KR20160064840A - Process for the preparation of 1-hexene and 1-oxtene - Google Patents

Abstract

The present invention relates to a manufacturing method of 1-hexene and 1-octene from an olefin under the presence of a catalyst composition. The catalyst composition comprises: at least one type of an organic ligand compound selected from the group consisting of a compound represented by chemical formula 1, a compound represented by chemical formula 2, and a compound represented by chemical formula 3; at least one type of transition metal or a transition metal precursor selected from the group consisting of group IV to group XII elements; and a promotor. The manufacturing method of the present invention reduces generation of byproducts, and can manufacture 1-hexene and 1-octene from an olefin with high selectivity and reaction activity.

Description

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

The present invention relates to a process for the production of 1-hexene and 1-octene, and more particularly to a process for producing 1-hexene and 1-octene with a high selectivity and a reaction activity.

Conventionally, in order to synthesize 1-hexene or 1-octene, oligomerization of mainly ethylene is carried out to prepare various 1-olefin mixtures, and then 1-hexene or 1- A method of producing a 1-olefin mixture by using a synthesis gas produced from coal, and extracting and separating 1-hexene or 1-octene therefrom have been used.

However, according to a conventionally known method, various olefins, especially polyolefins such as polyolefins, in addition to commercially useful 1-hexene or 1-octene are simultaneously produced and further separation and purification processes are required. Due to the cost for such separation and purification The cost of the final product is increased and the economical efficiency is lowered.

Accordingly, a catalyst technology and a manufacturing technique capable of selectively producing 1-hexene and 1-octene have been developed, and various studies are under way now.

For example, a method of oligomerizing ethylene using a chromium compound is known. Specifically, Korean Patent Publication Nos. 2009-0017929 and 7361623 disclose a 1-hexene and 1-octene production method using chromium. However, this method has a problem that the reaction activity decreases and the reaction rate decreases. In addition, the prior art has a problem in that a large amount of polymer is produced as a by-product of the oligomerization reaction, so that the selectivity of the oligomer is low and the production process can not proceed continuously.

Korea Patent Publication No. 2009-0017929 U.S. Patent No. 7361623

It is an object of the present invention to provide a process for reducing the formation of byproducts to provide 1-hexene and 1-octene from olefins with high selectivity and reactivity.

The present invention relates to a process for preparing a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3) At least one transition metal or transition metal precursor selected from the group consisting of Group 4 to Group 12 elements; And 1-hexene and 1-octene from olefins in the presence of a catalyst composition comprising a cocatalyst.

≪ Formula 1 >

(2)

(3)

In the above Formulas 1 to 3,

R ₁ to R ₁₂ are the same or different and are each independently hydrogen, deuterium, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, provided that the alkyl constituting R ₁ to R ₁₂ is Chain type or branch type, and two or more neighboring substituents of R ₁ to R ₁₂ may be connected to each other to form a ring,

n is an integer of 1 to 20,

E is an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P)

B ₁ and B ₂ are the same or different and are selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) B ₁ may form a ring with R _{9 and} R ₁₀ , and B ₂ may form a ring with R _{11 and} R ₁₂ .

According to one embodiment of the present invention, a method capable of stably synthesizing 1-hexene and 1-octene with a high selectivity ratio and a catalyst composition used therefor can be provided.

Hereinafter, the catalyst composition according to the specific embodiment of the present invention and the method for producing 1-hexene and 1-octene will be described in more detail.

In the present specification, alkyl is a monovalent functional group derived from an alkane, and alkenyl means a monovalent functional group derived from an alkene.

Also, aryl means a monovalent functional group derived from arene, alkylaryl means an aryl group having at least one linear or branched alkyl group introduced therein, and arylakyl means aryl Quot; means a linear or branched alkyl group having 1 or more groups introduced therein.

In addition, cycloalkyl means a monovalent functional group derived from cycloalkane, alkoxy means a monovalent functional group in which a straight-chain or branched-chain alkyl group is bonded to oxygen, and aryloxy refers to an aryloxy group in which an aryl group is oxygen ≪ / RTI >

Further, alkylsilyl and arylsilyl mean a silyl group bonded with an alkyl group and an aryl group, respectively.

In addition, alkylene means a divalent functional group derived from an alkane, alkenylene means a divalent functional group derived from an alkene, arylene means an arylene, refers to a divalent functional group derived from arene, wherein alkylarylene means an arylene group in which at least one alkyl group is substituted, and allylalkylene means an alkylene group in which at least one allyl group is substituted.

One embodiment of the present invention is a compound of the formula (I), a compound of the following formula (II) and a compound of the following formula (III): at least one organic ligand compound; At least one transition metal or transition metal precursor selected from the group consisting of Group 4 to Group 12 elements; And 1-hexene and 1-octene from olefins in the presence of a catalyst composition comprising a cocatalyst.

≪ Formula 1 >

(2)

(3)

The present inventors have found that when one or more organic ligand compounds selected from the group consisting of the compounds represented by the general formulas (1), (2) and (3) are used together with the transition metal or transition metal precursor and the cocatalyst, Hexene and 1-octene can be stably synthesized at a high selectivity.

In the above Formulas 1 to 3,

R ₁ to R ₁₂ are different from or equal to each other, and each independently hydrogen, heavy hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroaryl, hydrocarbyl, or substituted hetero hydrocarbyl, alkyl constituting a single R ₁ to R ₁₂ is a chain Chain type or branch type, and two adjacent substituents of R ₁ to R ₁₂ may be connected to each other to form a ring,

n is an integer of 1 to 20,

E is an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P)

B ₁ and B ₂ are the same or different and are selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) B ₁ may form a ring with R _{9 and} R ₁₀ , and B ₂ may form a ring with R _{11 and} R ₁₂ .

