KR20190139028A - 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 relates to: a method for manufacturing an ethylene tetramerization catalyst system comprising following steps of conducting a reaction of a borate compound and a first organoaluminum compound, and sequentially inputting a chrome compound and a bisphosphine ligand compound; a catalyst system manufactured by the same; and a novel bisphosphine ligand suitable for implementing high activity and selectivity. Through the same, the present invention can realize excellent selectivity and high economic efficiency for 1-octene when applied to the method for manufacturing an ethylene tetramerization (oligomerization reaction), and in particular, unlike an existing catalyst system, the present invention eliminates the use of expensive methylaluminoxane, thereby being able to secure excellent economic efficiency and stable process operation in a commercialization process.

Description

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

The present invention relates to a process for producing an ethylene tetramerization catalyst system, which is suitable for high-volume commercial processes, which is compatible with high activity and good economics, and to an ethylene tetramer production method using the catalyst system. It also relates to novel bisphosphine ligand compounds used in the catalyst system.

Ethylene tetramers such as 1-octene are compounds that are used in large quantities as comonomers in the polymerization of polyolefins such as, for example, polyethylene. In recent years, as the production of polyolefins using homogeneous metallocene catalysts has increased, the demand for such ethylene tetramers has been steadily increasing.

Conventional techniques include tetramerization of ethylene with Shell Higher Olefin Process (SHOP) based on nickel catalysts to produce various 1-alkenes of about 4 to about 30 carbon atoms, from which 1-octene It is known to obtain separately obtained.

As another conventional technique, for example, isoPrN (PPh ₂ ) _{2 which} is a chromium trivalent compound (CrCl ₃ or Cr (acac) ₃ ), a bisphosphine ligand, as in Patent Document 1 and Patent Document ₂ And a method of selectively tetramerizing ethylene through a catalyst system consisting of methylaluminoxane (MAO) to produce 1-octene.

However, the catalyst systems of Patent Documents 1 and 2 must use expensive methylaluminoxane (MAO) in excess (Al / Cr = 300 to 500) in order to secure sufficient activity for the reaction, and thus 1-octene There exists a problem that manufacturing cost rises and economic efficiency becomes low (nonpatent literature 1 and nonpatent literature 2).

In addition, as in Non-Patent Documents 3 to 5, the development of a catalyst system for avoiding the use of expensive methylaluminoxane (MAO) has been actively progressed, but the activity is significantly higher than that for a catalyst system using methylaluminoxane (MAO). Low and not suitable for commercial use.

As described above, researches for selectively preparing ethylene tetramers having a desired structure in the ethylene oligomerization catalyst technology have been continued, but it is not easy to achieve both high activity and economical efficiency at the same time with the conventional technology 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 when contacted with ethylene monomer, and at the same time achieving high activity and economic efficiency. .

(Prior art document)

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

Patent Document 2: US 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 Literature 4: Organometallics, 26 (2007) 2561-2569

Non Patent Literature 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 the ethylene tetramer production method (oligomerization reaction), and can be compatible with high activity and good economics, suitable for mass commercial process ethylene tetramerization catalyst A method of making a system, and an ethylene tetramerization catalyst system prepared therefrom.

Another object of the present invention is high selectivity to 1-octene through the above-described ethylene tetramerization catalyst system, methyl aluminoxane, unlike methyl aluminoxane, unlike the conventional catalyst system using methyl aluminoxane, modified methyl aluminoxane, It is possible to omit the use of modified ethylaluminoxane, and to provide a method for producing an ethylene tetramer, which is compatible with high activity and economics and is suitable for application in a large amount of commercial processes.

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

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; and a first organoaluminum compound represented by Formula 2; After reacting, a chromium compound represented by the following formula (3); And a bisphosphine ligand compound represented by the following Formula 4; relates to a method for producing an ethylene tetramerization catalyst system comprising sequentially preparing 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 carbon atoms;

[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 Which is either;

[Formula 3]

Cr (Z) ₃ (A) _n

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

Borate compounds 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 Formula 4; may have a molar ratio of 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1.

In Formula 2, R ¹ may be an ethyl group or an isobutyl group, and X may be an acetylacetonate group.

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

In Formula 4, Y may be halogen.

In 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, the borate compound represented by Formula 1: The first organoaluminum compound represented by Formula 2: The chromium compound represented by Formula 3: The molar ratio of the bisphosphine ligand compound represented by the 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.

