KR102087994B1 - Method for preparing ethylene tetramerization catalyst system, ethylene tetramerization catalyst system, manufacturing method for ethylene tetramer and bisphosphine ligand compound - Google Patents

Abstract

The present invention is a borate compound; and a first organoaluminum compound; After reacting, the chromium compound; And a bisphosphine ligand compound; a method for preparing an ethylene tetramerization catalyst system comprising sequentially injecting a catalyst system, and a novel bisphosphine ligand suitable for realizing high activity and selectivity. Through this, the present invention can realize excellent selectivity for 1-octene and high economical efficiency when applied to an ethylene tetramer production method (oligomerization reaction), and in particular, excludes the use of expensive methylaluminoxane unlike a conventional catalyst system. Therefore, it is possible to secure excellent economic efficiency and stable process operation in the commercialization process.

Description

METHOD FOR PREPARING ETHYLENE TETRAMERIZATION CATALYST SYSTEM, ETHYLENE TETRAMERIZATION CATALYST SYSTEM, MANUFACTURING METHOD FOR ETHYLENE TETRAMER AND BISPHOSPHINE LIGAND COMPOUND

The present invention relates to a method for preparing an ethylene tetramerization catalyst system suitable for a mass commercial process because it can achieve both high activity and excellent economic efficiency, an ethylene tetramerization catalyst system prepared therefrom, and a method for producing an ethylene tetramer using the catalyst system. It also relates to a novel bisphosphine ligand compound used in the catalyst system.

Ethylene tetramers such as 1-octene are compounds used in large quantities as comonomers when polymerizing polyolefins such as polyethylene. Recently, as the production of polyolefins using a homogeneous metallocene-based catalyst has increased, the demand for such ethylene tetramers has steadily increased.

Conventional technology produces a variety of 1-alkene having about 4 to about 30 carbon atoms by quantumizing ethylene with a Shell Higher Olefin Process (SHOP) based on a nickel catalyst, from which 1-octene is produced. The method of separating and separating is known.

Other conventional techniques include, for example, chromium trivalent compound (CrCl ₃ or Cr (acac) ₃ ), bisphosphine ligand isoPrN (PPh ₂ ) ₂ as in Patent Document 1 and Patent Document ₂ And a method for preparing 1-octene by selectively quantifying ethylene through a catalyst system composed of methylaluminoxane (MAO).

However, the catalyst systems of Patent Documents 1 and 2 require the use of expensive methyl aluminoxane (MAO) in excess (Al / Cr = 300-500) in order to secure sufficient activity for the reaction, thereby causing 1-octene. There is a problem that the manufacturing cost increases and the economic efficiency decreases (Non-Patent Document 1 and Non-Patent Document 2).

In addition, as in Non-Patent Documents 3 to 5, the development of a catalyst system for not using expensive methylaluminoxane (MAO) is also actively progressing, but most of the activity is significantly higher than that of a catalyst system using methylaluminoxane (MAO). It is low and is not suitable for commercial use.

As described above, in the ethylene oligomerization catalyst technology, research for selectively preparing an ethylene tetramer having a desired structure continues, but it is not easy to achieve both high activity and economic efficiency at the same time using conventional techniques alone.

Accordingly, there is an increasing need for the development of ethylene oligomerization technology capable of producing 1-octene with high selectivity and excellent productivity while being in contact with ethylene monomers, while at the same time achieving both high activity and economy. .

(Advanced technical literature)

Patent Document 1: Korean Patent Publication No. 10-2006-0002742

Patent Document 2: United States Patent Publication 7511183B2

Non-Patent Document 1: Organometallics, 27 (2008) 5712-5716

Non-Patent Document 2: Organometallics, 31 (2012) 6960-6965

Non-Patent Document 3: Organometallics, 26 (2007) 1108-1111

Non-Patent Document 4: Organometallics, 26 (2007) 2561-2569

Non-Patent Document 5: Organometallics, 26 (2007) 2782-2787

Non-Patent Document 6: ACS Omega, 2 (2017) 765-773

One object of the present invention is to implement an excellent selectivity for 1-octene when applied to an ethylene tetramer production method (oligomerization reaction), and can achieve both high activity and excellent economical efficiency, so it is an ethylene tetramerization catalyst suitable for mass commercial processes System manufacturing method, the ethylene tetramerization catalyst system produced therefrom.

Another object of the present invention, through the above-mentioned ethylene tetramerization catalyst system, shows a high selectivity to 1-octene, and shows high activity compared to a catalyst system using methylaluminoxane and modified methylaluminoxane, unlike conventional methyl aluminoxane, It is possible to omit the use of modified ethyl aluminoxane, and it is related to a method for producing an ethylene tetramer suitable for application in a large number of commercial processes because it is compatible with high activity and economy.

Another object of the present invention is to provide a bisphosphine ligand compound having properties that are advantageous for the preparation of the aforementioned ethylene tetramerization catalyst system.

The above and other objects of the present invention can be achieved by the present invention described below.

One embodiment of the present invention is a borate compound represented by Formula 1 below; and a first organoaluminum compound represented by Formula 2 below; After reacting, the chromium compound represented by the following formula (3); And a bisphosphine ligand compound represented by the following Chemical Formula 4; sequentially, to prepare a catalyst system.

[Formula 1]

[HQ _m ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^-

In Formula 1, m is 0 to 2, Q is an ether having 2 to 20 carbons;

[Formula 2]

(R ¹ ) ₂ Al (X)

In Chemical Formula 2, R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, X is a halogen group, an acetylacetonate group, a carboxylate group, an alkoxy group having 1 to 20 carbon atoms, and a phenoxy group having 6 to 30 carbon atoms. Is either;

[Formula 3]

Cr (Z) ₃ (A) _n

In Chemical Formula 3, Z is each independently a halogen group, an acetylacetonate group, or a carboxylate group, A is an ether or acetonitrile having 2 to 20 carbon atoms, and n is 0 or 3;

[Formula 4]

RN- [P (-C ₆ H ₄ -Y) ₂ ] ₂

In Formula 4, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, Y is a substituted or unsubstituted silyl group having 3 to 50 carbon atoms, halogen Group, a hydrocarbon group having 1 to 20 carbon atoms, or hydrogen.

A borate compound represented by Formula 1; A first organoaluminum compound represented by Formula 2; A chromium compound represented by Chemical Formula 3; And a bisphosphine ligand compound represented by Chemical Formula 4; the molar ratio may be 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1.

In Chemical Formula 2, R ¹ is an ethyl group or an isobutyl group, and X is an acetylacetonate group.

In Chemical Formula 4, Y may be a meta silyl group or a para silyl group.

In Chemical Formula 4, Y may be halogen.

In Chemical Formula 4, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).

Another embodiment of the present invention is prepared by the above-described method for preparing an ethylene tetramerization catalyst system, a borate compound represented by Formula 1: a first organoaluminum compound represented by Formula 2: a chromium compound represented by Formula 3: The molar ratio of the bisphosphine ligand compound represented by Chemical Formula 4 is 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1 relates to an ethylene tetramerization catalyst system.

Another embodiment of the present invention is the ethylene tetramerization catalyst system described above; A second organoaluminum compound represented by Formula 5 below; And ethylene monomers; It relates to a method for producing an ethylene tetramer comprising contacting.

[Formula 5]

(R ² ) ₃ Al

In Formula 5, R ² is a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms.

In Chemical Formula 5, R ² may be an ethyl group or an isobutyl group.

The ethylene tetramer production method may use methyl cyclohexane (CH ₃ C ₆ H ₁₁ ) as a reaction solvent.

Another embodiment of the present invention relates to a bisphosphine ligand compound, which is a compound represented by the following Chemical Formula 4A.

[Formula 4A]

RN- [P (-C ₆ H ₄ -Y ¹ ) ₂ ] ₂

In Formula 4A, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl group having 3 to 50 carbon atoms. .

In Chemical Formula 4A, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).

The bisphosphine ligand may be a compound represented by the following Chemical Formula 4-A1.

[Formula 4-A1]

In Formula 4-A1, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl having 3 to 50 carbon atoms. It is Ki.

In the above formula 4-A1, Y ¹ may be * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 0 to 20; q is an integer from 1 to 3) have.

In Chemical Formula 4-A1, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).

The bisphosphine ligand may be a compound represented by the following Chemical Formula 4-A2.

[Formula 4-A2]

In Formula 4-A2, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl having 3 to 50 carbon atoms. Or a halogen group.

In the above formula 4-A2, Y ¹ may be * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 0 to 20; q is an integer from 1 to 3) have.

In Chemical Formula 4-A2, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).

The present invention realizes excellent selectivity for 1-octene when applied to an ethylene tetramer production method (oligomerization reaction), and is capable of achieving both high activity and excellent economical efficiency, thereby producing an ethylene tetramerization catalyst system suitable for mass commercial processes, It provides an ethylene tetramerization catalyst system prepared therefrom, and also, through the aforementioned ethylene tetramerization catalyst system, has high selectivity to 1-octene and shows high activity compared to a catalyst system using methylaluminoxane. While it is possible to omit the use of oxalic acid, it is possible to achieve both high activity and economic efficiency, thereby providing a method for producing an ethylene tetramer suitable for application in a large number of commercial processes, and a ratio having advantageous properties for the production of the above-mentioned ethylene tetramerization catalyst system. Provided are phosphine ligand compounds.