The transition metal may preferably be chrome, and the transition metal precursor may be one or more selected from the group consisting of chromium (III) acetylacetonate, chromium tris tetrahydrofuran trichloride, and chromium (III) 2-ethylhexanoate Or more.

In particular, in the formulas (1) to (3)

R ₁ to R ₁₂ are the same or different and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, alkylsilyl having 1 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms, alkylaryl having 7 to 21 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkylsiloxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, Aryl, heteroaryl having 6 to 20 carbon atoms, alkenyl having 2 to 10 carbon atoms, halogen or amino, with the proviso that the alkyl constituting R ₁ to R ₁₂ is of the chain type or branch type .

E is preferably nitrogen (N) or sulfur (S).

B ₁ and B ₂ are the same or different and are preferably one element selected from the group consisting of carbon (C), nitrogen (N), and sulfur (S).

Specific examples of R ₁ to R ₁₂ include benzene, biphenyl, triphenyl, triphenylene, naphthalenyl, anthracenyl, phenalenyl, phenanthrenyl, fluorenyl, pyrenyl, Aromatic hydrocarbon cyclic compounds such as nyl; Dibenzothiophenyl, dibenzofuranyl, dibenzoselenophenyl, furanyl, thiophenyl, benzofuranyl, benzothiophenyl, benzoselenophenyl, carbazonyl, indolocarbazolyl, pyridylindolinine Thiazolyl, oxadiazolyl, oxatriazolyl, dioxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidyl, pyridazinyl, pyridazinyl, pyridazinyl, Pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, oxathiazinyl, oxadiazinyl, indolinine, benzimidazolyl, indazolyl, indoxaczinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, quinolinin, Wherein the heteroaryl group is selected from the group consisting of pyridyl, pyrimidinyl, pyrimidinyl, quinolinyl, quinolinyl, quinazolyl, quinoxalinin, naphthyridyl, phthalazinyl, phthalidinyl, xanthenyl, acridyl, phenazinyl, phenothiazinyl, Dipyridyl, benzothienopyridyl, thienodipyridylbenzoselenophenopyridyl, and cell Aromatic heterocyclic compounds such as nope nodi pyridyl; And aromatic hydrocarbons or aromatic heterocyclic compounds composed of 2 to 10 ring structures and containing at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and carbon in the ring.

Wherein each R ₁ to R ₁₂ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, Which may be further substituted with substituents selected from the group consisting of alkyl, alkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, When the alkyl constituting the substituent is a chain type or a branch type and when the substituent is two or more, a ring may be formed by a combination of substitution periods. The ligands according to the present invention can be prepared using various methods known to those skilled in the art.

In particular, in Formula 3,

R ₇ and R ₈ are the same as or different from each other and each represent hydrogen, deuterium, halide, alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, heteroalkyl of 6 to 20 carbon atoms, arylalkyl of 7 to 21 carbon atoms, Alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, amino, silyl, alkenyl having 2 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, heteroalkenyl having 2 to 10 carbon atoms, From the group consisting of alkynyl, aryl having 6 to 20 carbon atoms, heteroaryl having 6 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, The alkyl moiety constituting the substituent may be in the form of a chain or a chain and the adjacent two or more substituents may form a ring with each other, Preferable.

Particularly, in the above formula (3)

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ which are bonded to B ₁ and B ₂ are the same as or different from each other and each represent hydrogen, deuterium, halide, alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, Aryloxy having 1 to 20 carbon atoms, arylalkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, amino, silyl, alkenyl having 2 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, An alkynyl having 2 to 10 carbon atoms, an alkynyl having 2 to 10 carbon atoms, an aryl having 6 to 20 carbon atoms, a heteroaryl having 6 to 20 carbon atoms, an acyl, a carbonyl, a carboxylic acid, an ester, a nitrile, Sulfinyl, sulfonyl, and phosphino, wherein the alkyl moiety constituting the substituent may be in the form of a chain or a branch, wherein the adjacent Two or more substituents It is preferable that they can form a ring with each other.

On the other hand, the catalyst composition may further include a cocatalyst. The cocatalyst is a substance that reacts with a transition metal or transition metal precursor or ligand to have catalytic activity. Specific examples of such cocatalysts include at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6).

≪ Formula 4 >

In the general formula (4), R ₁₃ is alkyl having 1 to 10 carbon atoms, and r is an integer of 1 to 70.

≪ Formula 5 >

In Formula 5, R ₁₄ , R ₁₅ and R ₁₆ are the same or different and each is an alkyl having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or halogen,

Wherein R _14, R ₁₅ and R ₁₆ at least one of which is an alkyl group having 1 to 10 carbon atoms.

(6)

[CD]

In the above formula (6), C is a hydrogen ion-binding cation or oxidative metal or non-metal compound of a Lewis base, D is a compound of an organic substance with a Group 5 to 15 element, .

The compounds of the formulas (4) to (6) may act as scavengers for removing impurities acting as poisons in the catalysts in the reactants, or may be a compound in which ethylene reacts with the central metal by cationizing or activating the center metal of the transition metal compound It can play a role to be good.

In the catalyst composition, the number of moles of the transition metal compound: the number of moles of the compound of the formula 4 or 6 is 1: 1 to 1: 5,000, preferably 1:10 to 1: 1,000, more preferably 1:20 to 1: 1: 500. When the molar ratio is less than 1: 1, the effect of addition of the cocatalyst is insignificant. When the molar ratio is more than 1: 5,000, the excess alkyl groups that do not participate in the reaction and interfere with the catalytic reaction, The side reaction may proceed and excess aluminum or boron may remain in the polymer.