Yet another embodiment of the present invention is the ethylene tetramerization catalyst system described above; A second organoaluminum compound represented by Formula 5; And ethylene monomers; It relates to a method for producing 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 Formula 5, R ² may be an ethyl group or an isobutyl group.

In the ethylene tetramer manufacturing method, methylcyclohexane (CH ₃ C ₆ H ₁₁ ) may be used 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 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.

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

In 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. Group or a halogen group.

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

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

The present invention is a method for producing an ethylene tetramerization catalyst system suitable for high-volume commercial processes, which can achieve excellent selectivity for 1-octene when applied to the ethylene tetramer production method (oligomerization reaction), and can be compatible with high activity and excellent economic efficiency, There is provided an ethylene tetramerization catalyst system prepared therefrom, and also through the above-described ethylene tetramerization catalyst system, it has high selectivity for 1-octene and shows higher activity compared to a catalyst system using methylaluminoxane, and thus, conventional methylalumina. While it is possible to omit the use of noxic acid, it is possible to achieve both high activity and economic efficiency, thereby providing a method for producing an ethylene tetramer suitable for application to a large amount of commercial processes, and having a non-proprietary characteristic for producing the ethylene tetramerization catalyst system described above. Provided phosphine ligand compounds.

In the present application, the symbols H, B, C, N, O, F, P, Cr, Cl, etc. represented in the chemical formulas refer to atoms labeled by respective element symbols unless otherwise stated.

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

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

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

<Method for producing ethylene oligomerization catalyst system>

One embodiment of the present invention is a borate compound represented by Formula 1; and a first organoaluminum compound represented by Formula 2; After reacting, a chromium compound represented by the following formula (3); And a bisphosphine ligand compound represented by the following Formula 4; relates to a method for producing an ethylene tetramerization catalyst system comprising sequentially preparing 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 carbon atoms.

[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 Which is either.

[Formula 3]

Cr (Z) ₃ (A) _n

In Formula 3, Z is each independently a halogen group, an acetylacetonate group and 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, 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.

Through this, the present invention provides an ethylene tetramerization catalyst system that can implement excellent selectivity and reaction activity for 1-octene when applied to the ethylene tetramer production method (oligomerization reaction), and can achieve both high activity and excellent economic efficiency. This has the effect of realizing excellent productivity, economy and efficiency.

In addition, the ethylene tetramerization catalyst system produced through the ethylene tetramer production method of the present invention shows a higher activity than the catalyst system using a conventional methyl aluminoxane, the use of expensive materials such as methyl aluminoxane, modified methyl aluminoxane It is possible to omit, it can be compatible with high activity and economic efficiency has the effect of achieving excellent suitability when applied to a large number of commercial processes.

Ethylene tetramerization catalyst system of the present invention is a borate compound represented by the 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 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 this range, it is possible to achieve significantly higher activity compared to conventional catalyst systems using methylaluminoxane. In this case, the molar ratio of the borate compound is based on the non-coordinating anion of the borate compound, the molar ratio of the first organoaluminum compound is based on the aluminum atom, the molar ratio of the chromium compound is based on the chromium atom, and the ligand compound The molar ratio of is calculated based on the whole molecule.

When the borate compound represented by the formula (1) is used in an amount exceeding the above molar ratio, the amount of unreacted borate compound in the prepared catalyst system is high, the reaction efficiency and economic efficiency is lowered. On the contrary, when the borate compound represented by Formula 1 is used in an amount of less than the above molar ratio, the reaction activity of the prepared catalyst system is low, and thus the effect of replacing methylaluminoxane and / or modified methylaluminoxane cannot be realized.

Specifically, in the ethylene tetramerization catalyst system, the molar ratio of the non-coordinating anion of the borate compound, the sum of the molar ratios of aluminum atoms and chromium atoms, and the bisphosphine ligand compound may be 2: 2: 1. In this case, not only can realize a significantly higher activity than the conventional catalyst system, it can further improve the reactivity to ethylene in the ethylene tetramerization reaction. In addition, while omitting methyl aluminoxane and / or modified methyl aluminoxane, it is possible to implement the same or improved reaction activity as the case containing them.

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

Ethylene tetramerization catalyst system production method of the present invention precedes the step of reacting the borate compound represented by the formula (1); and the first organoaluminum compound represented by the formula (2), and then the chromium compound represented by the formula (3) By reacting with the addition of a compound of formula (A), it can be prepared.