In the present application, the symbols H, B, C, N, O, F, P, Cr, Cl, etc. indicated in the chemical formula refer to an atom that each elemental symbol indicates unless otherwise specified.

In the present application, '*' indicated in the chemical formula means a linking site in a chemical structure unless otherwise specified.

In the present application, the '-' indicated in the chemical formula means a binding site in a chemical structure, unless otherwise specified.

In the present application, Me represented by the formula represents methyl, Et is ethyl, Pr is propyl, iPr is isopropyl, Ph is phenyl, acac is acetylacetonate, and THF is tetrahydrofuran.

<Method for manufacturing ethylene oligomerization catalyst system>

One embodiment of the present invention is a borate compound represented by Formula 1 below; and a first organoaluminum compound represented by Formula 2 below; After reacting, the chromium compound represented by the following formula (3); And a bisphosphine ligand compound represented by the following Chemical Formula 4; sequentially, to prepare a catalyst system.

[Formula 1]

[HQ _m ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^-

In Chemical Formula 1, m is 0 to 2, and Q is an ether having 2 to 20 carbon atoms.

[Formula 2]

(R ¹ ) ₂ Al (X)

In Chemical Formula 2, R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, X is a halogen group, an acetylacetonate group, a carboxylate group, an alkoxy group having 1 to 20 carbon atoms, and a phenoxy group having 6 to 30 carbon atoms. It is either.

[Formula 3]

Cr (Z) ₃ (A) _n

In Formula 3, Z is each independently a halogen group, an acetylacetonate group or a carboxylate group, A is an ether or acetonitrile having 2 to 20 carbon atoms, and n is 0 or 3.

[Formula 4]

RN- [P (-C ₆ H ₄ -Y) ₂ ] ₂

In Formula 4, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, Y is a substituted or unsubstituted silyl group having 3 to 50 carbon atoms, halogen Group, a hydrocarbon group having 1 to 20 carbon atoms, or hydrogen.

Through this, the present invention provides an ethylene tetramerization catalyst system capable of realizing excellent selectivity and reaction activity for 1-octene when applied to an ethylene tetramer production method (oligomerization reaction), and achieving both high activity and excellent economic efficiency. In doing so, it has the effect of realizing excellent productivity, economic efficiency, and efficiency.

In addition, the ethylene tetramerization catalyst system produced through the ethylene tetramer production method of the present invention shows higher activity compared to the catalyst system using the conventional methyl aluminoxane, and uses expensive materials such as methyl aluminoxane and modified methyl aluminoxane. It is possible to omit, and it is possible to achieve both high activity and economic efficiency, and thus has an effect of realizing excellent suitability when applied to a large number of commercial processes.

The ethylene tetramerization catalyst system of the present invention comprises a borate compound represented by Formula 1; A first organoaluminum compound represented by Formula 2; A chromium compound represented by Chemical Formula 3; And a bisphosphine ligand compound represented by Chemical Formula 4; may have a molar ratio of 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1. Within the above range, it is possible to realize a significantly higher activity than the catalyst system using the conventional methyl aluminoxane. At this time, the molar ratio of the borate compound is based on a non-coordinating anion of the borate compound, the molar ratio of the first organic aluminum compound is based on an aluminum atom, the molar ratio of a chromium compound is based on a chromium atom, and the ligand compound The molar ratio of is calculated based on the total molecule.

When the borate compound represented by Chemical Formula 1 is used in an amount exceeding the molar ratio described above, the amount of unreacted borate compound in the prepared catalyst system is high, resulting in a decrease in reaction efficiency and economic efficiency. Conversely, when the borate compound represented by Chemical Formula 1 is used in an amount less than the molar ratio described above, the reaction activity of the prepared catalyst system is low, and thus it is impossible to implement the effect of replacing methylaluminoxane and / or modified methylaluminoxane.

Specifically, the ethylene tetramerization catalyst system may achieve a non-coordinating anion of a borate compound, a sum of aluminum atoms and chromium atoms (a sum of molar ratios), and a molar ratio of bisphosphine ligand compounds 2: 2: 1. In this case, not only can a remarkably high activity be achieved compared to a conventional catalyst system, but also responsiveness to ethylene may be further improved in an ethylene tetramerization reaction. In addition, while omitting methylaluminoxane and / or denatured methylaluminoxane, it is possible to implement the same or improved reaction activity as in the case of including them.

More specifically, the ethylene tetramerization catalyst system may achieve a molar ratio of uncoordinated anion, aluminum atom, chromium atom, and bisphosphine ligand compound of the borate compound to 2: 1: 1: 1. In this case, the activity in the ethylene tetramerization reaction and the reactivity to ethylene can be further improved.

The ethylene tetramerization catalyst system manufacturing method of the present invention precedes the step of reacting the borate compound represented by Formula 1; and the first organic aluminum compound represented by Formula 2; and then a chromium compound represented by Formula 3 By injecting and reacting, the compound of formula (A) can be prepared.

[Formula A]

_{[CrAl (Z) 3 (X} )] 2+ [B (C 6 F 5) 4] - 2

In the above formula A, Z is any one of a halogen group, an acetylacetonate group and a carboxylate group, and X is a halogen group, an acetylacetonate group, a carboxylate group, an alkoxy group having 1 to 20 carbon atoms and 6 to 30 carbon atoms. It is one of the phenoxy periods. The Z and X may be the same or different from each other.

The step of reacting the borate compound represented by Formula 1; and the first organic aluminum compound represented by Formula 2; for example, dispersing or dissolving the first organic aluminum represented by Formula 2 in a solvent, The borate compound represented by 1 may be added to react while stirring. At this time, the reaction time may be 1 to 10 minutes, but is not limited thereto.

After the step of reacting the borate compound represented by the formula (1); and the first organic aluminum compound represented by the formula (2), the chromium compound represented by the formula (3) is added, for example, in a solvent dispersed or dissolved. Can be reacted. At this time, the reaction time may be 1 to 15 hours, but is not limited thereto.

In addition, the type of the solvent used for dissolving or dispersing each of Formula 1, Formula 2 and Formula 3 in the above is not particularly limited as long as it does not inhibit the associated reaction. For example, it may be acetonitrile, an ether-based solvent, and the like.

In one embodiment, the reaction for preparing the compound of Formula A may be represented by the following Scheme A. Through this scheme A, alkanes (ethanes in scheme A) can be removed.

[Scheme A]

In the method for preparing an ethylene tetramerization catalyst system of the present invention, a compound of formula (A) is prepared as in reaction formula (A), and then a bisphosphine ligand compound represented by formula (4) is added to react to prepare a compound of formula (B). You can.

[Formula B]

_{[(RN- [P (-C 6} H 4 -Y) 2] 2) -CrAl (Z) 3 (X)] 2+ [B (C 6 F 5) 4] - 2

In the above formula B, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y is a substituted or unsubstituted silyl group having 3 to 50 carbon atoms, halogen Group, a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen, Z is any one of a halogen group, an acetylacetonate group and a carboxylate group, X is a halogen group, acetylacetonate group, carboxylate group, 1 to 20 carbon atoms Alkoxy group and a phenoxy group having 6 to 30 carbon atoms. The Z and X may be the same or different from each other.

The reaction for preparing the compound of Formula B is performed by dispersing or dissolving the compound of Formula A obtained in the above-described solvent in a solvent, for example, by introducing a bisphosphine ligand compound represented by Formula 4 dispersed or dissolved in a solvent. I can do it. At this time, the reaction time may be 1 to 15 hours, but is not limited thereto.

In addition, the type of the solvent used for dissolving or dispersing each of Formula A and Formula 4 in the above is not particularly limited as long as it does not inhibit the reaction. For example, acetonitrile, dichloromethane, and the like.

In one embodiment, the reaction for preparing the compound of Formula B may be represented by, for example, Scheme B below.

[Scheme B]

In the ethylene tetramerization catalyst system of the present invention, the borate compound represented by Chemical Formula 1 serves to further improve the reaction activity. The borate compound is not particularly limited as long as it has the structure of Formula 1.

In addition, the borate compound represented by Formula 1 may be used dissolved or dispersed in an ether-based solvent. In this case, in Chemical Formula 1, m is greater than 0, and is 2 or less, and Q may be an ether having 2 to 20 carbon atoms.

For example, the borate compound represented by Chemical Formula 1 is [H] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- , [H · (OEt ₂ ) ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- And the like.