The compound of Formula 4 may have a chain, cyclic or network structure. Specific examples thereof include methylaluminoxane, ethylaluminoxane, butylaluminoxane, Hexylaluminoxane, octylaluminoxane, decylaluminoxane, and the like can be given.

Specific examples of the compound of Formula 5 include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecyl aluminum, ); 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; Alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, and butyl aluminum dichloride, and the like can be given.

The compound of formula (6) may serve to cationize or activate the center metal of the transition metal compound to allow ethylene to react well with the central metal, and may include nonconjugated anions compatible with cations which are Bronsted acid can do. Preferred anions are relatively large in size and contain a single coordination complex containing a metalloid. Particularly, compounds containing a single boron atom in the anion moiety are widely used. From this viewpoint, anion-containing salts containing coordination complex compounds containing a single boron atom are preferred.

In the catalyst composition, the number of moles of the transition metal or transition metal precursor: the number of moles of the compound of Formula 6 may be 1: 1 to 1:10, preferably 1: 1 to 1: 4. When the molar ratio is less than 1: 1, the amount of the cocatalyst is relatively small, so that the activation of the metal compound is not completely performed and the activity of the main catalyst may not be sufficient. When the molar ratio is more than 1:10, However, there is a problem that the catalyst cost is excessively increased due to the use of unnecessary catalyst.

Specific examples of the compound of formula (6) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropyl ammonium tetraphenylborate, tributylammonium tetraphenylborate, tributylammonium tetraphenylborate, tetra phenylborate), trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and tripropylammonium tetrakis (Pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenyl borate, and the like. nylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) , Tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) , Tris (2,3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane (Tris (3,4,5-trifluophenyl) borane).

On the other hand, according to another embodiment of the present invention, it is possible to further include a zinc compound as an additive. Wherein the zinc compound is a compound comprising all types of zinc or zinc. Zinc compounds can react with trialkylaluminum to form a new class of zinc. Specific examples of the zinc compound include zinc, activated zinc, zinc halide, alkyl zinc salt, zinc oxygenate (zinc acetate, zinc acetyl acetonate, zinc carboxylate), zinc porphyrin and the like. Preferably, the zinc compound is zinc dialkyl, most preferably dimethylzinc or diethylzinc. The zinc compound is contained in a sufficient amount in a ratio of 1 to 10000, preferably 10 to 1000, more preferably 50 to 450, based on the molar amount of chromium in the chromium source. The zinc concentration in the reactor is 0.0001 mmol / L to 1 mol / L, preferably 0.001 mmol / L to 0.1 mol / L. The zinc compound may be added at any stage during the activation process and is preferably added directly to the reactor. Zinc may be used as a trialkylaluminum, or a mixed storage solution with other components. The use of the zinc compound can significantly reduce the amount of the polymer by-product without changing the catalytic activity during the oligomerization reaction.

On the other hand, according to another embodiment of the present invention, hydrogen may be further included as an additive. The content ratio of hydrogen to monomer is preferably from 0.0001 to 100, more preferably from 0.01 to 10, still more preferably from 0.1 to 2. [ Hydrogen may be added at any stage during the oligomerization process and is preferably added directly to the reactor. By using hydrogen in combination with the monomers, the amount of the polymer byproduct can be significantly reduced without changing the catalytic activity during the oligomerization reaction.

In the production method of this embodiment of the present invention, alpha-olefin can be synthesized by reacting the catalyst composition with ethylene in an organic solvent. Specifically, 1-hexene and 1-octene can be prepared by introducing the catalyst composition, ethylene and an organic solvent into the reactor to proceed the reaction, oligomerizing ethylene, specifically trimerizing or quantifying the reaction product.

The organic solvent that can be used is not limited to a great extent, but may be, for example, a purified hydrocarbon compound (for example, n-hexane, n-Heptane, cyclohexane, toluene Toluene, benzene, etc.) may be used.

In the method for producing an alpha-olefin of one embodiment, the catalyst composition and the organic solvent may be injected into the reactor simultaneously or sequentially, and the transition metal compound and the organic ligand compound are first reacted to prepare a complex, The reaction may be carried out by introducing the catalyst solution prepared by reacting the catalyst to the solvent into the reactor.

In the process for preparing alpha-olefins of one embodiment, the temperature of the trimerization or tetramerization of ethylene in the presence of the catalyst is from 0 ° C to 200 ° C, preferably from 20 ° C to 150 ° C, the reaction pressure is from 1 bar to 150 bar, Preferably from 20 to 100 bar.

On the other hand, the amount of the metal precursor, the catalyst ligand and the promoter compound to be used in the reactor is not particularly limited, but the amount of the metal precursor: catalyst ligand: co-catalyst: zinc compound is 1: 1: 1: : 10: 10 ^6: 100, preferably 1: 1: 100: 1 to 1: 3: 10 ^3: 20 may be used in the molar ratio.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

(1) In the following Examples, Comparative Examples and Experimental Examples, all synthetic reactions were carried out under an inert atmosphere such as nitrogen or argon, and a standard Schlenk technique and a glove box (Glove Box) technology was used.

