3-hydroxypropyl) diethylamine ( N- (1,2,3-Triimethyl-3-hydroxypropyl) diethylamine) It may have a form.

<1-hexene manufacturing catalyst>

The catalyst for producing 1-hexene according to the present invention includes (A) a novel transition metal compound-based main catalyst represented by any one of Formulas 1 to 3; And (B) a cocatalyst compound that reacts with the transition metal compound to activate the transition metal compound.

The cocatalyst compound catalyzes or activates the central metal (M) of the transition metal compound-based main catalyst (A) so that ethylene reacts well with the central metal.

The cocatalyst compound may be used without limitation, an alkylaluminum-based or weakly coordinating Lewis acid-based cocatalyst for preparing 1-hexene commonly known in the art, and may be more embodied by Chemical Formulas 5 to 7 illustrated below. However, the promoter compounds of the present invention are not limited by those illustrated below.

In Formula 5, R ³ is an alkyl group having 1 to 10 carbon atoms, and r is an integer of 1 to 70.

In Formula 6, R ⁴ , R ⁵ , R ⁶ are the same as or different from each other, each independently represent an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, or a halogen group, R ⁴ , R ⁵ , R At least one or more of ⁶ is an alkyl group having 1 to 10 carbon atoms.

In Chemical Formula 7, C is a Lewis ion cation or cation (oxidation) metal or non-metallic compound, D is an element and an organic material belonging to groups 5 to 15 of the periodic table Compound. In the absence of C, D is a compound having properties of Lewis acid.

In the present invention, the compound represented by Chemical Formula 5 may have a linear, cyclic or network structure, and non-limiting examples thereof include methylaluminoxane and ethylaluminoxane. Butyl aluminoxane (Butylaluminoxane), hexyl aluminoxane (Hexylaluminoxane), octyl aluminoxane (Octylaluminoxane), decyl aluminoxane (Decylaluminoxane), or a mixture thereof.

In addition, non-limiting examples of the compound represented by Formula 6 include Trimethylaluminum, Triethylaluminum, Tributylaluminum, Trihexylaluminum, Trioctyl aluminum, Tridecylluminum, Tridecyl Trialkylaluminum such as aluminum (Tridecylaluminum); Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum methoxide, and dibutylaluminum methoxide; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride; Alkyl aluminum dialkoxides such as methylaluminum dimethoxide, ethylaluminum dimethoxide, and butylaluminum dimethoxide; Alkylaluminum dihalide, such as methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride, etc. are mentioned.

In addition, non-limiting examples of the compound represented by the formula (7), trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium Tributylammonium tetraphenylborate, Trimethylammonium tetrakis (pentafluorophenyl) borate, Triethylammonium tetrakis (pentafluorophenyl) borate, Triethylammonium tetrakis (pentafluorophenyl) borate Tripropylammonium tetrakis (pentafluorophenyl) borate, Tributylammonium tetrakis (pentafluorophenyl) borate, Anilinium tetraphenylborate linium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate (Pyridinium tetrakis (pentafluorophenyl) borate borate), ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate (Silver tetrakis (pentafluorophenyl) borate ), Tris (pentafluorophenyl) borane, Tris (2,3,5,6-tetrafluorophenyl) borane (Tris (2,3,5,6-tetrafluorophenyl) borane ), Tris (2,3,4,5-tetraphenylphenyl) borane (Tris (2,3,4,5-tetraphenylphenyl) borane), tris (3,4,5-trifluorophenyl) borane ( Tris (3,4,5-trifluorophenyl) borane) etc. are mentioned. The cocatalyst compound according to the present invention is not limited to the above-exemplified compounds, and may be used alone or in admixture of two or more kinds in preparing the catalyst of the present invention.

Cocatalyst according to the present invention is not particularly limited as long as it activates the main catalyst represented by the above formulas (1) to (3), there may be a difference in the amount used. For example, the molar ratio between the promoter and the main catalyst may be mainly used within the range of 1: 1 to 10 ⁶ : 1, and preferably used within the range of 1: 1 to 5 × 10 ⁴ : 1.

<1-Hexene Manufacturing Method>

The present invention provides a method for preparing 1-hexene with high selectivity by introducing the above-described catalyst for producing 1-hexene into an ethylene trimerization reaction.

In order to express higher catalytic activity in the catalyst system of the present invention in performing the trimerization reaction of ethylene, an appropriate reaction solvent is used, and components necessary for the composition of the catalyst system, namely, a main catalyst, a promoter, and other additive compounds Is preferably used in a range of component ratios under selected reaction conditions. In this case, the trimerization reaction may be carried out in a slurry phase, a liquid phase, a gaseous phase, or a bulk, and when the reaction is performed in a slurry phase or a liquid phase, a reaction solvent may be used as a medium.

