KR20240028386A - Catalyst system for alpha-olefin trimerization, and preparing method of alpha-olefin trimer using the same - Google Patents

Abstract

The present application relates to an alpha-olefin trimerization catalyst system and a method for producing alpha-olefin trimer using the same. More specifically, the present invention is an alpha-activating agent that does not require the use of expensive activators such as methylaluminoxane (MAO), B(C ₆ F ₅ ) ₃ , [B(C ₆ F ₅ ) ₄ ^] -salt, etc. An olefin trimerization catalyst system is provided, and a method for selectively producing alpha-olefin trimers by contacting the same with alpha-olefin monomers.

Description

Alpha-olefin trimerization catalyst system and method for producing alpha-olefin trimer using the same {CATALYST SYSTEM FOR ALPHA-OLEFIN TRIMERIZATION, AND PREPARING METHOD OF ALPHA-OLEFIN TRIMER USING THE SAME}

The present invention relates to an alpha-olefin trimerization catalyst system and a method for producing alpha-olefin trimer using the same. More specifically, the present invention relates to commercially available ethylene trimerization without the use of expensive activators such as methylaluminoxane (MAO), B(C ₆ F ₅ ) ₃ , [B(C ₆ F ₅ ) ₄ ^] -salt, etc. Provided is an alpha-olefin trimerization catalyst system constructed through modification of the catalyst system, and a method for selectively producing alpha-olefin trimer by contacting it with an alpha-olefin monomer.

Lubricants play a role in saving energy and resources by reducing friction and extending the life of equipment. They are essential for the function of many types of equipment, such as automobiles, and annual global demand for lubricants is estimated at approximately 40 million tons.

PAO (poly(alpha-olefin)), which is synthesized through oligomerization of alpha-olefin (1-alkene), is widely used as a lubricating base oil and has a high viscosity index and excellent oxidation stability. For this reason, it is treated as a top-tier base oil and is produced worldwide at an annual volume of approximately 600,000 tons.

These PAO products are mainly released by oligomerizing 1-decene using a cation as an initiator. However, when alpha-olefin is oligomerized using a cationic initiator, a severe carbon skeleton isomerization side reaction occurs, resulting in a material with a structure containing many branched chains, and this structure is used in lubricating oil. There is a problem that reduces the performance of .

On the other hand, when polymerizing 1-decene with a cationic initiator, the trimerization product (C ₃₀ H ₆₂ ) of 1-decene is the main component, and in addition, dimerization (C20), tetramerization (C40), pentamerization (C50), etc. This mixed mixture is created, and by fractional distillation of the mixture, a large market is formed under the trade name of PAO-4 in the form of a mixture centered on the trimerized product and containing some tetramerized (C40) and pentameric (C50) products. It is done.

Recently, lubricating base oils produced by oligomerizing 1-decene using transition metal-based catalysts such as metalloce catalysts instead of using cationic initiators have been released (Dalton Trans. 2014, 43, 10132; Appl. Catal. A, Gen. 2018, 549, 40). The advantage of using a metallocene catalyst is that carbon skeleton isomerization side reactions can be prevented and high-performance lubricating base oil can be obtained. However, the method using a metallocene catalyst still involves dimerization (C20), trimerization (C30), tetramerization (C40), pentamerization (C50), and hexamerization (C60) of 1-decene, such as Schulz-Flory (Schulz-Flory). Flory) Since a mixture of distributions is created, additional fractional distillation must be performed to separate each component, and each component of the oligomer prepared from 1-decene has a very high boiling point, so a lot of energy is required to separate it through fractional distillation. This exists.

To solve this problem, a chromium-based catalyst system was reported that can selectively trimerize 1-decene to selectively produce only the trimerized product (C ₃₀ H ₆₂ ) component, and thereafter, a titanium-based catalyst was used to produce alpha-olefins. Although selective conversion to trimer has been reported, the reported catalyst system has a low turnover rate and is not sufficient for commercial use. Additionally, attempts have been made to develop a catalyst system that does not require the use of expensive activators, but expensive materials such as methylaluminoxane (MAO) or B(C ₆ F ₅ ) ₃ are still required as activators, so this is also not commercially feasible. There are limits to its use.

Meanwhile, catalysts capable of converting ethylene to alpha-olefins were discovered earlier and developed more extensively than alpha-olefin trimerization catalysts. Nickel- and zirconium-based catalysts that simultaneously produce a full range of alpha-olefins have been commercialized (Shell higher-olefin process and Sabic/Linde Alpha-SABLIN process). In addition, a Cr-based ethylene trimerization catalyst that selectively produces 1-hexene was discovered and commercialized by Phillips in the early 2000s, and another type of Cr-based selective catalyst that can produce 1-octene as the main product was developed by Sasol. was also discovered. However, the reported Cr-based catalysts are inactive for alpha-olefin trimerization reactions.

An important advantage of Phillips' ethylene trimerization catalyst system is that it does not require expensive activators such as MAO, B(C ₆ F ₅ ) _3, [B(C ₆ F ₅ ) ₄ ^] -salts, etc. Accordingly, the inventors of the present application developed an alpha-olefin trimerization catalyst system that can selectively produce alpha-olefin trimer without requiring an expensive activator by modifying Phillips' ethylene trimerization catalyst system.

The present application is intended to solve the problems of the prior art described above and provides an alpha-olefin trimerization catalyst system capable of selectively producing alpha-olephane trimer without requiring an expensive activator.

Additionally, a method for producing alpha-olefin trimer using the alpha-olefin trimerization catalyst system is provided.

However, the technical challenges sought to be achieved by the embodiments of the present application are not limited to the technical challenges described above, and other technical challenges may exist.

As a technical means for achieving the above-described technical problem, the first aspect of the present application includes a chromium (Cr) compound represented by the following formula (1); A pyrrol compound represented by Formula 2-1, Formula 2-2, or Formula 2-3 below; and an aluminum (Al) compound represented by the following formula (3); Provided is an alpha-olefin trimerization catalyst system comprising:

[Formula 1]

CrX ₃

(In _Formula 1 _,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

(In Formula 2-1 to Formula 2-3,

R ¹ to R ⁵ are each independently hydrogen or C ₁ -C ₂₀ alkyl,

M is Li, Na or K)

[Formula 3]

Al(R ⁶ ) ₃

(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).

According to one embodiment of the present application, the Cr compound may be chromium acetylacetonate (Cr(acac) ₃ ), but is not limited thereto.

