WO2016200000A1

WO2016200000A1 - Ligand compound, organic chrome compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using same

Info

Publication number: WO2016200000A1
Application number: PCT/KR2015/014032
Authority: WO
Inventors: 사석필; 이용호; 신은지; 이기수; 박진영; 임슬기
Original assignee: 주식회사 엘지화학
Priority date: 2015-06-12
Filing date: 2015-12-21
Publication date: 2016-12-15

Abstract

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

Description

[Name of invention]

Ligand compound, organic crum compound, catalyst system for ollepin oligomerization, and oligomerization method of ollepin using the same

[Cross Citation with Related Application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0083650 dated June 12, 2015 and Korean Patent Application No. 10-2015-0182257 dated December 18, 2015. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a ligand compound, an organic chromium compound, a catalyst system for urepin oligomerization comprising the ligand compound or an organic chromium compound, and a method for oligomerization of urepin using the same.

Background Art

Linear alpha-olefins, such as 1-nuxene and 1-octene, are used as detergents, lubricants, and plasticizers, and as comonomers for controlling the density of polymers in the production of high linear density polyethylene (LLDPE). It is used a lot.

These linear alpha-olefins were produced primarily through the Shell Higher Olefin Process. However, since the method synthesizes alpha-le-lephins of various lengths according to the Schultz-Flory distribution at the same time, it is cumbersome to undergo a separate separation process to obtain a specific alpha-le-lepine.

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

[Content of invention]

[Problem to solve] The present invention is to provide a novel ligand compound that enables the expression of high catalytic activity and selectivity in the reaction of oligomerization of olefins. The present invention also provides a novel organic chromium compound which 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.

In addition, the present invention is to provide a method for the oligomerization of urepin using the catalyst system.

[Measures of problem]

The present invention provides a ligand compound comprising at least one group represented by the following formula (1) in the molecule.

[Formula 1]

In Chemical Formula 1,

* Means that the group represented by the formula (1) is a radical,

A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb)

Each X is independently phosphorus (P), arsenic (As), or antimony (Sb),

R1 to R4 are each independently;

Optionally in the meta or para position, an aryl group having 6 to 20 carbon atoms, wherein one or more substituents selected from the group consisting of an alkyl group, an alkoxy, an alkylsulfanyl group, and an alkylsilyl group are substituted or bonded.

The present invention also provides an organic crumb compound comprising the ligand compound and chromium (Cr).

The present invention also provides a catalyst system for olefin oligomerization comprising the ligand compound, chromium source, and cocatalyst. The present invention also provides a method for the oligomerization of olephine, which comprises the step of undergoing the oligomerization reaction of olephine in the presence of the above-described catalyst system to form alpha- olephine.

【Effects of the Invention】

The olefin oligomerization catalyst system according to the invention exhibits high selectivity for 1-nuxene or 1-octene while having good catalytic activity, allowing the production of more efficient alpha-olefins. [Specific contents to carry out invention]

Hereinafter, a ligand compound, an organic cream compound, an olefin oligomerization catalyst system, and a oligomerization method of urepin 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 or numbers. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of steps, components, or combinations thereof.

As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. As such, it is to be understood that the present invention is not intended to be limited to the particular disclosed forms and includes all modification equivalents and substitutes included in the spirit and scope of the present invention.

In addition, throughout this specification, the term "catalyst system" means 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 the state which can be obtained with an active catalyst composition. Three components of the catalyst system Or the two components may be added in the presence or absence of a solvent and a monomer, and may be used in a supported or unsupported state.

According to one aspect of the invention, there is provided a ligand compound comprising at least one group represented by the formula (1) in the molecule.

[Formula 1]

X X

R2 R3

In Chemical Formula 1,

^* Means that the group represented by the formula (1) is a radical,

A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb),

Each X is independently phosphorus (P), arsenic (As), or antimony (Sb),

R1 to R4 are each independently;

Or an aryl group having 6 to 20 carbon atoms, optionally substituted at the meta or para position, with one or more substituents selected from the group consisting of alkyl groups, alkoxy, alkylsulfanyl groups, and alkylsilyl groups.

