KR101095796B1 - Ethylene Tetramerization Catalytst Systems for Immobilization and Process Using the Same - Google Patents

Abstract

The present invention relates to a supported catalyst system for use in the ethylene tetramerization reaction and to an ethylene tetramerization method using the catalyst system, specifically, a hetero atom ligand containing at least one of nitrogen or phosphorus and having a functional substituent, and a transition metal Or a supported ethylene tetramerization catalyst system comprising a transition metal precursor, wherein the functional substituent allows the ethylene tetramerization catalyst system to be easily fixed and supported on a porous support material. The catalyst system can be applied to ethylene tetramerization reaction under various reaction conditions such as heterogeneous system.

Octene, ethylene, tetramerization, dendrimer, silica, alumina, supported, catalyst

Description

Supported ethylene tetramerization catalyst system and ethylene tetramerization method using the same {Ethylene Tetramerization Catalytst Systems for Immobilization and Process Using the Same}

The present invention relates to a supported catalyst system for use in the ethylene tetramerization reaction and an ethylene tetramerization method using the catalyst system. More specifically, the present invention relates to a tetramerization reaction catalyst for synthesizing 1-octene, and to a catalyst system including a heterogeneous hetero atom ligand having a functional substituent for fixing to a support material, and an ethylene tetramerization method using the same.

1-octene is widely used in the production of various chemical products. For example, interfacial-active materials, plasticizers, lubricants and polymers are produced from 1-octene. Another large field of application is the use as comonomers of polymers, in particular polyethylene.

As such, despite the well-known value of 1-octene, much progress has not been made in the industry on successful methods of selectively producing 1-octene by tetramerizing ethylene.

The preparation of the higher alphaolefins necessary for the production of linear low density polyethylene is obtained by oligomerization of ethylene. Ethylene oligomerization is an inefficient aspect in which significant amounts of butenes, other octenes and hexenes isomers, certain higher oligomers and polyethylenes are produced together.

Conventional oligomerization techniques of ethylene provide a wide range of a-olefins depending on the Schulze-Flory or Poisson product distribution. By definition, their mathematical distribution is determined to limit the yield of the desired product. In this connection from the prior art (US Pat. No. 6,184,428) a chelating ligand, preferably 2-diphenyl phosphino benzoic acid (DPPBA), a nickel precursor, preferably NiCl ₂ .6H ₂ O and a catalytically active agent, preferably sodium It is known that nickel catalysts comprising tetraphenylborate catalyze the oligomerization of ethylene to provide a mixture containing 1-octene.

It is also known that chromium-based catalysts containing heteroatom ligands having phosphorus and nitrogen heteroatoms selectively catalyze the ethylene trimerization of 1-hexene. Examples of such hetero atom ligands for ethylene trimerization include bis (2-diethylphosphino-ethyl) amine (WO 03/053891) as well as (o-methoxyphenyl) ₂ PN (methyl) P (o-meth Methoxyphenyl) ₂ (WO 02/04119).

Recently, Sasol Technology Inc. has invented a technique for the high-selective production of octene-1 by the octene production method by ethylene tetramerization. (WO 04/056477, WO 04/056478, WO 04/056479, WO 04/056480, KR Publication 2005/0100600, KR Publication 2006/0002741, KR Publication 2006/0002742)

This suggests that chromium-based catalysts containing mixed heteroatom ligands having both phosphorus and nitrogen heteroatoms often select 1-octene with selectivity in excess of 70% by weight of ethylene without functional substituents on hydrocarbyl or heterohydrocarbyl groups on the phosphorus atom. It is found that it can be tetramerized.

However, the heteroatomic ligands according to the prior art, and the chromium precursor and the aluminoxane, which is a catalyst activating material, could be used only in the formation of a homogeneous system in a solvent, and commercially, a method for achieving ethylene tetramerization under various reaction conditions. However, the situation is not disclosed for a compound capable of realizing this.

An object of the present invention devised to solve the above problems is to provide a supported catalyst system that can be used in reaction conditions such as heterogeneous system (for example, reaction process without using a solvent) in ethylene tetramerization reaction. .

Another object of the present invention is to provide a method for ethylene tetramerization using the supported catalyst system.

