KR101543056B1 - 1 1 catalysts for preparing 1hexene and method for preparing 1hexene using the same - Google Patents

Abstract

The present invention relates to a novel catalyst for increasing the selectivity of 1-hexene in an ethylene trimerization reaction, an environmentally friendly non-chromium (Cr) catalyst and a novel catalyst capable of producing 1-hexene from ethylene with high selectivity ≪ / RTI >

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for preparing 1-hexene and a process for producing 1-hexene,

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

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

Up to now, the production method of 1-hexene is mainly prepared by oligomerization of ethylene to prepare various 1-olefin (1-olefin) mixtures and then separating and purifying 1-hexene from the prepared mixture, A method of extracting and separating 1-hexene from a 1-olefin mixture prepared using the produced synthesis gas, and the like were used. However, according to the above-mentioned method, since various olefins are contained simultaneously in addition to commercially useful 1-hexene and 1-octene (1-octene), separation costs are high.

Thus, an ethylene trimerization technique capable of selectively producing 1-hexene has been developed, and various studies are under way now. However, commercialized ethylene trimerization catalysts mainly use chromium (Cr) -based compounds, and the toxicity of these chromium compounds is likely to cause environmental problems. Further, since the performance of the catalyst is manifested at high temperature and high pressure, it can be said to be an energy consumption type process.

Accordingly, there is a desperate need to develop a novel catalyst having high selectivity to 1-hexene, while replacing chromium-based catalysts.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide a catalyst for the production of non-chromium (Cr) -modified 1-hexene with increased selectivity of 1-hexene.

Another object of the present invention is to provide a process for producing energy-lowering 1-hexene by using the above-mentioned chromium-1-hexene catalyst.

The present invention provides a transition metal compound represented by any one of the following general formulas (1) to (3), preferably a primary catalyst for producing 1-hexene.

In this formula,

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

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

B is a bridging group comprising an element from group 13 to group 16 on the periodic table in which the linking group may contain one or more heteroatoms or may 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, the substituents bonded to the ligand having a cyclopentadienyl skeleton are all 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 an oxygen atom and a nitrogen atom, respectively,

Q1, Q2 and Q3 are a linking group connecting an oxygen atom and a nitrogen atom,

R, R ¹ , and R ² are the same or different and each independently represents a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, Or a substituted or unsubstituted 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 A substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 7 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted C6- A substituted or unsubstituted aryloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylsiloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, Or an unsubstituted amino group Wherein the alkyl moiety constituting the substituent may be of a chain type or a branch type and when the substitution number of the substituent is two or more, a ring is formed by a bond between the substituents, In addition,

Y ¹ and Y ² are the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C 1 -C 20 arylalkyl group, a substituted or unsubstituted C 6 -C 20 arylalkyl group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 1 -C 20 arylalkyl group, A substituted or unsubstituted C6 to C20 arylsilyl group, and a substituted or unsubstituted C6 to C20 silylaryl group,

X ¹ and X ² are the same or different and each independently represents a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted C1 to C20 silylalkyl group, a substituted or unsubstituted C1 to C20 haloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, A substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 7 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms A substituted or unsubstituted aryloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylsiloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and a tetrahydroborate (Tetrahydroborate) 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).

B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms; A substituted or unsubstituted alkylsilylene group having 1 to 20 carbon atoms; A substituted or unsubstituted C6 to C20 haloalkylene group; A substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylsilylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylene group having 5 to 40 carbon atoms; A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkylsilylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylene group, A substituted or unsubstituted C6-C20 arylalkylene group, a substituted or unsubstituted C6-C20 arylsilylene group, and a substituted or unsubstituted C6-C20 arylalkylene group, ≪ / RTI > alkylarylene 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 forming a ring by being connected to each other.

The present invention also relates to (A) a transition metal compound based main catalyst as described above; And (B) an alkyl aluminum-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 process for producing 1-hexene, which comprises subjecting ethylene to a trimerization reaction in the presence of the above-mentioned catalyst for producing 1-hexene.

The novel chromium (Cr) transition metal based catalyst according to the present invention is applied to the trimerization reaction of ethylene to be useful not only for selectively producing 1-hexene, but also for environmentally friendly and economical manufacturing processes.

Hereinafter, the present invention will be described in detail.

The present invention relates to a non-chromium (Cr) based transition metal compound catalyst satisfying any one of the above formulas (1) to (3) as a main catalyst for use in producing 1-hexene from ethylene, 1-hexene. ≪ / RTI >

More specifically, in the present invention, by applying a combination of a non-Cr-based transition metal compound having catalytic activity to an ethylene trimerization reaction and an alcohol amine-based ligand, a ligand coordination pattern around the transition metal in which the trimerization reaction takes place, To control the characteristics of the catalysts involved in the ethylene trimerization reaction.