As a result of continuous experiments of the present inventors, when the ligand compound is applied to the catalyst system for oligomerization of olepin, it shows excellent catalytic activity.

It has been shown that high selectivity for 1-nuxene or 1-octene allows for the preparation of more efficient alpha-urepin.

According to one embodiment of the invention, the ligand compound comprises a group represented by the formula (1) in the molecule (particularly, diphosphino aminyl moiety), at the end of the diphosphino aminyl moiety, a specific substituent It may have a form that can be connected to an aryl group having and serve as a strong electron donating group by itself.

Due to this structural feature, the ligand compound can be applied to the lyremerization catalyst system of leupin to exhibit high lygomerization reaction activity. In particular, it can exhibit high selectivity for 1-hexene, 1-octene and the like. This can be considered to be due to the interaction between adjacent adjacent active points of activity, in particular in the diphosphino aminyl group, when an aryl is substituted or substituted by a specific substituent to the phosphorus (P) atom of the diphosphino aminyl group. The electron density increases at the phosphorus (P) atom and the nitrogen (N) atom, and the electrical and steric properties of the entire ligand compound may change.

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

Furthermore, a small amount in the oligomerization reaction can significantly reduce the amount of 1-nucleene isomers that have a great effect on the product, and concomitantly, separation may not be necessary due to an increase in 1-nucleene and a decrease in 1-nucenne 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 phosphorus (P), arsenic (As), or antimony (Sb). Preferably, the group represented by Formula 1 may be a diphosphino aminyl moiety in which each X is phosphorus (P).

And, in Formula 1, R1 to R4, R1 to R4, each independently;

An aryl group having 6 to 20 carbon atoms, in which one or more substituents selected from the group consisting of an alkyl group, an alkoxy, an alkylsulfanyl group, and an alkylsilyl group is substituted or bonded. When explaining R1 to R4 of the formula (1) in more detail, each of R1 to R4 independently; 6 or more carbon atoms, in which one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfanyl group having 1 to 10 carbon atoms, and an alkylsilyl group having 1 to 10 carbon atoms are substituted or bonded. It may be an aryl group of 20 to.

Substituted forms of R1 to R4, specifically, for example, R1 to R4 are each independently in the form of a phenyl group having 6 to 20 carbon atoms in total; Only one of the meta positions relative to the X linking site is a group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfanyl group having 1 to 10 carbon atoms, and an alkylsilyl group having 1 to 10 carbon atoms It may be substituted or combined with one substituent selected from.

Or R1 to R4 are each independently a phenyl group having 6 to 20 carbon atoms in total; At least two of the meta and para positions with respect to the X linking site may be an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfanyl group having 1 to 10 carbon atoms, and a carbon group having 1 to 10 carbon atoms. It may be substituted or bonded with one or more substituents selected from the group consisting of alkylsilyl groups. According to an embodiment of the present invention, X in formula 1 is phosphorus (P), and the residues represented by (R ¹ ) (R ² ) X- and (R ³ ) (R ⁴ ) X- of formula 1 ( Moiety) may be represented by the following structural formula, respectively, but is not necessarily limited thereto.

In addition, two or more groups represented by Formula 1 may be included in one compound. In this case, the linker connecting the two groups may be an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. It may include an alicyclic group of, a heteroalicyclic group of 2 to 20 carbon atoms, or the aliphatic group, heteroaliphatic group, alicyclic group, and heteroalicyclic group, more specifically, for example, non-limiting examples The linker may be an aliphatic group having 2 to 20 carbon atoms (for example, an alkylene group, an alkenylene group, an alkynylene group, or Heteroaliphatic group containing a hetero atom in the aliphatic group, alicyclic group having 2 to 20 carbon atoms (for example, cycloalkylene group , A cycloalkyl alkenylene group, cyclo alkynylene group, or wherein the alicyclic group contains a hetero atom ^■ heterocyclic aliphatic group), or the aliphatic (or heterocyclic aliphatic) group and the alicyclic (or by interrogating alicyclic) groups combined It may be in the form. As a non-limiting example of the above-mentioned ligand compound, the compound which has a structure as follows is mentioned. In the following example, the group represented by Formula 1 is represented by [A], [Α ′] or [Α ″] for convenience, and [Α], [Α ′] and [Α ″] may be the same or different.

