WO2016167455A1

WO2016167455A1 - Ligand compound, oligomerizing catalyst system, and method for olefin oligomerization using same

Info

Publication number: WO2016167455A1
Application number: PCT/KR2016/000823
Authority: WO
Inventors: 신은지; 이용호; 박진영; 사석필; 이기수; 임슬기
Original assignee: 주식회사 엘지화학
Priority date: 2015-04-15
Filing date: 2016-01-26
Publication date: 2016-10-20
Also published as: WO2016167455A8

Abstract

The present specification relates to a ligand compound, an oligomerizing catalyst system, and a method for olefin oligomerization using the same. The olefin oligomerizing catalyst system using the ligand compound according to the present specification has excellent catalytic activity, exhibits high selectivity to 1-hexene or 1-octene, and significantly reduces the amount of byproducts, such as isomers of 1-hexene, thereby enabling efficient preparation of α-olefin.

Description

【Specification】

[Name of invention]

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

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0053169 dated April 15, 2015 and Korean Patent Application No. 10-2016-0008490 dated January 25, 2016. All content disclosed in the literature is included as part of this specification. The present specification relates to a ligand compound, an oligomerization catalyst system, and an inlefin oligomerization method using the same.

Background Art

Linear alpha-olefins are widely used commercially as important substances used in comonomers, detergents, lubricants, plasticizers, etc. In particular, 1-nuxene and 1-octene are used in the production of linear low density polyethylene (LLDPE). It is often used as a comonomer to control the density. '

Conventional LLDPE (Linear Low-Density Polyethylene) manufacturing process is used to form a branch (p ymer backbone) in the polymer backbone (ethylene) with ethylene to control the density (density) to control the density (density), for example For example, the copolymerization was performed with comonomers such as 1-nuxene and 1-octene.

Therefore, there is a problem in that the price of the comonomer occupies a large part of the manufacturing cost for the production of LLDPE having a high comonomer content. In order to solve this problem, various attempts have been made.

In addition, since alpha-le-lefin has different types of market and market size, technology for selectively producing specific olefins is important commercially. Recently, 1-nucleene has been selected through selective ethylene igomerization. Or much research has been made on chromium catalyst technology for producing 1-octene with high selectivity. Conventional commercial manufacturing methods for producing 1-nuxene or 1-octene include SHOP process of Shell Chemical and Ziegler Process of Chevron Philips. Lower alpha-olefins can be produced with a wide distribution of C4 to C20.

A creme-based catalyst using a ligand of the general formula (R1) (R2) X-Y-X (R3) (R4) as a trimerization catalyst of ethylene has been proposed. Wherein X is phosphorus, arsenic or antimony, Y is a linking group such as -N (R5)-, and at least one of R1, R2, R3 and R4 has a polar or electron-donating substituent.

1 also under the catalyst condition-in (0-ethyl-phenyl) does not have a polar substituent on at least one of R1, R2, R3 and R4 compound as a ligand which does not exhibit catalytic activity for haeksen ₂ PN (Me) P (o- ethyl Phenyl) ₂ (C? Em. Commun., 2002, 858).

However, the ligand containing the heteroatoms of the prior art described above is still a situation that the demand for consistently sustained multimerization reaction activity and high selectivity in the reaction of 1-octene or 1-nucleene produced.

[Content of invention]

[Problem to solve]

The present specification provides a novel ligand compound capable of oligomerizing olefins with high catalytic activity and selectivity and greatly reducing the amount of by-products produced, an oligomerization catalyst system comprising the same, and an olefin oligomerization method using the same. will be.

[Measures of problem]

In this specification, the ligand compound represented by the following Chemical Formula 1 is provided. [Formula 1]

In Chemical Formula 1,

R1 to R4 are each independently an aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms,

R5 is an alkyl group having 1 to 20 carbon atoms,

R 6 is an alkyl group having 2 to 20 carbon atoms, with or without one or more hetero elements, an alkenyl group having 2 to 20 carbon atoms, one having at least one hetero element, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. An arylalkyl group, an alkylaryl group of 7 to 20 carbon atoms, an aryl alkenyl group of 7 to 20 carbon atoms, an alkenylaryl group of 7 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms, a heteroarylalkyl group of 6 to 20 carbon atoms, Heteroaryl alkenyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms with or without at least one hetero element and a cycloalkenyl group having 3 to 20 carbon atoms with or without at least one hetero element Selected,

R7 to R9 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an arylalkenyl group having 7 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms And a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms.