(2) Tetrahydrofuran (THF), n-Hexane, n-Pentane, Diethyl Ether, Methylene Chloride (CH2Cl2), toluene (C7H8) Was used while passing through an activated alumina column to remove water and then stored in an activated molecular sieve (Molecular Sieve 5, Yakuri Pure Chemicals Co). The NMR structure analysis of the compound Deuterated benzene-d6, C6D6, and dimethylsulfoxide-d6, C2D6S0) were purchased from Cambridge Isotope Laboratories and used as activated molecular sieves Molecular Sieve 5A, Yakuri Pure Chemicals Co).

(3) All reagents used in the following were purchased from Sigma-Aldrich and used without purification.

(4) 1H NMR was measured at room temperature using a Bruker Avance 400 Spectrometer. The chemical shift of the NMR spectrum was determined by using deuterated chloroform (CDCl ₃ ), deuterated benzene (C ₆ D ₆ ) And chemical shift values indicated by dimethyl sulfoxide (C ₂ D ₆ SO) = 7.24 ppm, 7.16 ppm, and 2.50 ppm, respectively.

≪ Synthesis Example: Synthesis of organic ligand compound >

1. Synthesis Example 1: Synthesis of 1,2- [C ₆ H ₂ (CH ₃ ) ₃ -imidazole] ₂ -C ₂ H ₄

(1) Synthesis Example 1-1: Synthesis of C ₆ H ₂ (CH ₃ ) ₃ -imidazole

After dissolving ammonium chloride (5.35 g, 100 mmol) in 20 mL of distilled water, add 100 mL of water, 100 mL of 1,4-dioxane, paraformaldehyde (3.00 g, 100 mmol), aqueous glyoxal solution (11.5 mL, ), And a mixture of mesityl ammonium salt (13.2 g, 200 mmol) was slowly added dropwise with stirring. After the addition was completed, the temperature of the reaction solution was raised to 100 C and refluxed for 3 hours.

After the reflux, the temperature was lowered to 0 캜, and an aqueous sodium hydroxide solution (1 M) was added dropwise until the pH became 12 or higher. After the dropwise addition was completed, the resultant was extracted with 1500 mL of hexane and dried using anhydrous magnesium sulfate. The solvent was evaporated on a rotary evaporator to give 2.71 g of white solid (S1-1).

1H NMR (CDCl3):? 7.50 (s), 6.98 (s), 6.92 (s), 2.35 (s), 2.00 (s).

(2) Synthesis Example _{1-2: [1,2-C 6 H} 2 (CH 3) 3 -imidazole 2 -C 2 H 4] Br 2

1,2-dibromoethane (0.94 g, 5 mmol) and the solid (S1-1) (1.72 g, 10 mmol) obtained in Synthesis Example 1-1 were dissolved in 100 mL of toluene and stirred. After completion of the stirring, the temperature of the reaction solution was raised to 120 DEG C, and the reaction solution was refluxed for 18 hours. After the reflux was completed, the temperature of the reaction solution was lowered to room temperature and filtered using a capstan to obtain 0.73 g (S1-2) of a white solid.

2.39 (s), 2.01 (s), 1.90 (s), 8.12 (s), 7.96 (s) (s), 1.32 (s).

(3) Synthesis Example 1-3: Synthesis of 1,2- [C ₆ H ₂ (CH ₃ ) ₃ -imidazole] ₂ -C ₂ H ₄

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise at room temperature to the solid (S1-2) (0.72 g, 1 mmol) obtained in Synthesis Example 1-2. After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered and concentrated using a caulk, and recrystallized at -50 캜 to obtain 0.58 g of a white solid (S1-3).

7.29 (s), 6.49 (s), 6.29 (s), 1.14 (s)

2. Synthesis Example 2: Synthesis of 1,4- [C ₆ H ₂ (CH ₃ ) ₃ -imidazole] ₂ -C ₄ H ₈

(1) Synthesis Example _{2-1: [1,4-C 6 H} 2 (CH 3) 3 -imidazole 2 -C 4 H 8] Br 2

Dibromobutane (1.08 g, 5 mmol) and the solid (S1-1) (1.72 g, 10 mmol) obtained in Synthesis Example 1-1 were dissolved in 100 mL of toluene and stirred.

The temperature of the reaction solution was raised to 120 DEG C and refluxed for 18 hours. After refluxing, the temperature of the reaction solution was lowered to room temperature and filtration was performed using a caulk to obtain 0.64 g of a white solid (S2-1).

(S), 7.21 (s), 7.21 (s), 4.26 (t), 3.09 (s), 2.33 (m), 1.21 (m), 1.09 (m).

(2) Synthesis Example 2-2: 1,4- [C ₆ H ₂ (CH ₃ ) ₃ -imidazole] ₂ -C ₄ H ₈

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise at room temperature to the solid (S2-1) (0.92 g, 1 mmol) obtained in Synthesis Example 2-1.

After the addition was completed, the reaction was carried out at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered and concentrated using a caulk, and recrystallized at -50 ° C to obtain 0.28 g of a white solid (S2-2).

1 H NMR (CDCl 3):? 7.45 (s), 6.37 (s), 6.00 (s), 2.39 (s), 2.21 (s), 1.11 (m).

3. Synthesis Example 3: 1,6- [C ₆ H ₂ (CH ₃ ) ₃ -imidazole] ₂ -C ₆ H ₁₂

(1) Synthesis Example _{3-1: [1,6-C 6 H} 2 (CH 3) 3 -imidazole 2 -C 6 H 12] Br 2

1,1-dibromohexane (0.94 g, 5 mmol) and the solid (S1-1) (1.72 g, 10 mmol) obtained in Synthesis Example 1-1 were dissolved in 100 mL of toluene and stirred. The temperature of the reaction solution was raised to 120 DEG C and refluxed for 18 hours. After the refluxing, the temperature of the reaction solution was lowered to room temperature and filtered using a calender to obtain 0.92 g of a white solid (S3-1).