The ethylene tetramerization catalyst system of the present invention is characterized by a molar ratio of chromium atom to borate anion of 1: 2. Mole ratio of the chromium atom and the anion: 2 compounds, e.g., [Cr (Z) (A ) n] 2+ [B (C 6 F 5) 4] - the compounds of structure ₂ are prepared is not easily not. The first organic aluminum compound represented by Chemical Formula 2 is reacted with a borate compound represented by Chemical Formula 1 to form a compound having a molar ratio of aluminum and borate anion of 1: 2 (ie, [Al (X) (A) _n ] ²⁺ [B _{(C 6 F 5) 4]} - 2) easy to manufacture, and where the molar ratio of the chromium atom and the anion feature of the invention by reacting a chromium compound of the formula 3: 2 compound (i.e., formula _{A: [CrAl (Z) 3} (X)] 2+ [B (C 6 F 5) 4] - 2 ) Can be prepared. The compound of formula (A) shows solubility in certain solvents, such as methylene chloride or acetonitrile, and thus can be easily utilized for catalyst preparation.

The first organoaluminum compound is not particularly limited as long as it has the structure of Formula 2. The organoaluminum compound of Chemical Formula 2 may be easily prepared by reacting (R ¹ ) ₃ Al with HX, for example, but is not limited thereto.

Specifically, in Formula 2, R ¹ may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, and more specifically an ethyl group or an isobutyl group. In this case, the reaction of the formula (A) proceeds smoothly, the supply and demand of raw materials is easy, and the unit cost is low, thereby further improving economic efficiency.

, 2,2,6,6-tetramethyl-3,5-heptanedionate

, 1,3-diphenyl-1,3-propanedionate

, 2-ethyl-1-hexanolate

, 2,6-di-tert-butyl-4-methylphenolate

, 2-phenylphenolate

, 2-ethylhexanoate

등으로 표시되는 구조일 수 있다. 이러한 경우, 고활성을 구현할 수 있고, 원료의 수급이 용이하며 단가가 저렴하여 경제성을 더욱 향상시킬 수 있다.Specifically, in Chemical Formula 2, X is acetylacetonate

, 2,2,6,6-tetramethyl-3,5-heptanedionate

, 1,3-diphenyl-1,3-propanedionate

, 2-ethyl-1-hexanolate

, 2,6-di-tert-butyl-4-methylphenolate

, 2-phenylphenolate

, 2-ethylhexanoate

It may be a structure represented by. In this case, high activity can be realized, and supply and demand of raw materials is easy, and the unit cost is low, thereby further improving economic efficiency.

In one embodiment, in Formula 2, R ¹ is an ethyl group or an isobutyl group, and X may be an acetylatetonate group. In this case, the reaction activity is higher, and the amount of by-product polymers is reduced, while the supply and demand of raw materials is easy and the cost is low, economical efficiency can be further improved.

In the ethylene tetramerization catalyst system of the present invention, the chromium compound represented by Chemical Formula 3 serves as a main catalyst. The chromium compound is not particularly limited as long as it can be used as a catalyst for the ethylene oligomerization reaction.

Specifically, the chromium compound represented by Chemical Formula 3 may be a chromium trivalent compound, and in this case, it is easy to supply and receive raw materials, so that it is more suitable for commercial processes, and also has excellent activity for ethylene oligomerization reaction.

For example, the chromium trivalent compound may include chromium (III) trisacetylacetonate, chromium (III) trichlorotristetrahydrofuran, chromium (III) tri (2-ethyl-hexanoate), and the like. .

In one embodiment, a chromium trivalent compound in which n in Formula 3 is 3, Z is halogen, and A is tetrahydrofuran may be used. In this case, not only the supply and demand of the raw material is easy, but also improved solubility can be achieved compared to other chromium trivalent compounds.

In the ethylene tetramerization catalyst system of the present invention, the bisphosphine ligand compound represented by Chemical Formula 4 serves to further improve the reaction activity. The bisphosphine ligand compound is not particularly limited as long as it has the structure of Formula 4.

Specifically, in Chemical Formula 4, Y may be a silyl group. For example, Y may be * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 0 to 20; q is an integer from 1 to 3). In this case, the bisphosphine ligand compound of Chemical Formula 4 can significantly improve activity when applied to a catalyst system for an ethylene tetramerization reaction while reducing the amount of by-product polymer compounds, which can be more advantageous for stable process operation.

More specifically, in Chemical Formula 4, Y may be a meta silyl group or a para silyl group. In this case, the bisphosphine ligand compound of Chemical Formula 4 can significantly reduce the activity of 1-hexene while significantly improving the activity when applied to a catalyst system for ethylene tetramerization reaction, compared to the case where Y is an ortho silyl group. The selectivity to 1-octene can be further improved.

Specifically, in Chemical Formula 4, Y may be a halogen group. In this case, the bisphosphine ligand compound of Chemical Formula 4 can significantly improve activity when applied to a catalyst system for an ethylene tetramerization reaction.

More specifically, in Chemical Formula 4, Y may be a chloride group (* -Cl). In this case, the bisphosphine ligand compound of Chemical Formula 4 may further improve activity when applied to a catalyst system for an ethylene tetramerization reaction, compared to the case where Y is fluorine, bromine or iodine.

Specifically, in Chemical Formula 4, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20). In this case, when the bisphosphine ligand compound of Formula 4 is applied to a catalyst system for an ethylene tetramerization reaction, solubility in an aliphatic hydrocarbon solvent may be further improved, and polymerization reaction and uniformity of a reaction product may be further improved.

<Ethylene tetramerization catalyst system>

Another embodiment of the present invention relates to an ethylene tetramerization catalyst system prepared by the method for preparing the ethylene tetramerization catalyst system described above.

The ethylene tetramerization catalyst system of the present invention can be implemented in a high activity while excluding the use of a conventional expensive aluminum aluminoxane, thereby securing the economic efficiency of the catalyst, which is advantageous for application in a large number of commercial processes.

The ethylene tetramerization catalyst system of the present invention comprises a borate compound represented by Formula 1; A first organoaluminum compound represented by Formula 2; A chromium compound represented by Chemical Formula 3; And a bisphosphine ligand compound represented by Chemical Formula 4; may have a molar ratio of 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1.

A borate compound represented by Formula 1; A first organoaluminum compound represented by Formula 2; A chromium compound represented by Chemical Formula 3; And a bisphosphine ligand compound represented by Chemical Formula 4; The details of each are as described above.

<Ethylene tetramer manufacturing method>

Another embodiment of the present invention relates to a method for preparing an ethylene tetramer comprising dispersing the aforementioned catalyst system in a reaction solvent, and then contacting with an ethylene monomer to perform an oligomerization reaction.

In the method for preparing the ethylene tetramer, the reaction conditions may be variously modified depending on the state of the composition of the catalyst system used (uniform or heterogeneous (supported)) and polymerization method (solution polymerization, slurry polymerization). Also, the degree of deformation can be easily changed by those skilled in the art.

The method for preparing an ethylene tetramer of the present invention includes reacting a catalyst system dispersed in the reaction solvent with an ethylene monomer, by introducing a second organoaluminum compound represented by the formula (5).

[Formula 5]

(R ² ) ₃ Al

In Formula 5, R ² is a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms. In this case, it is easy for the second organoaluminum compound represented by Chemical Formula 5 to remove the catalyst poison present in the reaction solvent prior to activation of the chromium catalyst, thereby realizing high activity.

In Chemical Formula 5, R ² may be an ethyl group or an isobutyl group, an ethylene tetramer. In this case, the effect of removing the catalyst poison present in the reaction solvent prior to catalyst activation is more excellent, so that the activity can be further improved.

Specifically, in the ethylene tetramer production method, the molar ratio of the second organic aluminum compound represented by Chemical Formula 5 to the number of chromium moles contained in the catalyst system may be 50 to 500 times. In the above-described method for producing an ethylene tetramer, the activity of the catalyst system may be higher.

The second organoaluminum compound represented by Chemical Formula 5 described above serves to activate the catalyst system and also acts as a scavenger to remove substances such as water and oxygen that can act as a catalyst poison, so that the additionally added The amount of the second organoaluminum compound represented by the formula (5) should be input according to the amount of the catalyst poison contained in the reaction solvent and ethylene. When the [Al] / [Cr] ratio is 50 or less, in the case of a high-activity catalyst, the amount of the second organoaluminum compound represented by Chemical Formula 5 is too small to remove the catalyst poison and the [Al] / [Cr] ratio is 500 or more There is a disadvantage that the driving cost increases.

Since the ethylene tetramerization catalyst system described above in the method for preparing an ethylene tetramer of the present invention may exist in a uniform solution state, as well as in a form supported on a carrier, insoluble particle form of a carrier, etc., the ethylene tetramer production method (ethylene oligomer Chemical reaction) may be a liquid phase polymerization reaction or a slurry phase polymerization reaction.

Specifically, when the ethylene tetramerization reaction (polymerization) is carried out in a liquid phase or a slurry phase, an aliphatic hydrocarbon solvent may be used as a medium. Examples of the aliphatic hydrocarbon solvent include methyl cyclohexene, cyclohexene, and hexene. When the above-described solvent is used, the polymerization activity is high and the product 1-octene is easily separated from the solvent after the ethylene oligomerization reaction.

In one embodiment, the hydrocarbon solvent may be methylcyclohexane (methylcyclohexan). In this case, the polymerization activity is further improved and it is easy to separate the product 1-octene and the solvent after the oligomerization reaction.

