KR102080285B1 - Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins and method for oligomerization of olefins using the catalyst system - Google Patents

Abstract

The present invention relates to a ligand compound, a catalyst system for olefin oligomerization and a method for oligomerization of olefins using the same. The olefin oligomerization catalyst system according to the invention exhibits high selectivity for 1-hexene or 1-octene while having good catalytic activity, allowing for the production of more efficient alpha-olefins.

Description

Ligand compound, organochrome compound, catalyst system for olefin oligomerization, and method for oligomerization of olefin using the same

The present invention relates to a ligand compound, an organochrome compound, a catalyst system for olefin oligomerization comprising the ligand compound or an organochrome compound, and a method for oligomerization of olefins using the same.

Linear alpha-olefins such as 1-hexene and 1-octene are used as detergents, lubricants, plasticizers, etc., and are particularly used as comonomers for controlling the density of polymers in the production of linear low density polyethylene (LLDPE). Used.

This linear alpha-olefin was produced mainly through the Shell Higher Olefin Process. However, since the method synthesizes alpha-olefins of various lengths simultaneously according to the Schultz-Flory distribution, it is cumbersome to undergo a separate separation process to obtain a specific alpha-olefin.

In order to solve this problem, a method of selectively synthesizing 1-hexene through trimerization of ethylene or selectively synthesizing 1-octene through tetramerization of ethylene has been proposed. In addition, much research has been made on catalyst systems that enable the oligomerization of such selective ethylene.

The present invention is to provide a novel ligand compound that enables the expression of high catalytic activity and selectivity in the oligomerization reaction of olefins.

In addition, the present invention is to provide a novel organic chromium compound that enables the expression of high catalytic activity and selectivity in the oligomerization reaction of olefins.

In addition, the present invention is to provide a catalyst system for olefin oligomerization comprising the ligand compound or an organic chromium compound.

The present invention also provides a method for oligomerization of olefins using the catalyst system.

The present invention provides a ligand compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

N is a nitrogen atom,

A 1 is a boron atom (B), a nitrogen atom (N), a phosphorus atom (P) or an antimony atom (Sb);

Each X is independently a phosphorus atom (P), an arsenic atom (As), or an antimony atom (Sb);

R1 to R4 are each independently, identically or differently, a hydrocarbyl group or a heterohydrocarbyl group;

R 5 is a substituent substituted on a carbon atom constituting the piperidine ring, a C 1-10 hydrocarbyl group or C 1-10 heterohydrocarbyl group,

Each carbon constituting the piperidine ring may be substituted or unsubstituted with one or more of the same as or different from each other by R 5;

R 6 is a functional group connected to the nitrogen of the piperidine ring, and a C 1 to C 10 hydrocarbyl group or heterohydrocarbyl group.

In addition, the present invention is a ligand compound; And chromium (Cr) wherein the ligand is coordinated.

In addition, the invention comprises i) a chromium source, said ligand compound, and a promoter; Or ii) the organic chromium compound, and a cocatalyst, for providing a catalyst system for olefin oligomerization.

The present invention also provides a method for oligomerization of olefins, which comprises the step of oligomerizing the olefins in the presence of the catalyst system to form alpha-olefins.

The olefin oligomerization catalyst system according to the invention exhibits high selectivity for 1-hexene or 1-octene while having good catalytic activity, allowing for the production of more efficient alpha-olefins.

Hereinafter, the ligand compound, the organic chromium compound, the catalyst system for olefin oligomerization, and the oligomerization method of olefin using the same according to embodiments of the present invention will be described in more detail.

Prior to this, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It is to be understood that the present invention does not exclude the possibility of adding or presenting numbers, steps, components, or combinations thereof.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In addition, throughout this specification, the term "catalyst system" refers to a three component comprising a chromium source, a ligand compound and a promoter, or alternatively, two components of an organic chromium compound and a promoter are added simultaneously or in any order. It means a state that can be obtained with an active catalyst composition. The three or two components of the catalyst system may be added in the presence or absence of a solvent and monomer, and may be used in a supported or unsupported state.