[Formula A]

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

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

Reacting the borate compound represented by Formula 1; and the first organoaluminum compound represented by Formula 2; for example, dispersing or dissolving the first organoaluminum represented by Formula 2 in a solvent, The borate compound represented by 1 may be added and reacted while stirring. In this case, the reaction time may be 1 to 10 minutes, but is not limited thereto.

After the step of reacting the borate compound represented by Formula 1; and the first organoaluminum compound represented by Formula 2, the chromium compound represented by Formula 3 is dispersed or dissolved in a solvent, for example. Can be reacted. In this case, the reaction time may be 1 to 15 hours, but is not limited thereto.

In addition, the kind of solvent used for dissolving or dispersing each of Formulas 1, 2 and 3 above is not particularly limited as long as it does not inhibit the associated reaction. For example, it may be acetonitrile, an ether 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 (ethane 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 Chemical Formula A is prepared by preparing a compound of Chemical Formula A, and then reacting by adding a bisphosphine ligand compound represented by Chemical Formula 4, thereby preparing a compound of Chemical Formula B below. Can be.

[Formula B]

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

In 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, an acetylacetonate group, a carboxylate group and 1 to 20 carbon atoms It is either an alkoxy group and a C6-C30 phenoxy group. Z and X may be the same as or different from each other.

The reaction for preparing the compound of Formula B is carried out by dispersing or dissolving the compound of Formula A obtained as described above in a solvent, for example, by adding a bisphosphine ligand compound represented by Formula 4 dispersed or dissolved in a solvent. You can. In this case, the reaction time may be 1 to 15 hours, but is not limited thereto.

In addition, the kind of solvent used for dissolution or dispersion of each of Formulas A and 4 is not particularly limited as long as it does not inhibit the associated reaction. For example, it may be acetonitrile, dichloromethane and the like.

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

Scheme B

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

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

For example, the borate compound represented by Formula 1 is [H] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- , [H · (OEt ₂ ) ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- It may be a compound such as.

The ethylene tetramerization catalyst system of the present invention is characterized in that the molar ratio of chromium atom and borate anion is 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 organoaluminum compound represented by Chemical Formula 2 is reacted with a borate compound by Chemical Formula 1 so that the molar ratio of aluminum to borate anions is 1: 2 (that is, [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) is easily soluble in a certain solvent, for example, methylene chloride or acetonitrile, so that it can be easily used for preparing a catalyst.

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, for example, reacting (R ¹ ) ₃ Al with HX, but is not limited thereto.

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

, 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 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, supply and demand of raw materials can be easily provided, and the unit price can be low, thereby further improving economic efficiency.

In an embodiment, in Formula 2, R ¹ may be an ethyl group or an isobutyl group, and X may be an acetylatetonate group. In this case, the reaction activity is higher, and while the amount of the by-product polymer is reduced, the supply and demand of raw materials is easy and the unit price is low, thereby further improving the economic efficiency.

In the ethylene tetramerization catalyst system of the present invention, the chromium compound represented by 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 ethylene oligomerization reaction.

Specifically, the chromium compound represented by Formula 3 may be a chromium trivalent compound. In this case, the supply of raw materials is easy, and thus, the chromium compound is not only more suitable for commercial processes but also has excellent activity for ethylene oligomerization.

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

In the ethylene tetramerization catalyst system of the present invention, the bisphosphine ligand compound represented by Formula 4 plays a role of further improving the reaction activity. The bisphosphine ligand compound is not particularly limited as long as it has a structure of Formula 4.

Specifically, in 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 Formula 4 can significantly reduce the amount of production of by-product polymer compound while improving the activity when applied to the catalyst system for ethylene tetramerization reaction, it can be more advantageous for stable process operation.

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

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

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

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

<Ethylene Quarterization Catalyst System>

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

The ethylene tetramerization catalyst system of the present invention can implement high activity while eliminating the use of conventional expensive methylaluminoxane, which can secure economical efficiency of the catalyst, which is advantageous for application to a large number of commercial processes.

Ethylene tetramerization catalyst system of the present invention is a borate compound represented by the 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 Formula 4; may have a molar ratio of 1.8 to 2.2: 0.9 to 1.1: 0.9 to 1.1: 1.

Borate compounds represented by Formula 1; A first organoaluminum compound represented by Formula 2; A chromium compound represented by Chemical Formula 3; And bisphosphine ligand compounds represented by Formula 4; Details of each are as described above.

<Ethylene tetramer manufacturing method>

Yet another embodiment of the present invention relates to a process for preparing ethylene tetramer, comprising dispersing the above catalyst system in a reaction solvent and then contacting with ethylene monomer to oligomerize.