In the method for preparing the ethylene tetramer, the amount of the catalyst system is not particularly limited, but since the above-described catalyst system of the present invention can realize high activity, it is possible to realize excellent yield even when a small amount is added to proceed with the reaction. have.

In one embodiment, when the ethylene tetramerization reaction in the ethylene tetramer production method is performed by a solution polymerization method, the above-described catalyst system has a molar concentration (based on chromium) of 0.005 mmol / L to 0.1 mmol / L, for example 1-octene can be prepared by injecting the mixture to be 0.01 mmol / L to 0.05 mmol / L, and continuously reacting with ethylene monomer for 30 minutes to 3 hours. Ethylene may be continuously added at a pressure of 15 bar to 80 bar, specifically 30 bar to 60 bar, for example, 45 bar.

In addition, in the method for preparing an ethylene tetramer, the temperature of the ethylene tetramerization reaction may be room temperature (20 ° C) to 100 ° C, for example, 40 ° C to 80 ° C.

In addition, in the method for producing an ethylene tetramer, the ethylene tetramerization reaction may be carried out batchwise, semi-continuously or continuously.

When the 1-octene is prepared from the ethylene monomer through the method for preparing the ethylene tetramer of the present invention, the production rate of the polyethylene polymer may be 2.0% or less, for example, 1.0%, 0.5%, 0.1% or less, and 10 carbon atoms. The production rate of the above-described oligomer may be 20.0% or less, for example, 10%, 9%, 8%, 7%, 6%, 5% or less.

When 1-octene is prepared from the ethylene monomer through the ethylene tetramer production method of the present invention, the production rate of 1-octene may be 50% or more, for example, 55% or more, 65% or more, 70% or more. In addition, in addition to the 1-octene, 1-hexene may be produced as a by-product, and the production rate of 1-hexene may be 30% or less, for example, 25% or more and 15% or less.

When the 1-octene is prepared from the ethylene monomer through the ethylene tetramer production method of the present invention, the activation degree is 500 Kg / Cr-g / hr or more, for example, 1,000 Kg / Cr-g / hr or more, 2,000 Kg / Cr-g / hr or more. Specifically, it is possible to implement ultra-high activity of 3000 Kg / Cr-g / hr or more.

<Bisphosphine ligand compound for ethylene tetramerization reaction>

Another embodiment of the present invention relates to a bisphosphine ligand compound, which is a compound represented by the following Chemical Formula 4A.

[Formula 4A]

RN- [P (-C ₆ H ₄ -Y ¹ ) ₂ ] ₂

In Formula 4A, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl group having 3 to 50 carbon atoms. .

In particular, the bisphosphine ligand compound represented by Chemical Formula 4A includes a silyl group at the phosphine terminal, thereby significantly improving activity when applied to a catalyst system for an ethylene tetramerization reaction, for example, expensive methylaluminoxane. (methylaluminoxane, MAO), it is possible to implement the effect of replacing modified methylaluminoxane (MMAO). In this case, it is possible to provide both high activity and economical efficiency, thereby providing an ethylene tetramerization catalyst system more suitable for application in a large amount of commercial processes, and a method for producing an ethylene tetramer using the same. In addition, it is advantageous for stable operation of the process due to the small amount of polymer produced as a byproduct.

The functional group that can be substituted with the silyl group may be, for example, a hydrocarbyl group including an alkyl group, an alkene group, an alkynyl group, an aryl group, a heteroaryl group, and the like. The substitutable functional groups may be linear, branched, or cyclic, respectively, but are not limited thereto.

Specifically, in Formula 4A, Y ¹ is * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 0 to 20; q is an integer from 1 to 3) You can. In this case, the bisphosphine ligand compound of Chemical Formula 4A can significantly reduce activity when applied to a catalyst system for an ethylene tetramerization reaction, while reducing the amount of a polymer compound as a dispersion, which is suitable for commercial process applications.

Specifically, in Chemical Formula 4A, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20). In this case, when the bisphosphine ligand compound of Formula 4A is applied to a catalyst system for an ethylene tetramerization reaction, solubility in an aliphatic hydrocarbon solvent may be further improved, and polymerization reaction and uniformity of a reaction product may be further improved.

More specifically, in Chemical Formula 4A, Y ¹ may be a meta silyl group or a para silyl group. In this case, the bisphosphine ligand compound of Chemical Formula 4A can significantly reduce the activity of 1-hexene while significantly improving the activity when applied to a catalyst system for an ethylene tetramerization reaction, compared to the case where Y is an ortho silyl group. The selectivity to 1-octene can be further improved.

In one embodiment, the bisphosphine ligand may be a compound represented by the following formula 4-A1.

[Formula 4-A1]

In Formula 4-A1, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl having 3 to 50 carbon atoms. It is Ki.

In the above formula 4-A1, Y ¹ may be * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 0 to 20; q is an integer from 1 to 3) have.

In Chemical Formula 4-A1, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).

In another embodiment, the bisphosphine ligand may be a compound represented by the following Chemical Formula 4-A2.

[Formula 4-A2]

In Formula 4-A2, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl having 3 to 50 carbon atoms. Or a halogen group.

In Chemical Formula 4-A2, * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 0 to 20; q is an integer from 1 to 3).

In Chemical Formula 4-A2, R may be [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).

The method for preparing the bisphosphine ligand compound represented by Chemical Formula 4A is not particularly limited. Specifically, an amine compound capable of imparting an R group to a compound of Formula 4 and a phosphine compound capable of imparting a silyl group can be prepared by reacting with each other. Alternatively, it may be prepared by reacting an organic compound capable of imparting a silyl group with a phosphine compound containing an amino group and an R group.

For example, the bisphosphine ligand compound of Chemical Formula 4 can be synthesized by reacting R-NH ₂ , an amine compound having an R group, and XP (-C ₆ H ₄ -Y ¹ ) ₂ , a phosphine compound having a silyl group. .

In one embodiment, the compound of Formula 4 wherein R is [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20) is an amine compound [CH ₃ (CH ₂ ) _n ] ₂ CH-NH ₂ And the phosphine compound (YC ₆ H ₄ ) ₂ P-Cl can be easily prepared, where [CH ₃ (CH ₂ ) _n ] ₂ CH-NH _{2 as a} raw material is [CH ₃ (CH ₂ ) _n ] Since it can be manufactured in large quantities from CO ₂ H, it is not only easy to supply and supply, but also has excellent economic efficiency, which makes it more likely to use commercial processes.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be interpreted as limiting the present invention by any means.

Preparation Example 1

As used in the following Examples and Comparative Examples _{[(CH 3 CN) 4 CrCl} 2] + [B (C 6 F 5) 4] - , was synthesized according to the method published in the paper of Non-Patent Document 6 (Non-Patent Document 6; ACS Omega 2017, 2, 765-773).

Preparation Example 2

[(CH ₃ ) (CH ₂ ) ₁₆ ] ₂ C (H) N (PPh ₂ ) ₂ used in the following Examples and Comparative Examples was synthesized according to the method published in the paper of Non-Patent Document 6 (Non-patent Document 6; ACS Omega 2017, 2, 765-773).

Preparation Example 3

Used in Examples and Comparative Examples [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-NH ₂ was prepared in the following manner.

After dissolving 18-pentatriacontanone (10 g, 19.7 mmol), NH ₂ OH.HCl (6.91 g, 98.8 mmol) and pyridine (9.56 g, 121 mmol) in ethanol (42 mL), 100 for 2 hours It was refluxed at ℃. After reacting by stirring at room temperature for 12 hours, the resulting white solid was isolated by filtration and washed sequentially with water (40 mL) and ethanol (30 mL). The remaining solvent was completely removed under reduced pressure in vacuo to obtain a white solid compound ([CH ₃ (CH ₂ ) ₁₆ ] ₂ C = NOH). The obtained compound [CH ₃ (CH ₂ ) ₁₆ ] ₂ C = NOH (9.53 g), Raney-Nickel dispersed in water (0.80 g), and ethanol (80 mL) were added to a high pressure reactor, followed by hydrogen gas ( 55 bar) and reacted by stirring at 90 ° C. for 12 hours. Before the reactor temperature was cooled, the high-pressure reactor was opened, and the hot solution was filtered using Celite to remove the solid compound formed as a by-product. The solid compound was washed with hot ethanol, the washing solution was combined with the filtrate, and the solvent was removed under reduced pressure in vacuo to obtain a white solid. After dissolving the obtained solid compound in toluene (30 mL), acetonitrile (30 mL) was added to precipitate the solid compound, and the precipitate was isolated by filtration and washed with acetonitrile (10 mL). The remaining solvent was removed under reduced pressure in vacuo to obtain a white solid compound (7.02 g, 90%).