In the present specification, the hydrocarbyl group refers to a monovalent group formed by removing one hydrogen atom from a hydrocarbon, and the heterohydrocarbyl group refers to a monovalent group formed while removing one hydrogen atom from a hydrocarbon including a hetero atom.

And, in each functional group, the functional group substituted means a state in which the other one or more hydrogen atoms are further removed and other functional groups or hetero elements are substituted in the hydrocarbon.

According to one aspect of the invention, there is provided a ligand compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

N is a nitrogen atom,

A 1 is a boron atom (B), a nitrogen atom (N), a phosphorus atom (P) or an antimony atom (Sb);

Each X is independently a phosphorus atom (P), an arsenic atom (As), or an antimony atom (Sb);

R1 to R4 are each independently, identically or differently, a hydrocarbyl group or a heterohydrocarbyl group;

R 5 is a substituent substituted on a carbon atom constituting the piperidine ring, a C 1-10 hydrocarbyl group or C 1-10 heterohydrocarbyl group,

Each carbon constituting the piperidine ring may be substituted or unsubstituted with one or more of the same as or different from each other by R 5;

R 6 is a functional group connected to the nitrogen of the piperidine ring, and a C 1 to C 10 hydrocarbyl group or heterohydrocarbyl group.

As a result of the continuous experiments of the present inventors, when the ligand compound is applied to a catalyst system for oligomerization of olefins, it shows excellent catalytic activity and high selectivity to 1-hexene or 1-octene, thus preparing more efficient alpha-olefins. It has been confirmed that this is possible.

According to one embodiment of the invention, the ligand compound comprises a diphosphino aminyl moiety in the molecule, this group is linked with a hetero ring, a hetero atom, that is, piperidi contained in the hetero ring The nitrogen atom of the nil group may increase the electron density at the diphosphino aminyl moiety with a strong electron donating effect, or may provide its ligand with its own non-covalent electron pair.

Due to these structural features, the ligand compound can be applied to an oligomerization catalyst system of olefins to exhibit high oligomerization activity, in particular high selectivity to 1-hexene, 1-octene and the like. This can be seen as the interaction between each adjacent chromium active point. In particular, the nitrogen atom of the hetero ring connected to the diphosphino aminyl group increases the electron density at the phosphorus (P) and nitrogen (N) atoms included in the diphosphino aminyl group, or the nitrogen atom of the nitrogen atom. Non-covalent electron pairs may be directly coordinated with chromium, thereby changing the electrical and steric properties of the entire ligand compound.

As a result, there is a change in the bond between the ligand and the chromium atom, thereby making the structure of the catalyst more stable, and by changing the energy of the transition state, that is, the activation energy of the reaction, compared to the conventional metallacycloheptane or metallacyclononane form, It is possible to form alpha-olefins with high activity and selectivity, and to further reduce the amount of by-products such as high molecular weight solid alpha-olefins such as PE Wax.

Furthermore, a small amount in the oligomerization reaction can significantly reduce the amount of 1-hexene isomers that have a great effect on the product, and concomitantly, separation may not be necessary due to an increase in 1-hexene and a decrease in 1-hexene isomers. It can also bring about energy savings.

Meanwhile, according to one embodiment of the present invention, X in Chemical Formula 1 may be each independently a phosphorus atom (P), an arsenic atom (As) or an antimony atom (Sb). Preferably, the group represented by Formula 1 may be a diphosphino aminyl moiety in which each X is phosphorus (P).

In addition, in Formula 1, R1 to R4 each independently, same or differently, represent a hydrocarbyl group or a heterohydrocarbyl group.

As a non-limiting example, each of R 1 to R 4 independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 15 carbon atoms. , A substituted or unsubstituted arylalkyl group having 7 to 15 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. Here, at least one hydrogen contained in the alkyl group, cycloalkyl group, aryl group, arylalkyl group, and alkoxy group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group. .