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

The method for producing ethylene tetramer of the present invention includes adding a second organoaluminum compound represented by Chemical Formula 5 when the catalyst system and ethylene monomer dispersed in the reaction solvent are added and reacted together.

[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, the second organoaluminum compound represented by Chemical Formula 5 is easy to implement high activity by preferentially removing the catalyst poison present in the reaction solvent prior to chromium catalyst activation.

In Formula 5, R ² may be an ethylene tetramer that is an ethyl group or an isobutyl group. In this case, the effect of removing the catalyst poison present in the reaction solvent before the catalyst activation is better, and the activity can be further improved.

Specifically, the molar ratio of the second organoaluminum compound represented by Formula 5 to the number of moles of chromium included in the catalyst system in the ethylene tetramer manufacturing method may be 50 to 500 times. In the ethylene tetramer production method in the above range, the activity of the catalyst system may be higher.

The second organoaluminum compound represented by Chemical Formula 5 described above is added as the scavenger serves to activate the catalyst system and to remove substances such as water and oxygen, which may act as catalyst poisons. The amount of the second organoaluminum compound represented by the formula (5) should be added differently depending on the amount of the catalyst poison contained in the reaction solvent and ethylene. When the ratio of [Al] / [Cr] is 50 or less, the amount of the second organoaluminum compound represented by Formula 5 is too small to remove the catalyst poison in the case of a high activity catalyst, and the ratio of [Al] / [Cr] is 500 or more. There is a disadvantage that the operating cost is high.

The ethylene tetramer catalyst system described above in the method for producing ethylene tetramer of the present invention may exist not only in a uniform solution state but also in a form supported on a carrier, insoluble particles of the carrier, and the like. May be a liquid phase polymerization reaction or a slurry phase polymerization reaction.

Specifically, when the ethylene tetramerization (polymerization) is carried out in the liquid or slurry phase, an aliphatic hydrocarbon solvent may be used as the medium. Methylcyclohexene, cyclohexene, hexene etc. can be illustrated as an aliphatic hydrocarbon solvent. When the solvent exemplified above is used, the polymerization activity is high and the separation of the solvent from the product 1-octene after the ethylene oligomerization reaction is easy.

In one embodiment, the hydrocarbon solvent may be methylcyclohexan. In this case, the polymerization activity is further improved and separation of the product 1-octene from the solvent after the oligomerization reaction is easy.

In the ethylene tetramer manufacturing method, the amount of the catalyst system used is not particularly limited, but the catalyst system of the present invention can realize high activity, and thus, even when a small amount is added to the reaction, excellent yield can be achieved. have.

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

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

In addition, the ethylene tetramerization reaction in the ethylene tetramer manufacturing method may be carried out batchwise, semi-continuous or continuous.

When producing 1-octene from the ethylene monomer through the ethylene tetramer manufacturing method 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, carbon number 10 The production rate of the oligomers or more may be 20.0% or less, for example, 10%, 9%, 8%, 7%, 6%, 5% or less.

When producing 1-octene 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, 1-hexene may be generated as a by-product together with 1-octene, 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 manufacturing 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, May be at least 2,000 Kg / Cr-g / hr. Specifically, ultra high activity of 3000 Kg / Cr-g / hr or more can be achieved.

<Bisphosphine Ligand Compound for Ethylene Quotaization 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 the formula (4A) can include a silyl group at the phosphine terminal, thereby significantly improving the activity when applied to the catalyst system for ethylene tetramerization reaction, for example, expensive methylaluminoxane (methylaluminoxane (MAO), modified methylaluminoxane (MAMAO) can be implemented to replace the effect. In this case, it is possible to provide both an ethylene tetramer catalyst system and a method for producing ethylene tetramer using the same, which can be compatible with high activity and economic efficiency, which is more suitable for a large volume of commercial processes. In addition, the amount of polymer by-products is low, which is advantageous for stable operation of the process.

The functional group substitutable for the silyl group may be, for example, a hydrocarbyl group including an alkyl group, an alken group, an alkynyl group, an aryl group, a heteroaryl group, and the like. The substitutable functional groups may be linear, branched, cyclic, or the like, 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 of 0 to 20; q is an integer of 1 to 3). Can be. In this case, the bisphosphine ligand compound of the general formula (4A) can reduce the production amount of the polymer compound as a dispersion while significantly improving the activity when applied to the catalyst system for ethylene tetramerization reaction, it is suitable for commercial process applications.