That is, by introducing a Bn-Ar group into the Cp group represented by the formulas (1) to (3), only the 1-hexene is selectively generated by changing the ligand coordination configuration and the main catalyst is activated by introducing the electron- And provides a catalyst exhibiting high activity to 1-hexene by stabilizing it when it becomes a cation.

<Transition metal compound catalyst>

The main catalyst for the production of 1-hexene according to the present invention may be represented by any one of the above-mentioned formulas (1) to (3).

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

In addition, the arrows shown in the formulas (1) to (3) signify a transannular interaction of the coordination bond form, and may or may not be generated according to the length of Q ¹ , Q ² and Q ³ .

In the general formulas (1) to (3) according to the present invention, the metal usable as M is preferably a Group 4 to 5 element in the periodic table having high activity. Zirconium (Zr), vanadium (V) and tantalum (Ta) so that 1-hexene can be produced at a lower temperature and pressure than the chromium-based catalyst .

Examples of the cyclopentadienyl skeleton-containing ligand (Cp) in the above Chemical Formulas 1 to 3 include cyclopentadienyl group, indenyl group, and fluorenyl group, and the like. have.

(B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P), and sulfur (S) , And more preferably a linking group containing carbon (C) and / or silicon (Si). Wherein B may optionally have heteroatoms and may form a ring.

Preferable examples of B that can be used include substituted or unsubstituted alkylene groups of 1 to 20 carbon atoms; A substituted or unsubstituted Cycloalkylene group having 3 to 20 carbon atoms; A substituted or unsubstituted alkylsilylene group having 1 to 20 carbon atoms; A substituted or unsubstituted C6 to C20 haloalkylene group; A substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylsilylene group having 6 to 20 carbon atoms; A substituted or unsubstituted arylene group having 5 to 40 carbon atoms; A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, A substituted or unsubstituted C6 to C20 haloalkylene group, a substituted or unsubstituted C6 to C20 arylenealkylene group, a substituted or unsubstituted C6 to C20 alkylene group, An arylsilylene group having 6 to 20 carbon atoms and a substituted or unsubstituted alkylarylene group having 7 to 20 carbon atoms, wherein the substituent is selected from the group consisting of 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 forming a ring by being connected to each other. For example, since carbon or silicon is a group 14 element, when two methyl groups are substituted, the two methyl groups may be connected to form a cyclopropyl-like ring.

In the general formulas (1) to (3), the aryl group (Ar) may be any of conventional aryl groups of 6 to 30 carbon atoms in the art in which? -Electrons are delocalized, O) or a heteroaryl group having 5 to 30 carbon atoms and containing a hetero atom (e.g., Hetero atom). Preferred examples include a phenyl group, a biphenyl group, a terphenyl naphthalyl group, anthracyl, phenanthryl, pyridinyl, pyrazinyl ( Pyrazinyl group, quinolinyl group and the like. 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.

The substituents described as "substituted or unsubstituted" in the above R, R ¹ , R ² , Q ¹ , Q ² , Q ³ , Y ¹ , Y ² , X ¹ and X ² are each independently halogen, May be substituted with at least one substituent selected from the group consisting of a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a C ₃ to C ₄₀ heterocycloalkyl group, and a C ₆ to C ₆₀ aryl group.

The term "alkyl group" as used herein means a saturated functional group containing only carbon and hydrogen atoms. In addition, the term "alkyl group" may mean a linear, branched or cyclic alkyl group. Examples of linear alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl and the like. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of the cyclic alkyl group include, without limitation, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like.

Also, if m is not 0 in the above Chemical Formulas 1 to 3 R _m (for example, 1 ~ 5), R may be the same or different even though the same title, each may be independently selected.

Meanwhile, the transition metal compound represented by the general formulas (1) to (3) according to the present invention includes an alcohol amine-based ligand having a plurality of bonding sites around the transition metal (M). Using alcohol Non-limiting examples of amine-based ligands is available, 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- (amine (N, N- bis- (3- hydroxypropyl 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 , Tris- N- (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, hydroxy-hexyl) amine (N, N, N- Tris- ( 6-Hydroxyhexyl) amine), (N- 2- hydroxyethyl) methyl amine (N- (2-hydroxyethyl) methylamine ), (N- 2- hydroxyethyl ethyl) amine (N- (2-hydroxyethyl) ethylamine ), N, N- bis- (2-hydroxyethyl) methyl amine (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) amine (N- (3-hydroxypropyl) ethylamine ), N, N- bis- (methylamine (N, N- bis- (3- hydroxypropyl 3-hydroxypropyl)) methylamine), N , N- bis (3-hydroxypropyl) amine (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- ) 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), N- (1,2- dimethyl-3-hydroxypropyl) amine (N- (1,2-dimethyl-3 -hydroxypropyl) amine), N- (1,2,3- trimethyl-3-hydroxy N- (1,2,3-Triimethyl-3-hydroxypropyl) amine),