According to one embodiment of the present application, in Formulas 2-1 to 2-3, R ¹ may be an isobutyl group, R ² and R ⁵ may be a methyl group, and R ³ and R ⁴ may be a hydrogen atom, but are limited thereto. That is not the case.

According to one embodiment of the present application, in Formula 3, R ⁶ may be an isobutyl group, but is not limited thereto.

In addition, a second aspect of the present application provides an alpha-olefin trimerization catalyst system comprising a Cr compound represented by the following formula (4) and an Al compound represented by the following formula (3):

[Formula 4]

(In Formula 4, R ⁷ to R ¹¹ are each independently hydrogen or C ₁ -C ₂₀ alkyl)

[Formula 3]

Al(R ⁶ ) ₃

(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).

According to one embodiment of the present application, in Formula 4, R ⁷ , R ¹⁰ , and R ¹¹ are methyl groups, R ⁸ and R ⁹ are hydrogen atoms, and in Formula 3, R ⁶ may be an isobutyl group, but is limited thereto. It doesn't work.

Additionally, a third aspect of the present disclosure provides an alpha-olefin trimerization catalyst system comprising a Cr compound represented by the following formula (5) and an Al compound represented by the following formula (3):

[Formula 5]

(In Formula 5, R ¹² to R ¹⁷ are each independently hydrogen or C ₁ -C ₂₀ alkyl).

[Formula 3]

Al(R ⁶ ) ₃

(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).

According to one embodiment of the present application, in Formula 5, R ¹² , R ¹³ , R ¹⁶ , and R ¹⁷ are methyl groups, R ¹⁴ and R ¹⁵ are hydrogen atoms, and in Formula 3, R ⁶ may be an isobutyl group. , but is not limited to this.

Additionally, a fourth aspect of the disclosure comprises contacting a catalyst system according to the first, second or third aspect of the disclosure with an alpha-olefin monomer to optionally produce an alpha-olefin trimer. A method for producing olefin trimer is provided.

According to one embodiment of the present application, the alpha-olefin monomer may include one selected from the group consisting of 1-octane, 1-decane, 1-dodecane, and combinations thereof, but is not limited thereto. .

According to one embodiment of the present application, the alpha-olefin monomer may include a mixture of 1-octane and 1-dodecene, but is not limited thereto.

According to one embodiment of the present application, the alpha-olefin monomer may be used as a monomer for alpha-olefin trimer and as a solvent for reaction, but is not limited thereto.

The above-described means of solving the problem are merely illustrative and should not be construed as intended to limit the present application. In addition to the exemplary embodiments described above, additional embodiments may be present in the drawings and detailed description of the invention.

Unlike the conventional alpha-olefin trimerization catalyst system, the alpha-olefin trimerization catalyst system according to the present application uses expensive activators such as MAO, B(C ₆ F ₅ ) _3, [B(C ₆ F ₅ ) ₄ ^] -salt, etc. It is a catalyst system that does not require the use of, and using this, alpha-olefin trimer can be produced with improved efficiency than conventional catalyst systems.

In addition, alpha-olefin trimer prepared using the alpha-olefin trimerization catalyst system according to the present application can achieve lubricating oil performance similar to poly(alpha-olefin) prepared through the oligomerization reaction of existing 1-decene.

However, the effects that can be obtained herein are not limited to the effects described above, and other effects may exist.

Figure 1 is a schematic diagram of the structure of [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ as revealed by X-ray crystallography according to an experimental example herein.
2 (A) and (B) respectively show 2,5-Me ₂ C ₄ H ₂ N-Cr[CH ₂ C ₆ H ₄ (ortho-NMe) confirmed by X-ray crystallography according to an experimental example of the present application. ₂ )-к ₂ C,N] ₂ and [η ⁵ -2,5-Me ₂ C ₄ H ₂ N-AlMe ₃ ]Cr(Me)CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C ,N] This is a schematic diagram of the structure of ₂ .
Figure 3 is a ¹ H NMR spectrum of a catalyst system according to an experimental example herein.
Figure 4 is a ¹ H NMR spectrum of a trimer prepared using a catalyst system according to an example of the present application before and after hydrogenation.
Figure 5 is a simulated distillation gas chromatography (SimDis GC) graph according to an experimental example herein.

Below, with reference to the attached drawings, embodiments of the present application will be described in detail so that those skilled in the art can easily implement them. However, the present application may be implemented in various different forms and is not limited to the embodiments described herein. In order to clearly explain the present application in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout this specification, when a part is said to be “connected” to another part, this includes not only the case where it is “directly connected,” but also the case where it is “electrically connected” with another element in between. do.

Throughout this specification, when a member is said to be located “on”, “above”, “at the top”, “below”, “at the bottom”, or “at the bottom” of another member, this means that a member is located on another member. This includes not only cases where they are in contact, but also cases where another member exists between two members.

Throughout the specification of the present application, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

As used herein, the terms “about,” “substantially,” and the like are used to mean at or close to a numerical value when manufacturing and material tolerances inherent in the stated meaning are presented, and to aid understanding of the present application. It is used to prevent unscrupulous infringers from unfairly exploiting disclosures in which precise or absolute figures are mentioned. Additionally, throughout the specification herein, “a step of” or “a step of” does not mean “a step for.”

Throughout this specification, the term "combination thereof" included in the Markushi format expression means a mixture or combination of one or more components selected from the group consisting of the components described in the Markushi format expression, It means including one or more selected from the group consisting of.

Throughout this specification, description of “A and/or B” means “A, B, or A and B.”

Hereinafter, the alpha-olefin trimerization catalyst system of the present application and the method for producing alpha-olefin trimer using the same will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments, examples, and drawings.

As a technical means for achieving the above-described technical problem, the first aspect of the present application includes a chromium (Cr) compound represented by the following formula (1); A pyrrol compound represented by Formula 2-1, Formula 2-2, or Formula 2-3 below; and an aluminum (Al) compound represented by the following formula (3); Provided is an alpha-olefin trimerization catalyst system comprising:

[Formula 1]

CrX ₃

(In _{Formula 1} ,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

(In Formula 2-1 to Formula 2-3,

R ¹ to R ⁵ are each independently hydrogen or C ₁ -C ₂₀ alkyl,

M is Li, Na or K)

[Formula 3]

Al(R ⁶ ) ₃

(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).