(i) a compound having a group connecting two or three carbon atoms between a plurality of A:

(iii) a compound having a group connecting a plurality of As with at least 5 carbon atoms:

Ligand compounds according to the present invention can be implemented in various combinations in the range satisfying the above conditions in addition to the above examples. In addition, the ligand compound may be synthesized by applying known reactions, and a more detailed synthesis method is described in the Examples section. On the other hand, according to another aspect of the present invention, there is provided an organic cream compound, including the above-described ligand compound and chromium (Cr).

The organic cream compound may be a compound in which the ligand compound is coordinated with a ligand, and a chromium atom as a center metal, and may include, for example, a group represented by the following Chemical Formula 1-1. .

[Formula 1-1]

In Chemical Formula 1-1,

* Means that the group represented by the formula 1-1 is a radical A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb),

χ is each independently phosphorus (p), arsenic (As), or antimony (Sb),

R1 to R4 are each independently;

An aryl group having 6 to 20 carbon atoms, optionally substituted at the meta or para position, with one or more substituents selected from the group consisting of an alkyl group, an alkoxy, an alkylsulfanyl group, and an alkylsilyl group;

Cr is chromium ，

Y 1 to Y 3 are each independently halogen, hydrogen, hydrocarbyl having 1 to 10 carbon atoms, or heterohydrocarbyl having 1 to 10 carbon atoms.

The organic chromium compound may be a chromium complex compound of the above-described ligand compound, and may have a form in which chromium of a creme source forms a coordinative bond to the X portion of the group represented by Formula 1. These organic kink compounds can be applied to the catalyst system for the oligomerization reaction mixture of olefins to exhibit good catalytic activity and high selectivity for 1-nuxene or 1-octene. In Formula 1-1, descriptions and specific examples of X and R1 to R4 are the same as those described for the ligand compound of Formula 1. On the other hand, according to another aspect of the invention,！) comprises a chromium source, the above-described ligand compound, and a promoter; Or ii) an organic cream compound comprising a group represented by the following Chemical Formula 1-1, and a promoter, and a catalyst system for olefin oligomerization is provided.

[Formula 1-1]

In Chemical Formula 1-1, ^* Means that the group represented by the formula 1-1 is a radical,

A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb),

Each X is independently phosphorus (P), arsenic (As), or antimony (Sb)

R1 to R4 are each independently;

An aryl group having 6 to 20 carbon atoms optionally substituted in the meta or para position, at least one substituent selected from the group consisting of an alkyl group, an alkoxy, an alkylsulfanyl group, and an alkylsilyl group;

Cr is chromium,

Y1 to Y3 are each independently halogen, hydrogen, hydrocarbyl having 1 to 10 carbon atoms, or heterohydrocarbyl having 1 to 10 carbon atoms.

Here, the description and specific examples of the ligand compound and the organic crum compound will be replaced with the above description.

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) a two-component catalyst comprising an organic crum compound and a promoter as described above. It may be a component catalyst system.

In the catalyst system, the chromium source is an organic or inorganic crescent compound in which the oxidation state of the crack is 0 to 6, for example chromium metal, or a compound in which any organic or inorganic radical is bonded to the crack. 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 may exhibit high activity in oligomerization of olepin and is easy to use and obtain, such as chromium (III) acetylacetonate, chromium chloride, tetrahydrofuran, chromium ( III) 2-Ethylnucleoate chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (ᅵ) laurate, chromium (ᅵ) Tris (2,2,6) , 6-tetramethyl-3.5-heptanedionate), and chromium (III) stearate.

Preferably, the promoter is an organic metal comprising a Group 13 metal As the compound, as long as it can be used when polymerizing the olefin under the catalyst of the transition metal compound, it can be applied without particular limitation.