N, N - bis- (2-methyl-3-hydroxypropyl) amine, N, N- 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 - (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 ( 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- ( N- tris- (1-methyl-3-hydroxypropyl) amine ( N, 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) methyl amine (N- (2-Methyl-2 -hyroxyethyl) methylamine), N- (1- methyl-2-hydroxyethyl) methyl amine (N- (1 -Methyl-2-hyroxyethyl) methylamine) , N- (1,2- dimethyl-2-hydroxyethyl) methyl amine (N- (1,2-dimethyl-2 -hyroxyethyl) methylamine), N, N- bis - (2-methyl-2-hydroxyethyl) methyl amine (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) amine (N- (2-Methyl-2 -hyroxyethyl) ethylamine), N- (1- methyl-2-hydroxyethyl) amine (N- (1 -Methyl-2-hyroxyethyl) ethylamine) , N- (1,2- dimethyl-2-hydroxyethyl) amine (N- (1,2-dimethyl-2 -hyroxyethyl) ethylamine), N, N- bis - (2-methyl-2-hydroxyethyl) amine (N, N- bis- (2- methyl-2-hyroxyethyl) ethylamine), N, N- bis - (1-methyl-2-hydroxyethyl) ethyl N, N- bis- (1-methyl-2-hydroxyethyl) ethylamine, N, N - bis- , 2-dimethyl-2-hydroxyethyl) ethylamine),

N- (3- methyl-3-hydroxypropyl) methyl amine (N- (3-Methyl-3 -hydroxypropyl) methylamine) methylamine, N- (2- methyl-3-hydroxy-propyl) - (N- (2 -Methyl-3-hydroxypropyl) methylamine) , N- (1- methyl-3-hydroxypropyl) methyl amine (N- (1-methyl-3 -hydroxypropyl) methylamine), N- (2,3- dimethyl-3 - hydroxypropyl) methyl amine (N- (2,3-dimethyl-3 -hydroxypropyl) methylamine), N- (1,3- dimethyl-3-hydroxypropyl) methyl amine (N- (1,3-dimethyl -3-hydroxypropyl) methylamine), N- (1,2- dimethyl-3-hydroxypropyl) methyl amine (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) amine (N- (3-Methyl-3 -hydroxypropyl) ethylamine), N- (2- methyl-3-hydroxypropyl) amine (N- (2 -Methyl-3-hydroxypropyl) ethylamine) , N- (1- methyl-3-hydroxypropyl) amine (N- (1-methyl-3 -hydroxypropyl) ethylamine), N- (2,3- dimethyl-3 -hydroxypropyl) amine (N- (2,3-dimethyl-3 -hydroxypropyl) ethylamine), N- (1,3- dimethyl-3-hydroxypropyl) amine (N- (1,3-dimethyl -3-hydroxypropyl) ethylamine), N- (1,2- dimethyl-3-hydroxypropyl) amine (N- (1,2-dimethyl-3 -hydroxypropyl) ethylamine), N- (1,2,3 (1,2,3-triimethyl-3-hydroxypropyl) ethylamine), N-

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

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

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

N- (3- methyl-3-hydroxypropyl) dimethylamine (N- (3-Methyl-3 -hydroxypropyl) dimethylamine) dimethylamine, N- (2- methyl-3-hydroxy-propyl) - (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) amine, diethyl (N- (3-Methyl-3 -hydroxypropyl) diethylamine), N- (2- methyl-3-hydroxypropyl) amine, diethyl (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) amine, diethyl (N- (2,3-dimethyl-3 -hydroxypropyl) diethylamine), N- (1,3- dimethyl-3-hydroxypropyl) amine, diethyl (N- ( 1,3-dimethyl-3-hydroxypropyl) diethylamine), N- (1,2- dimethyl-3-hydroxypropyl) amine, diethyl (N- (1,2-dimethyl-3 -hydroxypropyl) diethylamine), N- the (1,2,3-trimethyl-3-hydroxypropyl) amine, diethyl (N- (1,2,3-Triimethyl-3 -hydroxypropyl) diethylamine) and hydrogen ions from the hydroxyl group of compound (proton) is removed, And the like.