Unlike the conventional alpha-olefin trimerization catalyst system, the alpha-olefin trimerization catalyst system according to the present application uses expensive activators such as MAO, B(C ₆ F ₅ ) _3, [B(C ₆ F ₅ ) ₄ ^] -salt, etc. It is a catalyst system that does not require the use of, and using this, alpha-olefin trimer can be produced with improved efficiency than conventional catalyst systems.

Specifically, the alpha-olefin trimerization catalyst system according to the present application is a modification of Phillips' ethylene trimerization catalyst system. The original Phillips ethylene trimerization catalyst system consisted of 'Cr(2-ethylhexanoate) ₃ /2,5-Me ₂ C ₄ H ₂ NH/Et ₃ Al/Et ₂ AlCl', but the simplified form 'Cr (EH) ₂ OH/2,5-Me ₂ C ₄ H ₂ N-AlEt ₂ /Et ₃ Al·ClAlEt ₂ ^' , and both catalyst systems are known to exhibit similar activity. Therefore, the inventors of the present application applied a catalyst system composed of a Cr compound, a pyrrole compound, and an Al compound to the trimerization of alpha-olefin.

According to one embodiment of the present application, the Cr compound may be chromium acetylacetonate (Cr(acac) ₃ ), but is not limited thereto.

In the previously reported ethylene tetramerization catalyst system, the catalyst system composed of Cr(acac) ₃ (i.e., Cr(acac) ₃ /iPrN(PPh ₂ ) ₂ /MMAO) is 20 times stronger than the catalyst system composed of CrCl ₃ (THF) ₃ showed two times higher activity. In the reaction of LCrCl ₃ (L=SNS type ligand) with R ₃ Al, alkylation has been reported to be neither facile nor complete. Additionally, Cr(II) species were reported to be produced from the reaction of CrCl ₃ (THF) ₃ with aluminate species (e.g., Li ⁺ [Et ₂ Al(N(iPr) ₂ ) ₂ ] ^- ). These existing studies suggest that the use of CrCl ₃ (THF) ₃ as a catalyst component may be harmful. The reason is that for the generation of the hypothesized active species, all chloride ligands of the Cr complex must be replaced by alkyls to avoid transformation into Cr(II) species. Based on these previous studies, as a result of setting the Cr compound to Cr(acac) ₃ , it was confirmed that it showed better activity than when using CrCl ₃ (THF) ₂ or Cr(EH) ₂ OH as the Cr compound. .

According to one embodiment of the present application, in Formulas 2-1 to 2-3, R ¹ may be an isobutyl group, R ² and R ⁵ may be a methyl group, and R ³ and R ⁴ may be a hydrogen atom, but are limited thereto. That is not the case.

According to one embodiment of the present application, in Formula 3, R ⁶ may be an isobutyl group, but is not limited thereto.

The catalyst system according to the present disclosure, when the Al compound is (iBu) ₃ Al (i.e., when R ⁶ in Formula 3 is an isobutyl group), Al such as Me ₃ Al, Et ₃ Al (octyl) ₃ Al, etc. It may exhibit more excellent activity than when the catalyst system is composed of compounds, but is not limited thereto.

In addition, a second aspect of the present application provides an alpha-olefin trimerization catalyst system comprising a Cr compound represented by the following formula (4) and an Al compound represented by the following formula (3):

[Formula 4]

(In Formula 4, R ⁷ to R ¹¹ are each independently hydrogen or C ₁ -C ₂₀ alkyl)

[Formula 3]

Al(R ⁶ ) ₃

(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).

In the catalyst system according to the second aspect of the present application, the Cr compound represented by Formula 4 includes a pyrrole compound, and accordingly, the catalyst system according to the second aspect of the present application includes the catalyst system according to the first aspect of the present application and Likewise, it may include a Cr compound, a pyrrole compound, and an Al compound, but is not limited thereto.

According to one embodiment of the present application, in Formula 4, R ⁷ , R ¹⁰ , and R ¹¹ are methyl groups, R ⁸ and R ⁹ are hydrogen atoms, and in Formula 3, R ⁶ may be an isobutyl group, but is limited thereto. It doesn't work.

Additionally, a third aspect of the present disclosure provides an alpha-olefin trimerization catalyst system comprising a Cr compound represented by the following formula (5) and an Al compound represented by the following formula (3):

[Formula 5]

(In Formula 5, R ¹² to R ¹⁷ are each independently hydrogen or C ₁ -C ₂₀ alkyl).

[Formula 3]

Al(R ⁶ ) ₃

(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).

In the catalyst system according to the third aspect of the present application, the Cr compound represented by Formula 5 includes a pyrrole compound, and accordingly, the catalyst system according to the third aspect of the present application includes the catalyst system according to the first aspect of the present application and Likewise, it may include a Cr compound, a pyrrole compound, and an Al compound, but is not limited thereto.

According to one embodiment of the present application, in Formula 5, R ¹² , R ¹³ , R ¹⁶ , and R ¹⁷ are methyl groups, R ¹⁴ and R ¹⁵ are hydrogen atoms, and in Formula 3, R ⁶ may be an isobutyl group. , but is not limited to this.

Additionally, a fourth aspect of the disclosure comprises contacting a catalyst system according to the first, second or third aspect of the disclosure with an alpha-olefin monomer to optionally produce an alpha-olefin trimer. A method for producing olefin trimer is provided.

Regarding the method for producing an alpha-olefin trimer according to the fourth aspect of the present application, detailed description of parts overlapping with the first to third aspects of the present application has been omitted. However, even if the description is omitted, the first to third aspects of the present application are omitted. The content described in the third aspect can be equally applied to the fourth aspect of the present application.

According to one embodiment of the present application, the alpha-olefin monomer may include one selected from the group consisting of 1-octane, 1-decane, 1-dodecane, and combinations thereof, but is not limited thereto. .

According to one embodiment of the present application, the alpha-olefin monomer may include a mixture of 1-octane and 1-dodecene, but is not limited thereto.

According to one embodiment of the present application, the alpha-olefin monomer may be used as a monomer for alpha-olefin trimer and as a solvent for reaction, but is not limited thereto.

The present invention will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

[Example 1]

CrCl ₃ (THF) ₂ , [2,5-Me ₂ C ₄ H ₂ N-Al(C ₆ F ₅ ) ₃ ] ^- Li ⁺ , and (iBu) ₃ Al were mixed in a ratio of 3:3:16. A catalyst system was constructed.

[Example 2]

CrCl ₃ (THF) ₂ , [2,5-Me ₂ C ₄ H ₂ N-Al(C ₆ F ₅ ) ₃ ] ^- Li ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1.5:3.0:16. A catalyst system was constructed.