In the ligand compound, R 5 may be an alkyl group having 2 to 20 carbon atoms, or R 5 and R 6 may be different from each other. In an embodiment of the ligand compound, when R5 is a methyl group or an isopropyl group, an alkyl group having 2 to 20 carbon atoms with or without one or more hetero elements of R6 may be a linear alkyl group.

In embodiments of the ligand compound, R7 to R9 may be hydrogen, and R1 to R4 may be phenyl groups.

In addition, in a specific example of the ligand compound, R 5 is a methyl group, R 6 is a straight alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms containing at least one hetero element, and an aryl group having 6 to 20 carbon atoms. Aryl group having 7 to 20 carbon atoms, alkylaryl group having 7 to 20 carbon atoms, aryl alkenyl group having 7 to 20 carbon atoms, alkenylaryl group having 7 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, and 6 to 20 carbon atoms Heteroarylalkyl group, a heteroarylalkenyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms containing at least one hetero element, and a cycloalkenyl group having 3 to 20 carbon atoms containing at least one hetero element Can be.

The present disclosure also provides an oligomerization catalyst system comprising the ligand compound, the transition metal compound and the promoter, or the organic transition metal compound wherein the ligand compound is coordinated to the transition metal.

In this oligomerization catalyst system, the transition metal compound includes an organic cr compound, the organic chromium compound chromium (acetyl) acetyl acetonate, chromium trichloride tetrahydrofuran, chromium (ᅵ 1) -2-ethyl Nucleoanoate, chromium tris (2,2,6,6-tetramethyl-3,5-heptanedionate), crumb (III) benzoyl acetonate, chromium (Ml) nucleofluoro-2, It may be at least one selected from the group consisting of 4-pentanedionate and chromium (III) acetate hydroxide.

In addition, in such an oligomerization catalyst system, the organic transition metal compound may be an organic creme compound in which the ligand compound is coordinated to the creme.

In the catalyst system, the promoter may be at least one selected from the group consisting of compounds represented by Formulas 2 to 4 below:

[Formula 2]

[AI (R ₅ ) -0] c- In Formula 2, ₅ is the same as or different from each other, each independently represent a halogen radical C 1-20 hydrocarbyl radical, or a halogen substituted C 1-20 hydrocarbyl radical, c is an integer of 2 or more,

[Formula 3]

D (R ₆ ) ₃

In Chemical Formula 3,

D is aluminum or boron, R ₆ is the same as or different from each other, and each independently hydrogen or halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

[Formula 4]

[LH] ⁺ [Q (E) ₄ ] ^"

In Chemical Formula 4,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in a +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.

On the other hand, the present disclosure also provides a method for olephine oligomerization comprising the step of multimerizing the levine in the presence of the oligomerization catalyst system described above.

In an embodiment of this oligomerization method, the olefin may comprise ethylene.

According to the oligomerization method, olefins such as ethylene can be multiplied, for example trimerized or tetramerized, to obtain alpha-olefins such as 1-nuxene or 1-octene with high activity and selectivity. In addition to the alpha-lelpene to be produced, the by-product content of the solid alpha-lelpene form (e.g., isomer of 1-nucleene having 6 carbon atoms) can be reduced. In one example, the product produced by the oligomerization method may have a content of solid alpha-olefins, less than 1.0 weight ⁰ /.

【Effects of the Invention】 By using the catalyst system including the ligand compound according to the present specification, it is possible to oligomerize ethylene with higher catalytic activity and selectivity as compared to the conventional catalyst system, and greatly reduce the amount of nucleene isomers, which are byproducts.

[Specific contents to carry out invention]

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention. 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 should be understood that they do not preclude the existence or addition of numbers, steps, components, or combinations thereof _.