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

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

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

In 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. Group or a halogen group.

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

In 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, the amine compound capable of imparting the R group and the phosphine compound imparting the silyl group may be prepared by reacting with each other. Or it can also manufacture by making the organic compound which can provide a silyl group, and the phosphine compound containing an amino group and an R group react.

For example, the bisphosphine ligand compound of Formula 4 may be synthesized by reacting R-NH ₂ , which is an amine compound having an R group, and XP (-C ₆ H ₄ -Y ¹ ) ₂ , which is 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 10-20) is an amine compound [CH ₃ (CH ₂ ) _n ] ₂ CH-NH ₂ It can be easily prepared by reacting with a phosphine compound (YC ₆ H ₄ ) ₂ P-Cl, wherein the raw material [CH ₃ (CH ₂ ) _n ] ₂ CH-NH ₂ is [CH ₃ (CH ₂ ) _n ] CO ₂ H can be manufactured in large quantities, so it is easy to supply and receive, and it is also economical, and thus the possibility of using a commercial process is higher.

Example

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Preparation Example 1

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

Preparation Example 3

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

18-pentatriacontanone (10 g, 19.7 mmol), NH ₂ OH.HCl (6.91 g, 98.8 mmol) and pyridine (9.56 g, 121 mmol) were dissolved in ethanol (42 mL), followed by 100 for 2 hours. It was refluxed at ° C. After stirring for 12 hours at room temperature, the resulting white solid was separated by filtration and washed sequentially with water (40 mL) and ethanol (30 mL). The remaining solvent was completely removed by vacuum reduction 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 (0.80 g), and ethanol (80 mL) dispersed in water were added to a high pressure reactor, followed by hydrogen gas ( 55 bar) was reacted by stirring at 90 ° C for 12 hours. The high pressure reactor was opened before the reactor temperature was cooled, and the hot solution was filtered using Celite to remove the solid compound produced as a byproduct. The solid compound was washed with hot ethanol, the wash solution was combined with the filtrate, and the solvent was removed under reduced pressure under vacuum to obtain a white solid. The resulting solid compound was dissolved in toluene (30 mL) and then acetonitrile (30 mL) was added to precipitate the solid compound, and the precipitate was collected by filtration and washed with acetonitrile (10 mL). The remaining solvent was removed under reduced pressure in vacuo to yield 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 N-butyllithium (0.24 mL, 1.6 M hexane solution, 3.80 mmol) was injected at 占 폚, followed by stirring for 1 hour while maintaining at -78 占 폚. 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 hexane (10 mL) was added to remove white solids (lithium bromide and lithium chloride) that were not dissolved by filtration using celite. After the solvent was removed, trichlorophosphine (0.91 mL, 10.4 mmol) was added thereto, and the reaction was performed at 80 ° C. for 2 hours using a reflux cooling device. Vacuum distillation at 70 ° C. removed the vaporizable material and gave a yellow oil compound. The oil compound was dissolved in hexane and then stored in a refrigerator at -30 ° C. for 12 hours to precipitate a solid compound, 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 the refrigerator Cooled for 30 minutes at. [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-NH ₂ (0.203 g, 0.400 mmol) dissolved in dichloromethane (2 mL) was slowly added thereto, followed by reaction at room temperature for 12 hours. The solvent was removed under reduced pressure in vacuo, and then the desired product was dissolved in hexane (5 mL) and insoluble by-products were filtered off using celite. The solvent was removed under reduced pressure in vacuo, the product was dissolved in dichloromethane (1 mL), acetonitrile (10 mL) was added and stored in a -30 ^o C refrigerator for 5 hours to precipitate an oil compound. After removing the solvent of the upper layer to give an oil compound. The residual solvent was completely removed under reduced pressure in vacuo to afford 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 Compounds (2006.01)

[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-Me using p- (n-Bu) ₃ Si-C ₆ H ₄ Br (1.20 g, 3.38 mmol) ₃ Si-C ₆ H ₄ ) ₂ PCl as described in the manufacturing method Synthesis by the same method and conditions yielded 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 ) The method of preparing [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (C ₆ H ₄ -p-SiMe ₃ ) ₂ ] ₂ using ₂ PCl (0.400 g, 0.648 mmol). Synthesis was carried out by the same method and conditions to give an oil compound (0.395 g, yield 84%). 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 : Using 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 on the manufacturing method Synthesis was carried out by the same method and conditions to give an oil compound (0.546 g, 99% yield).