[Example 3]

CrCl ₃ (THF) ₂ , [2,5-Me ₂ C ₄ H ₂ N-Al(C ₆ F ₅ ) ₃ ] ^- Li ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1.0:3.0:16. A catalyst system was constructed.

[Example 4]

CrCl ₃ (THF) ₂ , [2,5-Me ₂ C ₄ H ₂ N-Al(C ₆ F ₅ ) ₃ ] ^- Li ⁺ , and (iBu) ₃ Al were mixed in a ratio of 0.75:3.0:16. A catalyst system was constructed.

[Example 5]

A catalyst system was constructed by mixing CrCl ₃ (THF) ₂ , 2,5-Me ₂ C ₄ H ₂ N-Li, and (iBu) ₃ Al at a ratio of 1.0:3.0:16.

[Example 6]

A catalyst system was constructed by mixing CrCl ₃ (THF) ₂ , 2,5-Me ₂ C ₄ H ₂ N-Li, and Et ₃ Al in a ratio of 1.0:3.0:16.

[Example 7]

CrCl ₃ (THF) ₂ , 2,5-Me ₂ C ₄ H ₂ N-Li, and Et ₂ AlCl were mixed at a ratio of 1.0:3.0:16 to form a catalyst system.

[Example 8]

A catalyst system was constructed by mixing CrCl ₃ (THF) ₂ , 2,5-Me ₂ C ₄ H ₂ N-Li, and MAO in a ratio of 1.0:3.0:16.

[Example 9]

CrCl ₃ (THF) ₂ , 2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₂ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to form a catalyst system.

[Example 10]

A catalyst system was constructed by mixing Cr(EH) ₂ OH, 2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₂ , and (iBu) ₃ Al in a ratio of 1:3:10.

[Example 11]

Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₂ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to form a catalyst system.

[Example 12]

Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₂ , and (iBu) ₃ Al were mixed in a ratio of 1:2:10 to form a catalyst system.

[Example 13]

Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₂ , and (iBu) ₃ Al were mixed in a ratio of 1:1:10 to form a catalyst system.

[Example 14]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-AlEt ₂ , and (iBu) ₃ Al in a ratio of 1:1:10.

[Example 15]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-AlEt ₂ , and (iBu) ₃ Al in a ratio of 1:2:10.

[Example 16]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-AlEt ₂ , and (iBu) ₃ Al in a ratio of 1:3:10.

[Example 17]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Li, and (iBu) ₃ Al in a ratio of 1:3:10.

[Example 18]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Na, and (iBu) ₃ Al in a ratio of 1:3:10.

[Example 19]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Na, and (iBu) ₃ Al in a ratio of 1:2:10.

[Example 20]

A catalyst system was constructed by mixing Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ N-Na, and (iBu) ₃ Al in a ratio of 1:1:10.

[Example 21]

A catalyst system is formed by mixing Cr(acac) ₃ , [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al in a ratio of 1:3:10. did.

[Example 22]

CrCl ₃ (THF) ₂ , [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to prepare a catalyst system. It was composed.

[Example 23]

Cr(EH) ₂ OH, [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to prepare the catalyst system. It was composed.

[Example 24]

A catalyst system is formed by mixing Cr(acetate) ₃ , [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al in a ratio of 1:3:10. did.

[Example 25]

Cr(acac) ₃ , [2,5-Me ₂ C ₄ H ₂ N-AlMe ₃ ] ^- Na ⁺ , and Me ₃ Al were mixed in a ratio of 1:3:10 to form a catalyst system.

[Example 26]

Cr(acac) ₃ , [2,5-Me ₂ C ₄ H ₂ N-AlEt ₃ ] ^- Na ⁺ , and Et ₃ Al were mixed in a ratio of 1:3:10 to form a catalyst system.

[Example 27]

A catalyst system is formed by mixing Cr(acac) ₃ , [2,5-Me ₂ C ₄ H ₂ N-Al(octyl) ₃ ] ^- Na ⁺ , and (octyl) ₃ Al in a ratio of 1:3:10. did.

[Example 28]

Cr(acac) ₃ , [C ₄ H ₄ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to construct a catalyst system.

[C ₄ H ₄ N-Al(iBu) ₃ ] ^{-Na +} is a compound represented by the following formula.

[Example 29]

Cr(acac) ₃ , [3-MeC ₄ H ₃ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to construct a catalyst system.

[3-MeC ₄ H ₃ N-Al(iBu) ₃ ] ^{-Na +} is a compound represented by the following formula.

[Example 30]

Cr(acac) ₃ , [2,4-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to form a catalyst system. did.

[2,4-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ is a compound represented by the following formula.

[Example 31]

Cr(acac) ₃ , [2-EtC ₄ H ₃ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to form a catalyst system.

[2-EtC ₄ H ₃ N-Al(iBu) ₃ ] ^{-Na +} is a compound represented by the following formula.

[Example 32]

Cr(acac) ₃ , [2,5-Me ₂ -3-EtC ₄ HN-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to prepare the catalyst system. It was composed.

[2,5-Me ₂ -3-EtC ₄ HN-Al(iBu) ₃ ] ^{-Na +} is a compound represented by the following formula.

[Example 33]

Cr(acac) ₃ , [Me ₄ C ₄ N-Al(iBu) ₃ ] ^- Na ⁺ , and (iBu) ₃ Al were mixed in a ratio of 1:3:10 to construct a catalyst system.

[Me ₄ C ₄ N-Al(iBu) ₃ ] ^{-Na +} is a compound represented by the following formula.

[Experimental Example 1] Trimerization reaction of 1-octene using a catalyst system consisting of CrCl ₃ (THF) ₂ , 2,5-dimethylpyrrolide lithium species, and alkylaluminum

Alpha-olefin trimerization catalyst using CrCl ₃ (THF) ₂ as a chromium compound, 2,5-dimethylpyrrolide lithium species as a pyrrole compound, and alkylaluminum as an aluminum compound. The system was configured.

The 2,5-dimethylpyrrolide lithium species is [2,5-Me ₂ C ₄ H ₂ N-Al(C ₆ F ₅ ) ₃ ] ^- Li ⁺ or 2,5-Me ₂ C ₄ H ₂ N-Li was used, and the alkyl aluminum was (iBu) ₃ Al, Et ₃ Al, Et ₂ AlCl, or MAO.