<Catalyst for producing 1-hexene>

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

The promoter compound serves to cationize or activate the center metal (M) of the transition metal compound-based main catalyst (A) so that ethylene reacts well with the core metal.

The above-mentioned promoter compound can be used without limitation in the alkylaluminum-based or weakly coordinated Lewis acidic promoter for 1-hexene, which is commonly known in the art, and can be further specified by the following formulas (5) to (7). However, the cocatalyst compound of the present invention is not limited by the following examples.

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

R ⁴ , R ⁵ , and R ⁶ are the same or different from each other and each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen group, and R ⁴ , R ⁵ , R ⁶ &gt; is an alkyl group having 1 to 10 carbon atoms.

In the above formula (7), C is a proton-binding cation of a Lewis base or an oxidizing metal or a nonmetal compound, D is an element belonging to Groups 5 to 15 in the periodic table, / RTI &gt; When C is absent, D is a compound having the property of Lewis acid.

In the present invention, the compound represented by Formula 5 may have a chain, cyclic or network structure, and examples thereof include methylaluminoxane, ethylaluminoxane, Butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, or a mixture thereof. The term &quot; hexylaluminoxane &quot;

Non-limiting examples of the compound represented by Formula 6 include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, Trialkylaluminum such as aluminum (Tridecylaluminum); Dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum methoxide, and dibutylaluminum methoxide; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride; Alkylaluminum dialkoxide such as methylaluminum dimethoxide, ethylaluminum dimethoxide, and butylaluminum dimethoxide; And alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride, and the like.

Non-limiting examples of the compound represented by the formula (7) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium Tetrabutylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate (Ani), tetrabutylammonium tetrakis (tetrakis (pentafluorophenyl) borate), pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, and the like. ) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate ), Tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, ), Tris (2,3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane Tris (3,4,5-trifluorophenyl) borane) and the like. The promoter compound according to the present invention is not limited to the above-exemplified compounds, and may be used alone or in combination of two or more thereof in the production of the catalyst of the present invention.

The amount of the cocatalyst according to the present invention is not particularly limited as long as the main catalyst represented by the above general formulas (1) to (3) is activated. For example the molar ratio between co-catalyst and the main catalyst is from 1: 1 to 10 ^6: 1, and can be mainly used in the range, 1: is preferably used in the range 1: 1 to 5 × 10 ^4.

&Lt; Production method of 1-hexene >

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

In order to exhibit higher catalytic activity in the catalytic system of the present invention in the ethylene trimerization reaction, an appropriate reaction solvent is used, and the components necessary for constituting the catalyst system, that is, the main catalyst, the cocatalyst, Is preferably used in a certain range of composition ratios under the selected reaction conditions. In this case, the trimerization reaction can be carried out in slurry, liquid, gaseous and massive form, and a reaction solvent can be used as a medium when a reaction is carried out in a slurry phase or a liquid phase.

As a preferable example of the above production method, 1-hexene can be produced by introducing the above-mentioned 1-hexene production catalyst (for example, a main catalyst, a cocatalyst), ethylene and a solvent into a reactor and trimerizing ethylene.

As a solvent to be added to the reactor for producing 1-hexene, a conventional solvent known in the art may be used without limitation, and it is preferable to use the above-mentioned catalyst for producing 1-hexene and the one having excellent solubility in ethylene. As the usable solvent, a purified hydrocarbon compound can be used. Non-limiting examples thereof include n-hexane, n-heptane, cyclohexane, toluene, benzene, etc. or a mixture thereof.

In addition to the above-mentioned catalyst for producing 1-hexene and a solvent, conventional additives used for producing 1-hexene may be used in the present invention.

The process for producing 1-hexene according to the present invention comprises the steps of: i) injecting a solvent, a cocatalyst, and a metallocene compound as main catalysts in the order of a reactor, or ii) injecting a solvent and a part of a cocatalyst into the reactor, And activating the main catalyst and then injecting the catalyst.

On the other hand, the amount of the transition metal compound (A) and the co-catalyst compound (B) is not particularly limited when the catalyst of the present invention is added to the reactor. For example, the molar ratio of (B) / 1/1 and 10 may be a ^6/1 range, preferably be used in a molar ratio of ^{1/1 ~ 5 × 10 4/1} .

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, the reaction pressure is 1 to 100 bar, preferably 5 ~ 20 bar. The reaction duration may vary depending on the activity of the catalyst system, but the reaction can be effectively completed by applying the reaction time in the range of 5 minutes to 3 hours.

