KR20150002549A - Catalyst compositon and preparation method of alpha-olefin - Google Patents

Abstract

The present invention relates to a catalyst composition including: an organic ligand compound of a specific chemical structure; and a chrome compound, and to a method for synthesizing alpha-olefin using the catalyst composition. The catalyst composition has high selectivity and reaction activity, thereby stably synthesizing alpha-olefin. More specifically, the present invention provides a catalyst composition including an organic ligand compound selected from a group consisting of a compound of chemical formula 1 and a compound of chemical formula 2; and a transition metal compound including group 4 to 12 transition metals.

Description

[0001] CATALYST COMPOSITON AND PREPARATION METHOD OF ALPHA-OLEFIN [0002]

More particularly, the present invention relates to a catalyst composition capable of stably synthesizing an alpha-olefin having a high selectivity and a reaction activity, and a catalyst composition capable of stably synthesizing an alpha-olefin And a manufacturing method thereof.

Conventionally, in order to synthesize 1-hexene or 1-octene, various 1-olefin mixtures are prepared by mainly oligomerizing ethylene, 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 the conventionally known methods, a variety of olefins other than 1-hexene or 1-octene which are commercially useful are simultaneously prepared and further separation and purification processes are required. Due to the cost of such separation and purification, 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, there is known a method of oligomerizing ethylene using a chromium compound. US Patent No. 6943224, U.S. Patent No. 6924248 and U.S. Patent No. 6900152 disclose a method of oligomerization of a transition metal containing chromium A method of oligomerizing ethylene through coordination complexes has been introduced. US 6344594 also discloses TaCl ₅ as a catalyst for the production of 1-hexene or 1-octene.

However, commercialized catalysts known so far have a limitation in that the selectivity of 1-hexene and 1-octene is low, the specific ligands or compounds must be used, the production cost is high, and the reaction stability of the catalyst is not so high.

U.S. Patent No. 6943224 United States Patent No. 6924248 US Patent No. 6900152 United States Patent No. 6344594

The present invention is to provide a catalyst composition capable of stably synthesizing alpha-olefins with high selectivity and reaction activity.

The present invention also provides a process for synthesizing alpha-olefins using the catalyst composition.

The present invention relates to an organic ligand compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2); And a transition metal compound comprising a transition metal of group 4 to group 12.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R ₁ to R ₈ may be the same or different from each other and each represent hydrogen, straight or branched chain alkyl of 1 to 10 carbon atoms, straight or branched chain alkenyl of 2 to 10 carbon atoms, aryl of 6 to 20 carbon atoms, An arylalkyl having 7 to 21 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, an aryloxy having 6 to 20 carbon atoms, an alkylsilyl having 1 to 10 carbon atoms, an arylalkyl having 6 to 20 carbon atoms Arylsilyl or halogen,

Two or more adjacent two of R ₁ to R ₈ may be connected to form a ring,

n is an integer of 1 to 20,

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

Each of a and b is 0 or 1,

R ₁₁ and R ₁₂ may be the same or different and are each a straight or branched alkyl of 1 to 10 carbon atoms, a straight or branched alkenyl of 2 to 10 carbon atoms, an aryl of 6 to 20 carbon atoms, Arylalkyl having 7 to 21 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, aryloxy having 6 to 20 carbon atoms, alkylsilyl having 1 to 10 carbon atoms, arylsilyl having 6 to 20 carbon atoms Or halogen,

R ₁₁ and R ₁₂ may be connected to each other to form a ring,

Y and Z may be the same or different and each represents a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, An alkylarylene group having 1 to 20 carbon atoms, or an arylalkylene group having 7 to 20 carbon atoms.

The present invention also provides a process for preparing alpha-olefins using the catalyst composition.

According to the present invention, there can be provided a catalyst composition capable of stably synthesizing an alpha-olefin having a high selectivity and a reaction activity, and a method of synthesizing an alpha-olefin using the catalyst composition.

Particularly, when the catalyst composition is used, 1-hexene and 1-octene can be stably synthesized while ensuring high selectivity and catalytic activity.

Hereinafter, a catalyst composition and a method for producing an alpha-olefin according to a specific embodiment of the present invention will be described in 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.

In addition, 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 Means a linear or branched alkyl group having at least one aryl group introduced thereto.

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 >

Also, alkylsilyl and arylsilyl mean a silyl group bonded to 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 the alkylarylene group means an arylene group in which one or more alkyl groups are substituted, and the allylalkylene group means an alkylene group in which at least one allyl group is substituted.

According to an embodiment of the present invention, an organic ligand compound selected from the group consisting of the compound of Formula 1 and the compound of Formula 2; And a transition metal compound comprising a transition metal of group 4 to group 12.