Table 1 below shows the results of the 1-octene trimerization reaction performed with a catalyst system consisting of CrCl ₃ (THF) ₂ , 2,5-dimethylpyrrolide lithium species, and alkylaluminum according to Example 1 of the present application.

[Table 1] ^Results a for the 1-octene trimerization reaction performed with a catalyst system consisting of CrCl ₃ (THF) ₂ , 2,5-dimethylpyrrolide lithium species, and alkylaluminum

^a CrCl ₃ (THF) ₂ and [2,5-Me ₂ C ₄ H ₂ N-Al(C ₆ F ₅ ) ₃ ] ^- Li ⁺ (or 2,5-Me ₂ C ₄ H ₂ N-Li, 23 μmol) was reacted in CH ₂ Cl ₂ for 1 hour, volatile substances were removed, and the separated solid was combined with alkylaluminum (120 μmol) in pure 1-octene (2.0 g) at 20°C to 25°C. ^b CrCl ₃ (THF) ₂ and 2,5-Me ₂ C ₄ H ₂ N-Li were fed directly into 1-octene without prior reaction.

Referring to Table 1 above, CrCl ₃ (THF) ₂ /2,5-Me ₂ C ₄ H ₂ N-Li/(iBu) ₃ Al catalyst system (Example 5) is an expensive and explosive Al(C ₆ F ₅ ) It was possible to selectively produce 1-octene trimer while avoiding the use of ₃ . The conversion rate over 2 hours (TON at 2h) was similar to the catalyst system constructed using Al(C ₆ F ₅ ) ₃ (Examples 1 to 4), but the conversion rate over 24 hours (TON at 24h) was lower. Specifically, when comparing Examples 3 and 5, the conversion rates for 2 hours were 650 and 690, respectively, and the conversion rates for 24 hours were 1920 and 1180, respectively.

Additionally, in Example 5 ^b , when CrCl ₃ (THF) ₂ and 2,5-Me ₂ C ₄ H ₂ N-Li were directly supplied to 1-octene without prior reaction, the conversion rate for 24 hours decreased from 1180 to 770. In the catalyst system (Examples 6 to 8) using Et ₃ Al, Et ₂ AlCl or MAO instead of (iBu) ₃ Al, it was confirmed that the activity was seriously reduced.

[Experimental Example 2] Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ NM (M=Al(iBu) ₂ , AlEt ₂ , Li, or Na) and (iBu) ₃ A catalyst system consisting of Al Trimerization reaction of 1-octene using

Cr(acac) ₃ as a chromium compound, 2,5-Me ₂ C ₄ H ₂ NM as a pyrrole compound (wherein, M is Al(iBu) ₂ , AlEt ₂ , Li, or Na), and as an aluminum compound ( iBu) ₃ Al was used to construct an alpha-olefin trimerization catalyst system.

Table 2 below shows Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ NM (M=Al(iBu) ₂ , AlEt ₂ , Li, or Na) and (iBu) ₃ according to Example 2 of the present application. This is the result of the trimerization reaction of 1-octene using a catalyst system composed of Al.

[Table 2] Cr(acac) ₃ , 2,5-Me ₂ C ₄ H ₂ NM (wherein M is Al(iBu) ₂ , AlEt ₂ , Li, or Na), and (iBu) ₃ Al Results ^c for the 1-octene trimerization reaction performed with the configured catalyst system

^c (iBu) ₃ Al (380 μmol), pyrrolide, and Cr precursor (38 μmol) were sequentially added to 1-octene (10 g) and stirred at 20°C to 25°C.

Referring to Table 2, it can be seen that the catalyst system composed of Cr(acac) ₃ exhibits much higher activity than the catalyst system composed of CrCl ₃ (THF) ₂ or Cr(EH) ₂ OH (Examples 9 to 9) 10). Additionally, in the case of pyrrole compounds, the activity increased when 2,5-Me ₂ C ₄ H ₂ N-Li was replaced with 2,5-Me ₂ C ₄ H ₂ N-Na (Examples 17 to 18). It was confirmed that the activity decreased when the ratio of the chromium compound and the pyrrole compound was lowered from 1:3 to 1:2 (Examples 18 and 19). Therefore, it was confirmed that the optimal ratio of chromium compound and pyrrole compound was 1:3.

[Experimental Example 3] 1-octene trimerization reaction performed with a catalyst system consisting of Cr compound/[pyrrolide-AlR ₃ ] ^- Na ⁺ /(iBu) ₃ Al

[η ⁵ -2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ]To test the hypothesis of Cr-type active species, Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N- Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al catalyst system was evaluated.

Prior to the 1-octene trimerization reaction, 2,5-Me ₂ C ₄ H ₂ N-Na and excess (iBu) ₃ Al were reacted in toluene to obtain [2,5-Me ₂ C ₄ H ₂ N-Al( iBu) ₃ ] ^- Na ⁺ was obtained (yield: 87%). Unlike 2.5-Me ₂ C ₄ H ₂ N-Na, which is poorly soluble in toluene, [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ is highly soluble and forms a single crystal when the hot toluene solution is cooled. was precipitated.

Figure 1 is a schematic diagram of the structure of [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ as revealed by X-ray crystallography according to an experimental example herein.

Referring to Figure 1, it can be seen that the structure of the polymer contact ion pair chain has been discovered. Specifically, the sodium ion is surrounded by two pyrrolide rings within the chain, while the two rings are tilted at 43.2°. The Na ⁺ ion pulls on the methylene-carbon of the Al(iBu) ₃ fragment, ultimately placing it close to Na ⁺ (Na-C15 distance, 3.077(2) Å) and moving the Al atom slightly away from the pyrrolide ring.

Using this, a catalyst system was constructed as shown in Table 3 below, and the trimerization reaction of 1-octene was performed.

Table 3 below shows the results of the trimerization reaction of 1-octene using the catalyst system according to Example 3 of the present application.

[Table 3] Results ^d for the 1-octene trimerization reaction performed with a catalyst system consisting of Cr compound/[substituted pyrrolide-AlR ₃ ] ^- Na ⁺ /R ₃ Al

^d 1-octene (10 g) containing R ₃ Al (380 μmol) (Cr:pyrrolide:Al=1:3:10) was added to the flask containing Cr precursor (38 μmol) and pyrrole compound (114 μmol). Added to. Cr(acac) ₃ in 1-octene (10 g) containing ^e (iBu) ₃ Al and half of [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ was added.