(M), 2.12 (m), 1.45 (s), 7.32 (s), 7.21 (s), 4.11 (t), 3.12 (m), 1.11 (m).

(2) Synthesis Example 3-2: 1,6- [C ₆ H ₂ (CH ₃ ) ₃ -imidazole] ₂ -C ₆ H ₁₂

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise to the solid (S3-1) (0.88 g, 1 mmol) obtained in Synthesis Example 3-1 at room temperature.

After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered and concentrated using a caulk, and recrystallized at -50 캜 to obtain 0.45 g of a white solid (S3-2).

1 H NMR (CDCl 3):? 7.32 (s), 6.21 (s), 6.12 (s), 2.61 (s), 2.31 (s), 1.88 (m), 1.23 (m).

4. Synthesis Example 4: Synthesis of 1,2- [C ₃ H ₇ -imidazole] ₂ -C ₂ H ₄

(1) Synthesis Example 4-1: Synthesis of C ₃ H ₇ -imidazole

After dissolving ammonium chloride (5.35 g, 100 mmol) in 20 mL of distilled water, add 100 mL of water, 100 mL of 1,4-dioxane, paraformaldehyde (3.00 g, 100 mmol), aqueous glyoxal solution (11.5 mL, ), And isopropylammonium salt (7.55 g, 200 mmol) were slowly added dropwise with stirring. After the addition was completed, the temperature of the reaction solution was raised to 100 C and refluxed for 3 hours.

After the reflux, the temperature was lowered to 0 캜, and an aqueous sodium hydroxide solution (1 M) was added dropwise until the pH became 12 or higher. After the dropwise addition was completed, the resultant was extracted with 1500 mL of hexane and dried using anhydrous magnesium sulfate. The solvent was evaporated on a rotary evaporator to give 3.59 g of white solid (S4-1).

1 H NMR (CDCl 3):? 7.11 (s), 2.21 (m), 1.77 (d).

(2) Synthesis Example 4-2: [1,2-C ₃ H ₇ -imidazole ₂ -C ₂ H ₄ ] Br ₂

Dibromobutane (1.08 g, 5 mmol) and the solid (S4-1) (1.72 g, 10 mmol) obtained in Synthesis Example 4-1 were dissolved in 100 mL of toluene and stirred. The temperature of the mixed solution was raised to 120 ° C and refluxed for 18 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered using a caulk press to obtain 0.65 g of a white solid (S4-2).

1 H NMR (DMSO-d 6):? 10.20 (s), 9.22 (s), 4.12 (t), 3.66 (s), 2.33 (m), 1.11 (d).

(3) Synthesis Example 4-3: Synthesis of 1,2- [C ₃ H ₇ -imidazole] ₂ -C ₂ H ₄

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise at room temperature to the solid (S4-2) (0.87 g, 1 mmol) obtained in Synthesis Example 4-2.

After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered and concentrated using a caulk, and recrystallized at -50 캜 to obtain 0.33 g of a white solid (S4-3).

1 H NMR (CDCl 3):? 7.21 (s), 6.32 (s), 2.32 (m), 2.23 (m), 1.12 (m).

5. Synthesis Example 5: Synthesis of [C ₆ H ₂ (CH ₃ ) ₃ -imidazole- (C ₂ H ₄ )] ₂ -C ₃ H ₇ N

(1) Synthesis Example 5-1: Br ₂ [C ₆ H ₂ (CH ₃ ) ₃ -imidazole- (C ₂ H ₄ )] ₂ -C ₃ H ₇ N

_{(BrC 2 H 4) 2 -C} 3 H 7 N (1.21 g, 5 mmol) and stirred to dissolve the solid (S1-1) (1.72 g, 10 mmol) obtained in the Synthesis Example 1-1 in toluene 100 mL Respectively. The temperature of the mixed solution was raised to 120 ° C and refluxed for 18 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered using a calender to obtain 0.42 g of a white solid (S5-1).

(S), 8.12 (s), 7.34 (s), 7.12 (s), 4.33 (t), 4.22 (s), 3.09 (b), 2.11 (m), 1.32 (m), 1.08 (m).

(2) Synthesis Example 5-2: [C ₆ H ₂ (CH ₃ ) ₃ -imidazole- (C ₂ H ₄ )] ₂ -C ₃ H ₇ N

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise at room temperature to the solid (S5-1) (0.92 g, 1 mmol) obtained in Synthesis Example 5-1. After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered and concentrated using a caulk, and recrystallized at -50 ° C to obtain 0.47 g of a white solid (S5-2).

(S), 7.23 (s), 6.93 (s), 6.77 (s), 5.23 (t), 4.99 (s), 2.23 (m), 1.12 (m), 0.92 (m).

6. Synthesis Example 6: [C ₃ H ₇  -imidazole- (C ₂ H ₄ )] ₂ -C ₃ H ₇ N

(1) Synthesis Example 6-1: Br ₂ [C ₃ H ₇ -imidazole- (C ₂ H ₄ )] ₂ -C ₃ H ₇ N

_{(BrC 2 H 4) 2 -C} 3 H 7 N (1.91 g, 5 mmol) and stirred and then the solid (S1-1) (1.72 g, 10 mmol) obtained in the Synthesis Example 1-1 was dissolved in 100 mL toluene Respectively. The temperature of the mixed solution was raised to 120 ° C and refluxed for 18 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered using a calender to obtain 0.97 g of a white solid (S6-1).