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 : [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [using (p-CH ₃ (CH ₂ ) ₇ (Me) ₂ Si-C ₆ H ₄ ) ₂ PCl (0.348 g, 0.713 mmol) P (C ₆ H ₄ -p-SiMe ₃ ) ₂ ] ₂ Described on the manufacturing method Synthesis was carried out by the same method and conditions to give an oil compound (0.384 g, 80% yield). 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)

Using (4-FC ₆ H ₄ ) ₂ PCl (0.350 g, 1.364 mmol) purchased from Alfa Aisa said [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ Described on the manufacturing method Synthesis by the same method and conditions yielded 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 Alfa Aisa was used after purification through recrystallization using a toluene and hexane solvent at -30 ° C. Using (4-Cl-C ₆ H ₄ ) ₂ PCl (0.330 g, 1.14 mmol) purified by the above method, [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) ₂ ] ₂ Described on the manufacturing method Synthesis was carried out in the same manner and to give an oily compound (0.424 g, 88% yield). 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 was carried out in the same manner and conditions as in the synthesis, to obtain a solid compound (0.377 g, 90%).

(4-Br-C ₆ H ₄ ) ₂ [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H ₄ ) using ₂ PCl (0.164 g, 0.433 mmol) ₂ ] ₂ Described on the manufacturing method Synthesis was carried out by the same method and conditions to give an oil compound (0.209 g, 89% yield). 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 Alfa Aisa was used after purification by vacuum distillation at 150 ° C. [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N [P (4-Me ₃ Si-C ₆ H) was purified using purified (4-Me-C ₆ H ₄ ) ₂ PCl (0.350 g, 1.407 mmol). ₄ ) ₂ ] ₂ Described in the manufacturing method Synthesis was carried out by the same method and conditions to give 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 : 4- T butylphenylmagnesium bromide (10 mL, 5.000 mmol, 0.5 M 2-methyl-tetrahydrofuran solution) purchased from Alpha ASA Co., Ltd. After dipping into a temperature of −78 ° C., dichloro (diethylamino) phosphine (0.435 g, 2.50 mmol) was injected for 5 minutes, and the temperature was raised to room temperature to react for 12 hours. The reaction was then carried out according to the same methods and conditions described in (4-Me ₃ Si-C ₆ H ₄ ) ₂ PCl synthesis to give a white solid compound (0.460 g, 67% yield).

(4- t Bu-C ₆ H ₄ ) ₂ PCl (0.350 g, 1.05 mmol) using the above [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 was carried out by the same method and conditions to give 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: (4-Me ₃ Si-) was prepared using 1-bromo-3-trimethylsilylbenzene (2.500 g, 10.908 mmol) purchased from Alfa Aisa. Synthesis was carried out by the same method and conditions as the synthesis of C ₆ H ₄ ) ₂ PCl to obtain a white solid compound (1.87 g, 94% yield).

(3-Me ₃ Si-C ₆ H ₄ ) ₂ PCl (0.350 g, 0.959 mmol) using the above [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 was carried out by the same method and conditions to give an oil compound (0.318 g, 69% yield). 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 a Catalyst System (1)

Diethylaluminum chloride (0.120 g, 1.00 mmol) was dissolved in acetonitrile (1.5 mL) and then dissolved in acetonitrile (20 mL) [H · (OEt ₂ ) ₂ ] ⁺ [B (C ₆ 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 yield a green compound. The obtained compound was dissolved in dichloromethane (10 mL) and then dissolved in acetonitrile (10 mL) [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.876 g, 1.000 mmol) was added slowly. After stirring for 12 hours, the reaction mixture was removed under vacuum pressure to give 2.644 g of a cyan 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 99% at, and the elemental analysis data closely matched 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} 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), followed by stirring at room temperature for 20 minutes to react, diethyl aluminum acetylacetonate. Was prepared. After vacuum removal under reduced pressure, 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 stirring for 5 minutes, CrCl ₃ (THF) ₃ (0.374 g, 0.100 mmol) dissolved in acetonitrile (1.0 mL) was further slowly added thereto, followed by stirring for 12 hours. The solvent was removed under reduced pressure in vacuo to yield a green compound. The obtained compound was dissolved in dichloromethane (10 mL) and then dissolved in acetonitrile (10 mL) [CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.875 g, 0.100 mmol). After stirring for 12 hours, the reaction mixture was removed under reduced pressure in vacuo to yield 0.256 g of a cyan 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 ] ^The yield was 94% under the assumption of _-2 , and the elemental analysis data closely matched 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 12-16 Preparation of Catalyst Systems (3)-(7)