For example, the promoter may be at least one compound selected from the group consisting of compounds represented by Formulas 4 to 6 below:

[Formula 4]

-[AI (Rx) -O] _c -In Formula 4, Rx is the same or different from each other, and each independently a halogen radical, a hydrocarbyl radical of 1 to 20 carbon atoms, or a hydro of 1 to 20 carbon atoms substituted with halogen A carbyl radical, c is an integer of 2 or more, and [Formula 5]

D (Ry) ₃

In Formula 5, D is aluminum or boron, Ry is 1 to carbon atoms

20 '' hydrocarbyl or halogen substituted by high '' rocabil,

[Formula 6]

[LH] ⁺ [Q (E) ₄ ] ^'

In Chemical Formula 6,

L is a neutral Lewis base, [LH] ⁺ is Bronsted acid, Q is boron or aluminum in the +3 type oxidation state, each E is independently at least one hydrogen atom is halogen, a hydrocarbyl having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group.

According to one embodiment, the compound represented by Formula 4 may be alkyl aluminoxane, such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane.

According to one embodiment, the compound represented by Chemical Formula 5 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, di Ethylchloroaluminum ， triisopropylaluminum ， tri-S-butylaluminum ， tricyclopentylaluminum, Tripentyl aluminum, triisopentyl aluminum, trinuclear sil aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum triphenyl aluminum, tri-P- ryl aluminum, dimethyl aluminum hydroxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, Triisobutyl boron, tripropyl boron, tributyl boron and the like. In addition, according to one embodiment, the compound represented by Formula 6 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Tetra (P-Lyl) boron, tripropyl ammonium tetra (P-lryl) boron ᅳ triethyl ammonium tetra (ο, ρ-dimethylphenyl) boron, trimethyl ammonium tetra (ο, ρ-dimethylphenyl) boron, tri Butyl ammonium tetra (Ρ-trifluoromethylphenyl) boron, trimethyl ammonium tetra (Ρ-trifluoro methylphenyl) boron,

Tributylammonium tetrapentapulophenylphenyl, Ν, Ν- diethylanilinium tetraphenyl boron, Ν, Ν-diethylanilinium tetraphenylboron, Ν, Ν- diethylanilinium tetrapentafluoro Rophenylboron,

Diethyl ammonium tetrapentaplefluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tree Propyl Ammonium Tetraphenyl Aluminum, Trimethyl Ammonium Tetra (Ρ-rylryl) Aluminum, Tripropyl Ammonium Tetra (Ρ-rylryl) Aluminum, Triethyl Ammonium Tetra (ο, ρ-dimethylphenyl) Aluminum, Tributyl Ammonium Tetra (Ρ-trifluoromethylphenyl) aluminum, trimethylammonium tetra (Ρ- trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, Ν, Ν-diethylanilinium tetraphenylaluminum Ν, Ν- diethylanilinium tetraphenylaluminum, Ν, Ν- diethylanilinium tetrapentafluorophenyl Aluminum,

Diethylammonium tetrapentafluorophenylaluminum,

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (ρ ᅳ trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron and the like. In addition, 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 combination 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-lefin. 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: 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 moiety: cocatalyst of the organic kneading compound is 1: 1 to 1: 10,000, or 1: 1 to 1: 5,000, or 1: 1 to 1: 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, cyclonucleic acid, methylcyclonucleic acid, 1-nuxene 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, Oxides, carbonates, sulfates, nitrates of metals such as Na ₂ O, K ₂ CO 3, BaS0 ₄ , Mg (N0 ₃ ) _2, and the like.

Such a catalyst system can preferably be used for the quaternization reaction of ethylene, allowing the production of 1-octene with high selectivity as described above. On the other hand, according to another aspect of the present invention, in the presence of the above-described catalyst system, proceeding the oligomerization reaction of the olepin, to form the alpha- olepin; comprising; This is provided.