As a preferable example of the production method, 1-hexene can be prepared by subjecting the above-described catalyst for producing 1-hexene (eg, main catalyst, cocatalyst), ethylene and a solvent to trimerization of ethylene.

As a solvent added to the reactor for preparing 1-hexene, a conventional solvent known in the art may be used without limitation, and it is preferable to use a catalyst for preparing 1-hexene and one having excellent solubility in ethylene. As a usable solvent, a purified hydrocarbon compound may be used, and non-limiting examples thereof include normal hexane, normal heptane, cyclohexane, toluene, benzene, and the like, or mixtures thereof.

In addition to the catalyst and solvent for preparing 1-hexene described above, the present invention may use conventional additives used for preparing 1-hexene.

1-hexene production process according to the present invention is largely iii) injecting a solvent and a cocatalyst, a metallocene compound as the main catalyst in the reactor, or ii) injecting a part of the solvent and the cocatalyst into the reactor, the remaining cocatalyst This can be done by activating the main catalyst and then injecting it.

On the other hand, in adding the catalyst of the present invention to the reactor, the content of the (A) transition metal compound and (B) cocatalyst compound is not particularly limited, for example, the molar ratio of (B) / (A) used in the reaction system 1/1 and 10 may be a ^6/1 range, preferably be used in a molar ratio of ^{1/1 ~ 5 × 10 4/1} .

In addition, the reaction conditions for trimerizing ethylene in the presence of the catalyst of the present invention are not particularly limited. For example, the reaction temperature is 0 to 200 ° C, preferably 20 to 100 ° C, and the reaction pressure is 1 to 100 bar, preferably 5 ~ 20 bar. The reaction duration varies depending on the activity of the catalyst system, but the reaction can be effectively completed by applying a reaction time in the range of 5 minutes to 3 hours.

As a result of performing the reaction to selectively produce 1-hexene by trimerizing ethylene in the catalyst system of the present invention, 1-hexene selectivity is improved in a wide range of catalytic activity depending on the structural and chemical properties of the ligand to be combined. Could be obtained (see Table 1 below).

Hereinafter, embodiments of the present invention will be described in more detail. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined in the appended claims. It is possible.

<Materials and Measuring Equipment>

All of the following synthesis reactions were conducted under an Inert Atmosphere such as Nitrogen or Argon, using standard Schlenk technology and Glove Box technology.

Synthetic solvents such as tetrahydrofuran (THF), normal hexane (n-Hexane), normal pentane (n-Pentane), diethyl ether, methylene chloride (Methylene Chloride, CH ₂ Cl ₂ ) Solvent was used to remove water by passing through an activated alumina layer and then stored on an activated molecular sieve (Molecular Sieve 5 ㅕ, Yakuri Pure Chemicalst Co.).

The dihydrosubstituted chloroform (Chloroform-d, CDCl ₃ ) and deuterated benzene (benzene-d ₆ , C ₆ D ₆ ) used in the NMR structure analysis of the compound were purchased from Cambridge Isotope Laboratories and then activated molecular sieves (Molecular Sieve 5A, Yakuri Pure Chemicals Co) was used for drying.

N-Butyllithium (2.5M Solution in n-Hexane), Phenyllithium (1.8M solution in Dibutyl ether), 1-Bromo-3,5-dimethylbenzene (1-Bromo-3, 5-dimethylbenzene), 6,6-dimethylfulvene, triethanolamine, triethylamine, 6,6-pentamethylfulvene, trimethylsilyl chloride Trimethylsilyl chloride, titanium chloride (TiCl ₄ ), tantalum chloride (TaCl ₅ ), anhydrous magnesium sulfate (Magnesium sulfate, anhydrous) and the like were purchased from Sigma-Aldrich and used without purification.

¹ H NMR was measured using a Bruker Advance 400 Spectrometer at room temperature, and the chemical shift of the NMR spectrum was determined by deuterated chloroform (CDCl ₃ ) and deuterated benzene (C ₆ D ₆ ). The values δ = 7.24 ppm and 7.16 ppm were respectively indicated by reference.

< Example  1-5. Transition metal compound Main catalyst  Synthesis>

Example 1. [η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis [Catalyst 1]