The supported ethylene tetramerization catalyst system according to the present invention for achieving the above object is a hetero atom ligand represented by one of the following formulas (1) to (3) and having a functional substituent of X ¹ to X ^{3 that} can be fixed and supported on the porous support material , And

And a transition metal or transition metal precursor.

여기서 X¹ 및 X² 는, 서로 같거나 다르게, 할로겐, 할로겐-함유 알킬, 아마이드, 알킬실릴, 할로겐-함유 실릴, 디페닐실릴 또는 트리페닐실릴이며; X³는 할로겐-함유 알킬렌, 알킬렌-실릴렌(alkylene-silylene), 또는 할로겐-함유 실릴렌이고; 그리고 R¹, R², R³, R⁴ 및 R⁵는, 서로 같거나 다르게, 탄소수 1 내지 6의 알킬 치환체로부터 선택되거나 페닐기이다.

Wherein X ¹ and X ² are the same or different from each other, halogen, halogen-containing alkyl, amide, alkylsilyl, halogen-containing silyl, diphenylsilyl or triphenylsilyl; X ³ is halogen-containing alkylene, alkylene-silylene, or halogen-containing silylene; And R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different from each other or are selected from alkyl substituents having 1 to 6 carbon atoms or are phenyl groups.

delete

On the other hand, the ethylene tetramerization method for achieving another object of the present invention is characterized in that the ethylene tetramerization under heterogeneous conditions using the supported ethylene tetramerization catalyst system.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention is to provide a catalyst system capable of inducing ethylene tetramerization reaction in a variety of reaction conditions, for example, heterogeneous reaction system in the catalytic ethylene tetramerization reaction, the catalyst system according to the present invention is a porous support material A catalyst system comprising a hetero atom ligand having a functional substituent that can be easily fixed is disclosed.

The hetero atom ligand is represented by the following Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, and contains at least one of nitrogen or phosphorus and has a functional substituent.

Formula 1

Formula 2

Formula 3

Wherein X ¹ and X ² are the same or different from each other, halogen, halogen-containing alkyl, amide, alkylsilyl, halogen-containing silyl, diphenylsilyl or triphenylsilyl; X ³ is halogen-containing alkylene, alkylene-silylene, or halogen-containing silylene; And R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different from each other or are selected from alkyl substituents having 1 to 6 carbon atoms or are phenyl groups.

Heteroatom ligands containing nitrogen or phosphorus to which the functional substituents are bonded are prepared by using an ethylene tetramerization catalyst supported by reaction and fixing with functional substituents of these ligands on the surface of the support material, preferably even in a heterogeneous reaction system. Ethylene tetramerization reaction can be carried out.

The functional substituent bonded to the hetero atom ligand represented by Formula 1, Formula 2, or Formula 3 may react with the support material, and may be preferably fixed to the surface thereof as shown in the following Formula 4 or Formula 5.

In addition, the supported ethylene tetramerization catalyst can be provided by impregnating the pores of the support material with heteroatomic ligands and / or metal salts, particularly chromium precursors, in the catalyst system for ethylene tetramerization.

The support material is well developed pores, excellent thermal and mechanical stability, and should have a property of dispersing the active material well, dendrimer, silica, alumina, magnesium oxide, calcium oxide, titanium oxide, zinc oxide, iron oxide, Copper oxide, zirconium oxide and mixtures thereof.

The ethylene tetramerization reaction catalyst according to the present invention is a transition metal catalyst system containing a hetero atom ligand, wherein the hetero atom ligand has at least one of nitrogen or phosphorus and also includes functional substituents for easier support on a support material. .

Although it is possible to be supported on the ligand and the support material without the functional substituent, it is preferable to be supported by the functional substituent to promote the catalytic activity.

The catalyst having the hetero atom ligand and / or the transition metal precursor supported on the support material has an increased active surface area, thereby improving selectivity, and enabling ethylene tetramerization under various reaction conditions.