As a result of carrying out the reaction of selectively trimerizing ethylene in the catalyst system of the present invention to produce 1-hexene, the results of 1-hexene selectivity improvement in a wide range of catalytic activities, depending on the structural and chemical properties of the ligands to be combined (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 Instruments>

All the synthesis reactions described below were carried out under an inert atmosphere such as nitrogen or argon, and standard Schlenk technique and glove box technique were used.

A solvent for synthesis such as tetrahydrofuran (THF), n-hexane, n-pentane, diethyl ether and methylene chloride (CH ₂ Cl ₂ ) Solvent was passed through an activated alumina column to remove water and used on the activated molecular sieve (Molecular Sieve 5 ㅕ, Yakuri Pure Chemical Co.).

The double hydrogen-substituted chloroform (chloroform-d, CDCl ₃ ) and deuterated benzene (benzene-d ₆ , C ₆ D ₆ ) used in the NMR analysis of the compound were purchased from Cambridge Isotope Laboratories, Sieve 5A, Yakuri Pure Chemicals Co.).

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

The chemical shifts of the NMR spectra were determined by chemical shifts of deuterated chloroform (CDCl ₃ ) and deuterated benzene (C ₆ D ₆ ) at ¹ H NMR at room temperature using a Bruker Advance 400 Spectrometer. Values 隆 = 7.24 ppm and 7.16 ppm, respectively.

< Example  1 to 5. Transition metal compound Of the main catalyst  Synthesis>

Example 1. [? ^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 ) [Catalyst 1]

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

After dissolving 1.15 g (5.3 mmol) of [C ₅ H ₄ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] Li in 50 ml diethyl ether, the temperature was lowered with ice water and 0.7 ml (0.6 g, 5.5 mmol) The silyl chloride solution was added dropwise, slowly raised to room temperature, and stirred overnight. The resulting white suspension was then cooled to -30 [deg.] 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, cooled down with ice water, and 0.8 ml (0.7 g, 6.4 mmol) of trimethylsilyl chloride solution was added dropwise to the reaction mixture slowly at room temperature. Then, the obtained mixed solution 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. The solvent was evaporated with a rotary evaporator and the resulting yellow oil was distilled under a pressure of 0.4 torr at 160 ° C 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 in 66 % Yield.

The results of ¹ H NMR confirmed the synthesis of the C ₅ H ₃ (SiMe ₃ ) ₂ CMe _2- 3,5-Me ₂ C ₆ H ₃ 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, ArCH3), 1.51 (s, 6H, C (CH3) 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

After dissolving 1.18 g (3.3 mmol) of the above C ₅ H ₃ (SiMe ₃ ) ₂ CMe _2- 3,5-Me ₂ C ₆ H ₃ in 40 ml dichloromethane, the temperature was lowered to -40 ° C. and an equivalent amount of titanium chloride sol'n in MC) slowly. The temperature was raised to room temperature and stirred overnight. After evaporation of the volatiles in vacuo, the residue was removed with n-pentane to give 1.02 g (2.3 mmol, 72%) of light brown crystals.

The results of ¹ H NMR confirmed the synthesis of [? ₅ - (3-SiMe ₃ ) C ₅ H ₃ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] TiCl ₃ 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 [? -5- (3-SiMe ₃ ) C ₅ H ₃ CMe _2- 3,5-Me ₂ C ₆ H ₃ ] TiCl ₃ prepared in the above Synthesis Example 1-2 was dissolved in 50 ml toluene, And the equivalent of triethanolamine and triethylamine in toluene was added dropwise to the solution, and the solution was heated to 50 DEG C and stirred overnight. The orange suspension was filtered through celite, dried in vacuo and washed with hexane to give about 1 g (2.095 mmol, 35%) of ivory solid.

The results of ¹ H NMR confirmed the synthesis of [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 ) 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. (? ^5- C ₅ H ₄ CMe ₂ Ph) Ti (N (CH ₂ CH ₂ O) ₃ ) [Catalyst 2]

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

After dissolving the phenyllithium solution (2.0 M sol in dibutyl ether, 7.5 ml, 15 mmol) in 20 ml of diethyl ether, the temperature was lowered to -40 ° C and 20 ml of an equivalent amount of 6,6-dimethylpullene (1.593 g, 15 mmol) 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 (15 ml x 3) and dried in vacuo to isolate a white solid.

The resulting solid was dissolved again in tetrahydrofuran solution, and the temperature was lowered to 0 ° C, and 2.27 ml of trimethylsilyl chloride (1.2955 g, 18 mmol) was slowly added dropwise thereto at room temperature. The resulting pale yellow solution was then poured into ice water (100 ml). 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 resulting yellow oil was distilled at 180 ° C and 0.4 torr to obtain the ligand C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph of the brown oil in a yield of 58%.