Example 1: Preparation of bisphosphine ligand compound (1)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-SiMe ₃ ) ₂ ] ₂  (Formula 4; Y = SiMe ₃ , R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(4-Me ₃ Si-C ₆ H ₄ ) ₂ PCl Synthesis : Dissolve 1-bromo-4-trimethylsilylbenzene (0.871 g, 3.80 mmol) purchased from TCI in tetrahydrofuran (10 mL), -78 After injecting n-butyllithium (0.24 mL, 1.6 M hexane solution, 3.80 mmol) at ℃, the mixture was stirred for 1 hour while maintaining -78 ℃. Dichloro (diethylamino) phosphine (0.331 g, 1.900 mmol) dissolved in tetrahydrofuran (2 mL) was injected for 5 minutes, and the temperature was raised to room temperature and reacted for 12 hours. The solvent was removed under reduced pressure in vacuo, and white solids (lithium bromide and lithium chloride) that were not dissolved in hexane (10 mL) were removed by filtration using Celite. After removing the solvent, trichlorophosphine (0.91 mL, 10.4 mmol) was added and reacted at 80 ° C. for 2 hours using a reflux cooling device. Vacuum distillation at 70 ° C. removed the vaporizable material and a yellow oil compound was obtained. After dissolving the oil compound in hexane, the solid compound was precipitated by storage in a refrigerator at -30 ° C for 12 hours, followed by decantation to obtain a precipitated solid compound ((4-Me ₃ Si-C ₆ H ₄ ) ₂ PCl) ( 0.616 g, 89%).

(4-Me ₃ Si-C ₆ H ₄ ) ₂ PCl (0.350 g, 0.959 mmol) was dissolved in dichloromethane (3 mL), triethylamine (0.56 mL, 3.995 mmol) was added, and then a refrigerator was added. Cooled for 30 minutes. [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-NH ₂ (0.203 g, 0.400 mmol) dissolved in dichloromethane (2 mL) was slowly added and reacted by stirring at room temperature for 12 hours. After removing the solvent under reduced pressure in vacuo, the desired product was dissolved in hexane (5 mL), and the insoluble by-product was removed by filtration using Celite. The solvent was removed under reduced pressure in vacuum, the product was dissolved in dichloromethane (1 mL), acetonitrile (10 mL) was added, and stored in a refrigerator at -30 ^o C for 5 hours to precipitate an oily compound. After removing the solvent in the upper layer to obtain an oil-like compound. The residual solvent was completely removed under reduced pressure in vacuo to obtain the desired compound [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ . ¹ H NMR (C ₆ D ₆ ): δ 8.17-7.19 (br, 8H), 7.47 (d, J = 6.0 Hz, 8H), 3.58 (m, J = 3.0 Hz, 1H, N-CH), 2.13 ( m, 2H, CH ₂ ), 1.88 (m, 2H, CH ₂ ), 1.43-1.13 (br, 60H, CH ₂ ), 0.92 (t, J = 7.2 Hz, 6H, CH ₃ ), 0.21 (s, 36H , SiMe ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 53.546, 49.298 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₇₁ H ₁₂₃ NP ₂ Si ₄ ) 1164.8286, found 1164.8281.

Example 2: Preparation of bisphosphine ligand compound (2)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Si (n-Bu) ₃ ) ₂ ] ₂  (Formula 4; Y = Si (n-Bu) ₃ , R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(p- (n-Bu) ₃ Si-C ₆ H ₄ ) ₂ PCl synthesis : p- (n-Bu) ₃ Si-C ₆ H ₄ Br (1.20 g, 3.38 mmol) using (p-Me ₃ Si-C ₆ H ₄ ) ₂ PCl Synthesis by the same method and conditions to give an oil compound (p- (n-Bu) ₃ Si-C ₆ H ₄ ) ₂ PCl) (1.03 g, 98% yield).

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Si (n-Bu) ₃ ) ₂ ] ₂ Synthesis : (p- (n-Bu) ₃ Si-C ₆ H ₄ ) using ₂ PCl (0.400 g, 0.648 mmol) described in the [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-SiMe ₃ ) ₂ ] ₂ preparation method Synthesis by the same method and conditions to obtain an oil compound (0.395 g, 84% yield). ¹ H NMR (C ₆ D ₆ ): δ 8.12-7.20 (br, 8H), 7.45 (s, 8H), 3.64 (m, J = 3.0 Hz, 1H, N-CH), 2.13 (m, 2H, CH ₂ ), 1.85 (m, 2H, CH ₂ ), 1.58-1.16 (br, 132H, CH ₂ ), 0.95 (t, J = 6.0 Hz, 6H, CH ₃ ), 0.92-0.79 (m, 36H, Si ( n-Bu) ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 54.170, 49.123 ppm.

Example 3: Preparation of bisphosphine ligand compound (3)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-SiMe ₂ (CH ₂ ) ₇ CH ₃ ) ₂ ] ₂  (Formula 4; Y = SiMe ₂ (CH ₂ ) ₇ CH ₃ ) ₂ , R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(p-CH ₃ (CH ₂ ) ₇ (Me) ₂ Si-C ₆ H ₄ ) ₂ PCl synthesis : BrC ₆ H ₄ -p-SiMe ₂ (CH ₂ ) ₇ CH ₃ (0.700 g, 2.14 mmol) (P-Me ₃ Si-C ₆ H ₄ ) ₂ PCl Described in the manufacturing method Synthesis by the same method and conditions to obtain an oil compound (0.546 g, yield 99%).

Of _{[CH 3 (CH 2) 16} ] 2 CH-N [P (C 6 H 4 -p-SiMe 2 (CH 2) 7 CH 3) 2] 2 Synthesis : Using (p-CH ₃ (CH ₂ ) ₇ (Me) ₂ Si-C ₆ H ₄ ) ₂ PCl (0.348 g, 0.713 mmol), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [ P (C ₆ H ₄ -p-SiMe ₃ ) ₂ ] ₂ Described in the manufacturing method Synthesis by the same method and conditions to obtain an oil compound (0.384 g, yield 80%). ¹ H NMR (C ₆ D ₆ ): δ 8.26-7.28 (br, 8H), 7.51 (s, 8H), 3.65 (m, J = 4.2 Hz, 1H, N-CH), 2.13 (m, 2H, CH ₂ ), 1.87 (m, 2H, CH ₂ ), 1.48-1.16 (br, 108H, CH ₂ ), 0.93 (t, J = 6.6 Hz, 6H, CH ₃ ), 0.89 (t, J = 7.8 Hz, 12H , CH ₃ ), 0.77 (t, J = 9.0 Hz, 8H, CH ₃ ), 0.27 (s, 24H, Si-CH ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 53.721, 49.123 ppm.

Example 4: Preparation of bisphosphine ligand compound (4)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-F) ₂ ] ₂  (Formula 4; Y = F, R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C) using (4-FC ₆ H ₄ ) ₂ PCl (0.350 g, 1.364 mmol) purchased from Alpha A ₆ H ₄ ) ₂ ] ₂ Described in the manufacturing method Synthesis by the same method and conditions to give a white solid compound (0.459 g, 85%). ¹ H NMR (C ₆ D ₆ ): δ 7.74-7.16 (br, 8H), 6.81 (t, J = 7.8 Hz), 3.32 (m, J = 3.6 Hz, 1H, N-CH), 1.91 (m, 2H, CH ₂ ), 1.65 (m, 2H, CH ₂ ), 1.47-1.09 (br, 60H, CH ₂ ), 0.92 (t, J = 6.6 Hz, 6H, CH ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 50.85, 49.46 ppm. ¹⁹ F { ¹ H} NMR (C ₆ D ₆ ): δ -111.48 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₅₉ H ₈₇ F ₄ NP ₂ ) 948.6328, found 948.6332.

Example 5: Preparation of bisphosphine ligand compound (5)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄₀ -p-Cl) ₂ ] ₂  (Formula 4; Y = Cl, R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(4-Cl-C ₆ H ₄ ) ₂ PCl purchased from Alpha A was used after purification through recrystallization using a toluene and hexane solvent at -30 ° C. [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C) using (4-Cl-C ₆ H ₄ ) ₂ PCl (0.330 g, 1.14 mmol) purified by the above method ₆ H ₄ ) ₂ ] ₂ Described in the manufacturing method Synthesis by the same method and conditions to obtain an oil-like compound (0.424 g, yield 88%). ¹ H NMR (C ₆ D ₆ ): δ 7.80-6.82 (br, 8H), 7.04 (d, J = 7.8 Hz, 8H), 3.24 (m, J = 3.0 Hz, 1H, N-CH), 1.85 ( m, 2H, CH ₂ ), 1.58 (m, 2H, CH ₂ ), 1.48-1.06 (br, 60H, CH ₂ ), 0.92 (t, J = 6.6 Hz, 6H, CH ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 51.56, 49.44 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₅₉ H ₈₇ Cl ₄ NP ₂ ) 1012.5146, found 1012.5144.

Example 6: Preparation of bisphosphine ligand compound (6)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Br) ₂ ] ₂  (Formula 4; Y = Br, R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(4-Br-C ₆ H ₄ ) ₂ PCl synthesis : (4-Me ₃ Si-C ₆ H ₄ ) ₂ PCl using 1,4-dibromobenzene (0.472 g, 2.000 mmol) purchased from TCI Synthesis in the same manner and conditions as the synthesis to obtain a solid compound (0.377 g, 90%).