The supported ethylene tetramerization catalyst system according to the present invention is a catalyst system composed of a transition metal compound and a heterogeneous atomic ligand having a chemical formula of (R) _n ABC (R) _m , and as a form that can be supported on the support material such as a dendrimer. In the hetero atom ligand represented by the above formula, B is a group connecting A and C, and at the same time, a group compound containing a functional group capable of fixing to the support material, and is represented _by (CH ₂ ) _x Y (CH ₂ ) _y . Compound,

Y is the same as or different from each other, -P (R ⁶ _i X)-, -N (R ⁶ _i X)-, As (R ⁶ _i X)-, -Sb (R ⁶ _i X)- X and y are each an integer of 0-5, and R ⁶ is a chain structure connecting the catalyst ligand and the support material, and is the same as or different from each other (-CR ⁷ R ^8- ), (-SiR ⁷ R ^8- ), (-O-SiR ⁷ R ^8- ), phenyl, benzyl, (-CR ⁷ R ⁸ -NH-), and R ⁷ and R ⁸ are the same as or different from each other. With hydrogen, methyl, ethyl, isopropyl, normal propyl, isobutyl, normal butyl, tonyl, phenyl, benzyl, methoxyl, ethoxyl, isopropoxyl, normal propoxyl, isobutoxyl, normal butoxyl, amine and halogen It is selected from the group consisting of, X is a functional structure that connects the dendrimer at the chain end may be selected from hydrogen, halogen.

A and C may be selected from the same or different compounds group consisting of phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium and nitrogen, n and m are determined by the valence and oxidation state of A, C do.

The transition metal that may be used in the ethylene tetramerization reaction catalyst system according to the present invention may include chromium, the transition metal may be derived from a transition metal precursor, and the transition metal precursor is chromium trichloride tritetrahydrofuran chromium complex. A chromium precursor selected from the group consisting of water, (benzene) scacarbonyl chromium, chromoctanoate, chromium acetylacetonate, chromium hexacaboyl or chromium (III) 2-ethylhexanoate can be used.

The chromium precursor may be used in the form impregnated with the support material, and it is possible to use the chromium precursor supported on the support material by calcining at about 500 to 900 ° C, preferably 600 to 900 ° C.

According to the present invention, the supported ethylene tetramerization catalyst system can be used to tetramerize ethylene under heterogeneous conditions, and 1-octene is a representative compound that tetramerizes ethylene.

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Examples, but is not limited thereto.

Preparation Example 1

Synthesis of N, N-Bis (diphenylphosphino) amine

1,1,3,3,3-hexamethyldisilazane (1,1,1,3,3,3-Hexamethyldisilazane) (1.93 ml, 9.2 mmol) was added to a flask containing 30 ml of toluene. At 0 ° C., chloro diphenylphosphine (Chlorodiphenylphosphine) (3.31 ml, 18.4 mmol) was added thereto, raised to room temperature, and refluxed for 3 hours. After reflux, triethylamine was added dropwise at room temperature, triethylamine and chlorotrimethylsilane were distilled, and then toluene was removed. 50 ml of toluene was added to the flask from which the solvent was removed, followed by extraction and recrystallization to obtain N, N-bis (diphenylphosphino) amine (3.2 g 8.3 mmol).

Yield: 91%

¹ H-NMR (C ₆ D ₆ ) delta = 3.04 (s, 1H, N H ), 7.03-7.37 (t, t, d 20H, Ar- H ) ppm.

<References>

H. Noeth and L. Meinel, Z. Anorg. Allg. Chem. 1967, 349, 225

Production Example 2

Synthesis of Lithium-N, N-bis (diphenyl phosphino) amide

N, N-bis (diphenylphosphino) amine (0.74 g, 1.92 mmol) of Preparation Example 1 was added to a flask containing 20 ml of benzene, followed by normal-butyllithium (1.32 ml, 1.6 M in hexane) at room temperature. Was added dropwise and reacted for 30 minutes. After the reaction, the benzene layer was removed, hexane (10 ml x 3 times) was added thereto, and hexane was removed to obtain N, N-bis (diphenylphosphino) lithium amide (0.67 g, 1.71 mmol).

Yield: 89%

<References>

A. Wohlleben-Hammer, Dissertation Techn. Univ. Munich, 1978.

Production Example 3

Synthesis of Trimethylsilyl-N, N-bis (diphenylphosphino) amide

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) of Preparation Example 2 was added to a flask containing 30 ml of tetrahydrofuran, followed by chlorotrimethylsilane (0.63 ml, 4.98 m) at room temperature. Mol) was added dropwise and refluxed (60 ° C.) for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of hexane, and recrystallized to give trimethylsilyl-ene, ene-bis (diphenylphosphino) amide (1.21 g, 2.65 mmol).