Preferably, R1 to R4 are each independently methyl, ethyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xyl Xylyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl (o-methoxyphenyl), o-isopropoxyphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, mt- Butylphenyl (m-butylphenyl), m-methoxyphenyl, m-isopropoxyphenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, pt-butyl Phenyl (pt-butylphenyl), p-methoxyphenyl, p-isopropoxyphenyl, cumyl, mesityl, biphenyl, naphthyl ( naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, or trimethylsilyl ) May be a group.

R 5 is a substituent substituted on a carbon atom constituting the piperidine ring, a C 1-10 hydrocarbyl group or a C 1-10 heterohydrocarbyl group, and constitutes the piperidine ring. Each carbon, by R5, may be the same or different, each of which may be substituted or unsubstituted, and unsubstituted means that the carbon is present in the form of a hydrocarbon without special substituents.

R 6 is a functional group connected to the nitrogen of the piperidine ring, and a C 1 to C 10 hydrocarbyl group or heterohydrocarbyl group.

Specific examples of the hydrocarbyl group or the heterohydrocarbyl group of R5 and R6 are as described above, wherein only carbon number is limited to 1 to 10.

The piperidine ring can efficiently perform the above-described electron donating effect or a role of providing a lone pair of electrons directly to chromium, and in particular, a highly stable form having 6 atoms in the ring, through a sigma bond, diphosphino amino It is easy to increase the electron density of the niel moiety, and it is also very easy to provide a lone pair of chromium atoms directly through the three-dimensional structure.

According to another aspect of the invention, the ligand compound represented by the formula (1); And chromium (Cr) in which the ligand is coordinated.

[Formula 1]

In Chemical Formula 1,

N is a nitrogen atom,

A 1 is a boron atom (B), a nitrogen atom (N), a phosphorus atom (P) or an antimony atom (Sb);

Each X is independently a phosphorus atom (P), an arsenic atom (As), or an antimony atom (Sb);

R1 to R4 are each independently, identically or differently, a hydrocarbyl group or a heterohydrocarbyl group;

R 5 is a substituent substituted on a carbon atom constituting the piperidine ring, a C 1-10 hydrocarbyl group or C 1-10 heterohydrocarbyl group,

Each carbon constituting the piperidine ring may be the same or differently substituted with one or more, or not, each substituted by R 5, and the details are as described in the ligand compound portion.

The organic chromium compound is a chromium complex compound of the ligand compound described above, and may have a form in which chromium of the chromium source has a coordinating bond with the X moiety of the group represented by Formula 1. Such organic chromium compounds can be applied to catalyst systems for the oligomerization of olefins to exhibit good catalytic activity and high selectivity for 1-hexene or 1-octene.

According to one embodiment of the invention, the organic chromium compound, in the ligand compound of Formula 1, A1, N, and it may be preferable that any one or more of the non-covalent electron pairs of two X coordinated to the chromium atom. That is, as described above, in addition to the phosphorus atom or nitrogen atom of the diphosphino aminyl moiety, the nitrogen atom of the hetero ring can provide a lone pair of electrons to the chromium atom, and in particular, three pairs of lone pairs of coordination are coordinated. The tridentated state may be preferred.

On the other hand, according to another aspect of the invention, i) comprises a chromium source, the ligand compound, and a promoter; Or ii) the organic chromium compound, and a cocatalyst, there is provided a catalyst system for olefin oligomerization.

That is, according to one embodiment of the invention, the catalyst system for olefin oligomerization comprises: i) a three-component catalyst system comprising a chromium source, a ligand compound and a promoter as described above, or ii) an organic chromium compound and a promoter as described above. It may be a two component catalyst system.

Specific descriptions and examples of the ligand compound and the organic chromium compound are replaced by the above description.