Throughout this specification, "catalyst system", "catalyst composition" or "catalyst system" means a three component comprising a transition metal source (e.g., a transition metal compound such as an organic chromium compound), a ligand compound and a promoter, or Alternatively, it is meant that the ligand compound is in a state where two components of the organic transition metal compound and the cocatalyst coordinated to the transition metal can be added simultaneously or in any order to obtain an active catalyst composition. Three or two components of the catalyst system may be added in the presence or absence of a solvent and a monomer, and the three terms may be commonly used. In the present specification, the hydrocarbyl group refers to all compounds consisting of only carbon and hydrogen, and examples thereof include an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, and the like. Unless otherwise specified, it can mean both straight and branched chains, and both unsubstituted and substituted Can mean. For example, the group which is an alkyl group having 1 to 20 carbon atoms may mean methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, etc. The aryl group having 6 to 20 carbon atoms includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, and the like, but is not limited thereto.

In the present specification, the alkylafil group means an aryl group having at least one alkyl group as a substituent, and the arylalkyl group means an alkyl group having at least one aryl group as a substituent.

In the present specification, the hetero element may mean N, O, S, or P, and the heteroaryl group may mean that any one of carbons in the aromatic ring is substituted with a hetero element, such as a pyridyl group. The same may also apply to the heteroarylalkyl group, the heteroalkylaryl group, the heteroalkenylaryl group, and the like. Ligand Compound

According to the present specification, in a catalyst system used for oligomerization of an olefin, a ligand compound is provided that is highly coordinated with a transition metal to provide high selectivity for alpha-olefins and low amount of by-products, and enhances catalytic activity. According to one embodiment of the present specification, the ligand compound is represented by the following Chemical Formula 1.

In Chemical Formula 1, R1 to R4 are each independently an aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms,

R5 is an alkyl group having 1 to 20 carbon atoms,

R 6 is an alkyl group having 2 to 20 carbon atoms, with or without one or more hetero elements, an alkenyl group having 2 to 20 carbon atoms, one or more aryl groups having 6 to 20 carbon atoms, and having 7 to 20 carbon atoms, including or not including one or more hetero elements. An arylalkyl group, an alkylaryl group of 7 to 20 carbon atoms, an aryl alkenyl group of 7 to 20 carbon atoms, an alkenylaryl group of 7 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms, a heteroarylalkyl group of 6 to 20 carbon atoms, Heteroarylalkenyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms with or without one or more hetero elements, and a cycloalkenyl group having 3 to 20 carbon atoms with or without one or more hetero elements Selected,

As described above, the ligand compound represented by Formula 1 may be, for example, a compound in which carbons 2 and 6 of the aniline compound are substituted with R5 and R6, and a group substituted with carbons 2 and 6 ( R5 and R6), respectively, may change the properties of the ligand compound and the oligomerization catalyst system including the same.

In particular, in the case where an alkyl group having 2 or more carbon atoms, for example, 2 to 20 carbon atoms is substituted for the carbon number 2 (R5), or a methyl group is substituted for the carbon number 2 (R5), etc., an asymmetric structure is used. So that a substituent having a structure different from the substituent at the carbon position 2 may be bonded to the carbon position (R6).

In one example of such a ligand compound, when R5 is a methyl group or isopropyl group, R6 may be a straight chain alkyl group having 2 to 20 carbon atoms with or without a hetero element, or as described above. It may be an asymmetric substituent (that is, a substituent having a structure different from R5), more suitably a straight chain alkyl group having 2 to 20 carbon atoms, a substituent including one or more hetero elements, or a substituent including one or more aromatic groups. have.

In a more specific example, when R5 is a methyl group, R6 is a C2-C20, C2-C3 linear alkyl group with or without a hetero element, C2-C20 with one or more hetero elements, or Alkenyl group having 2 to 3 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, alkylaryl group having 7 to 20 carbon atoms, aryl alkenyl group having 7 to 20 carbon atoms, alkenylaryl having 7 to 20 carbon atoms Group, a heteroaryl group having 5 to 20 carbon atoms, a heteroarylalkyl group having 6 to 20 carbon atoms, a heteroaryl alkenyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms containing at least one hetero element, and at least one hetero element It may be selected from the group consisting of cycloalkenyl group containing 3 to 20 carbon atoms.