1-1. C ₅ H ₃ (SiMe ₃ ) ₂ CMe _2- 3,5-Me ₂ C ₆ H ₃ Synthesis of

Dissolve 1.15 g (5.3 mmol) [C ₅ H ₄ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] Li in 50 ml diethyl ether, lower the temperature with ice water, and add 0.7 ml (0.6 g, 5.5 mmol) trimethyl. The silyl chloride solution was added dropwise and slowly raised to room temperature and stirred overnight. The resulting white suspension was then cooled to −30 ° C. and 5.4 mmol (2.5 M sol'n in hexanes) of butyllithium solution was added dropwise. The reaction mixture was warmed to room temperature, stirred for 3 hours, lowered in temperature with ice water, and then slowly added to a solution of 0.8 ml (0.7 g, 6.4 mmol) trimethylsilyl chloride dropwise to room temperature and stirred overnight. Then, the obtained mixed liquid is poured into ice water (100 ml). Only the organic layer was extracted with diethyl ether (50 ml x 2), collected, dried over anhydrous magnesium sulfate, and filtered. After evaporating the solvent with a rotary evaporator, the yellow oil obtained was distilled at 160 ° C. and 0.4 torrr to obtain 1.26 g (3.5 mmol) of C ₅ H ₃ (SiMe ₃ ) ₂ CMe _2- 3,5-Me ₂ C ₆ H ₃ 66 Obtained in% yield.

The result of the _{C 5 H 3 (SiMe 3)} 2 CMe 2- 3,5-Me 2 C 6 H 3 1 H NMR confirmed the synthesis of this is as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.90 (s, 2H, Ar oH), 6.78 (s, 1H, Ar pH), 6.37 (m, 2H, Cp H), 6.19 (m, 1H, Cp H ), 2.24 (s, 6H, ArCH 3), 1.51 (s, 6H, C (CH 3) 2), -0.05 (s, 18H, Si (CH ₃ ) ₃ ).

1-2. [? ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] TiCl ₃ Synthesis of

The _{C 5 H 3 (SiMe 3)} 2 CMe 2- 3,5-Me 2 C 6 H 3 1.18g (3.3mmol) after a 40ml dissolved in dichloromethane, the equivalent amount of titanium cooled to -40 ℃ chloride (1M sol'n in MC) was added slowly. The temperature was raised to room temperature and then stirred overnight. After evaporation of the volatiles in vacuo, the residue was removed with normal pentane to yield 1.02 g (2.3 mmol, 72%) of light brown crystals.

The result of the _{[η5- (3-SiMe 3)} C 5 H 3 CMe 2- 3,5-Me 2 C 6 H 3] 1 H NMR confirmed the synthesis of TiCl ₃ is as follows.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 6.96 (m, 1H, Cp H), 6.69 (s, 2H, Ar oH), 6.64 (m, 2H, Cp H and Ar p H), 6.55 ( m, 1H, Cp H), 2.08 (s, 6H, ArCH ₃ ), 1.70 (s, 6H, C (CH ₃ ) 2), 0.13 (s, 9H, Si (CH ₃ ) ₃ ).

1-3. [? ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis of

5.917 mmol of [η5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ H ₃ ] TiCl ₃ prepared in Synthesis Example 1-2 was dissolved in 50 ml toluene, and then −78 ° C. The temperature was lowered, and an equivalent amount of triethanolamine and three equivalents of triethylamine toluene solution were added dropwise to room temperature, followed by heating overnight at 50 ° C. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane to give about 1 g (2.095 mmol, 35%) ivory solid.

The _{^{[η 5- (3-SiMe 3}} ) C 5 H 3 CMe 2 - 3,5-Me 2 C 6 H 3] Ti (N (CH 2 CH 2 O) 3) Results of ¹ H NMR confirmed the synthesis of Is as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.87 (s, 2H, Ar-o), 6.77 (s, 1H, Ar-p), 6.35-6.37 (q, 3H, Cp), 4.26-4.3 (q , 6H, NCH ₂ CH ₂ O), 2.26-2.96 (t, 6H, NCH ₂ CH ₂ O), 2.27 (s, 6H, ArCH ₃ ), 1.7 (s, 6H, C (CH ₃ ) ₂ ) 0.18 ( s, 9H, Si (CH ₃ ) ₃ ).

Example 2. (η ^5- C ₅ H ₄ CMe ₂ Ph) Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis of [Catalyst 2]

2-1. C ₅ H ₄ (SiMe ₃ CMe ₂ Synthesis of Ph

Dissolve phenyllithium solution (2.0M sol in dibutyl ether, 7.5ml, 15mmol) in 20ml of diethyl ether, lower the temperature to -40 ℃ and 20ml of equivalent 6,6-dimethylpulbene (1.593g, 15mmol) It was dissolved in diethyl ether and slowly added. The reaction mixture was warmed to room temperature and stirred for 1 hour. The solvent was removed in vacuo, washed with hexane (15ml x 3) and dried in vacuo to separate white solid.

After dissolving the obtained solid in tetrahydrofuran solution again, the temperature was lowered to 0 ° C., and 2.27 ml of 1.2 equivalents of trimethylsilyl chloride (1.955 g, 18 mmol) was added dropwise and stirred slowly at room temperature. Then, the obtained pale yellow solution was poured into ice water (100 ml). Only the organic layer was extracted with diethyl ether (50 ml x 3), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated with a rotary evaporator, and the yellow oil obtained was distilled at 0.4 torr at 180 ° C. to obtain a ligand C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph of brown oil in a yield of 58%.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph are as follows.