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

Examples 17 to 25 Preparation of Catalyst Systems (8) to (16)

Each _{[CH 3 (CH 2) 16} ] 2 CH-N (PPh 2) 2 instead of _{[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), Different types of bisphosphes of [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) A spin ligand was prepared and used in the same manner as in Example 11, except that the ligand was 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 a high pressure reactor in a dry box, and then the temperature was removed from the dry box. Raised to ℃. iPrN (PPh ₂ ) ₂ (0.50 umol) and Cr (acac) ₃ (0.50 umol) were dispersed in methylcyclohexane (MeC ₆ H ₁₁ ) (1.0 mL), taken by syringe and injected into the reactor for the catalyst system of Comparative Example 1 Was prepared.

Comparative Example 2

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.100 g, 0.114 mmol) was dissolved in dichloromethane (2 mL) and then [(CH ₃ CN) ₄ CrCl ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- (0.110 g, 0.114 mmol) was slowly added to a solution of dichloromethane (2 mL) in which it was dissolved. The catalyst system of Comparative Example 2 was prepared by stirring for 12 hours. The solvent was then removed under reduced pressure in vacuo to yield 0.138 g of a cyan compound. The yield is 99% assuming 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 ] ^- .

Comparative Example 3

[CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.100 g, 0.114 mmol) was dissolved in dichloromethane (2 mL) and then [(CH ₃ CN) ₄ CrCl ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- (0.220 g, 0.228 mmol) was slowly added to a solution of dichloromethane (3 mL) in which was dissolved. The reaction system was stirred for 12 hours to prepare a catalyst system of Comparative Example 3. The solvent was then removed under reduced pressure in vacuo to yield 0.279 g of a cyan 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 yield was 99% and the elemental analysis data was in good agreement 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

CrCl ₃ (THF) ₃ (20.0 mg, 0.0533 mmol) and AlCl ₃ (7.11 mg, 0.0533 mmol) were dissolved in acetonitrile (2.0 mL) and then [Ag (NCCH ₃ ) ₄ ] ⁺ [(CH ₃ CN _{) 4 B (C 6 F 5} ) 4] - (0.101 g, 0.107 mmol) were slowly added to acetonitrile (1.0 mL) solution dissolved. After stirring for 12 hours, the byproduct AgCl was removed by filtration. The solvent was removed under reduced pressure in vacuo to yield a green compound. The obtained compound was again dissolved in dichloromethane (3 mL), and then dichloromethane (CH ₃ (CH ₂ ) ₁₆ ] ₂ CH-N (PPh ₂ ) ₂ (0.0468 g, 0.0533 mmol) was dissolved. 1 mL) and mixed with the solution. The reaction system was stirred for 12 hours to prepare a catalyst system of Comparative Example 4. The solvent was then removed under reduced pressure in vacuo to yield 0.143 g of a cyan 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 99% and the elemental analysis data was in good agreement 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} 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

Methylcyclohexane (19 mL) and iBu ₃ Al (14.9 mg, 0.0750 mmol) or Et ₃ Al (8.56 mg, 0.0750 mmol) were added to a high pressure reactor, and 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), injected into a reactor by a syringe, and ethylene was continuously injected under a pressure of 45 bar. By the heat of polymerization, the temperature rose to 60 ° C. within a few minutes, after which the reaction was carried out for 60 minutes while controlling the temperature to 60 ° C. Ice was used to lower the reactor temperature and the valve was opened to remove residual ethylene gas. For gas chromatography analysis, nonane was quantified by standard (˜700 mg), and some samples were taken to quantify the product through GC analysis. The formed polymer was separated by filtration and dried in a vacuum oven to measure the mass.

Examples 27-42 and Comparative Examples 5-9

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

The results of the ethylene tetramerization reaction carried out 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 an equivalent or higher activity than the catalyst system using MAO without using an excessively expensive MAO.

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

The catalyst system of the present invention is characterized in that the molar ratio of uncoordinated anions, Cr (or Cr + Al), and bisphosphine ligands 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 molar ratio of borate anion, chromium, and bisphosphine ligand was 2: 2: 1 by the reaction at a 1: 1 molar ratio to synthesize ethylene to evaluate the ethylene reactivity, it was implemented using methylaluminoxane (MAO) as in Comparative Example 7. The same level of activity was achieved with the prepared catalyst (Comparative Example 7).