[Delta] 8.09 (s), 7.43 (s), 7.12 (s), 6.89 (s), 6.21 (t), 5.33 (m).

(2) Synthesis Example 6-2: [C ₃ H ₇ -imidazole- (C ₂ H ₄ )] ₂ -C ₃ H ₇ N

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise to the solid (S6-1) (0.9 g, 1 mmol) obtained in Synthesis Example 6-1 at room temperature. After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered and concentrated using a caulk, and recrystallized at -50 ° C to obtain 0.47 g of a white solid (S6-2).

0.47 g of 1 H NMR (DMSO-d 6):? 2) was obtained and concentrated. -50. 3.99 (t), 1.59 (m), and 1.21 (m) obtained in Synthesis Example 6-1.

7. Synthesis Example 7: Synthesis of 1,2- [CH ₃ -imidazole] ₂ -C ₂ H ₄

(1) Synthesis Example 7-1: Synthesis of CH ₃ -imidazole

After dissolving ammonium chloride (5.35 g, 100 mmol) in 20 mL of distilled water, add 100 mL of water, 100 mL of 1,4-dioxane, paraformaldehyde (3.00 g, 100 mmol), aqueous glyoxal solution (11.5 mL, ), And a methylammonium salt (3.4 g, 200 mmol) was slowly added dropwise with vigorous stirring. After dropwise addition, the temperature of the reaction solution was raised to 100 DEG C and refluxed for 3 hours.

After the reflux, the temperature was lowered to 0 캜, and an aqueous sodium hydroxide solution (1 M) was added dropwise until the pH became 12 or higher. After the dropwise addition was completed, the resultant was extracted with 1500 mL of hexane and dried using anhydrous magnesium sulfate. The solvent was evaporated on a rotary evaporator to give 5.74 g of white solid (S7-1).

1 H NMR (CDCl 3):? 7.34 (s), 7.11 (s), 0.91 (s).

(2) Synthesis Example 7-2: [1,2-CH ₃ -imidazole ₂ -C ₂ H ₄ ] Br ₂

1,2-dibromoethane (0.94 g, 5 mmol) and the solid (S7-1; 0.82 g, 10 mmol) obtained in Synthesis Example 7-1 were dissolved in 100 mL of toluene and stirred. The temperature of the mixed solution was raised to 120 ° C and refluxed for 18 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered using a cal press to obtain 0.70 g of a white solid (S7-2).

7.23 (s), 7.23 (s), 7.03 (s), 7.01 (s), 4.21 (t), 3.24 (s), 2.44 (s), 2.02 (s), 1.25 (s), 1H NMR (DMSO- s).

(3) Synthesis Example 7-3: Synthesis of 1,2- [CH ₃ -imidazole] ₂ -C ₂ H ₄

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise at room temperature to the solid (S4-2; 0.35 g, 1 mmol) obtained in Synthesis Example 7-2.

After the addition was completed, the mixed solution was reacted at room temperature for 12 hours. After completion of the reaction, the reaction solution was filtered using a caulk, concentrated, and recrystallized at -50 ° C. to obtain 0.12 g of a white solid (S7-3).

1H NMR (CDCl3):? 7.53 (s), 6.21 (s), 2.66 (m), 2.32 (m), 1.11 (m).

8. Synthesis Example 8: Synthesis of 1,2- [C ₆ H ₅ -imidazole] ₂ -C ₂ H ₄

(1) Synthesis Example 8-1: Synthesis of C ₆ H ₅ -imidazole

100 mL of water, 100 mL of 1,4-dioxane, paraformaldehyde (3.00 g, 100 mmol), and aqueous glyoxal solution (11.5 mL, 100 mmol) were dissolved in 20 mL of distilled water. ), And a phenylammonium salt (9.45 g, 200 mmol) was slowly added dropwise with vigorous stirring. After dropwise addition, the temperature of the reaction solution was raised to 100 DEG C and refluxed for 3 hours.

After refluxing, the temperature was lowered to 0 캜, and an aqueous solution of sodium hydroxide (1 M) was added dropwise until the pH reached 12 or higher. After the dropwise addition was completed, the resultant was extracted with 1500 mL of hexane and dried using anhydrous magnesium sulfate. The solvent was evaporated on a rotary evaporator to give 3.41 g of white solid (S8-1).

1 H NMR (CDCl 3):? 7.56 (s), 7.07 (s), 2.14 (m), 1.01 (s).

(2) Synthesis Example 8-2: [1,2-C ₆ H ₅ -imidazole ₂ -C ₂ H ₄ ] Br ₂

1,2-dibromoethane (0.94 g, 5 mmol) and the solid (S8-1; 1.94 g, 10 mmol) obtained in Synthesis Example 8-1 were dissolved in 100 mL of toluene and stirred. The temperature of the mixed solution was raised to 120 ° C and refluxed for 18 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered using a cal press to obtain 0.94 g of a white solid (S8-2).

1.39 (s), 1.94 (s), 7.51 (s), 7.04 (s), 7.04 (s) s).

(3) Synthesis Example 8-3: Synthesis of 1,2- [C ₆ H ₅ -imidazole] ₂ -C ₂ H ₄

Potassium bistrimethylsilylamide (1 mL, 1 M THF solution) was slowly added dropwise at room temperature to the solid (S8-2; 0.48 g, 1 mmol) obtained in Synthesis Example 8-2.

After the addition was completed, the mixed solution was reacted at room temperature for 12 hours. After completion of the reaction, the reaction solution was filtered using a caulk, concentrated, and recrystallized at -50 ° C to obtain 0.16 g of a white solid (S8-3).