Preferably, the oligomerization reaction of the olefin may be a quaternization reaction of ethylene, and may form 1-octene as a reaction product. According to the present invention, the method for the ligomerization of leupine can be carried out by applying the above-described catalyst system with conventional elepine (for example, ethylene) as a raw material and conventional apparatus and contacting techniques. By way of non-limiting example, the ligomerization reaction of leulevine may be a homogeneous liquid reaction in the presence or absence of an inert solvent, or a slurry reaction in which the catalyst system is partially or completely undissolved, or a product of alpha-olefin. It may be carried out as a bulk reaction, or as a gas reaction, acting as the main medium.

And, the oligomerization reaction of the olepin can be performed under an inert solvent. As a non-limiting example, the inert solvent may be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, n-nucleic acid, 1-nuxene, 1-octene, etc. have.

And, the oligomerization reaction of the olefin can be carried out at a temperature of about 0 to about 200 ° C, or about 0 to about 150 ^° C, or about 30 to about 100 ^° C, or about 50 to about 100 ° C. have. 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, through the specific examples of the invention, the operation and effects of the invention It will be described in detail. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

All reactions were performed under argon using the Schlenk technique or gloN ebox¾. The synthesized ligand was analyzed by 1H (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 H3PC.

Ligand Compound Synthesis

Under argon, 2-ethyl-6-methylaniline (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL). While the flask was immersed in a water bath, chlorobis (3, 5-dimethylphenyl) phosphine (20 mmol) was slowly added thereto and stirred overnight. After the solvent was removed in vacuo, other solvents such as diethyl ether, tetrahydrofuran or hexane were added and sufficiently stirred to remove triethylammonium chloride salt with an air-free glass filter. The solvent was removed from the filtrate to give the product.

3 ¹ P NMR (202 MHz, CDCI ₃ ): 49.6 (br m), 53.8 (br m), 61.8 (br s)

2-ethyl-6-methylaniline (10 mmol) and triethylamine under argon (3 equiv. to amine) was dissolved in dichbromethane (80 ml_). Chlorobis (3-methylphenyl) phosphine (20 mmol) was slowly added while the polar flask was soaked in a water bath and stirred overnight. After the solvent was removed in vacuo, another solvent, diethyl ether, tetrahydrofuran or hexane, was added to the mixture and stirred. The triethylammonium chloride salt was removed using an air-free glass filter. The solvent was removed from the filtrate to give the product.

³¹ P NMR (202 MHz, CDCI ₃ ): 56.2 (br s)

Under argon, 2-ethyl-6-methylaniline (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL). While the flask was immersed in a water bath, chlorobis (3, 4-dimethylphenyl) phosphine (20 mmol) was slowly added thereto and stirred overnight. After the solvent was removed in vacuo, another solvent, diethyl ether, tetrahydrofuran or hexane, was added to the mixture and stirred. The triethylammonium chloride salt was removed using an air-free glass filter. The solvent was removed from the filtrate to give the product.

³¹ P NMR (202 MHz, CDCI ₃ ): 50.0 (m)

Under argon, 2-isopropylcyclohexan-1 -amine (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL)-chlorabis (3, 5- with a full-laser in a water bath). Dimethylphenyl) phosphine (20 mmol) was slowly added and stirred overnight. After the solvent was removed in vacuo, another solvent, diethyl ether, tetrahydrafuran or hexane, was added to the mixture and stirred. The triethylammonium chloride salt was removed using an air-free glass filter. The solvent was removed from the filtrate to give the product.

3 ¹ P NMR (202 MHz, CDCI ₃ ): 52.3 (s)

synthesis

Under argon, 2-isopropylcyclohexan-1 -amine (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL). · CNOrobis (3-methylphenyl) phosphine (20 mmol) while the flask was immersed in a water bath. ) Was slowly added and stirred overnight. After the solvent was removed in vacuo, another solvent, diethyl ether, tetrahydrofuran or hexane, was added to the mixture and stirred. The triethylammonium chloride salt was removed using an air-free glass filter. The solvent was removed from the filtrate to give the product.