Further, as in Comparative Example 6, [CrCl ₂ (NCCH ₃ ) ₄ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ⁻ and [(C ₁₇ H ₃₅ ) ₂ C (H) N (PPh ₂ ) ₂ were replaced with 1: 1. The molar ratio of borate anion, chromium, and bisphosphine ligands is 1: 1: 1 by reaction at 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, to prepare a catalyst having a molar ratio of borate anion, chromium and bisphosphine ligand 2: 1: 1, CrCl ₃ (THF) ₃ was added in 2 equivalents of [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 molar ratio of 2: 1: 1: 1 was prepared to evaluate ethylene reactivity, very high activity was realized. However, the borate compound was converted into an expensive silver compound ([Ag (CH ₃ CN) ₄ ] ⁺ [B ( C ₆ F ₅ ) ₄ ] ^- ) is used, the cost of producing the catalyst is high, and the supply and demand of raw materials is difficult to apply to commercial processes.

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 reaction of (THF) ₃ followed by one equivalent of the bisphosphine ligand compound, the same level of catalytic activity was achieved as the catalyst prepared from the silver compound.

Examples 11 to 16 may prepare a highly active catalyst using aluminum compounds having various structures, that is, (R ¹ ) ₂ AlX represented by Chemical Formula 1, instead of Et ₂ AlCl in preparing a catalyst. X in (R ¹ ) ₂ AlX may be halogen, acetylacetonate, alkoxy having 1 to 20 carbon atoms, or phenoxy having 6 to 30 carbon atoms, and a high activity catalyst may be prepared using an aluminum compound having such a structure. It confirmed through the Example.

Particularly, in Example 11, X is an acetylatetonate, which is preferable because the catalyst activity is high, the amount of by-products produced is low, and the catalyst production cost is low.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen 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; And
To the bisphosphine ligand compound represented by the following formula (4);
Method for producing an ethylene tetramerization catalyst system comprising the 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 carbon atoms;
[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. Which is either;
[Formula 3]
Cr (Z) ₃ (A) _n
In Formula 3, Z is each independently a halogen group, an acetylacetonate group and 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, 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.
The method of claim 1,
Borate compounds represented by Formula 1;
A first organoaluminum compound represented by Formula 2;
A chromium compound represented by Chemical Formula 3; And
Of the bisphosphine ligand compound represented by Formula 4;
The molar ratio is 1.8-2.2: 0.9-1.1: 0.9-1.1: 1, The manufacturing method of the ethylene tetramerization catalyst system.
The method of claim 1,
In Chemical Formula 2, R ¹ is an ethyl group or an isobutyl group, X is an acetylacetonate group;
The method of claim 1,
In Formula 4, Y is a metasilyl group or a parasilyl group.
The method of claim 1,
In Chemical Formula 4, Y is halogen.
The method of claim 1,
In Chemical Formula 4, R is [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20).
A borate compound prepared by the ethylene tetramerization catalyst system according to any one of claims 1 to 6 and represented by Formula 1: A first organoaluminum compound represented by Formula 2: Chromium represented by Formula 3 Compound: Ethylene tetramerization catalyst system having a molar ratio of bisphosphine ligand compound represented by the formula (4) is 1.8 ~ 2.2: 0.9 ~ 1.1: 0.9 ~ 1.1: 1.
An ethylene tetramerization catalyst system according to claim 7; A second organoaluminum compound represented by Formula 5; And ethylene monomers; Ethylene tetramer manufacturing method comprising the step of 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 Formula 5, R ² is an ethyl group or isobutyl group ethylene tetramer manufacturing method.
The method of claim 8,
The method for producing ethylene tetramer is an ethylene tetramer manufacturing 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 3 to 50 carbon atoms. .
The method of claim 11,
In Formula 4A, R is [CH ₃ (CH ₂ ) _d ] ₂ CH- * (d is 10 to 20) bisphosphine ligand compound.
The method of claim 11,
The bisphosphine ligand is a bisphosphine ligand compound which is 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.
The method of claim 13,
In Formula 4-A1, Y ¹ is * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer of 0 to 20; q is an integer of 1 to 3). Phosphine ligand compounds.
The method of claim 11,
The bisphosphine ligand is a bisphosphine ligand compound which is a compound represented by the following 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. Qi.
The method of claim 15,
In Formula 4-A2, Y ¹ is * -Si-[(CH ₂ ) _p CH ₃ ] _q [CH ₃ ] _3-q (p is an integer of 0 to 20; q is an integer of 1 to 3). Phosphine ligand compounds.