In the catalyst system, the chromium source is an organic or inorganic chromium compound in which the oxidation state of chromium is 0 to 6, for example, a chromium metal, or a compound in which any organic or inorganic radical is bonded to chromium. Here, the organic radical may be an alkyl, alkoxy, ester, ketone, amido, carboxylate radical, etc. having 1 to 20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, oxide, or the like.

Preferably, the chromium source is a compound that can exhibit high activity in oligomerization of olefins and is easy to use and obtain, such as chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2 Ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl- 3.5-heptanedionate), and chromium (III) stearate.

And, preferably, the cocatalyst is an organometallic compound including a Group 13 metal, and may be applied without particular limitation as long as it can be generally used when polymerizing olefins under a catalyst of a transition metal compound.

For example, the promoter may be at least one compound selected from the group consisting of compounds represented by Formulas 2 to 6 below:

[Formula 2]

-[Al (Rx) -O] _c-

In Formula 2, Al is aluminum,

Rx is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,

[Formula 3]

D (Ry) ₃

In Chemical Formula 3, D is aluminum or boron, Ry is C1-20 hydrocarbyl or halogen substituted by C1-20 hydrocarbyl,

[Formula 4]

[LH] ⁺ [Q (E) ₄ ] ^-

In Chemical Formula 4,

L is a neutral Lewis base, [LH] ⁺ is Bronsted acid, Q is boron or aluminum in +3 type oxidation state, each E is independently at least one hydrogen atom is halogen, hydrocarbyl having 1 to 20 carbon atoms, It is a C6-C20 aryl group or C1-C20 alkyl group unsubstituted or substituted by the alkoxy functional group or the phenoxy functional group.

According to one embodiment, the compound represented by Formula 2 may be alkyl aluminoxane, such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane.

According to one embodiment, the compound represented by Chemical Formula 3 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, di Ethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p Tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.

Further, according to one embodiment, the compound represented by Formula 4 is triethylammonium tetraphenylboron, tributyl ammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tri Butyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetrapentafluorophenyl boron, N, N-diethylanilinium tetraphenyl Boron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, Trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tri Propyl ammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoro Romethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilini Umtetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethyl Sponium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl May be boron and the like.

As a non-limiting example, the promoter may be an organoaluminum compound, an organoboron compound, an organomagnesium compound, an organozinc compound, an organolithium compound, or a mixture thereof. According to one embodiment, the promoter is preferably an organoaluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum (triisobutyl aluminum), ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane It may be one or more compounds selected from the group consisting of

On the other hand, the content ratio of the components constituting the catalyst system may be determined in consideration of the catalytic activity and the selectivity to the linear alpha-olefin. According to one embodiment, in the three component catalyst system, the molar ratio of diphosphino aminyl residue: chromium source: cocatalyst of the ligand compound is about 1: 1: 1 to 10: 1: 10,000, or about 1: 1 It is advantageous to adjust from: 100 to 5: 1: 3,000. And, in the case of the two-component catalyst system, the molar ratio of diphosphino aminyl residue: cocatalyst of the organic chromium compound is 1: 1 to 1: 10,000, or 1: 1 to 1: 5,000, or 1: 1 to 1: It is advantageous to adjust to 3,000.

The components constituting the catalyst system can then be added simultaneously or in any order, in the presence or absence of suitable solvents and monomers, to act as an active catalyst system. At this time, suitable solvents include heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like. Can be.

In addition, according to one embodiment of the invention, the catalyst system may further comprise a carrier. That is, the ligand compound of Formula 1 may be applied to ethylene oligomerization in a form supported on a carrier. The carrier may be a metal, a metal salt, a metal oxide, or the like applied to a conventional supported catalyst. As a non-limiting example, the carrier may be silica, silica-alumina, silica-magnesia, and the like, and oxides, carbonates, sulfates, vaginas of metals such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , Mg (NO ₃ ) _2, and the like. It may comprise a trisalt component.