¹ H-NMR (400 MHz, 22 ° C., CDCl ₃ ): d 0.29 (s, 9 H, SiMe ₃ ), 1.87 (s, 6 H, CMe ₂ ), 6.70-6.47 (m, 4 H, C ₅ H ₄ ), 7.64-7.43 (m, 5H, Ph).

2-2. (? ^5- C ₅ H ₄ CMe ₂ Ph) TiCl ₃ Synthesis of

The ligand C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph (2.2395 g, 6.278 mmol) prepared in 2-1 was dissolved in 30 ml of dichloromethane, and then the temperature was lowered to -78 ° C and the equivalent amount of titanium chloride (1 M sol). in dichloromethane) 6.23ml was added slowly, raised to room temperature and stirred overnight. When all of the solvent of the resulting dark red solution was removed with vacuum oil in the form of ^{_{(η 5- C 5 H 4 CMe}} 2 Ph) 1.059g to obtain a TiCl ₃ in 50% yield.

Results of ¹ H NMR confirming the synthesis of (η ^5- C ₅ H ₄ CMe ₂ Ph) TiCl ₃ are as follows.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 7.03 (d, 2H, Ar-m), 6.95 (t, 1H, Ar-p), 6.84 (d, 2H, Ar-o), 1.53 (s, 6H, 2Me)

2-3. (? ^5- C ₅ H ₄ CMe ₂ Ph) Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis of

6 mmol of (η ^5- C ₅ H ₄ CMe ₂ Ph) TiCl ₃ prepared in Synthesis Example 2-2 was dissolved in 50 ml of toluene, and then the temperature was lowered to -78 ° C, and an equivalent of triethanolamine and three equivalents of triethylamine toluene. After the solution was added dropwise, the solution was raised to room temperature and then stirred overnight while heating to 50 ° C. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane to give about 1.357 g (3.6 mmol, 60%) ivory solid.

Results of ¹ H NMR confirming the synthesis of (η ^5- C ₅ H ₄ CMe ₂ Ph) Ti (N (CH ₂ CH ₂ O) ₃ ) are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.70-6.48 (m, 5H, ArH), 4.28 (m, 6H, NCH ₂ CH ₂ O), 3.08 (m, 6H, NCH ₂ CH ₂ O), 1.70 ( s, 6H, C (CH ₃ ) ₂ )

Example 3. {η ^5- C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis of [Catalyst 3]

3-1. C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ Synthesis of Ph

Dissolve phenyllithium solution (2.0M sol in dibutyl ether, 4g, 48mmol) in 200ml diethyl ether, lower the temperature to -50 ℃ and add equivalent 6,6-pentamethylenepulbene (6.95g, 48mmol) 20ml di It was dissolved in ethyl ether and slowly added. The reaction mixture was warmed to room temperature and stirred for 3 hours. The yellow solution was lowered to 0 ° C. and 2.27 ml of 6.4 ml (5.5 g, 51 mmol) trimethylsilyl chloride (1.955 g, 18 mmol) was added dropwise and slowly stirred to room temperature and stirred overnight. The pale yellow solution obtained was then poured into ice water (250 ml). Only the organic layer was extracted with diethyl ether (100 ml × 2), collected, washed with 200 ml brine solution, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated with a rotary evaporator, and the resulting yellow oil was distilled at 0.4 torr at 165 ° C. to obtain ligand C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph in an isomer mixed state in 63% yield.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph are as follows.

¹ H NMR (400 MHz, CDCl ₃ , main isomer): δ 7.40 (m, 2H, Ph oH), 7.33 (m, 2H, Ph mH), 7.15 (m, 1H, Ph pH), 6.43 (m, 2H , Cp H), 6.15 (s, 1H, Cp H), 3.27 (s, 1H, Cp H), 2.17 (m, 4H, α-CH ₂ ), 1.65-1.40 (m, 6H, β- and γ- CH ₂ ), -0.03 (s, 9H, Si (CH ₃ ) ₃ ).

3-2. {η5-C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ Synthesis of

Ligand C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph 3.70 g (12.5 mmol) prepared in 3-1 above was dissolved in 40 ml of methylene chloride, and the temperature was lowered to -40 ° C, followed by titanium chloride. 1.4ml (2.4g, 12.7mmol) was added slowly, then raised to room temperature and stirred overnight. The solvents were removed in vacuo and washed with 30 ml of pentane. The supernatant was removed, extracted with methylene chloride from the remaining residue, and recrystallized at a ratio of 1: 1 (v / v) of pentane methylene chloride to give a reddish brown {C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph} TiCl ₃ was obtained in a yield of 78%.