Yield: 80%

¹ H-NMR (C ₆ D ₆ ) δ = 0.31 (s, 3H, SiC H ₃ ), 7.01-7.7.6 (t, t, d, 20H, Ar- H ) ppm.

Preparation Example 4

Synthesis of diphenylsilyl-N, N-bis (diphenylphosphino) amide (diphenylsilyl-N, N-bis (diphenylphosphino) amide)

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) of Preparation Example 2 was added to a flask containing 30 ml of tetrahydrofuran, followed by diphenylsilane (0.65 ml, 3.32 m) at room temperature. Mol) was added dropwise and refluxed (60 ° C.) for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of toluene, and recrystallized with toluene / hexane to obtain diphenylsilyl-ene, ene-bis (diphenylphosphino) amide (1.13 g, 2.00 mmol).

Yield: 65%

¹ H-NMR (C ₆ D ₆ ) δ = 5.89 (s, 1H, Si H ), 7.07-7.70 (t, t, d, t, t, d, 30H, Ar- H ) ppm.

Preparation Example 5

Synthesis of dimethylsilyl-N, N-bis (diphenylphosphino) amide

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) of Preparation Example 2 was added to a flask containing 30 ml of tetrahydrofuran, followed by dimethylsilane (0.55 ml, 4.98 mmol) at room temperature. ) Was added dropwise and refluxed (60 ° C.) for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of toluene, and recrystallized with toluene / hexane to obtain dimethylsilyl-ene, ene-bis (diphenylphosphino) amide (1.07 g, 2.42 mmol).

Yield: 73%

¹ H-NMR (C ₆ D ₆ ) δ = 0.30 (s, 6H, SiC H ₃ ), 3.57 (s, 1H, Si H ), 6.95 ~ 7.37 (t, t, d, 20H, Ar- H ) ppm .

Preparation Example 6

Synthesis of Triphenylsilyl-N, N-bis (diphenylphosphino) amide (triphenylsilyl-N, N-bis (diphenylphosphino) amide)

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) of Preparation Example 2 was added to a flask containing 30 ml of tetrahydrofuran, and triphenylsilane (0.98 g, 3.32) was added at room temperature. mmol) was added dropwise and refluxed (60 ° C.) for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of toluene, and recrystallized with toluene / hexane to give triphenylsilyl-ene, ene-bis (diphenylphosphino) amide (1.43 g, 2.22 mmol).

Yield: 67%

¹ H-NMR (C ₆ D ₆ ) delta = 7.04-7.72 (t, t, d, t, t, d, 35H, Ar- H ) ppm.

Preparation Example 7

(N, N-bis- (diphenylphosphino) aminomethyl) dimethylsilyl-en, en-bis (diphenylphosphino) amide ((N, N-Bis- (diphenylphosphino) aminomethyl) dimethylsilyl-N, N- Synthesis of bis (diphenylphosphino) amide)

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) of Preparation Example 2 was added to a flask containing 30 ml of tetrahydrofuran, followed by chloro (chloromethyl) dimethylsilane (0.11) at room temperature. ML, 1.66 mmol) was added dropwise and refluxed at 60 ° C for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of toluene, and recrystallized from toluene / hexane (en, ene-bis- (diphenylphosphino) aminomethyl) dimethylsilyl-ene, ene-bis (diphenylphosphino). ) Amide (0.67 g, 0.80 mmol) was obtained.

Yield: 48%, ¹ H-NMR (C ₆ D ₆ ) δ = 0.30 (s, 6H, SiC H ₃ ), 0.46 (t, 2H, SiC H ₂ ), 7.01 ~ 7.38 (t, t, d, t , t, d, 40H, Ar- H) ppm.

Preparation Example 8

1,1,3,3-tetramethyl-1,3-ene, ene-bis (diphenylphosphino) aminodisiloxane (1,1,3,3-Tetramethyl-1,3-N, N-bis- Synthesis of (diphenylphosphino) amino-disiloxane)

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) was added to a flask containing 30 ml of tetrahydrofuran, and then 1,3-dichloro-1,1,3,3 at room temperature. Tetramethyl-disiloxane (0.32 mL, 1.66 mmol) was added dropwise and refluxed (60 ° C.) for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of toluene, recrystallized with toluene / hexane, and then 1,1,3,3-tetramethyl-1,3-ene, ene-bis (diphenylphosphino) aminodisiloxane (1.19 g, 1.32 mmol) was obtained.