As described above, the ligand compound of Formula 1 may have an asymmetric substituent structure in which at least R5 and R6 are not all methyl groups or R5 and R6 have different structures from each other. In a more suitable example, the ligand compound may be R 6 is a straight alkyl group having 2 or more carbon atoms, or a substituent containing one or more hetero elements or aromatic groups.

Due to the structural characteristics of the substituents of the aniline group, the catalyst system including the ligand compound easily interacts with PNP-Cr according to various conditions such as electronic and steric environment around the transition metal, resulting in high oligomerization reaction activity. In addition, it can exhibit high selectivity, especially for 1-nuxene, 1-octene, and the like. Furthermore, the production of by-products in the form of solid alpha-lelephine, such as isomers of 1-nucleene, which have a large effect on the product even in small amounts in oligomerization, can be greatly reduced. The reduction can also result in energy savings, as separation can be unnecessary. On the other hand, in the above-described ligand compound of Formula 1, R1 to R4 and R7 to R9 may be already a variety of substituents described above, in a more specific example, R7 to R9 may be hydrogen, R1 to R4 is a phenyl group Can be

In addition, the ligand compound described above may be synthesized in the same manner as in Banung Formula 1 below, but is not limited thereto.

[Banungsik 1]

In Formula 1, G1 may be a phenyl group having R5 to R9 of Formula 1, G2 and G3 may each be R1 to R4 of Formula 1, and X may be a halogen group.

The reaction formula 1 is a general reaction formula for synthesizing the ligand compound represented by Formula 1, and may be a reaction system in which amine and phosphine react to generate diphosphinoamine. That is, the amine may be a reaction reaction leaving and leaving a leaving group represented by X of the phosphine as a nucleophile, X is not particularly limited as long as it is a stable functional group easy to leave after leaving, typical halogen, CI, Br, or I may be present. Oligomerization Catalyst

According to another embodiment of the present specification, an oligomerization catalyst system may be provided that includes the above-described ligand compound, transition metal compound and cocatalyst, or wherein the ligand compound comprises an organic transition metal compound coordinated to the transition metal. As used herein, the term "oligomerization" means that the olefin is small polymerized. Depending on the number of olefins to be polymerized may be trimerization, tetramerization, etc., may be collectively referred to as igomerization. In particular in this specification the major of LLDPE from ethylene It may mean to selectively prepare the comonomers 1-nuxene and 1-octene. This selective olefin oligomerization reaction is closely related to the catalyst system used. The catalyst system used during the olefin oligomerization reaction includes a transition metal compound serving as a main catalyst, a ligand compound and a promoter, wherein the structure of the active catalyst species can be changed according to the chemical structure of the ligand compound. As a result, the selectivity of leupin or the amount of active or by-products may be different.

The transition metal compound of the oligomerization catalyst system of one embodiment according to the present specification serves as a main catalyst, and the ligand compound may be in the form of an organic transition metal compound coordinated to the transition metal, and is present in a mixed state with the ligand compound. It may be in the form of a catalyst composition. In one example of the organic transition metal compound, phosphorus (P) of the diphosphinoamine group of the ligand compound may be a site that is coordinated while receiving electrons in the transition metal.

In a specific embodiment, the transition metal compound represented by MX ₃ and the ligand compound represented by Chemical Formula 1 may have a form of the organic transition metal compound by coordinating with a form represented by the following Chemical Formula 1-1:

[ -One]

In Formula 1-1, R1 to R9 are the same as in Formula 1, M may be a transition metal, preferably Cr, and X1 to X3 may be each independently of each other H, F, CI, Br , I, or an alkyl group having 1 to 6 carbon atoms, It may be an alkenyl group, an arylalkyl group, a heteroalkyl group, a heteroalkenyl group or a heteroarylalkyl group, or a halogen group.