Results of ¹ H NMR confirming the synthesis of {C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph} TiCl ₃ are as follows.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 7.16-7.06 (m, 4H, Ph o- and mH), 7.01 (m, 1H, Ph pH), 6.31 (ps t, 3JHH) 2.8, 2H, Cp H), 5.97 (ps t, 3JHH) 2.8, 2H, Cp H), 2.45 (d, 2JHH) 13.2, 2H, α-CH _eq ), 1.88 (m, 2H, α-CH _ax ), 1.37 (br , 3H, β- and γ-CH2), 1.25-1.05 (m, 3H, β- and γ-CH2).

3-3. Synthesis of {η5-C ₅ H ₄ C [( CH ₂ ) ₅ ] Ph } Ti (N ( CH ₂ CH ₂ O ) ₃ )

1.92 mmol (0.722 g) of {η ^5- C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ prepared in 3-2 was dissolved in 50 ml toluene, and then the temperature was lowered to -78 ° C and an equivalent amount of triethanol. An amine and three equivalents of triethylamine toluene solution were added dropwise and then raised to room temperature, followed by stirring overnight with heating to 60 ° C. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane to give about 0.48 g (1.152 mmol, 60%) ivory solid.

Results of ¹ H NMR confirming the synthesis of {η5-C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ ) are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.45 (d, 2H, ArH), 7.26 (d, 2H, ArH), 7.15 (m, 1H, ArH), 6.18 (s, 2H, Cp), 6.09 (s , 2H, Cp), 4.17 (m, 6H, NCH ₂ CH ₂ O), 2.85 (m, 6H, NCH ₂ CH ₂ O), 2.65 (d, 2H,-(CH ₂ ) ₅ ), 2.02 (t, 2H,-(CH ₂ ) ₅ ), 1.56 (b, 3H,-(CH ₂ ) ₅ ), 1.39 (m, 3H,-(CH ₂ ) ₅ )

Example 4. [? ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis of [Catalyst 4]

4-1. C ₅ H ₃ (SiMe ₃ ) ₂ C [(CH ₂ ) ₅ Synthesis of Ph

1.67 g (7.3 mmol) of {C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} Li was dissolved in 70 ml diethyl ether, lowered to 0 ° C., and 0.8 ml (0.7 g, 6.4 mmol) trimethylsilyl chloride was added dropwise. After stirring overnight. After lowering the white suspension to -30 ° C, 7.3mmol of 2.5M butyllithium hexane solution was added dropwise, and then slowly raised to room temperature and stirred for 3 hours. After the reaction solution was lowered to 0 ° C., 0.9 ml (0.8 g, 7.4 mmol) trimethylsilyl chloride was added dropwise and stirred at room temperature overnight. The reaction solution was poured into 100 ml of ice water, extracted twice with 50 ml of diethyl ether, dried over MgSO ₄ , blown off, and distilled at 160 ° C. 0.4 torr to obtain 1.28 g (3.5 mmol, 55%) of the product.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₃ (SiMe ₃ ) ₂ C [(CH ₂ ) ₅ ] Ph are as follows.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.45-7.1 (m, 5H, Ph H), 6.50 (m, 1H, Cp H), 6.39 (m, 1H, Cp H), 6.18 (m, 1H, Cp H), 2.2 (m, 4H, α-CH 2), 1.55 (m, 6H, β- and γ-CH 2), -0.07 (s, 18H, Si (CH ₃ ) ₃ )

4-2. [? ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ Synthesis of

After 0.34ml (0.6g, 3.2mmol) titanium tetrachloride 40ml dichloromethane solution was lowered to -40 ° C, 1.2g (3.3 mmol) C ₅ H _3- (SiMe ₃ ) ₂ C [(CH ₂ ) ₅ ] Ph was added dropwise and stirred overnight at room temperature. The volatiles were removed in vacuo and the residue was washed with pentane to remove the residue and extracted with dichloromethane to yield 0.68 g (1.5 mmol, 40%) of reddish brown crystals.

Results of ¹ H NMR confirming the synthesis of the above [η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ are as follows.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 7.13 (m, 4H, Ph o- and mH), 7.01 (m, 1H, Cp H), 6.93 (m, 1H, Ph pH), 6.45 (m , 2H, Cp H), 2.54 (m, 2H, α-CH _eq ), 2.07, 1.86 (m, 1H each, α-CH _ax ), 1.4 (br, 3H, β- and γ-CH2), 1.15 ( br, 3H, β- and α-CH 2), 0.13 (s, 9H, Si (CH ₃ ) ₃ )

4-3. [? ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ )

1.94 mmol (0.869 g) Dissolve {η5-C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ in 50 ml toluene, lower the temperature to -78 ° C, add dropwise equivalent of triethanolamine and three equivalents of triethylamine toluene solution After raising to room temperature and heated to 60 ℃ stirred overnight. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane to yield about 0.569 g (1.164 mmol, 60%) ivory solid.