On the other hand, according to another aspect of the present invention, in the presence of the catalyst system described above, by performing an oligomerization reaction of the olefin, to form an alpha-olefin, there is provided a method for oligomerization of the olefin.

The process for oligomerization of olefins according to the present invention can be carried out by applying conventional equipment and contacting techniques with the catalyst system described above as the raw material of olefins (eg ethylene). As a non-limiting example, the oligomerization reaction of the olefin may be a homogeneous liquid phase reaction in the presence or absence of an inert solvent, or a slurry reaction in which the catalyst system is partially or completely insoluble, or the product alpha-olefin is the main medium. It can be carried out in a bulk phase reaction, or in a gas phase reaction.

In addition, the oligomerization reaction of the olefin may be performed under an inert solvent. By way of non-limiting example, the inert solvent may be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and the like. .

And, the oligomerization reaction of the olefin may be carried out at a temperature of about 0 to about 200 ℃, or about 0 to about 150 ℃, or about 30 to about 100 ℃, or about 50 to about 100 ℃. In addition, the reaction may be performed under a pressure of about 15 to about 3000 psig, or about 15 to about 1500 psig, or about 15 to about 1000 psig.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

<Example>

All reactions were run under argon using the Schlenk technique or glovebox. The synthesized ligand was analyzed by ¹ H (500 MHz) and ³¹ P (202 MHz) NMR spectra using a Varian 500 MHz spectrometer. Shift is expressed in ppm in the downfield from TMS with the residual solvent peak as a reference. Phosphorous probes were calibrated with aqueous H ₃ PO ₄ .

Synthesis Example 1

의 합성

Synthesis of

Under argon, 1-Methyl-4-piperidinylamine (10 mmol) and triethylamine (3 to 10 equiv. To amine) were dissolved in dichloromethane (80 ml). While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol) was slowly added thereto and stirred overnight. After the solvent was removed in vacuo, tetrahydrofuran was added thereto, followed by sufficient stirring to remove triethylammonium chloride salt with an air-free glass filter. The solvent was removed from the filtrate to obtain the compound.

³¹ P NMR (202 MHz, CdCl ₃ ): 51.0 (br, s)

Synthesis Example 2

의 합성

Synthesis of

Synthetic Method:

Under argon, 1-Isopropyl-4-piperidinylamine (10 mmol) and triethylamine (3 to 10 equiv. To amine) were dissolved in dichloromethane (80 ml). While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol) was slowly added thereto and stirred overnight. After the solvent was removed in vacuo, tetrahydrofuran was added thereto, followed by sufficient stirring to remove triethylammonium chloride salt with an air-free glass filter. The solvent was removed from the filtrate to obtain the compound.

³¹ P NMR (202 MHz, CdCl ₃ ): 52.4 (br, s)

Preparation of Catalytic Systems and Ethylene Oligomerization  Reaction progress

[Examples 1 and 2]

In an argon gas atmosphere, chromium (III) acetylacetonate (17.5 mg, 0.05 mmol) and the ligand compound (0.025 mmol) according to Synthesis Examples 1 and 2 were placed in a flask, and then 10 ml of cyclohexane was added thereto, followed by stirring. A catalyst solution of 5 mM (Cr basis) was prepared.

A 600 ml Parr reactor was prepared and vacuumed at 120 ° C. for 2 hours, after which the interior was replaced with argon and the temperature was reduced to 60 ° C. Thereafter, 180 ml of cyclohexane and 1 ml of MAO (isoheptane solution, Al / Cr = 600) were injected, and 0.5 ml (2.5 μmol Cr) of the catalyst solution was injected. After stirring at 500 rpm for 2 minutes, the valve of the ethylene line set at 45 bar was opened to fill the reactor with ethylene, and then adjusted to be desuperheated at 45 ° C. and stirred at 500 rpm for 15 minutes. The ethylene line valve was shut off, the reactor was cooled to 0 ° C. using a dry ice / acetone bath, slowly unvented ethylene was vented, and 0.5 ml of nonane (GC internal standard) was added thereto. After stirring for 10 seconds, 2 ml of the liquid portion of the reactor was taken and quenched with water, and the obtained organic portion was filtered with a PTFE syringe filter to make a GC-FID sample. And the distribution of liquid product was analyzed by GC. In addition, 400 ml of ethanol / HCl (10 vol% of aqueous 12M HCl solution) was added to the remaining reaction solution, followed by stirring and filtering to analyze the amount of solids. The polymer obtained was dried overnight in a 65 ° C. vacuum oven.