Specifically, the organic transition metal compound, the ligand compound may be an organic cream compound coordinated with chromium. At this time, as a creme compound (that is, a chromium compound coordinated to a ligand compound) for the formation of the organic creme compound, for example, chromium (ᅵ) acetylacetonate, chromium trichloride tristetrahydrofuran, chromium 2-ethylnucleonoate, chromium (III) tris (2,2, 6,6-tetramethyl-3,5-heptanedionate), chromium (III) benzoylacetonate, crumb (III) nucleofluor One or more selected from the group consisting of -2,4-pentanedionate and chromium (III) acetate hydroxide can be used.

The cocatalyst is an organometallic compound including a Group 13 metal, and is not particularly limited as long as it can be used in the multimerization of olefins under a transition metal compound catalyst. Specifically, the cocatalyst may be one or more selected from the group consisting of compounds represented by the following formulas (2) to (4).

[Formula 2]

-[AI (R ₅ ) -0] c- In Formula 2, R ₅ 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 1 to 20 carbon atoms substituted with halogen. Is a hydrocarbyl radical, c is an integer of 2 or more, and is [Formula 3]

D (R ₆ ) ₃

In Chemical Formula 3,

[Formula 4]

[LH] ⁺ [Q (E) ₄ ] — in the formula 4, L is a neutral Lewis base, [LH] ⁺ is a 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.

As the compound represented by Formula 2, for example, modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like.

Examples of the alkyl metal compound represented by Formula 3 include trimethylaluminum, triethylaluminum triisobutylaluminum tripropylaluminum, tributylaluminum, dimethylchloroaluminum dimethylisobutylaluminum, dimethylethylaluminum and diethylchloroaluminum tri Isopropyl Aluminum, Tri-S-Butyl Aluminum, Tricyclopentyl Aluminum Tripentyl Aluminum, Triisopentyl Aluminum, Trinuclear Aluminum Ethyl Dimethyl Aluminum Methyl Diethyl Aluminum, Triphenyl Aluminum, Tri-P-Trilled Aluminum, Dimethyl Aluminum methoxide Dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like. Examples of the compound represented by the formula (4) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P). -Lyl) boron, tripropyl ammonium tetra (P-lryl) boron, triethyl ammonium tetra (ο, ρ-dimethylphenyl) boron, trimethyl ammonium tetra (ο, ρ- dimethylphenyl) boron, tributyl ammonium Tetra (Ρ-trifluoromethylphenyl) boron, trimethylammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron, Ν, Ν-diethylanilinium tetraphenyl boron, Ν, Ν-diethylanilinium tetraphenylboron, Ν, Ν- diethylanilinium tetrapentafluoro Phenylboron,

Diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, Tripropylammonium tetraphenylaluminum, trimethylammonium tetra (P-lryl) aluminum, tripropylammonium tetra (P-lryl) aluminum, triethylammonium tetra (ο, ρ-dimethylphenyl) aluminum, tributylammonium Tetra (Ρ-trifluoromethylphenyl) aluminum, trimethylammonium tetra (Ρ-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, Ν, Ν-diethylanilinium tetraphenylaluminum, Ν, Ν- diethylanilinium tetraphenylaluminum, Ν, Ν-diethylanilinium tetrapentafluorophenylaluminum,

Diethylammonium tetrapentafluorophenylaluminum ，

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron and the like.

As the co-catalyst of the oligomerization catalyst system of the above embodiment, an aluminoxane compound may be preferably used, and more preferably, methyl aluminoxane (ΜΑΟ) or modified methylaluminoxane (ΜΜΑΟ) may be used. The oligomerization catalyst system has a molar ratio of the ligand compound: transition metal compound: cocatalyst in the range of about 0.5: 1: 1 to about 10: 1: 10,000 days in order to increase the selectivity to the linear alpha olefin and to increase the multimerization reaction activity. And preferably from about 0.5: 1: 100 to about 5: 1: 3,000. However, the oligomerization catalyst system according to the present specification is not limited thereto.