Referring to Table 3, among the various catalyst systems constructed, the Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al catalyst system is It was confirmed that the highest activity was observed (Example 21). Specifically, for the catalyst system of Example 21, the TON measured at 2 hours and 24 hours was 1640 and 2230, respectively (1-octene conversion 70% and 96%). On the other hand, for the catalyst system of Example 21 ^e where the catalyst concentration was reduced by half (i.e., Cr(acac) ₃ , [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) in the same amount of 1-octene ₃ ] ^- When the supply of Na ⁺ was reduced by half), TON increased to 2000 and 2800 at 2 and 24 hours, respectively.

On the other hand, it was confirmed that the activity decreased when Cr(acac) ₃ was replaced with other Cr compounds such as CrCl ₃ (THF) ₂ , Cr(EH) ₂ OH or Cr(acetate) ₃ (Examples 22 to 24). Additionally, the choice of aluminum compound was also important. The catalyst system composed of Me ₃ Al (Example 25) was almost inactive, whereas the catalyst system composed of Et ₃ Al or (octyl) ₃ Al (Examples 26 and 27, respectively) was inferior to the catalyst system of Demonstration Example 21. However, it showed quite high activity.

On the other hand, in the case of a catalyst system consisting of several [substituted pyrrolide-AlR ₃ ] ^- Na ⁺ (Examples 28 to 33), [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na It was inferior to the catalyst system composed of ⁺ . Specifically, the catalyst systems of Examples 28 and 29 showed low activity (220 and 250 TON (at 24h), respectively), while the catalyst systems of Examples 30 and 31 showed intermediate activity (650 and 590 TON (at 24h), respectively. 24h)). The catalyst systems of Examples 32 and 33 showed significantly higher activities (1200 and 1300 TON (at 24h), respectively).

[Experimental Example 4]

Scheme 1 below shows the preparation of pyrrolide-Cr complex and reaction with Me ₃ Al.

[Scheme 1]

When treating (ortho- _{Me 2 NC 6} H ₄ CH ₂ -к ₂ C,N) ₃ Cr using 2,5-Me 2 C ₄ H ₂ NH in toluene, 2,5-Me ₂ C ₄ H ₂ N-Cr[CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C,N] ₂ could be produced. (ortho-Me ₂ NC ₆ H ₄ CH ₂ -к ₂ C,N) Even when 3 equivalents of 2,5-Me ₂ C ₄ H ₂ NH were treated, only 1 equivalent of ₃ Cr reacted to form 2,5-Me ₂ C ₄ H ₂ N-Cr[CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C,N] ₂ was produced.

2 (A) and (B) respectively show 2,5-Me ₂ C ₄ H ₂ N-Cr[CH ₂ C ₆ H ₄ (ortho-NMe) confirmed by X-ray crystallography according to an experimental example of the present application. ₂ )-к ₂ C,N] ₂ and [η ⁵ -2,5-Me ₂ C ₄ H ₂ N-AlMe ₃ ]Cr(Me)CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C ,N] This is a schematic diagram of the structure of ₂ .

Referring to Figure 2, a pyrrolide-N atom and two benzyl-CH ₂ atoms form a trigonal bipyramidal structure forming the basal plane, the two amine nitrogen atoms occupy the axial position, and the Cr atom is almost perfectly aligned with the pyrrolide ring. You can see that they are on the same plane.

Figure 3 is a ¹ H NMR spectrum of a catalyst system according to an experimental example herein. Specifically, 1 of (iBu) ₃ Al and 2,5-Me ₂ C ₄ H ₂ N-Cr[CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C,N] ₂ in C _{6 D} 6 The reactions were reported at :1 molar ratio (A) and 3:1 molar ratio (B).

Referring to Figure 3, for ¹ H NMR study, an equimolar amount of (iBu) ₃ Al was reacted with 2,5-Me ₂ C ₄ H ₂ N-Cr[CH ₂ C ₆ H ₄ (ortho-NMe) of C ₆ D _{6 2} )-к ₂ C,N] ₂ When added to the solution, the characteristic (iBu) ₃ Al signal was not detected. Instead, a very broad signal appeared from 1.0 ppm to 1.7 ppm with no other signals (Figure 3(A)). This means that (iBu) ₃ Al is combined with a paramagnetic Cr complex to form [η ⁵ -2,5-Me ₂ C ₄ H ₂ N-AlMe ₃ ]Cr(Me)CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C,N] Indicates that the creation of ₂ is inferred. When 3.0 eq (iBu) ₃ Al was treated, new signals corresponding to ortho-Me ₂ NC ₆ H ₄ CH ₂ Al(iBu) ₂ , isobutene and isobutane appeared along with a broad signal from 1.0 to 1.7 ppm ( (B) in Figure 3). The reaction was so slow that 3 days were needed for the (iBu) _3Al signal to completely disappear. This observation is consistent with the ortho-dimethyl of [η ⁵ -2,5-Me ₂ C ₄ H ₂ N-AlMe ₃ ]Cr(Me)CH ₂ C ₆ H ₄ (ortho-NMe ₂ )-к ₂ C,N] ₂ The aminobenzyl ligand is paramagnetic [η ⁵ -2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ]Cr(iBu) ₂ (diamagnetic ortho-Me ₂ NC ₆ H ₄ CH ₂ Al(iBu) ₂ (with glass), which means that (iBu) ₃ is slowly replaced by iBu by the activity of Al, from which β-elimination and subsequent reductive elimination reactions occur to produce isobutene and isobutane. TON was lower than that of the best catalyst system Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al under the same conditions.

[Experimental Example 5] Large-scale production of alpha-olefin trimer

Cr(acac) ₃ /[2,5-Me ₂ C 4 H ₂ N-Al(iBu) ₃ ] ^-Na in the catalyst system composed of the chromium compound, pyrrole compound, and aluminum _compound disclosed in Examples 1 to 4 above. The catalyst system of ⁺ /(iBu) ₃ Al showed the best performance in terms of activity and simplicity of preparation.

Under the same amount of catalyst components, the catalyst concentration was gradually reduced by increasing the amount of 1-octene from 10 g to 20, 30, 40, 50, 60 and 100 g, resulting in a TON of 2800 in 24 hours (Example in Table 3 21 ^e ), it gradually increased to 4300, 5200, 5700, 6500, 7500, and 11000, respectively.

Table 4 below shows the results of measuring the change in TON according to reaction time.