The results of ¹ H NMR confirmed the synthesis of C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph.

^{1 H-NMR (400 MHz,} 22 ℃, 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 the above 2-1 was dissolved in 30 ml of dichloromethane, the temperature was lowered to -78 ° C, and an equivalent amount of titanium tetrachloride in dichloromethane) was slowly added to the solution, and then the solution was stirred at room temperature. The solvent of the resulting deep red solution was removed in vacuo to give 1.059 g of (η ^{5 -} C ₅ H ₄ CMe ₂ Ph) TiCl ₃ in 50% yield in the form of oil.

The results of ¹ H NMR confirmed the synthesis of (? ^5- C ₅ H ₄ CMe ₂ Ph) TiCl ₃ as follows.

_{^{1 H NMR (400MHz, 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

Prepared in the above Synthesis Example ^{_{2-2 (η 5- C 5 H 4}} CMe 2 Ph) TiCl ₃ 6mmol triethyl behind the dissolved in 50ml toluene and the equivalent amount of cooled to -78 ℃ triethanolamine, three equivalents of amine in toluene The solution was added dropwise to room temperature, heated to 50 &lt; [deg.] &Gt; C and stirred overnight. The orange suspension was filtered through Celite, dried in vacuo and washed with hexanes to give about 1.357 g (3.6 mmol, 60%) of ivory solid.

The results of ¹ H NMR confirmed the synthesis of (η ⁵ -C ₅ H ₄ CMe ₂ Ph) Ti (N (CH ₂ CH ₂ O) ₃ ) as follows.

_{^{1 H NMR (400MHz, 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 ) [Catalyst 3]

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

After dissolving the phenyllithium solution (2.0M sol in dibutyl ether, 4g, 48mmol) in 200ml of diethyl ether, the temperature was lowered to -50 ° C and an equivalent amount of 6,6-pentamethylene fulvene (6.95g, 48mmol) Dissolved in ethyl ether and slowly added. The reaction mixture was cooled to room temperature and stirred for 3 hours. The yellow solution was cooled to 0 &lt; 0 &gt; C and 2.27 ml of 6.4 ml (5.5 g, 51 mmol) trimethylsilyl chloride (1.955 g, 18 mmol) was added dropwise slowly to the room temperature and stirred overnight. The resulting pale yellow solution was then poured into ice water (250 ml). Only the organic layer was extracted with diethyl ether (100 ml x 2), collected, rinsed with 200 ml of brine solution, dried over anhydrous magnesium sulfate and filtered. The solvent was evaporated on a rotary evaporator and the resulting yellow oil was distilled at 165 ° C and 0.4 torr to obtain the ligand C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph in an isomeric mixture at a yield of 63%.

The results of ¹ H NMR confirmed the synthesis of the C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph.

^{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 4H, a-CH ₂ ), 1.65-1.40 (m, 6H,? - and? -CH ₂ ) CH ₂ ), -0.03 (s, 9H, Si (CH ₃ ) ₃ ).

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

3.70 g (12.5 mmol) of the ligand C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph prepared in the above 3-1 was dissolved in 40 ml of methylene chloride, the temperature was lowered to -40 ° C., 1.4 ml (2.4 g, 12.7 mmol) was slowly added thereto, followed by stirring at room temperature. The solvent both to remove the vacuum and extracted with out kick, washed with 30ml pentane supernatant, methylene chloride from the remaining residue was purified pentane-methylene chloride 1: 1 (v / v) {C 5 H 4 of the red-brown and recrystallized in a ratio of (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph} TiCl ₃ was obtained in a yield of 78%.

The results of ¹ H NMR confirmed the synthesis of {C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph} TiCl ₃ .

^{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,? - and? -CH2), 1.25-1.05 (m, 3H,? - and? -CH2).

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

1.92 mmol (0.722 g) of {? ^5- C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ prepared in the above step 3-2 was dissolved in 50 ml toluene, the temperature was lowered to -78 ° C., Amine and three equivalents of triethylamine toluene solution were added dropwise thereto, and the mixture was heated to 60 DEG C and stirred overnight. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane to give about 0.48 g (1.152 mmol, 60%) of ivory solid.

The results of ¹ H NMR confirmed the synthesis of the above {? 5-C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ ).

_{^{1 H NMR (400MHz, 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

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

The results of ¹ H NMR confirmed the synthesis of the C ₅ H ₃ (SiMe ₃ ) ₂ C [(CH ₂ ) ₅ ] Ph.