In a catalyst system comprising a ligand compound represented by Formula 1, a transition metal compound, and a cocatalyst, the three components of the catalyst system are added together in the presence or absence of monomer in any suitable solvent simultaneously or sequentially in any order. Can be obtained as an active catalyst. Suitable solvents include, but are not limited to, heptane, toluene, cyclonucleic acid, methylcyclonucleic acid, 1-nuxene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methane, acetone, and the like. It doesn't work. Elevine oligomerization method According to another embodiment of the present disclosure, there may be provided a method for preparing an olefin oligomer comprising the step of multimerizing the olefin in the presence of the oligomerization catalyst system. In this method, the activity and selectivity of the reaction can be improved by using the catalyst system for olefin oligomerization described above. In addition, the content of by-products resulting from oligomerization can be greatly reduced. In this case, the olefin may include ethylene.

The oligomerization according to the present specification is a homogeneous liquid reaction in the presence or absence of an inert solvent using a conventional apparatus and contacting technique with the oligomerization catalyst system, a slurry reaction in which the catalyst system is not partially dissolved or completely dissolved. Phase liquid / liquid reactions, or bulk reactions or gaseous reactions in which the product olefins act as the main medium, may be preferred, homogeneous liquid reactions. The olefin oligomerization reaction can be carried out in any inert solvent that does not react with the catalyst compound and the active agent. Suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, nucleic acid, pentane, butane, isobutane and the like. At this time, the solvent can be used by removing a small amount of water or air, etc. acting as a catalyst poison by treating with a small amount of alkylaluminum.

The olefin oligomerization reaction may be carried out at a temperature of about 5 ^° C to about 200 ^° C, preferably at a temperature of about 30 ^° C to about 150 ^° C. The olefin oligomerization reaction can be carried out at a pressure of about 1 bar to about 300 bar, preferably at a pressure of about 2 bar to about 150 bar.

The range of temperature and pressure conditions may be the conditions of the family register to multiply olefins, when the olefins in the silver range and pressure range, the selectivity for the desired alpha-lephine may be excellent and In addition, the amount of by-products can be reduced, the efficiency of the process operation can be increased and the cost can be reduced. According to one embodiment of the present specification, the catalyst system using the compound represented by Chemical Formula 1 as a ligand has improved activity compared to the conventional oligomerization catalyst system, and when oligomerization of ethylene using the same, 1-nuxene and 1-octene Can be selectively synthesized, and the amount of 1-nucleene isomers can be greatly reduced, which can be confirmed in the following examples. Example

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

All reactions were performed under argon using the Schlenk technique or glove box. The synthesized ligand was analyzed by ¹ H (500 MHz) and ³¹ P (202 MHz) NMR spectra using a Varian 500 MHz spectrometer. The shift is expressed in ppm in the downfield from TMS with the residual solvent peak as reference Phosphorous probes were calibrated with aqueous H ₃ P0 ₄ .

Under argon 2-ethyl-6-methylaniline (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL). While the flask was soaked in a water bath, chlorodiphenylphosphine (20 mm) was slowly added and stirred overnight. After vacuuming to blow off the solvent, add another solvent (diethyl ether, tetrahydrofuran or hexane) and stir thoroughly with an air-free glass filter to give triethylammonium chloride. chloride salt) was removed. The solvent was removed from the filtrate to give the product.

The ligand compound was prepared in the same manner as in Synthesis Example 1, except that 2,6-diethylaniline was used instead of 2-ethyl-6-methylaniline used in Synthesis Example 1.

The ligand compound was prepared in the same manner as in Synthesis Example 1, except that 2-methoxy-6-methylaniline was used instead of 2-ethyl-6-methylaniline used in Synthesis Example 1.

The ligand compound was prepared in the same manner as in Synthesis Example 1, except that 2,4-dimethyl-6-phenylaniline was used instead of 2-ethyl-6-methylaniline used in Synthesis Example 1. Comparative Synthesis Example 1 Ph _? P "Ph The ligand compound was prepared in the same manner as in Synthesis Example 1, except that 2,6-dimethylaniline was used instead of 2-ethyl-6-methylaniline in Synthesis Example 1. Comparative Synthesis Example 2

P

₂ The ligand compound was prepared in the same manner as in Synthesis Example 1, except that 2-methylaniline was used instead of 2-ethyl-6-methylaniline used in Synthesis Example 1.