Using (4-Br-C ₆ H ₄ ) ₂ PCl (0.164 g, 0.433 mmol), the [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ Described in the manufacturing method Synthesis by the same method and conditions to obtain an oil compound (0.209 g, yield 89%). ¹ H NMR (C ₆ D ₆ ): δ 7.60-6.71 (br, 8H, PPh- O H), 7.25 (d, J = 7.8 Hz, 8H, PPh- p H), 3.20 (m, J = 4.2 Hz , 1H, N-CH), 1.82 (m, 2H, CH ₂ ), 1.54 (m, 2H, CH ₂ ), 1.50-1.01 (br, 60H, CH ₂ ), 0.92 (t, J = 7.2 Hz, 6H , CH ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 51.45, 49.14 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₅₉ H ₈₇ Br ₄ NP ₂ ) 1188.3125, found 1188.3120.

Example 7: Preparation of bisphosphine ligand compound (7)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Me) ₂ ] ₂  (Formula 4; Y = Me, R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(4-Me-C ₆ H ₄ ) ₂ PCl purchased from Alpha A was purified by vacuum distillation at 150 ° C. and used. Using purified (4-Me-C ₆ H ₄ ) ₂ PCl (0.350 g, 1.407 mmol), the [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ Synthesis by the same method and conditions to obtain an oil compound (0.492 g, 90%). ¹ H NMR (C ₆ D ₆ ): δ 8.09-6.86 (br, 8H), 6.03 (d, J = 7.2 Hz, 8H), 3.59 (m, J = 4.2 Hz, 1H, N-CH), 2.12 ( s, 12H, CH ₃ ), 2.04 (m, 2H, CH ₂ ), 1.87 (m, 2H, CH ₂ ), 1.48-1.11 (br, 60H, CH ₂ ), 0.92 (t, J = 6.6 Hz, 6H , CH ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 52.21, 49.85 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₆₃ H ₉₉ NP ₂ ) 932.7331, found 932.7334.

Example 8: Preparation of bisphosphine ligand compound (8)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-C-Me ₃ ) ₂ ] ₂  (Formula 4; Y = t Bu, R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(4- t Bu-C ₆ H ₄ ) ₂ PCl synthesis : Schrank flask with 4- t butylphenylmagnesium bromide (10 mL, 5.000 mmol, 0.5 M 2-methyl-tetrahydrofuran solution) purchased from Alpha A Into the mixture, and after lowering the temperature to -78 ° C, dichloro (diethylamino) phosphine (0.435 g, 2.50 mmol) was injected for 5 minutes, and the temperature was raised to room temperature and reacted for 12 hours. Subsequently, the reaction was carried out according to the same method and conditions described in the above (4-Me ₃ Si-C ₆ H ₄ ) ₂ PCl synthesis to obtain a white solid compound (0.460 g, yield 67%).

(4- t Bu-C ₆ H ₄ ) ₂ PCl (0.350 g, 1.05 mmol) using [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ Synthesis by the same method and conditions to obtain an oil compound (0.419 g, yield 87%). ¹ H NMR (C ₆ D ₆ ): δ 8.30-7.19 (br, 8H), 7.30 (d, J = 7.2 Hz, 8H), 3.64 (m, J = 3.6 Hz, 1H, N-CH), 2.12 ( m, 2H, CH ₂ ), 1.88 (m, 2H, CH ₂ ), 1.48-1.10 (br, 60H, CH ₂ ), 1.23 (s, 36H, CH ₃ ), 0.92 (t, J = 7.2 Hz, 6H , CH ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 51.77, 47.45 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₇₅ H ₁₂₃ NP ₂ ) 1100.9209, found 1100.9212.

Example 9: Preparation of bisphosphine ligand compound (9)

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -m-Si-Me ₃ ) ₂ ] ₂  (Formula 4; Y = Me ₃ Si, R = [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH)

(3-Me ₃ Si-C ₆ H ₄ ) ₂ PCl Synthesis: Using the 1-bromo-3-trimethylsilylbenzene (2.500 g, 10.908 mmol) purchased from Alpha Aisa, the above (4-Me ₃ Si- C ₆ H ₄ ) ₂ PCl Synthesis was carried out in the same method and condition as the synthesis to obtain a white solid compound (1.87 g, yield 94%).

(3-Me ₃ Si-C ₆ H ₄ ) Using ₂ PCl (0.350 g, 0.959 mmol), the [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ Synthesis by the same method and conditions to obtain an oil compound (0.318 g, yield 69%). ¹ H NMR (C ₆ D ₆ ): δ 8.52-7.03 (br, 8H, PPh- o H), 7.50-7.38 (br, 4H, PPh- p H), 7.34-7.19 (br, 4H, PPh- m H), 3.67 (m, J = 4.2 Hz, 1H, N-CH), 2.17 (m, 2H, CH ₂ ), 1.91 (m, 2H, CH ₂ ), 1.58-1.11 (br, 60H, CH ₂ ) , 0.92 (t, J = 7.2 Hz, 6H, CH ₃ ), 0.18 (s, 36H, SiMe ₃ ) ppm. ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 53.44, 51.87 ppm. HRMS (FAB): m / z calcd ([M + H] ⁺ C ₇₁ H ₁₂₃ NP ₂ Si ₄ )

Example 10: Preparation of catalyst system (1)

After diethyl aluminum chloride (0.120 g, 1.00 mmol) was dissolved in acetonitrile (1.5 mL), [H · (OEt ₂ ) ₂ ] ⁺ [B (C ₆ ) dissolved in acetonitrile (20 mL) F ₅ ) ₄ ] ^- (1.657 g, 2.000 mmol) was added slowly. After stirring for 5 minutes, CrCl ₃ (THF) ₃ (0.375 g, 1.000 mmol) dissolved in acetonitrile (4 mL) was further slowly added thereto, followed by stirring for 12 hours. After reacting for 12 hours, the solvent was removed under reduced pressure in vacuo to obtain a green compound. After dissolving the obtained compound in dichloromethane (10 mL), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.876 g, 1.000) dissolved in acetonitrile (10 mL) mmol) was slowly added. After stirring and reacting for 12 hours, the solvent was removed by vacuum decompression to obtain 2.644 g of a turquoise compound. The composition of the resulting compound _{[{(CH 3 (CH 2} ) 16) 2 CH-N (PPh 2) 2} CrAlCl 4 (THF) 3] 2+ [B (C 6 F 5) 4] - 2 assumption that The yield was at 99%, and the elemental analysis data were consistent with the composition, and a THF signal was observed in the ¹ H NMR spectrum. Anal. _{Calcd for [{(CH 3 (} CH 2) 16) 2 CH-N (PPh 2) 2} CrAlCl 4 (THF) 3] 2+ [B (C 6 F 5) 4] - 2 (2671.51 g mol-1 ): C 53.5, H 4.34%. Found: C 51.24, H 3.31%.

Example 11: Preparation of catalyst system (2)

Acetyl acetone (10.00 mg, 0.1000 mmol) was added to triethylaluminum (11.40 mg, 0.1000 mmol) dissolved in methylcyclohexane (70 mg) and stirred at room temperature for 20 minutes to react, diethyl aluminum acetylacetonate. Was prepared. After removing the solvent under reduced pressure in vacuum, the obtained compound was dissolved in acetonitrile (1.0 mL) and then dissolved in acetonitrile (2 mL) [H · (OEt ₂ ) ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- (0.165 g, 0.200 mmol) was added slowly. After reacting with stirring for 5 minutes, CrCl ₃ (THF) ₃ (0.374 g, 0.100 mmol) dissolved in acetonitrile (1.0 mL) was further slowly added, followed by stirring for 12 hours. The solvent was removed under reduced pressure in vacuo to obtain a green compound. After dissolving the obtained compound in dichloromethane (10 mL), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.875 g, 0.100) dissolved in acetonitrile (10 mL) mmol) slowly. After stirring and reacting for 12 hours, the solvent was removed under reduced pressure in vacuo to obtain 0.256 g of a turquoise compound. The composition of the resulting compound is [{(CH ₃ (CH ₂ ) ₁₆ ) ₂ CH-N (PPh ₂ ) ₂ } CrAl (acac) Cl ₃ (THF) ₃ ] ²⁺ [B (C ₆ F ₅ ) ₄ ] ^In the assumption of ₂ , the yield was 94%, and the elemental analysis data were consistent with the composition, and the THF signal was observed in the ¹ H NMR spectrum. Anal. _{Calcd for [{(CH 3 (} CH 2) 16) 2 CH-N (PPh 2) 2} CrAl (acac) Cl 3 (THF) 3] 2+ [B (C 6 F 5) 4] - 2 2590.96 g mol ^-1 : C 53.41, H 3.92%. Found: C 51.35, H 3.78%.

Examples 12 to 16: Preparation of catalyst systems (3) to (7)

2,2,6,6-tetramethyl-3,5-heptanedione (Example 10), 1,3-diphenyl-1,3-propanedione (Example 11), 2-ethyl-1-hexanol (implementation instead of acetylacetone) Example 12), except that different types of first organoaluminum compounds were produced using 2,6-di-tert-butyl-4-methylphenol (Example 13) and 2-phenylphenol (Example 14), It was prepared in the same manner as in Example 11.