¹ H NMR (300 MHz, CDCl ₃ ):? 7.45-7.1 (m, 5H, Ph H), 6.50 Cp H), 2.2 (m, 4H, α-CH2), 1.55 (m, 6H, β- and γ-CH2), -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

0.34ml (0.6g, 3.2mmol) was lowered into a solution of methane titanium tetra fluoride croissant 40ml Dijk to -40 ℃ 1.2g (3.3 mmol) C 5 H 3- (SiMe 3) 2 C [(CH 2) 5] Ph was added dropwise and the mixture was stirred overnight at room temperature. After removing the volatile substances by vacuum, the residue was washed with pentane and then extracted with dichloromethane to obtain 0.68 g (1.5 mmol, 40%) of reddish brown crystals.

The results of ¹ H NMR confirmed the synthesis of [? ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ .

¹ H NMR (300 MHz, C ₆ D ₆ ):? 7.13 (m, 4H, Ph o- and mH), 7.01 , 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- CH2), 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) {η5-C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ was dissolved in 50 ml of toluene, the temperature was lowered to -78 ° C. and an equivalent amount of triethanolamine and triethylamine toluene solution was added dropwise After the temperature was raised to room temperature, the mixture was heated to 60 ° C and stirred overnight. The orange suspension was filtered through Celite, dried in vacuo and washed with hexanes to give about 0.569 g (1.164 mmol, 60%) of ivory solid.

The results of ¹ H NMR confirmed that 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 ) .

_{^{1 H NMR (400MHz, 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. {? ^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

After dissolving 1.12 g (0.010 mol) of 3,5-dimethylphenyllithium in 50 ml of diethyl ether and lowering the temperature to 0 ° C., 1.46 g (0.010 mol) of 6,6-pentamethyl fulvene was added dropwise and the mixture was stirred at room temperature for 12 hours. Filtered, washed with diethyl ether and dried in vacuo. The cloudy yellow powder was dissolved in 40 ml of ether / tetrahydrofuran (5: 1, v / v) and then cooled to 0 ° C. 1.08 g (0.010 mol) of trimethylsilyl chloride was added and the white suspension was stirred at room temperature for 2 hours. After the temperature was lowered to 0 占 폚, 4.8 ml of 2.5 M (0.012 mol) butyllithium hexane solution was added and stirred for 5 hours. Then, 1.52 g (0.014 mol) of trimethylsilyl chloride was added. The mixture was gradually warmed to room temperature and stirred overnight. The volatile materials were removed in vacuo and then extracted three times with 15 ml of dichloromethane. The solvent was removed by passing through silica, and the orange oil was immediately dissolved in 30 ml of dichloromethane. The temperature was lowered to -20 ° C., and 1.5 g (0.008 mol) Titanium tetrachloride was added. The reaction solution was slowly warmed to room temperature and stirred for 12 hours. Subsequently, the volatile materials were removed by vacuum and extracted with 30 ml of hexane. Reduction to -30 [deg.] C gave 1.1 g of red crystals with a yield of 23%.

The results of ¹ H NMR confirmed the synthesis of the above {侶^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃ .

^{1 H-NMR (400MHz, 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, (Br, 2H), 6.41 (t, 1H, 3JHH = 3.1 Hz), 6.47 (t, IH, 3JHH = 3.1 Hz), 6.64 (br,

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 )

(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 was dissolved in 50 ml of toluene, The temperature was lowered to 78 ° C, triethanolamine equivalent of triethanolamine and triethylamine toluene solution were added dropwise, and then the temperature was raised to room temperature. The mixture was heated to 60 ° C and stirred overnight. The orange suspension was filtered through Celite and then dried in vacuo, then washed with hexane to give about 0.378 g (0.732 mmol, 60%) ivory solid.

The synthesis of {{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 ) The result of ¹ H NMR confirmed was as follows.

_{^{1 H NMR (400MHz, 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>

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

Experimental Example 1. Ethylene trimerization and evaluation of catalyst properties

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

The reactor was completely purged with nitrogen, and 500 g of toluene, methylaluminoxane (MAO) was added so that the molar ratio of Al / Ti was 40 μmol (based on the number of moles of the central metal) and the transition metal compound was 2000, . At this temperature, the ethylene was continuously fed to the ethylene partial pressure of 10.0 atm and the reaction was continued for 30 minutes. Then, the ethylene supply was stopped and the unreacted ethylene was vented to the outside of the reactor. The remaining MAO was deactivated by the addition of 20 ml of ethanol. The reactants were separated into liquid and solid components by distillation and filtration. The liquid components were analyzed by gas chromatography and the solid components were washed in acidified ethanol for 1 hour and then dried at 70 ° C. under vacuum . The catalyst activity and selectivity were evaluated and the results are shown in Table 1 below.