Example 1

(Step 1)

Cr (acac) ₃ (17.5 mg, 0.05 mmol) under argon gas and the ligand compound (1.1 eq. To Cr) prepared according to Synthesis Example 1 were added to a flask, and 100 ml of methylcyclonucleic acid was added thereto, followed by stirring. A solution of mM (Cr basis) was prepared.

(Step 2)

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 temperature was lowered to 60 ^° C. Then, 140 g of methylcyclonucleic acid and 1 .6 ml of MMAO (8.6 wt%, isoheptane solution) were injected (Al / Cr = 1200), and 5 ml (2.5um) of the 0.5 mM solution was added to the reactor. Injected. The valve of the ethylene line set at 60 bar was opened to fill the reaction vessel with ethylene and stirred at 500 rpm for 15 minutes. Ethylene line valve After locking, the reaction mixture was cooled to 0 ^° C. using a dry ice / acetone bath, and then slowly ventilated with banung ethylene and 1 ml of nonane (GC internal standard) was added thereto. Thereafter, a small portion of the liquid portion of the reaction was quenched with water, and the organic layer was filtered with a PTFE syringe filter to perform GC analysis.

(Step 3)

400 ml of ethanol / HCI (10 vol%) was added to the remaining reaction solution, followed by stirring and filtering to obtain a polymer. The obtained polymer was dried overnight in a 60 ^° C vacuum oven, and weighed. Example 2

Except for using the ligand compound prepared in Synthesis Example 2 instead of the ligand compound prepared in Synthesis Example 1 was carried out ligomerization, GC analysis and weighing of the polymer obtained in the same manner as in Example 1. Example 3

Except for using the ligand compound prepared in Synthesis Example 3 instead of the ligand compound prepared in Synthesis Example 1 was carried out by the same method as Example 1 was carried out ligomerization, GC analysis and weighing of the obtained polymer. Example 4

Except for using the ligand compound prepared in Synthesis Example 4 instead of the ligand compound prepared in Synthesis Example 1 was carried out ligomerization, GC analysis and weighing of the polymer obtained in the same manner as in Example 1. Comparative Example 1

The oligomerization, GC analysis and weighing of the obtained polymer were carried out in the same manner as in Example 1, except that the ligand compound prepared in Comparative Synthesis Example 1 was used instead of the ligand compound prepared in Synthesis Example 1. Comparative Example 2 The oligomerization, GC analysis and weighing of the obtained polymer were carried out in the same manner as in Example 1, except that the ligand compound prepared in Comparative Synthesis Example 2 was used instead of the ligand compound prepared in Synthesis Example 1. The results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1 below.

Table 11

Through Table 1, when the ligand compounds of Synthesis Examples 1 and 2 were used, it was confirmed that the amount of by-products such as nucleene isomers was smaller than that of the ligand compounds of Comparative Synthesis Example 1, and the HAO selectivity was high.

In addition, even in the case of Example 3 using a ligand compound substituted with a hetero atom-containing compound (Synthesis Example 3), even if a group in which a hetero element is substituted, there was no problem in using the catalyst system for oligomerization reaction. In the case of Example 4 using a ligand compound substituted with an aryl group (Synthesis Example 4), it was confirmed that it was also very useful for the oligomerization reaction.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims

[Claims] [Claim 1] A ligand compound represented by the following formula (1):

[Formula 1]

2 3

In Formula 1,

R5 is an alkyl group having 1 to 20 carbon atoms,

R6 is an alkyl group having 2 to 20 carbon atoms with or without one or more hetero elements, an alkenyl group with 2 to 20 carbon atoms with or without one or more hetero elements, an aryl group with 6 to 20 carbon atoms, or an aryl group with 7 to 20 carbon atoms. Arylalkyl group, alkylaryl group with 7 to 20 carbon atoms, arylalkenyl group with 7 to 20 carbon atoms, alkenylaryl group with 7 to 20 carbon atoms, heteroaryl group with 5 to 20 carbon atoms, heteroarylalkyl group with 6 to 20 carbon atoms, carbon number Selected from the group consisting of a heteroarylalkenyl group of 6 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms with or without one or more hetero elements, and a cycloalkenyl group of 3 to 20 carbon atoms with or without one or more hetero elements. And