Examples 17 to 25: Preparation of catalyst systems (8) to (16)

Instead of [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) _{2 respectively} [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Si-Me ₃ ) ₂ ] ₂ (Example 17), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -pF) ₂ ] ₂ (Example 18), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH -N [P (C ₆ H ₄ -p-Cl) ₂ ] ₂ (Example 19), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Br) ₂ ] ₂ (Example 20), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Me) ₂ ] ₂ (Example 21), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -pC-Me ₃ ) ₂ ] ₂ (Example 22), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -m-SiMe ₃ ) ₂ ] ₂ (Example 23), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Si- (nBu) ₃ ) ₂ ] ₂ (Example 24), [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-Si-Me ₂ (CH ₂ ) ₇ CH ₃ ) ₂ ] ₂ (Example 25) different types of bisphos It was prepared in the same manner as in Example 11, except that the spin ligand was generated and used.

Comparative Example 1

Methylcyclohexane (19 mL) and MMAO (modified-MAO, manufactured by Akzo-Nobel, 7 wt% -Al, 57.0 mg, 0.150 mmol) were added to the high-pressure reactor in a dry box, and then taken out of the dry box to bring the temperature to 45. Raised to ℃. The catalyst system of Comparative Example 1 by dispersing iPrN (PPh ₂ ) ₂ (0.50 umol) and Cr (acac) ₃ (0.50 umol) in methylcyclohexane (MeC ₆ H ₁₁ ) (1.0 mL) into a reactor by injecting it into a reactor Was prepared.

Comparative Example 2

[CH ₃ (CH ₂ ) ₁₆ ] ₂ After dissolving CH-N (PPh ₂ ) ₂ (0.100 g, 0.114 mmol) in dichloromethane (2 mL), [(CH ₃ CN) ₄ CrCl ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- (0.110 g, 0.114 mmol) was slowly added to a dichloromethane (2 mL) solution. The catalyst system of Comparative Example 2 was prepared by reacting with stirring for 12 hours. Thereafter, the solvent was removed under reduced pressure to obtain 0.138 g of a turquoise compound. In the assumption that the composition of the resulting compound is [{(CH ₃ (CH ₂ ) ₁₆ ) ₂ CH-N (PPh ₂ ) ₂ } CrCl ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- , the yield is 99%. .

Comparative Example 3

[CH ₃ (CH ₂ ) ₁₆ ] ₂ After dissolving CH-N (PPh ₂ ) ₂ (0.100 g, 0.114 mmol) in dichloromethane (2 mL), [(CH ₃ CN) ₄ CrCl ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- (0.220 g, 0.228 mmol) was slowly added to a dichloromethane (3 mL) solution. The catalyst system of Comparative Example 3 was prepared by reacting with stirring for 12 hours. Thereafter, the solvent was removed under reduced pressure to obtain 0.279 g of a turquoise compound. The composition of the resulting compound _{[{(CH 3 (CH 2} ) 16) 2 CH-N (PPh 2) 2} Cr 2 Cl 4] 2+ [B (C 6 F 5) 4] - yield from the assumption that the ₂ The silver yield was 99% and the elemental analysis data were consistent with the composition. Anal. _{Calcd for [{(CH 3 (} CH 2) 16) 2 CH-N (PPh 2) 2} Cr 2 Cl 4] 2+ [B (C 6 F 5) 4] - 2 (2480.21 g mol-1): C 51.82, H 3.70%. Found: C 48.89, H 3.53%.

Comparative Example 4

After dissolving CrCl ₃ (THF) ₃ (20.0 mg, 0.0533 mmol) and AlCl ₃ (7.11 mg, 0.0533 mmol) in acetonitrile (2.0 mL), [Ag (NCCH ₃ ) ₄ ] ⁺ [(CH ₃ CN ) ₄ B (C ₆ F ₅ ) ₄ ] ^- (0.101 g, 0.107 mmol) was slowly added to a solution of acetonitrile (1.0 mL) in which it was dissolved. After reacting with stirring for 12 hours, by-product AgCl was removed by filtration. The solvent was removed under reduced pressure in vacuo to obtain a green compound. The obtained compound was dissolved in dichloromethane (3 mL) again, and then [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.0468 g, 0.0533 mmol) was dissolved in dichloromethane ( 1 mL) solution. The catalyst system of Comparative Example 4 was prepared by reacting with stirring for 12 hours. Then, the solvent was removed under reduced pressure in vacuum to obtain 0.143 g of a turquoise compound.

The composition of the resulting compound _{[{(CH 3 (CH 2} ) 16) 2 CH-N (PPh 2) 2} CrAlCl 4 (THF) 3] 2+ [B (C 6 F 5) 4] - 2 assumption that At, the yield was 99%, and the elemental analysis data were consistent with the composition, and a THF signal was observed in the ¹ H NMR spectrum. Anal. _{Calcd for [{(CH 3 (} CH 2) 16) 2 CH-N (PPh 2) 2} CrAlCl 4 (THF) 3] 2+ [B (C 6 F 5) 4] - 2 (2671.51 g mol-1 ): C 53.5, H 4.34%. Found: C 51.20, H 3.41%.

Example 26

After adding methylcyclohexane (19 mL) and iBu ₃ Al (14.9 mg, 0.0750 mmol) or Et ₃ Al (8.56 mg, 0.0750 mmol) to the high pressure reactor, the temperature was raised to 45 ° C. The catalyst (0.25 μmol-Cr) prepared in Comparative Example 1 was dispersed or dissolved in methylcyclohexane (1.0 mL), taken with a syringe, injected into the reactor, and then ethylene was continuously injected under a pressure of 45 bar. The temperature rose by itself to 60 ° C. within a few minutes by the heat of polymerization, and then tetramerization was performed for 60 minutes while controlling the temperature to 60 ° C. After the reactor temperature was lowered using ice, the valve was opened to remove residual ethylene gas. For gas chromatography analysis, nonane was quantified in standard (~ 700 mg), and then some samples were taken and the product was quantitatively analyzed through GC analysis. The formed polymer was separated through filtration and dried in a vacuum oven to measure mass.

Examples 27 to 42 and Comparative Examples 5 to 9

Ethylene tetramerization reaction was performed in the same manner as in Example 26, except that the catalyst system used and the type of the second organic aluminum compound were changed as shown in Tables 1 and 2.

The results of the ethylene tetramerization reaction performed using the catalyst systems prepared in Examples and Comparative Examples are shown in Tables 1 and 2 below.

Catalyst system 2nd organoaluminum compound activation
(Kg / g-Cr / h) 1-C8 (wt%) 1-C6 (wt%) cy-C6 (wt%) > C10 (wt%) PE
(wt%) Example 26 Example 10 iBu ₃ Al 1110 63.3 21.8 3.9 10.6 1.7 Example 27 Example 10 Et ₃ Al 770 63.4 20.6 3.5 12.0 1.9 Example 28 Example 11 iBu ₃ Al 1120 67.7 16.7 3.1 12.1 0.93 Example 29 Example 12 iBu ₃ Al 1100 53.5 27.4 4.9 13.9 0.77 Example 30 Example 13 iBu ₃ Al 680 62.0 15.3 2.9 19.5 1.6 Example 31 Example 14 iBu ₃ Al 710 64.0 20.1 3.6 11.9 1.1 Example 32 Example 15 iBu ₃ Al 1300 60.9 24.5 4.4 9.8 1.2 Example 33 Example 16 iBu ₃ Al 670 66.7 16.9 3.1 12.9 1.7 Comparative Example 5 Comparative Example 1 - 280 70.7 13.4 3.6 11.3 0.39 Comparative Example 6 Comparative Example 2 iBu ₃ Al 0 - - - - - Comparative Example 7 Comparative Example 3 iBu ₃ Al 350 63.7 18.6 3.2 14.1 1.9 Comparative Example 8 Comparative Example 4 iBu ₃ Al 1080 61.8 24.7 3.9 9.0 1.0 Comparative Example 9 Comparative Example 4 Et ₃ Al 720 64.3 21.4 3.8 10.1 0.76

Catalyst system 2nd organoaluminum compound activation
(Kg / g-Cr / h) 1-C8
(wt%) 1-C6
(wt%) cy-C6
(wt%) > C10
(wt%) PE
(wt%) Example 34 Example 17 iBu ₃ Al 3100 59.83 23.96 3.74 12.27 0.08 Example 35 Example 18 iBu ₃ Al 1390 57.35 24.8 5.85 11.65 0.89 Example 36 Example 19 iBu ₃ Al 2710 53.57 25.29 6.27 14.46 0.83 Example 37 Example 20 iBu ₃ Al 970 56.67 25.57 6.44 10.9 1.93 Example 38 Example 21 iBu ₃ Al 580 62.38 25.82 3.33 8.3 0.61 Example 39 Example 22 iBu ₃ Al 1170 60.95 25.33 3.06 10.52 0.25 Example 40 Example 23 iBu ₃ Al 2110 62.00 19.27 4.11 14.27 0.40 Example 41 Example 24 iBu ₃ Al 4300 60.39 24.04 3.88 11.46 0.10 Example 42 Example 25 iBu ₃ Al 3200 60.64 24.06 3.89 11.21 0.05

Through the above results, it can be seen that the present invention can provide an ethylene tetramerization catalyst system capable of realizing equal or higher activity than a catalyst system using MAO without using an excessively expensive MAO.