The present inventors have newly synthesized the compound of Formula 1 and the compound of Formula 2 and found that when these compounds are used together with the transition metal compound, alpha-olefin can be stably synthesized with high selectivity and reaction activity from ethylene Was confirmed through experiments and the invention was completed.

In particular, the use of the compound of formula (1), the compound of formula (2), or a mixture thereof with a transition metal compound provides a catalyst having enhanced catalytic activity compared to other previously known transition metal catalysts, Can be synthesized efficiently and stably as a selection ratio.

As described above, the catalyst composition of this embodiment can be used for the reaction of synthesizing an alpha-olefin from ethylene. The alpha-olefins synthesized may include 1-hexene and 1-octene, and may additionally include other alpha-olefins.

R _1, R _2, R ₃ , R ₄ , R ₅ and R ₆ may be the same or different from each other and each represent a hydrogen atom, a carbon number 1 A straight chain or branched alkyl group having from 1 to 10 carbon atoms, a cycloalkyl group having from 4 to 8 carbon atoms, or an aryl group having from 6 to 20 carbon atoms.

R ₇ and R ₈ in Formula 1 may be the same or different and each is a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

More specifically, R ₃ , R ₄ , R ₅ and R ₆ in Formula 2 may be the same or different from each other and each represent hydrogen, a straight chain having 1 to 10 carbon atoms Or a branched alkyl group, a cycloalkyl group having 4 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

R ₇ and R ₈ in Formula 2 may be the same or different and each is a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms An alkylaryl group of 7 to 20 carbon atoms or an arylalkyl group of 7 to 20 carbon atoms.

X in the formula (2) may be nitrogen, and Y may be the same or different from each other and each may be an alkylene group having 1 to 5 carbon atoms, a may be 1, and b may be 0.

R ₁₁ in Formula 2 is a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, Lt; / RTI >

In the catalyst composition of this embodiment, the organic ligand compound and the transition metal compound may form a coordination bond. More specifically, the non-covalent electron pair of the compound of Formula 1 or the compound of Formula 2 and the transition metal of the transition metal compound are coordinated to each other Can be formed.

The transition metal compound may include a transition metal of Groups 4 to 12, and may be the transition metal itself or an organic compound containing the transition metal.

The transition metal compound may include a chromium compound.

The chromium compound may be a chromium metal or an organic compound containing chromium. Specifically, the chromium compound may be chromium, chromium (III) acetylacetonate, chromium tris (tetrahexyl) chromium trichloride, chromium (III) 2-ethylhexanoate, or a mixture of two or more thereof.

On the other hand, the catalyst composition may include 0.5 to 2.0 mol, preferably 0.8 to 1.2 mol, of the organic ligand compound per mol of the transition metal compound.

If the content of the organic ligand compound is too small as compared with the transition metal compound, the reaction active sites of the catalyst composition may not be sufficiently formed, the activity of the catalyst may be decreased, and the selectivity to the synthesized alpha-olefin may be decreased have. If the content of the organic ligand compound is too high as compared with the transition metal compound, the reaction active site of the catalyst composition may not be sufficiently exposed to the outside, and thus the activity of the catalyst and the selectivity to the alpha-olefin And the like may be rather deteriorated.

On the other hand, the catalyst composition may further include a cocatalyst. Specific examples of such cocatalysts include compounds represented by the following general formula (11), (12), (13), or a mixture of two or more thereof.

(11)

In Formula 11, R ₁₃ is an alkyl group having 1 to 10 carbon atoms, and r may be an integer of 1 to 70.

[Chemical Formula 12]

R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or halogen, and R ₁₄ , R ₁₅ and R ₁₆ may be an alkyl group having 1 to 10 carbon atoms.

[Chemical Formula 13]

^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -

In Formula 11, L is a neutral or cationic Lewis base, [LH] + or [L] ⁺ is a Bronsted acid, H is a hydrogen atom, Z is a Group 13 element,

E may be the same or different and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy functional group and phenoxy functional group, wherein at least one functional group is substituted or unsubstituted having 6 to 20 An aryl group; Or an alkyl group having 1 to 20 carbon atoms in which at least one functional group selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy functional group and phenoxy functional group is substituted or unsubstituted.

The compound of formula (11) or (12) may act as a scavenger for removing impurities acting as poison to the catalyst in the reactant, 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 Formula 11 or 12 is 1: 1 to 1: 5,000, preferably 1:10 to 1: 1,000, 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 11 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 (12) include, for example, trimethylalumium, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum 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; There may be mentioned alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, and butyl aluminum dichloride.