[Table 4] TON profile according to reaction time, Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ performed with Al catalyst system The trimerization reaction of 1-octene, 1-decene and 1-dodecene was monitored ^a

^a (iBu) ₃ Al (360 μmol), [2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ (58 μmol) and Cr(acac) ₃ (19 μmol) in succession. Alpha-olefin (0.90 mol; 100, 125 and 150 g for 1-octene, 1-decene and 1-dodecene respectively) was added and stirred at 20°C to 25°C.

Referring to Table 4 above, the increase in TON was insignificant after 2 hours even at the low catalyst concentration of 19 μmol-Cr/100 g of 1-octene (i.e., 0.14 mM-Cr). TON 7570 in 2 hours increased to 11000 in 24 hours. The catalyst system was also active for 1-decene and 1-dodecene, showing slightly higher TON than that observed for 1-octene. For 1-octene, 1-decene, and 1-dodecene, respectively, the TON at 2 hours was 7570, 8310, and 8290, and the TON at 24 hours was 11000, 11500, and 12200. The obtained TON values correspond to activities of 24, 31 and 40 kg/g-Cr for 1-octene, 1-decene and 1-dodecene, respectively.

To evaluate the lubricating properties, trimers of 1-octene, 1-decene, and 1-dodecene and 1-octene/1-dodecene isotrimer were prepared (∼170 g). Since the catalyst was deactivated, the catalyst component (Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ 1:3 molar ratio) was divided into four volumes and each A dose was fed every 8 hours to the reactor containing pure monomer ([monomer]/[total Cr]=11600) and (iBu) ₃ Al (acting as activator and scavenger, [Al]/[total Cr]=7.25). did. Through this method, a monomer conversion rate of 60% to 68% was achieved and 160 g to 170 g of trimer was prepared within a total reaction time of 32 hours. The prepared double bond-containing trimer was hydrogenated under pure conditions without additional solvent using a conventional Pd/C catalyst.

Figure 4 is a ¹ H NMR spectrum of a trimer prepared using a catalyst system according to an example of the present application before and after hydrogenation.

Referring to Figure 4, it can be seen that the vinyl and allyl signals observed in the ¹ H NMR spectrum of the trimer completely disappeared after hydrogenation.

[Experimental Example 5] SimDis GC analysis of alpha-olefin trimer

Figure 5 is a simulated distillation gas chromatography (SimDis GC) graph according to an experimental example herein. Specifically, (A) and the inset of Figure 5 are 1-octene and its hydrogenated form, (B) is 1-decene, (C) is 1-dodecene, and (D) is 1-octene at a 1:1 molar ratio. Octene/1-dodecene isotrimer, (E) is a SimDis GC graph of 1-octene/1-dodecene isotrimer at a 1:2 molar ratio.

Referring to Figure 5, simulated distillation gas chromatography (SimDis GC) analysis indicated that trimers of 1-octene, 1-decene, and 1-dodecene were selectively produced without the formation of other higher or lower fractions. Each trimer fraction was split into three isomeric signals. However, the largest signals seemingly consisted of more than one signal. The intensity ratio of the three isomer signals was 79.9:16.9:3.2. The signal patterns and ratios of the three isomer signals did not change between trimers of 1-octene, 1-decene, and 1-dodecene. SimDis GC analysis of the 1-octene/1-dodecene homotrimer showed four fractions: C ₂₄ H ₄₈ , C ₂₈ H ₅₆ , C ₃₂ H ₆₄ and C ₃₆ H ₇₂ . The intensity ratio of the four fractions was 0.10:0.36:0.40:0.14 for the 1:1 molar ratio 1-octene/1-dodecene isotrimer, which is in good agreement with the statistical integration of each monomer. The molar ratio of the C ₂₄ H ₄₈ , C ₂₈ H ₅₆ , C ₃₂ H ₆₄ and C ₃₆ H ₇₂ fractions calculated based on statistical integration is 0.125: 0.375: 0.375: 0.125 (i.e. 0.5 × 0.5 × 0.5 : 3 × 0.5 × It is converted to a weight ratio of 0.5×0.5 : 3×0.5×0.5×0.5 : 0.5×0.5×0.5). The intensity ratios of the four fractions observed for the 1:2 molar ratio 1-octene/1-dodecene cotrimer were also in good agreement with the ratios calculated based on statistical integration (0.03:0.20:0.45:0.32:0.027: 0.192 : 0.438 : 0). After hydrogenation, the SimDis GC signal pattern changed significantly. Four signals were observed at a ratio of approximately 21:73:3:3 in the elution time sequence, with overlapping second and third signals (inset of Figure 5(A)).

Scheme 2 below shows the isomer distribution of alpha-olefin dimer generated through a metal ring (metallacycle) mechanism.

[Scheme 2]

Referring to Scheme 2, the metal ring mechanism is generally accepted for selective ethylene trimerization, ethylene tetramerization, and alpha-olefin trimerization catalysts. In-depth ¹³ C NMR spectroscopy studies performed using ¹³ C labeled 1-hexene trimers revealed that for the trimers produced with the [trialkyltriazacyclohexane]CrCl ₃ /MAO system, the isomer distribution ranges from 65% to 74% A + B, 16 It was found to be % to 20% C, 4% to 9% D, 3% to 5% E + F and 1% to 4% G + H. The ratio varied depending on the alkyl group of the Cr complex. After hydrogenation, the A + B, C + D, E + F and G + H isomers were converted to four alkane isomers I, J, K and L, respectively. Assuming that the same metal ring mechanism operates in the Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al catalyst system, I, J, We tentatively assigned four signals (approximately 73:21:3:3 ratio) observed in the SimDis GC analysis of the hydrogenated trimer (inset of Figure 5a) to the K and L isomers, respectively. Also, A + B + D + G + H (i.e. 73% I + 4% D + 3% L), C (i.e. 21% J 4% D) and E + F (i.e. 3% K). In particular, the Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al catalyst system has higher C compared to the [trialkyltriazacyclohexane]CrCl ₃ /MAO system. and inhibited the formation of D isomers.