In particular, the catalyst system of the present invention can increase the activity by 20 times or more compared to the catalyst system that does not use the previously reported MAO as a new catalyst system for the ethylene tetramerization reaction. That is, the catalyst system without using MAO reported in Non-Patent Document 5 (Organometallics, 26 (2007) 2782) ([iPrN (PPh ₂ ) ₂ Cr (CO) ₄ ] ⁺ [Al (OC (CF ₃ ) ₃ ) ₃ ) ₄ ] ^- ) has an activity of 140 Kg / g-Cr / h, but the catalyst system of the present invention can realize up to 4300 Kg / g-Cr / h activity.

The catalyst system of the present invention is characterized in that the molar ratio of non-coordinating anion, Cr (or Cr + Al), and bisphosphine ligand is 2: 2: 1. For example, the catalyst system of the present invention _{[CrCl 2 (NCCH 3) 4} ] + [B (C 6 F 5) 4] - and [(C ₁₇ H _{35) 2} to _{CH-N (PPh 2) 2} 2 When the ethylene reactivity was evaluated by synthesizing that the molar ratio of the borate anion, chromium, and bisphosphine ligands is 2: 1 by reacting in a molar ratio of 1, it is implemented using methyl aluminoxane (MAO) as in Comparative Example 7. The same level of activity as the catalyst was achieved (Comparative Example 7).

In Comparative Example 6, as _{[CrCl 2 (NCCH 3) 4} ] + [B (C 6 F 5) 4] - for the _{[(C 17 H 35) 2} C (H) N (PPh 2) 2 1: The molar ratio of the borate anion, chromium, and bisphosphine ligands is 1: 1 by reacting in a 1 molar ratio (ie, [(C ₁₇ H ₃₅ ) ₂ CH-N (PPh ₂ ) ₂ ] CrCl ₂ ] ⁺ [ When the ethylene reactivity was evaluated by synthesizing B (C ₆ F ₅ ) ₄ ] ^- ), no activity was realized.

In addition, in order to prepare a catalyst having a molar ratio of borate anion, chromium, and bisphosphine ligands of 2: 1, 2 equivalents of CrCl ₃ (THF) ₃ [Ag (CH ₃ CN) ₄ ] ⁺ [B (C ₆ F _{5) 4]} ^- it was reacted with ^{[CrCl] 2+ [B (C} 6 F 5) 4] - failed can not be separated from the solubility of the resulting tried the synthesis of compound ₂ is reduced by-product AgCl.

Comparative Example 8 and Comparative Examples 9 and one equivalent of AlCl ₃ of the CrCl ₃ (THF) ₃ in the presence two equivalents of _{[Ag (CH 3 CN) 4} ] + , such as _{[B (C 6 F 5)} 4] - and reacted when the solubility in the compound ^{_{([CrAlCl 4] 2+ [B}} (C 6 F5) 4] - guess ₂₎ was is obtained, by reacting it with a bisphosphine ligand final anion, Al, Cr, and bisphosphine When a catalyst having a ligand molar ratio of 2: 1: 1: 1: 1 was prepared to evaluate ethylene reactivity, a very high activity was realized, but a borate compound was used as an expensive silver compound ([Ag (CH ₃ CN) ₄ ] ⁺ [B ( Since C ₆ F ₅ ) ₄ ] ^- ) is used, the manufacturing cost of the catalyst is high, and it is difficult to apply to commercial processes due to difficulty in supplying and receiving raw materials.

Example 26 and 27 is the same composition as the catalyst is a compound instead of ^{[H] + [B (C} 6 F 5) 4] - low prepared using the catalyst unit can be applied to commercial processes which require mass production. Further, in Examples 26 and ^{27, [H] + [B} (C 6 F 5) 4] - the Et ₂ AlCl and 2: by reacting a molar ratio of 1 and induced ethane elimination reaction, followed by one equivalent of CrCl ₃ When the catalyst was prepared through the step of reacting (THF) ₃ and subsequently reacting 1 equivalent of a bisphosphine ligand compound, the same level of catalytic activity as the catalyst prepared with the silver compound was realized.

In Examples 11 to 16, a high-activity catalyst can be prepared by using aluminum compounds having various structures instead of Et ₂ AlCl, that is, (R ¹ ) ₂ AlX represented by Chemical Formula 1 in the catalyst preparation. (R ¹ ) _{2 In} AlX, X is halogen, acetylacetonate, alkoxy having 1 to 20 carbons, or phenoxy having 6 to 30 carbons, and a high activity catalyst can be prepared using an aluminum compound having such a structure. It was confirmed through Examples.

Particularly, in Example 11, X was preferred because acetylacetonate had high catalytic activity and low by-product polymer production and low catalyst production cost.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (16)

A borate compound represented by Formula 1 below; and a first organoaluminum compound represented by Formula 2 below; After reacting,
A chromium compound represented by Formula 3 below; And
Bisphosphine ligand compound represented by Formula 4 below;
A method of making an ethylene tetramerization catalyst system comprising steps:
[Formula 1]
[HQ _m ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^-
In Formula 1, m is 0 to 2, Q is an ether having 2 to 20 carbons;
[Formula 2]
(R ¹ ) ₂ Al (X)
In Formula 2, R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, X is a halogen group, an acetylacetonate group, a carboxylate group, an alkoxy group having 1 to 20 carbon atoms, and a phenoxy group having 6 to 30 carbon atoms. Is either;
[Formula 3]
Cr (Z) ₃ (A) _n
In Chemical Formula 3, Z is each independently a halogen group, acetylacetonate group, or carboxylate group, A is a C 2 to C 20 ether or acetonitrile, and n is 0 or 3;
[Formula 4]
RN- [P (-C ₆ H ₄ -Y) ₂ ] ₂
In Chemical Formula 4, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y is a substituted or unsubstituted silyl group having 3 to 50 carbon atoms, halogen. Group, a hydrocarbon group having 1 to 20 carbon atoms, or hydrogen.
According to claim 1,
A borate compound represented by Formula 1;
A first organoaluminum compound represented by Formula 2;
A chromium compound represented by Chemical Formula 3; And
Bisphosphine ligand compound represented by Formula 4;
The molar ratio of 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1 ethylene tetramerization catalyst system manufacturing method.
According to claim 1,
In Formula 2, R ¹ is an ethyl group or an isobutyl group, X is an acetylacetonate group; ethylene tetramerization catalyst system production method.
According to claim 1,
In Chemical Formula 4, Y is a meta silyl group or a para silyl group.
According to claim 1,
In Formula 4, Y is halogen Ethylene tetramerization catalyst system manufacturing method.
According to claim 1,
In Formula 4, R is [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20) ethylene tetramerization catalyst system production method.
The ethylene tetramerization catalyst system according to any one of claims 1 to 6, the borate compound represented by the formula (1): the first organic aluminum compound represented by the formula (2): chromium represented by the formula (3) Compound: An ethylene tetramerization catalyst system in which the molar ratio of the bisphosphine ligand compound represented by Chemical Formula 4 is 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1.
An ethylene tetramerization catalyst system according to claim 7; A second organoaluminum compound represented by Formula 5 below; And ethylene monomers; Method for producing an ethylene tetramer comprising contacting.
[Formula 5]
(R ² ) ₃ Al
In Formula 5, R ² is a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms.
The method of claim 8,
In Chemical Formula 5, R ² is an ethyl group or an isobutyl group, an ethylene tetramer production method.
The method of claim 8,
The ethylene tetramer production method is a ethylene tetramer production method using methylcyclohexane (CH ₃ C ₆ H ₁₁ ) as a reaction solvent.
Bisphosphine ligand compound, which is a compound represented by the following formula 4A:
[Formula 4A]
RN- [P (-C ₆ H ₄ -Y ¹ ) ₂ ] ₂
In Formula 4A, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl group having 10 to 50 carbon atoms. .
The method of claim 11,
In Chemical Formula 4A, R is [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).
The method of claim 11,
The bisphosphine ligand is a bisphosphine ligand compound represented by the following Chemical Formula 4-A1:
[Formula 4-A1]

In Formula 4-A1, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl having 10 to 50 carbon atoms. It is Ki.
The method of claim 13,
In the above formula 4-A1, Y ¹ is * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 7 to 20; q is an integer from 1 to 3) Sphosphine ligand compound.
The method of claim 11,
The bisphosphine ligand is a bisphosphine ligand compound represented by the following Chemical Formula 4-A2:
[Formula 4-A2]

In Chemical Formula 4-A2, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and Y ¹ is a substituted or unsubstituted silyl having 10 to 50 carbon atoms. It is Ki.
The method of claim 15,
In the above formula 4-A2, Y ¹ is * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer from 7 to 20; q is an integer from 1 to 3) Sphosphine ligand compound.