As a result of the experiment, it was confirmed that the chromium transition metal catalyst according to the present invention has a 1-hexene selectivity equivalent to that of the catalyst of the comparative example, and has a catalytic activity remarkably high.

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 properties

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

In Example 8, the catalyst injection method was changed from a syringe method to a catalyst tank method. For reference, the syringe method is a method in which the catalyst is injected while blocking the air injection into the reactor as much as possible while flowing nitrogen, and the method of using the tanks is separately performed in the reactor when the reactor condition reaches the set temperature and ethylene pressure And injected into the attached catalyst tank at a high pressure instantaneously.

As a result of the experiment, it was confirmed that the novel transition metal catalyst according to the present invention exhibits excellent catalytic activity and 1-hexene selectivity simultaneously under various conditions. Especially, the higher the amount of cocatalyst and the partial pressure of ethylene, the higher the catalytic activity and 1-hexene selectivity.

Catalytic activity Selectivity (wt%) MAO Sheep
(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: Modification of catalyst injection system (syringe → catalyst tank)
- Example 9: Reaction temperature 20 ° C to 50 ° C
Example 10: Solvent change from toluene to cyclohexane

Claims (11)

1. A transition metal compound represented by the following formula (1)
[Chemical Formula 1]

In this formula,
M is Ti,
Cp is a ligand having a cyclopentadienyl skeleton,
B is an alkylene group having 1 to 20 carbon atoms; A cycloalkylene group having 3 to 20 carbon atoms; An alkylsilylene group having 1 to 20 carbon atoms; An arylalkylene group having 6 to 20 carbon atoms, and an alkylarylene group having 7 to 20 carbon atoms;
n is an integer of 1 to 10,
m is an integer from 0 to 5, and when m is 0, the substituents bonded to the ligand having a cyclopentadienyl skeleton are all 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 an oxygen atom and a nitrogen atom, respectively,
Q1, Q2 and Q3 are a linking group connecting an oxygen atom and a nitrogen atom,
[Chemical Formula 4]

R, R ¹ , and R ² are the same or different and each independently represents a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, Or an unsubstituted alkylsilyl group having 1 to 20 carbon atoms and a substituted or unsubstituted silylalkyl group having 1 to 20 carbon atoms,
The aryl group, the heteroaryl group, the alkyl group, the cycloalkyl group, the alkylsilyl group and the silylalkyl group in the above R, R ¹ , R ² , Q ¹ , Q ² , Q ³ and Ar each independently represent a halogen, a C 1 to C 40 An alkyl group, a C3 to C40 cycloalkyl group, a C3 to C40 heterocycloalkyl group, and a C6 to C60 aryl group. delete delete The method according to claim 1,
Ar is selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group naphthalyl group, anthracyl, phenanthryl, pyridinyl, pyrazinyl group, quinolinyl group,
Each of the substituents is a hydrogen atom, an alkyl (Alky) group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted C1- An arylalkyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, , A silylaryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group having 1 to 20 carbon atoms, Wherein the substituent is substituted with at least one substituent selected from the group consisting of an aryloxy group, a halogen group, and an amino group. (A) a transition metal compound based main catalyst according to claim 1; And
(B) an alkyl aluminum-based or weakly coordinating Lewis acid-based promoter compound which reacts with the transition metal compound to activate the transition metal compound. 6. The method of claim 5,
Wherein the promoter compound (B) is a 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 or different and each independently represents 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 Is an alkyl group having 1 to 10 carbon atoms,
C is a hydrogen ion-binding cation of a Lewis base, an oxidizing metal or a non-metal compound,
D is a compound of an element belonging to Groups 5 to 15 on the periodic table and an organic substance, and in the absence of C, D is a compound having Lewis acidity. The method according to claim 6,
Wherein the compound represented by Formula 5 is 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 above-mentioned general formula (6) is preferably selected from the group consisting of trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, dimethylaluminum Selected from the group consisting of chloride, diethylaluminum chloride, dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride By weight based on the total weight of the catalyst. The method according to claim 6,
The compound represented by the general formula (7) may be at least one selected from the group consisting of trimethylammonium tetraphenylborate, triethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate, tributylammoniumtetraphenylborate, trimethylammoniumtetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, anilinium tetraphenyl borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (Pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis Tris (pentafluorophenyl) borane, (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetraphenylphenyl) borane, and tris (3,4,5-trifluorophenyl) Phosphorus, and phosphorus. A process for producing 1-hexene, which comprises subjecting ethylene to a trimerization reaction in the presence of the catalyst for the production of 1-hexene according to claim 5. The process for producing 1-hexene according to 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.