Results of ¹ H NMR confirming the synthesis of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ ) are as follows. .

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.44 (d, 2H, ArH), 7.24 (d, 2H, ArH), 7.08 (t, 1H, ArH), 6.29 (s, 1H, Cp), 6.17 (s , 2H, Cp), 4.14 (m, 6H, NCH ₂ CH ₂ O), 2.82 (m, 6H, NCH ₂ CH ₂ O), 2.71 (d, 1H,-(CH ₂ ) ₅ ), 2.57 (d, 1H,-(CH ₂ ) ₅ ), 2.06 (m, 2H,-(CH ₂ ) ₅ ), 1.53 (br, 3H,-(CH ₂ ) ₅ ), 1.4 (m, 3H,-(CH ₂ ) ₅ )

Example 5. {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } Ti (N (CH ₂ CH ₂ O) ₃ ) Synthesis of [Catalyst 5]

5-1. {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃

1.12 g (0.010 mol) 3,5-dimethylphenyllithium was dissolved in 50 ml diethyl ether, lowered to 0 ° C., and then 1.46 g (0.010 mol) 6,6-pentamethylpulbene was added dropwise and stirred at room temperature for 12 hours. Filtered and washed with diethyl ether and dried in vacuo. The pale yellow powder was dissolved in 40 ml ether / tetrahydrofuran (5: 1, v / v), lowered to 0 ° C., 1.08 g (0.010 mol) trimethylsilyl chloride was added, and the white suspension was stirred at room temperature for 2 hours. After lowering to 0 ° C., 4.8 ml of 2.5M (0.012 mol) butyllithium hexane solution was added thereto, followed by stirring for 5 hours. Then, 1.52 g (0.014 mol) trimethylsilyl chloride was added thereto. After slowly raising to room temperature, the mixture was stirred overnight. The volatiles were removed in vacuo and extracted three times with 15 ml of dichloromethane, passed through silica to remove the solvent, and the orange oil was immediately dissolved in 30 ml dichloromethane, lowered to -20 ° C, and then 1.5 g (0.008 mol). Tetrachlorotitanium was added. The reaction solution was slowly warmed up to room temperature, stirred for 12 hours, and then volatiles were removed in vacuo and extracted with 30 ml hexane. Lowered to −30 ° C. to give 1.1 g of red crystals with a yield of 23%.

Results of ¹ H NMR confirming the synthesis of the above {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃ are as follows. .

¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 0.10 (s, 9H), 1.20-1.50 (m, 6H), 1.78-2.10 (m, 2H), 2.10 (s, 6H), 2.64 (m, 2H), 6.41 (t, 1H, 3JHH = 3.1 Hz), 6.47 (t, 1H, 3JHH = 3.1 Hz), 6.64 (br, 1H), 6.96 (br, 1H), 7.12 (br, 2H)

5-2. {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } Ti (N (CH ₂ CH ₂ O) ₃ )

1.22 mmol (0.582 g) {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃ dissolved in 50 ml toluene, The temperature was lowered to 78 ° C., and an equivalent amount of triethanolamine and three equivalents of triethylamine toluene solution were added dropwise, and then raised to room temperature, and stirred at 60 ° C. overnight. The orange suspension was filtered through Celite and dried in vacuo, then washed with hexane to give about 0.378 g (0.732 mmol, 60%) ivory solid.

^{Synthesis of the} above {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } Ti (N (CH ₂ CH ₂ O) ₃ ) results of ¹ H NMR confirmed this is as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.42 (s, 2H, ArH), 6.92 (s, 1H, ArH), 6.5 (s, 1H, Cp), 6.39 (s, 1H, Cp), 6.35 (s , 1H, Cp), 4.38 (m, 6H, NCH ₂ C H ₂ O), 3.24 (m, 6H, NC H ₂ CH ₂ O), 2.85 (d, 1H,-(CH ₂ ) ₅ ), 2.77 ( d, 1H,-(CH ₂ ) ₅ ), 2.46 (s, 6H, 2Me), 2.42 (t, 1H,-(CH ₂ ) ₅ ), 2.16 (t, 1H,-(CH ₂ ) ₅ ), 1.72 (br, 3H,-(CH ₂ ) ₅ ), 1.48 (br, 3H,-(CH ₂ ) ₅ ), 0.25 (s, 9H, SiMe ₃ )

<Comparative Example>

In the comparative example, tantalum chloride was used as a catalyst, and used tantalum chloride was purchased from Sigma-Aldrich and used without purification.