The compound of formula (13) 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 contain non-coordinating anions compatible with the cations as the 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 compound: the number of moles of the compound of Formula 13 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, so that the activity of the transition metal catalyst may not be sufficient. When the molar ratio is more than 1:10, The activity may be increased, but the use of unnecessarily cocatalyst may cause a problem of a large increase in production cost.

Specific examples of the compound of formula (13) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium 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. enylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetra phenylborate, 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-trifluophenyl) borane).

On the other hand, according to another embodiment of the present invention, a process for producing an alpha-olefin using the above-described catalyst composition can be provided.

As described above, the organic ligand compound selected from the group consisting of the compound of Formula 1 and the compound of Formula 2; And a transition metal compound comprising a transition metal of group 4 to group 12 can be stably synthesized from ethylene with alpha-olefin having a high selectivity and reaction activity. Especially, when the catalyst composition is used, 1-hexene and 1-octene can be efficiently and stably synthesized at a high selectivity ratio while securing an improved catalytic activity as compared with other previously known transition metal catalysts.

The details of the compound of Formula 1, the compound of Formula 2 and the transition metal compound are as described above.

As described above, the catalyst composition may optionally further include a cocatalyst.

In the process for preparing alpha-olefins of the embodiment, alpha-olefins can be synthesized by reacting the catalyst composition with ethylene in an organic solvent. Specifically, the catalyst composition, ethylene and an organic solvent are introduced into the reactor to conduct the reaction to oligomerize ethylene to synthesize alpha-olefins. Particularly, ethylene is subjected to trimerization or tetramerization to produce 1-hexene and 1- Octene can be produced.

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.

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 moisture and then stored on an activated molecular sieve (Molecular Sieve 5 Å, 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? = 7.24 ppm, 7.16 ppm, and 2.50 ppm represented by dimethyl sulfoxide (C ₂ D ₆ SO), 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 caulk 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: Synthesis of [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: [{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 is completed, And reacted 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: Synthesis of [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 mixture 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: Synthesis of [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).

[Example 1: oligomerization reaction of ethylene with trichlorotetrahydrofuran chromium]

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 45 ° C. In a glove box, 11 mg (0.030 mmol) of trichlorotetrahydrofuran chromium in 10 mL of toluene was taken in a 50 mL Schlenk vessel, 0.030 mmol of each of the ligands obtained in Synthesis Example 1 was mixed, and the mixture was stirred at room temperature for 5 minutes. .

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.

[Examples 2 to 8: Oligomerization reaction of ethylene with trichlorotetrahydrofuran chromium]

An organic layer sample, polyethylene, was obtained in the same manner as in Example 1 except that the ligands of Synthesis Examples 2 to 8 were used instead of the ligands of Synthesis Example 1, respectively

[Example 9: oligomerization reaction of ethylene with chromium (III) 2-ethylhexanoate]

Except that 14 mg (0.03 mmol) of chromium (III) 2-ethylhexanoate was used instead of 11 mg (0.030 mmol) of trichlorotetrahydrofuran chromium in 10 mL of toluene, , And polyethylene.

[Example 10: oligomerization reaction of ethylene with chromium (III) acetylacetonate]

Except that 10 mg (0.03 mmol) of chromium (III) acetylacetonate was used instead of 11 mg (0.030 mmol) of trichlorotetrahydrofuran chromium in 10 mL of toluene, and the organic layer sample, polyethylene ≪ / RTI >

≪ 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 a catalyst for ethylene oligomerization.

The results of the production of 1-hexene or 1-octene in Examples 1 to 10 and Comparative Examples are shown in Table 1 below.

Catalytic activity and analytical results Catalytic activity * Selectivity (wt%) Ligand Transition metal 1-hexene 1-octene 1-decene Polyethylene
(PE) Example 1 Synthesis Example 1 Trichloride trithahydrofuran chromium 1,456 21.5 77.0 - 1.4 Example 2 Synthesis Example 2 Trichloride trithahydrofuran chromium 1,213 24.2 74.1 - 1.7 Example 3 Synthesis Example 3 Trichloride trithahydrofuran chromium 936 19.4 78.3 - 2.3 Example 4 Synthesis Example 4 Trichloride trithahydrofuran chromium 424 21.5 76.6 - 1.9 Example 5 Synthesis Example 5 Trichloride trithahydrofuran chromium 562 27.2 70.1 - 2.7 Example 6 Synthesis Example 6 Trichloride trithahydrofuran chromium 467 32.1 65.8 - 2.1 Example 7 Synthesis Example 7 Trichloride trithahydrofuran chromium 512 42.7 54.3 3.0 Example 8 Synthesis Example 8 Trichloride trithahydrofuran chromium 643 39.4 57.2 3.4 Example 9 Synthesis Example 1 Chromium (?) 2-ethylhexanoate 1,521 22.6 76.4 1.0 Example 10 Synthesis Example 1 Chromium (?) Acetylacetonate 1,468 26.5 72.5 1.0 Comparative Example 350 83.3 - 13.5 3.2

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

As shown in Table 1, when the catalyst compositions of Examples 1 to 10 were used, it was possible to synthesize 1-hexene and 1-octene with high selectivity ratio while exhibiting relatively high catalytic activity, It is possible to confirm that it can proceed.