Referring to Figure 4, ¹ H NMR spectrum of the trimer produced by Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al. In , vinyl signals were observed in three well-separated regions, 5.58 ppm to 5.42 ppm, 5.25 ppm to 5.10 ppm, and 4.95 ppm to 4.90 ppm (1.0:0.77:0.77 intensity ratio). The former two regions were assigned to vinylene (-CH=CH-, i.e. A and F to H), while the latter were assigned to vinylidene (H ₂ C=C, i.e. B to E). The intensity of the vinylidene signal was relatively low compared to that observed for the trimer produced with [tri(dodecyl)triazacyclohexane]CrCl ₃ /MAO with an intensity ratio of 1.0:0.86:1.43. The decrease in vinylidene signal intensity suggests that the Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al system leads to the formation of C and D isomers. This supports the previously mentioned suggestion of deterrence. Isomers J (from C and D), which contain two methyl branches, may be less resistant to oxidative degradation than the other isomers I, K and L, which contain one or no methyl branches. Therefore, fluids containing lower amounts of isomer J may serve as better lubricating base oils.

[Experimental Example 6] Lubricant properties

Table 5 below is a table measuring the lubricating properties of hydrogenated alpha-olefin trimers and commercial grade PAOs prepared in accordance with the present disclosure.

[Table 5]

Referring to Table 5, Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ by sharing the same metal ring (metallacycle) mechanism. Lubrication properties of hydrogenated 1-decene trimer produced with Al catalyst system (kinematic viscosity at 40°C (KV ⁴⁰ ), 13.4 cSt; kinematic viscosity at 100°C (KV ¹⁰⁰ ), 3.38 cSt; viscosity index (VI), 128; pour point ( PP), <-60°C, item 1) of Table 5 above is produced with the [trialkyltriazacyclohexane]CrCl ₃ /MAO system (KV ⁴⁰ , 11.8 to 13.8 cSt; KV ¹⁰⁰ , 3.1 to 3.4 cSt; VI, 125 to 137) It was similar to Here, the viscosity index (VI) is an arbitrary, unitless measurement of the change in fluid viscosity, and the higher the VI compared to temperature, the less the viscosity effect due to temperature changes, making it suitable as a lubricant base oil. The lubricant properties were also determined by the ansa-metallocene catalyst Me ₂ Si(tetrahydroindenyl) ₂ ZrCl ₂ /[PhNMe ₂ (H)] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (KV ⁴⁰ , 13.5 cSt; KV ¹⁰⁰ , 3.39 cSt) ; VI, 128; PP, -75°C). Both the hydrogenated 1-decene trimer fractionated from the oligomer produced with (thiophene-fused cyclopentadienyl) ₂ ZrCl ₂ /MMAO and the hydrogenated 1-decene trimer obtained via cationic (BF ₃ catalyzed) oligomerization of 1-decene. It showed slightly higher viscosity than that prepared in this work (KV ⁴⁰ , 15.1 and 15.6 cSt; KV ¹⁰⁰ , 3.70 and 3.7 cSt, VI, 137 and 122, respectively). Commercial grade PAO-4.0, which is mainly 1-decene trimer with a few tetramers and pentamers fractionated on cationic oligomerization, is slightly thicker (KV) with a VI (123) slightly inferior to the as-prepared hydrogenated 1-octene trimer. ⁴⁰ , 17.4 cSt; KV ¹⁰⁰ , 3.93 cSt).

The hydrogenated 1-octene trimer produced by Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N-Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ Al catalyst system is 1-decene. It showed almost the same KV ¹⁰⁰ value as the derived commercial grade PAO-2.5, but the KV ⁴⁰ value and VI value were differentiated. KV and VI values increased with increasing chain length, and the hydrogenated 1-dodecene trimer had high viscosity with high VI. The supply and demand situation for large quantities of 1-decene obtained from fractionation in the full range of ethylene oligomerization processes is tight. Fluids in which 1-decene was replaced with a 1:1 molar ratio of 1-octene/1-dodecene mixture exhibited lubricating properties similar to those obtainable with the hydrogenated 1-decene trimer. Feeding a 1:2 molar ratio of 1-octene/1-dodecene blend resulted in a lubricant base oil exhibiting similar properties to PAO-4.0 with a higher VI.

Although the original Phillips system is inactive toward alpha-olefins, the alpha-olefin trimerization catalyst system according to the present disclosure was developed by modifying the Phillips ethylene trimerization catalyst system. In other words, the catalyst system according to the present invention was active toward alpha-olefins, causing selective production of trimers, and Cr(acac) ₃ /[2,5-Me ₂ C ₄ H ₂ N, which is the optimal catalyst system among several catalyst systems. -Al(iBu) ₃ ] ^- Na ⁺ /(iBu) ₃ The activity of Al could be improved by reducing the catalyst concentration and achieved high values of 11000, 11500 and 12200 for 1-octene, 1-decene and 1-dodecene, respectively. I was able to get a TON. SimDis GC analysis confirmed the selective generation of trimers without any other higher or lower fractions. The hydrogenated 1-decene trimer obtained using the catalyst system according to the invention was less viscous than the commercial product PAO-4.0, which showed advantageously higher VI values. Fluids with lubricating properties similar to the 1-decene trimer were obtained with a 1:1 molar ratio of 1-octene/1-dodecene blend, while PAO-4.0-like fluids were obtained with a 1:2 molar ratio of 1-octene/1-dodecene blend. Obtained as a strong blend.

The description of the present application described above is for illustrative purposes, and those skilled in the art will understand that the present application can be easily modified into other specific forms without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present application is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present application.

Claims (6)

An alpha-olefin trimerization catalyst system comprising a Cr compound represented by the following formula (4) and an Al compound represented by the following formula (3):
[Formula 4]

(In Formula 4, R ⁷ to R ¹¹ are each independently hydrogen or C ₁ -C ₂₀ alkyl)
[Formula 3]
Al(R ⁶ ) ₃
(In Formula 3, R ⁶ is each independently an alkyl of C ₁ -C ₂₀ ).
According to claim 1,
In Formula 4, R ⁷ , R ¹⁰ , and R ¹¹ are methyl groups, R ⁸ and R ⁹ are hydrogen atoms,
In Formula 3, R ⁶ is an isobutyl group,
Alpha-olefin trimerization catalyst system.
comprising contacting the catalyst system according to claim 1 with an alpha-olefin monomer to selectively produce an alpha-olefin trimer.
Method for preparing alpha-olefin trimer.
According to claim 3,
The alpha-olefin monomer includes one selected from the group consisting of 1-octane, 1-decane, 1-dodecane, and combinations thereof,
Method for preparing alpha-olefin trimer.
According to claim 4,
The alpha-olefin monomer includes a mixture of 1-octane and 1-dodecene,
Method for preparing alpha-olefin trimer.
According to claim 3,
The alpha-olefin monomer is used as a monomer for alpha-olefin trimer and as a solvent for the reaction,
Method for preparing alpha-olefin trimer.