1 H NMR (CDCl 3):? 7.78 (s), 7.37 (m), 6.55 (s), 2.25 (m), 1.92 (m), 1.02 (m).

[Oligomerization reaction of ethylene with trichlorotrifluoride chromium and zinc compounds]

≪ Example 1 >

A 2 L stainless steel reactor was charged with nitrogen, 1 L of cyclohexane was added, 9.0 mmol of MAO (10 wt% in toluene, Albermale) was added and the temperature was raised to 75 ° C. In a glove box, 11 mg (0.030 mmol) of trichlorotetrahydrofuran chromium in 10 mL of toluene was taken in a 50 Schlenk vessel, 0.030 mmol of the ligand obtained in Synthesis Example 1 was mixed, and the mixture was stirred at room temperature for 5 minutes and then added to the reactor.

The pressure reactor was charged with 30 bar of ethylene and stirred at a stirring speed of 300 rpm. After one hour, the ethylene feed to the reactor was stopped, the stirring was stopped to stop the reaction and the reactor was cooled to below 10 < 0 > C.

After the excess ethylene was discharged from the reactor, ethanol containing 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. A small amount of organic layer sample was passed over silica gel, dried and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried in an oven at 80 DEG C for 8 hours and then weighed to give polyethylene.

≪ Example 2 >

The reaction was carried out in the same manner as in Example 1 except that 0.030 mmol of the ligand obtained in Synthesis Example 1 and 0.03 mmol of diethylzinc were mixed at room temperature for 5 minutes and then added to the reactor to obtain an organic layer sample, .

≪ Example 3 >

The reaction was carried out in the same manner as in Example 1 except that 0.030 mmol of the ligand obtained in Synthesis Example 1 and 0.06 mmol of diethylzinc were mixed at room temperature for 5 minutes and then added to the reactor, .

<Example 4>

The reaction was carried out in the same manner as in Example 1 except that 0.030 mmol of the ligand obtained in Synthesis Example 1 and 0.12 mmol of diethyl zinc were mixed at room temperature for 5 minutes and then added to the reactor to obtain an organic layer sample, .

The production results of 1-hexene or 1-octene in Examples 1 to 4 are shown in Table 1 below.

Catalytic activity and analytical results
Diethylzinc (mmol)
Selectivity (% by weight) 1-hexene + 1-octene Polyethylene Example 1 0 98.8 1.2 Example 2 0.03 99.0 1.0 Example 3 0.06 99.1 0.9 Example 4 0.12 99.6 0.4

* Catalytic activity unit: g- (1-Hexene + 1-Octene) /mmol-Metal.h

[Oligomerization reaction of ethylene with trichloride trichloride and hydrogen]

&Lt; Example 5 >

A 2 L stainless steel reactor was charged with nitrogen, 1 L of cyclohexane was added, 9.0 mmol of MAO (10 wt% in toluene, Albermale) was added and the temperature was raised to 75 ° C. In a glove box, 11 mg (0.030 mmol) of trichlorotetrahydrofuran chromium in 10 mL of toluene was taken in a 50 Schlenk vessel, 0.030 mmol of the ligand obtained in Synthesis Example 1 was mixed, and the mixture was stirred at room temperature for 5 minutes and then added to the reactor .

The pressure reactor was charged with 25 bar of ethylene and 5 bar of hydrogen, and stirred at a stirring speed of 300 rpm. After one hour, the ethylene feed to the reactor was stopped, the stirring was stopped to stop the reaction and the reactor was cooled to below 10 &lt; 0 &gt; C.

After the excess ethylene was discharged from the reactor, ethanol containing 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. A small amount of organic layer sample was passed over silica gel, dried and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried in an oven at 80 DEG C for 8 hours and then weighed to give polyethylene.

&Lt; Example 6 >

The reaction was carried out in the same manner as in Example 5 except that ethylene was charged at 30 bar and hydrogen at 5 bar, and an organic layer sample, polyethylene, was obtained.

&Lt; Example 7 >

The reaction was carried out in the same manner as in Example 5 except that ethylene was charged at 30 bar and hydrogen at 5 bar, and an organic layer sample, polyethylene, was obtained.

&Lt; Example 8 >

The reaction was carried out in the same manner as in Example 5 except that ethylene was charged to 30 bar and hydrogen to 15 bar to obtain an organic layer sample, polyethylene.

&Lt; Example 9 >

The reaction was carried out in the same manner as in Example 5 except that ethylene was charged at 30 bar and hydrogen at 20 bar, and an organic layer sample, polyethylene, was obtained.

&Lt; Comparative Example: Oligomerization Reaction Using Ethylene Oligomerization Catalyst >

An organic layer sample, polyethylene, was obtained in the same manner as in Example 1, except that TaCl ₅ disclosed in U.S. Patent No. 6344594 was used as the catalyst for ethylene oligomerization.

The production results of 1-hexene or 1-octene in Examples 5 to 8 and Comparative Examples are shown in Table 2 below.

Catalytic activity and analytical results Ethylene
(bar) Hydrogen
(bar) Selectivity (% by weight) 1-hexene + 1-octene Polyethylene Example 1 30 0 98.8 1.2 Example 5 25 5 99.0 1.0 Example 6 30 5 99.0 1.0 Example 7 30 15 99.6 0.4 Example 8 30 20 > 99.9 trace Comparative Example 30 0 96.8 3.2

* Catalytic activity unit: g- (1-Hexene + 1-Octene) /mmol-Metal.h

As shown in Tables 1 and 2, when the catalyst compositions of Examples 1 to 8 were used, it was possible to synthesize 1-hexene and 1-octene at a high selectivity ratio, I could confirm.