Claims (12)

An organic ligand compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2); And
A transition metal compound comprising a transition metal of Group 4 to 12;
≪ / RTI >
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R ₁ to R ₈ may be the same or different from each other and each represent hydrogen, straight or branched chain alkyl of 1 to 10 carbon atoms, straight or branched chain alkenyl of 2 to 10 carbon atoms, aryl of 6 to 20 carbon atoms, An arylalkyl having 7 to 21 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, an aryloxy having 6 to 20 carbon atoms, an alkylsilyl having 1 to 10 carbon atoms, an arylalkyl having 6 to 20 carbon atoms Arylsilyl or halogen,
Two or more adjacent two of R ₁ to R ₈ may be connected to form a ring,
n is an integer of 1 to 20,
X is an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P)
Each of a and b is 0 or 1,
R ₁₁ and R ₁₂ may be the same or different and are each a straight or branched alkyl of 1 to 10 carbon atoms, a straight or branched alkenyl of 2 to 10 carbon atoms, an aryl of 6 to 20 carbon atoms, an aryl of 7 to 21 carbon atoms Alkylaryl, arylalkyl having 7 to 21 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, aryloxy having 6 to 20 carbon atoms, alkylsilyl having 1 to 10 carbon atoms, arylsilyl having 6 to 20 carbon atoms, or Lt; / RTI >
R ₁₁ and R ₁₂ may be connected to each other to form a ring,
Y and Z may be the same or different and each represents a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, An alkylarylene group having 1 to 20 carbon atoms, or an arylalkylene group having 7 to 20 carbon atoms.
The method according to claim 1,
A catalyst composition for use in the reaction of synthesizing an alpha-olefin from ethylene.
The method according to claim 1,
In Formula 1,
Each of R _1, R _2, R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and is selected from the group consisting of hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, An aryl group having 6 to 20 carbon atoms,
R ₇ and R ₈ may be the same or different and are each a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 7 to 20 carbon atoms An aryl group or an arylalkyl group having 7 to 20 carbon atoms.
The method according to claim 1,
In Formula 2,
R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each represents hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms ego,
R ₇ and R ₈ may be the same or different and are each a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms Or an arylalkyl group having 7 to 20 carbon atoms,
Wherein X is nitrogen,
Y may be the same or different from each other and is an alkylene group having 1 to 5 carbon atoms,
Wherein a is 1, b is 0,
R ₁₁ is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
The method according to claim 1,
Wherein the non-covalent electron pair of the compound of Formula 1 or the compound of Formula 2 forms a coordination bond with the transition metal of the transition metal compound.
The method according to claim 1,
Wherein the transition metal compound comprises a chromium compound.
The method according to claim 6,
Wherein the chromium compound comprises at least one member selected from the group consisting of chromium (Cr), chromium (III) acetylacetonate, chromium trichlorotris tetrafluoride, and chromium (III) 2-ethylhexanoate.
The method according to claim 1,
And from 0.5 mole to 2.0 mole of said organic ligand compound per mole of said transition metal compound.
The method according to claim 1,
4. The catalyst composition of claim 1, further comprising a cocatalyst.
10. The method of claim 9,
Wherein the cocatalyst comprises at least one compound selected from the group consisting of the following formulas (11) to (13):
(11)

Wherein R ₁₃ is an alkyl group having 1 to 10 carbon atoms, r is an integer of 1 to 70,
[Chemical Formula 12]

R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or halogen, and R ₁₄ , R ₁₅ and R ₁₆ is an alkyl group having 1 to 10 carbon atoms,
[Chemical Formula 13]
^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -
In Formula 11, L is a neutral or cationic Lewis base, [LH] + or [L] ⁺ is Bronsted acid, H is a hydrogen atom,
Z is a Group 13 element,
E may be the same or different and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy functional group and phenoxy functional group, wherein at least one functional group is substituted or unsubstituted having 6 to 20 An aryl group; Or an alkyl group having 1 to 20 carbon atoms in which at least one functional group selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy functional group and phenoxy functional group is substituted or unsubstituted.
A process for the preparation of alpha-olefins by reaction of ethylene with the catalyst composition of claim 1.
11. The method of claim 10,
Olefin having a reaction temperature of 0 to 200 DEG C and a reaction pressure of 1 to 150 bar.