Experimental Example 1. Evaluation of Ethylene Trimmer and Catalyst Properties

In order to evaluate the catalytic properties of each transition metal compound prepared in Examples 1 to 5, ethylene was trimerized as follows using a 2L high pressure reactor. As a control, tantalum chloride of the comparative example was used as a catalyst.

The reactor was completely replaced with nitrogen, 500 g of toluene, 40 μmol of each of the transition metal compounds (based on the number of moles of the center metal), and methylaluminoxane (MAO) were added so that the Al / Ti ratio was 2000, and the reactor temperature was 20 ° C. Maintained. At this temperature, the ethylene was continuously supplied for 30 minutes while the ethylene was continuously fed to have an ethylene partial pressure of 10.0 atm, and then the ethylene supply was stopped, and the unreacted ethylene was vented out of the reactor. The remaining MAO was inactivated by the addition of 20 ml of ethanol. The reactants were separated into liquid and solid components through distillation and filtration, and the liquid components were analyzed by gas chromatography. The solid components were washed in acidified ethanol for 1 hour and then dried at 70 ° C. in vacuo. . The catalyst activity and selectivity were then evaluated and the results are shown in Table 1 below.

As a result, it was confirmed that the non-chromium transition metal catalyst according to the present invention had 1-hexene selectivity comparable to that of the comparative example and a significantly higher catalytic activity.

Catalytic activity
(g C6 / mmol metal, h) Selectivity (wt%) 1-hexene 1-decene Polyethylene (PE) Example 1 6,550 84.0 13.2 2.8 Example 2 2,670 76.5 19.2 4.3 Example 3 820 79.1 16.3 4.6 Example 4 2,290 87.0 10.7 2.3 Example 5 1,870 74.1 18.9 7.0 Comparative example 280 70.9 21.5 7.6

Experimental Example  2. Ethylene Trimerization  And catalyst characterization

The activity and selectivity under various conditions of the catalyst of Example 1 were evaluated as shown in Table 2 below.

At this time, Example 8 is changed from the syringe injection method (syringe) to the catalyst tank (tank) method. For reference, the syringe method is a method of injecting a catalyst while blocking the injection of air into the reactor as much as possible while flowing nitrogen, and the method of using a tank individually when the temperature of the reactor reaches the set temperature and ethylene pressure. It is a method of injection by instant injection at high pressure to the attached catalyst tank.

As a result, it was confirmed that the novel transition metal catalyst according to the present invention simultaneously shows excellent catalytic activity and 1-hexene selectivity under various conditions. In particular, as the amount of promoter and the ethylene partial pressure increased, it was found that the catalyst had significantly higher catalytic activity and 1-hexene selectivity.

Catalytic activity Selectivity (wt%) MAO quantity
(eq) EL pressure
(bar) (g C6 / mmol metal, h) 1-hexene 1-decene Polyethylene (PE) Example 1 2000 10 6,550 84.0 13.2 2.8 Example 6 1500 10 8,920 83.2 15.7 1.1 Example 7 10000 15 11,800 90 7.2 2.8 Example 8 1500 10 4,400 92 6.9 1.1 Example 9 1500 10 2,500 92 5.3 2.7 Example 10 1500 10 6,600 89 9.6 1.4 Example 8 catalyst injection mode change (syringe → catalyst tank)
Example 9: reaction temperature 20 ° C. → 50 ° C.
Example 10: solvent change from toluene to cyclohexane

Claims (11)

A transition metal compound characterized by represented by any one of the following Chemical Formulas 1 to 3:
[Formula 1]

(2)

(3)

In this formula,
M is selected from the group consisting of Group 3 to Group 10 elements on the periodic table,
Cp is a ligand having a substituted or unsubstituted cyclopentadienyl skeleton,
B is a bridging group containing elements of Groups 13-16 on the periodic table, where the linking group may contain one or more heteroatoms or form a ring with adjacent groups,
n is an integer of 1 to 10,
m is an integer from 0 to 5, and when m is 0, all substituents bound to the ligand having a cyclopentadienyl skeleton are hydrogen,
Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 30 carbon atoms,
O and N are oxygen atoms and nitrogen atoms, respectively
Q1, Q2 and Q3 are a linking group connecting an oxygen atom and a nitrogen atom, and are represented by the following Chemical Formula 4,
[Chemical Formula 4]