Claims (16)

At least one organic ligand compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3); At least one transition metal or transition metal precursor selected from the group consisting of Group 4 to Group 12 elements; And 1-hexene and 1-octene from the olefin in the presence of a catalyst composition comprising a cocatalyst.
&Lt; Formula 1 >

(2)

(3)

In the above Formulas 1 to 3,
R ₁ to R ₁₂ are the same or different and are each independently hydrogen, deuterium, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, provided that the alkyl constituting R ₁ to R ₁₂ is Chain type or branch type, and two or more neighboring substituents of R ₁ to R ₁₂ may be connected to each other to form a ring,
n is an integer of 1 to 20,
E is an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P)
B ₁ and B ₂ are the same or different and are selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) B ₁ may form a ring with R _{9 and} R ₁₀ , and B ₂ may form a ring with R _{11 and} R ₁₂ . The method according to claim 1,
A process for producing 1-hexene and 1-octene, further comprising a zinc compound as an additive. 3. The method according to claim 1 or 2,
A process for the preparation of 1-hexene and 1-octene, further comprising hydrogen as an additive. 3. The method according to claim 1 or 2,
Wherein the transition metal is chromium-containing 1-hexene and 1-octene. The method according to claim 1,
Wherein the transition metal precursor is selected from the group consisting of 1-hexene and 1-hexene, including at least one selected from the group consisting of chromium (III) acetylacetonate, chromium tristrifluoride tetrahydrofuran and chromium (III) Octene. The method according to claim 1,
R ₁ to R ₁₂ are the same or different and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, alkylsilyl having 1 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms, alkylaryl having 7 to 21 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkylsiloxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, Aryl, heteroaryl having 6 to 20 carbon atoms, alkenyl having 2 to 10 carbon atoms, halogen or amino, provided that the alkyl constituting R ₁ to R ₁₂ is a chain type or branch type,
E is nitrogen (N) or sulfur (S)
B ₁ and B ₂ are the same or different and are an element selected from the group consisting of carbon (C), nitrogen (N) and sulfur (S), respectively. The method according to claim 1,
In Formula 3,
R ₇ and R ₈ are the same as or different from each other and each represent hydrogen, deuterium, halide, alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, heteroalkyl of 6 to 20 carbon atoms, arylalkyl of 7 to 21 carbon atoms, Alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, amino, silyl, alkenyl having 2 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, heteroalkenyl having 2 to 10 carbon atoms, From the group consisting of alkynyl, aryl having 6 to 20 carbon atoms, heteroaryl having 6 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, Wherein the alkyl constituting the substituent may be in the form of a chain or a chain and the adjacent two or more substituents may form a ring together with one or more substituents selected from 1-hexene And 1- The method of Lichtenstein. The method according to claim 1,
In Formula 3,
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ which are bonded to B ₁ and B ₂ are the same as or different from each other and each represent hydrogen, deuterium, halide, alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, aryloxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, amino, silyl, alkenyl having 2 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, A heteroaryl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms, an acyl, a carbonyl, a carboxylic acid, an ester, a nitrile, , Sulfinyl, sulfonyl, and phosphino, wherein the alkyl constituting the substituent may be in the form of a chain or a chain, and the adjacent 2 The above substituents may be the same or different, Capable of forming, method for producing 1-hexene and 1-octene. The method according to claim 1,
Wherein the cocatalyst comprises at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6)
&Lt; Formula 4 >

In Formula 4, R ₁₃ is alkyl having 1 to 10 carbon atoms, r is an integer of 1 to 70,
&Lt; Formula 5 >

In Formula 5, R ₁₄ , R ₁₅ and R ₁₆ are the same or different and each is an alkyl having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or halogen,
At least one of R ₁₄ , R ₁₅ and R ₁₆ is alkyl having 1 to 10 carbon atoms,
(6)
[CD]
In the above formula (6), C is a hydrogen ion-binding cation or oxidative metal or non-metal compound of a Lewis base, D is a compound of an organic substance with a Group 5 to 15 element, . 3. The method of claim 2,
Wherein the zinc compound is selected from the group consisting of zinc, activated zinc, zinc halide, alkyl zinc, zinc oxigenate, zinc porphyrin, and 1-octene. 5. The method of claim 4,
Hexene and 1-octene, wherein the zinc compound is contained in a weight ratio of 1 to 10000 relative to the molar amount of chromium in the chromium source. The method of claim 3,
Wherein the content ratio of hydrogen to monomer is from 0.0001 to 100, 1-hexene and 1-octene. 10. The method of claim 9,
The compound represented by the general formula (4) may be at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, 1-hexene and 1-octene. 10. The method of claim 9,
The compound represented by the general formula (5) may be a trialkylaluminum, a dialkylaluminum alkoxide, a dialkylaluminum halide, an alkylaluminum dialkoxide, an alkylaluminum dihalide, Hexene and 1-octene. 10. The method of claim 9,
The compound represented by the general formula (6) is preferably selected from the group consisting of trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, (Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, and triethylammonium tetrakis (Pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetraphenylborate, Anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, ferroimide tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, silver tetra phenylborate, silver tetrakis (pentafluorophenyl) borate, Tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, 2,3,4,5-tetraphenylphenyl) borane, or tris (3,4,5-trifluorophenyl) borane (Tris (3, , 4,5-trifluoro phenyl) borane). The method according to claim 1,
A process for the production of 1-hexene and 1-octene wherein the reaction temperature is from 0 to 200 ° C and the reaction pressure is from 1 to 150 bar.