The results of the above examples are summarized in the table below.

Activity 1-C6 1-C8 HAO In product
Polymer kg / molCr / hr wt% wt% wt% wt% Example 1 14,153 23.2 61.5 84.7 65.4 Example 2 4,503 20.2 71.5 91.7 31.6

Referring to Table 1 above, the catalyst system including the organic chromium compound of the present invention exhibits high selectivity to 1-hexene or 1-octene while having excellent catalytic activity in the olefin oligomerization reaction, thereby making it more efficient to use alpha- It can be confirmed that the production of olefins is possible.

Claims (8)

Ligand compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
N is a nitrogen atom,
A 1 is a boron atom (B), a nitrogen atom (N), a phosphorus atom (P) or an antimony atom (Sb);
Each X is independently a phosphorus atom (P), an arsenic atom (As), or an antimony atom (Sb);
R1 to R4 are each independently, identically or differently, a hydrocarbyl group or a heterohydrocarbyl group;
R 5 is a substituent substituted on a carbon atom constituting the piperidine ring, a C 1-10 hydrocarbyl group or C 1-10 heterohydrocarbyl group,
Each carbon constituting the piperidine ring may be substituted or unsubstituted with one or more of the same as or different from each other by R 5;
R 6 is a functional group connected to the nitrogen of the piperidine ring, and a C 1 to C 10 hydrocarbyl group or heterohydrocarbyl group.
The method of claim 1,
R 1 to R 4 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, substituted or unsubstituted A arylalkyl group having 7 to 15 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
Ligand compound represented by the formula (1); And
An organic chromium compound comprising chromium (Cr) coordinated with the ligand:
[Formula 1]

In Chemical Formula 1,
N is a nitrogen atom,
A 1 is a boron atom (B), a nitrogen atom (N), a phosphorus atom (P) or an antimony atom (Sb);
Each X is independently a phosphorus atom (P), an arsenic atom (As), or an antimony atom (Sb);
R1 to R4 are each independently, identically or differently, a hydrocarbyl group or a heterohydrocarbyl group;
R 5 is a substituent substituted on a carbon atom constituting the piperidine ring, a C 1-10 hydrocarbyl group or C 1-10 heterohydrocarbyl group,
Each carbon constituting the piperidine ring may be substituted or unsubstituted with one or more of the same as or different from each other by R 5;
R 6 is a functional group connected to the nitrogen of the piperidine ring, and a C 1 to C 10 hydrocarbyl group or heterohydrocarbyl group.
The method of claim 3,
The organic chromium compound is an organic chromium compound of the ligand compound of Formula 1, in which any one or more lone pairs of A1, N, and X are coordinated with a chromium atom.
i) a chromium source, the ligand compound of claim 1, and a promoter;
or
ii) comprising the organic chromium compound of claim 3 and a promoter; Catalyst system for olefin oligomerization.
The method of claim 5,
The chromium source is chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentano At least one selected from the group consisting of eight, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium (III) stearate A catalyst system for olefin oligomerization.
The method of claim 5,
The promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesquichloride, diethyl aluminum Catalyst system for olefin oligomerization, comprising one or more selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane .
A process for oligomerization of an olefin comprising the step of proceeding with the oligomerization reaction of the olefin in the presence of the catalyst system according to claim 5 to form an alpha-olefin.