R, R ¹ and R ² are the same as or different from each other, and each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, substituted Or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 aryl Groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6 ˜20 silylaryl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C1-C20 alkylsiloxy groups, substituted or unsubstituted C6-C20 aryloxy groups, and substituted Or an unsubstituted amino group It is selected from the group, wherein these form an adjacent ring group (ring) or a non-form and
Y ¹ and Y ² are the same as or different from each other, and each independently a hydrogen atom, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 cycloalkyl group, a substituted or unsubstituted carbon number 1-20 alkylsilyl groups, substituted or unsubstituted C1-C20 silylalkyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted It is selected from the group consisting of a substituted C7-20 alkylaryl group, a substituted or unsubstituted C6-C20 arylsilyl group, and a substituted or unsubstituted C6-C20 silylaryl group,
X ¹ and X ² are the same as or different from each other, and each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted A substituted C1-C20 alkylsilyl group, a substituted or unsubstituted C1-C20 silylalkyl group, a substituted or unsubstituted C1-C20 haloalkyl group, a substituted or unsubstituted C6-C20 aryl group, Substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 alkylaryl group, substituted or unsubstituted C6-20 arylsilyl group, substituted or unsubstituted C6-20 Silylaryl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C1-C20 alkylsiloxy groups, substituted or unsubstituted C6-C20 aryloxy groups, and tetrahydroborate Tetrahydroborate group It is selected from the group consisting. The method of claim 1,
The M is a transition metal compound, characterized in that selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V) and tantalum (Ta). The method of claim 1,
B is a substituted or unsubstituted C 1-20 alkylene group; A substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms; Substituted or unsubstituted C1-C20 alkylsilylene group; A substituted or unsubstituted haloalkylene group having 6 to 20 carbon atoms; Substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms; Substituted or unsubstituted arylsilylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylene group having 5 to 40 carbon atoms; And substituted or unsubstituted C1-C20 alkylene group, substituted or unsubstituted C3-C20 cycloalkylene group, substituted or unsubstituted C1-C20 alkylsilylene group between two arylene groups, substituted or Unsubstituted C6-C20 haloalkylene group, substituted or unsubstituted C6-C20 arylalkylene group, substituted or unsubstituted C6-C20 arylsilylene group, and substituted or unsubstituted C7-C20 It is selected from the group consisting of functional groups containing two alkyl arylene groups, wherein when two or more substituents are bonded to carbon and silicon, these substituents are selected from a functional group that can be linked to each other to form a ring compound. The method of claim 1,
Ar is selected from the group consisting of phenyl group, biphenyl group, terphenyl group naphthalyl group, anthracyl, phenanthryl, pyridinyl, pyrazinyl group, quinolinyl group,
The substituents each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 1 to 20 carbon atoms. Silylalkyl groups, C1-C20 haloalkyl groups, C6-C20 aryl groups, C6-C20 arylalkyl groups, C6-C20 arylsilyl groups , C6-C20 silylaryl group, C7-C20 alkylaryl (Alkylaryl) group, C1-C20 alkoxy group, C1-C20 Alkylsiloxy group, C6-C20 Transition metal compound, characterized in that substituted by one or more substituents selected from the group consisting of aryloxy group, halogen (Halogen) group and amino (Amino group). (A) the transition metal compound-based main catalyst of claim 1; And
(B) A catalyst for producing 1-hexene comprising an alkylaluminum-based or weakly coordinated Lewis acid-based promoter compound which reacts with the transition metal compound to activate the transition metal compound. The method of claim 5,
The cocatalyst compound (B) is a catalyst for producing 1-hexene, characterized in that the compound represented by any one of the following formulas (5) to (7):
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In this formula,
R ³ is an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 70,
R ⁴ , R ⁵ , and R ⁶ are the same as or different from each other, and each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen group, wherein at least one of R ⁴ , R ⁵ , and R ⁶ The above is an alkyl group having 1 to 10 carbon atoms,
C is a hydrogen ion bonding cation of a Lewis base, an oxidizing metal or nonmetallic compound,
D is a compound of an element and an organic substance belonging to Groups 5 to 15 of the periodic table. In the absence of C, D is a compound having Lewis acid property. The method according to claim 6,
The compound represented by the formula (5) is 1-hexene production catalyst, characterized in that selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane, octyl aluminoxane, and decyl aluminoxane. The method according to claim 6,
The compound represented by the formula (6) is trimethyl aluminum, triethyl aluminum, tributyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, dimethyl aluminum methoxide, diethyl aluminum methoxide, dibutyl aluminum methoxide, dimethyl aluminum Selected from the group consisting of chloride, diethylaluminum chloride, dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride 1-hexene production catalyst, characterized in that. The method according to claim 6,
Compound represented by the formula (7) is trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium Tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anninium tetraphenylborate, anninium tetrakis (pentafluoro Phenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, Tris (pentafluorophenyl) borane, Lis (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetraphenylphenyl) borane, and tris (3,4,5-trifluorophenyl) bore Catalyst for producing 1-hexene, characterized in that it is selected from the group consisting of phosphorus. Method for producing 1-hexene, characterized in that the ethylene trimerization reaction in the presence of the catalyst for producing 1-hexene of claim 6. The method of claim 10, wherein the reaction temperature is in the range of 0 to 200 ° C, and the reaction pressure is in the range of 1 to 100 bar.