³¹ P NMR (202 MHz, CDCI ₃ ): 51.8 (br s)

Under argon, 2-isopropylcyclohexan-1 -amine (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL). While the flask was immersed in a water bath, chbrobis (3,4-dimethylphenyl) phosphine (20 mmol) was slowly added thereto and stirred overnight. After removing the solvent under vacuum, other solvents such as diethyl ether, tetrahydrofuran or Hexane was added sufficiently to remove hexane and triethylammonium chloride salt was removed using an air-free glass filter. The solvent was removed from the filtrate to give the product.

3 P NMR (202 MHz, CDCI ₃ ): 54.5 (br s)

[Comparative h ₂

Dichloromethane (80 ml) was dissolved in 2-aminopropane (10 mmol) and triethylamine (3 to 10 equiv. To amine) under synthetic argon of Ph ₂ . In a state in which the polar flask was soaked in a water bath, chloradiphenylphosphine (20 mmol) was slowly added thereto and stirred overnight. After removing the solvent in vacuo, tetrahydrofuran was added to the mixture was sufficiently stirred to remove triethylammonium chloride salt¾- with an air-free glass filter. The solvent was removed from the filtrate to obtain the compound.

³¹ P NMR (202 MHz, CDCI ₃ ): 48.4 (br s)

Comparative Example 2

Synthesis of

Under 0 rgon, 3- (aminomethyl) -3,5,5-trimethylcyclohexanamine (5 mmol) and triethylamine (3 to 10 equiv. To amine) were dissolved in dichloromethane (80 ml). While the flask was immersed in a water bath, chloradiphenylphosphine (20 mmol) was slowly added thereto and stirred overnight. After removing the solvent in vacuo, tetrahydrofuran was added and stirred thoroughly 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, CDC! ₃ ): 45.6 (br s), 56.2 (br s) Preparation of catalyst system and progress of ethylene oligomerization reaction

[Examples 1 to 6 and Comparative Examples 1 to 2]

In an argon gas atmosphere, chromium (III) acetylacetonate (17.5 mg, 0.05 mmol) and a ligand compound (0.025 mmol) according to the above synthesis and comparative synthesis examples were put in a flask, and 10 ml of cyclonucleic acid was added thereto. By stirring, 5 mM (based on Cr) of the catalyst solution was prepared.

Parr reaction vessels of 600 ml capacity were prepared and vacuumed at 120 ^° C for 2 hours, after which the interior was replaced with argon and the silver was lowered to 60 ^° C. Thereafter, 180 ml of cyclonucleic acid and 2 ml of MMAO (isoheptane solution, Al / Cr = 1200) were injected, and 0.5 ml (2.5 micromol Cr) of the catalyst solution was injected. After stirring at 500 rpm for 2 minutes, the valve of the ethylene line set to 60 bar was opened to fill the reaction vessel with ethylene, and then adjusted to be defrosted at 45 ^° C. and stirred at 500 rpm for 15 minutes. After closing the ethylene line valve, 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 reaction mixture was 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 the liquid product was analyzed by GC. In addition, 400 ml of ethanol / HCI (10 vol% of aqueous 12M HCI solution) was added to the remaining reaction solution, followed by stirring and filtering to analyze the amount of solids. The obtained polymer was dried overnight in a 65 ^° C vacuum oven. The results of the Examples and Comparative Examples are summarized in the table below.

Table 11

Referring to Table 1, in the case of the embodiment of the present invention, compared to the comparative example, it can be seen that the selectivity of HAO (higher alpha is efin) is improved, and also, the content of PE Wax, which is a solid alpha-olefin, is reduced. You can check it.

That is, as in the present invention, when the diphosphine group of the ligand compound having a specific structure includes an aryl group substituted with a separate substituent, alpha-olefins (1-nuxene and 1-octene) in the ligomerization reaction are included. It can be seen that the selectivity can be improved, and the amount of PE Wax, which is alpha-olepin and solid alpha-olefin in the form of undesirable isomers, can be reduced.