R7 to R9 are each independently hydrogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 1 to 20 carbon atoms, an arylalkyl group with 7 to 20 carbon atoms, an arylalkenyl group with 7 to 20 carbon atoms, and a cycloalkyl group with 3 to 20 carbon atoms. ，Carbon number It is selected from the group consisting of a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms.

【Claim 2】

In clause 1,

The R5 is an alkyl group having 2 to 20 carbon atoms, or

A ligand compound in which R5 and R6 are different substituents.

【Claim 3】

According to claim 1,

If R5 is a methyl group or isopropyl group,

The ligand compound wherein the alkyl group of R6 with or without one or more hetero elements and having 2 to 20 carbon atoms is a straight-chain alkyl group.

【Claim 4】

According to clause 1,

A ligand compound in which R7 to R9 of Formula 1 are hydrogen.

【Claim 5】

According to clause 1,

A ligand compound in which R1 to R4 of Formula 1 are phenyl groups.

【Claim 6】

According to clause 3,

R5 is a methyl group,

R6 is a straight-chain alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms containing one or more hetero elements, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. group, arylalkenyl group with 7 to 20 carbon atoms, alkenyl aryl group with 7 to 20 carbon atoms, heteroaryl group with 5 to 20 carbon atoms, heteroarylalkyl group with 6 to 20 carbon atoms, 6 to 20 carbon atoms 20 heteroarylalkenyl group, 3 to 3 carbon atoms containing one or more hetero elements

A ligand compound selected from the group consisting of a cycloalkyl group of 20 and a cycloalkenyl group of 3 to 20 carbon atoms containing one or more hetero elements.

【Claim 7】

It contains the ligand compound, transition metal compound, and cocatalyst of any one of claims 1 to 6, or

An oligomerization catalyst system wherein the ligand compound includes an organic transition metal compound coordinated to a transition metal.

【Claim 8】

According to clause 7,

The transition metal compound includes a CrM compound, and the CrM compound includes chromium (III) acetyl acetonate, CrM Tris tetrahydrofuran trichloride, CrM (11ᅵ)-2-ethylhexanoate, CrM (ᅵ1ᅵ) Tris (2,2,6,6-tetramethyl-3,5-heptanedionate), chromium ᅵ) benzoyl acetonate, chromium (III) hexafluoro-2,4-pentanedionate and chromium (ᅵᅵᅵ) An oligomerization catalyst system comprising at least one selected from the group consisting of acetate hydroxide.

【Claim 9】

According to clause 7,

The organic transition metal compound is an oligomerization catalyst system in which the ligand compound is an organic chromium compound coordinated to chromium.

[Claim 10]

In clause 7,

An oligomerization catalyst system wherein the cocatalyst is at least one selected from the group consisting of compounds represented by the following formulas 2 to 4:

[Formula 2]

-[AI(R ₅ )-O]c- In Formula 2, R ₅ is the same as or different from each other, and each independently represents a halogen radical, a hydrocarbyl radical with 1 to 20 carbon atoms, or a hydrocarbyl radical with 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more. ，

[Formula 3]

D(R ₆ ) ₃

In Formula 3 above,

D is aluminum or boron, R ₆ are the same or different from each other, and are each independently hydrogen or halogen, a hydrocarbyl with 1 to 20 carbon atoms, or a hydrocarbyl with 1 to 20 carbon atoms substituted with halogen,

[Formula 4]

[LH] ⁺ [Q(E) ₄ ]- In Formula 4,

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

【Claim 1 1】

An olefin oligomerization method comprising the step of polymerizing and reacting olefin in the presence of the oligomerization catalyst system of item 7.

【Claim 12】

According to clause 11,

A method for olefin oligomerization, wherein the olefin includes ethylene.