Claims

Claims Ligand compound comprising at least one group represented by the following formula (1) in claim 11 molecule:

[Formula 1]

In Chemical Formula 1,

^* Means that the group represented by the formula (1) is a radical,

A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb),

Each X is independently phosphorus (P), arsenic (As), or antimony (Sb),

R1 to R4 are each independently;

[Claim 2]

According to claim 11,

R1 to R4 of Formula 1, each independently;

6 to 6 carbon atoms in which at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfanyl group having 1 to 10 carbon atoms, and an alkylsilyl group having 1 to 10 carbon atoms is substituted or bonded. Ligand compound which is an aryl group of 20.

[Claim 3]

The method of claim 1,

R 1 to R 4 in Formula 1 are each independently a phenyl group having 6 to 20 carbon atoms; Any one of meta positions relative to the X-linking site, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfanyl group having 1 to 10 carbon atoms, and an alkylsilyl group having 1 to 10 carbon atoms Ligand compound substituted or bonded with one substituent selected from.

[Claim 4]

The method of claim 1,

R 1 to R 4 in Formula 1, each independently, represent a phenyl group having 6 to 20 carbon atoms in total;

Or more of the meta and para positions relative to the X linking site, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfanyl group having 1 to 10 carbon atoms, and a carbon group having 1 to 10 carbon atoms Ligand compound substituted or bonded with one or more substituents selected from the group consisting of alkylsilyl groups.

[Claim 5]

The method of claim 1,

X in the formula (1) is phosphorus (p), A is nitrogen (Ν),

The moiety represented by (R ¹ ) (R ² ) X- and (R ³ ) (R ⁴ ) X- in Formula 1 are each represented by a ligand compound.

[Claim 6]

An organic chromium compound comprising the ligand compound of claims 1 to 5 and chromium (Cr).

[Claim 7]

The method of claim 6,

An organic chromium compound containing a group represented by the following Chemical Formula 1-1:

[Formula 1-1]

In Chemical Formula 1-1,

* Means that the group represented by the formula 1-1 is a radical,

A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb),

Each X is independently phosphorus (P), arsenic (As), or antimony (Sb),

R1 to R4 are each independently;

An aryl group having 6 to 20 carbon atoms, optionally substituted in the meta or para position, at least one substituent selected from the group consisting of an alkyl group, an alkoxy, an alkylsulfanyl group, and an alkylsilyl group; Cr is the creme,

Y 1 to V 3 are each independently halogen, hydrogen, hydrocarbyl having 1 to 10 carbon atoms, or heterohydrocarbyl having 1 to 10 carbon atoms.

[Claim 8]

i) a crum source, the ligand compound of claims 1 to 5, and a promoter;

or

i) an organic krum compound comprising a group represented by the following formula (1-1), and a catalyst system for urepin oligomerization, comprising a promoter:

[Formula 1-1]

In Chemical Formula ¹ _1,

* Means that the group represented by the formula 1-1 is a radical,

A is boron (B), nitrogen (N), phosphorus (P) or antimony (Sb),

Each X is independently phosphorus (P), arsenic (As), or antimony (Sb),

R1 to R4 are each independently;

An aryl group having 6 to 20 carbon atoms, optionally substituted in the meta or para position, at least one substituent selected from the group consisting of an al¾ group, an alkoxy, an alkylsulfanyl group, and an alkylsilyl group;

Cr is chromium ，

[Claim 9]

According to claim 18,

The chromium source is chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylnucleoanoate, chromium (III) acetate, chromium (III) butyrate, chromium (pent) 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.

[Claim 10]

The method of claim 8,

The promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, diethylaluminum For olefin oligomerization, comprising at least one member selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane Catalyst system.

[Claim 111]

The method of claim 8,

Catalytic Semireaction Catalyst System for Ethylene.

[Claim 12]

A process for oligomerization of olefins, comprising the step of undergoing oligomerization reaction of olepin in the presence of a catalyst system according to claim 8 to form an alpha-olefin.

[Claim 13]

In the presence of the catalyst system according to claim 8, the quaternization reaction of ethylene is carried out. Proceeding, forming the octene, 1-octene production method.