Yield: 80%, ¹ H-NMR (C ₆ D ₆ ) δ = 0.36 (s, 12H, SiC H ₃ ), 6.98-7.69 (t, t, d, 40H, Ar- H ) ppm.

Preparation Example 9

Dimethylvinylsilyl Yen Yen Vis ( Diphenylphosphino ) Amide Synthesis of (Dimethylvinylsilyl-N, N-bis (diphenylphosphino) amide)

Lithium-ene, ene-bis (diphenylphosphino) amide (1.3 g, 3.32 mmol) of Preparation Example 2 was added to a flask containing 30 ml of tetrahydrofuran, followed by dimethyl vinyl silane (0.69 ml, 4.98 m) at room temperature. Mol) was added dropwise and refluxed (60 ° C.) for 3 hours. After the reaction, tetrahydrofuran was removed, extracted with 30 ml of hexane, and recrystallized to obtain dimethylvinylsilyl-ene, ene-bis (diphenylphosphino) amide (1.09 g, 2.32 mmol).

Yield: 70%, ¹ H-NMR (C ₆ D ₆ ) δ = 0.35 (s, 6H, SiC H ₃ ), 5.62 (t, 1H, SiC H ), 5.70 (d, 2H, SiCHC H ₂ ), 7.03 ˜7.63 (t, t, d, 20H, Ar— H ) ppm.

Manufacture example 10-manufacture example 16

Silica Impregnated PNP Ligand

Preparation Example 10 is a 250 ml round bottom flask, which was sufficiently dried and replaced with nitrogen, containing 9.0 g of dried silica (Davison Grace, XPO2412) powder for 24 hours in a vacuum at 200 ° C., dispersed in 60 ml of toluene, and then 20.0 ml. MMAO-7 in Toluene solution of (Akzo Novel, 7.7wt% aluminum, specific gravity 0.88g / ml) was added. After stirring at 40 ° C. for 1 hour, the filtrate was removed, the slurry solid was washed with 200 ml of purified toluene, and the solid was pore dried to obtain fine particles having free flowability.

60 ml of toluene was added thereto, and 0.39 g (1.0 mmol) of PNP ligand (hereinafter referred to as ligand having a P-N-P skeleton) obtained in Production Example 1 was added thereto, and the mixture was uniformly mixed and heated to 70 ° C with stirring for 4 hours. The temperature was lowered again to remove the filtrate, and then washed five times with 100 ml of toluene. The obtained solid was dried in vacuo to obtain a silica-supported PNP ligand substance of microuniform powder with free flowability. The material was analyzed by infrared spectroscopy and metal element analyzer, and the PNP ligand content was 0.051 mmol / g and aluminum content 13.0 wt%.

Preparation Examples 11 to 16 were the same as the preparation method except for the case where 1.0 mmol was added to the functional PNP ligands obtained in Preparation Examples 3 to 8 instead of the ligand of Preparation Example 1. As a result, the PNP ligand content and aluminum content are shown in Table 1, respectively.

PNP and aluminum content of silica impregnated functional PNP ligands         Manufacture example PNP Ligand Content (mmol / g) Al content (wt%)           Preparation Example 10 0.051 13.0           Preparation Example 11 0.035 15.0 Production Example 12             0.042 11.2 Preparation Example 13 0.065 17.3 Preparation Example 14 0.057 13.4 Preparation Example 15 0.043 12.6 Production Example 16 0.055 13.7

Production Example 17

Silica Impregnated Chromium Precursor

In a 250 ml round bottom flask, which had been sufficiently dried and replaced with nitrogen, 9.0 g of powder of silica (Davison Grace, XPO2412) dried at 200 ° C. in a vacuum for 24 hours, dispersed in 60 ml of toluene, and then placed in 20.0 ml of toluene solution. MMAO-7 was added (Akzo Novel, 7.7 wt% aluminum, specific gravity 0.88 g / ml). After stirring at 40 ° C. for 1 hour, the filtrate was removed, the slurry solid was washed with 200 ml of purified toluene, and the solid was pore dried to obtain fine particles having free flowability.

60 ml of toluene was added thereto, and 0.39 g (1.0 mmol) of chromium (III) acetylacetonoate was added thereto, mixed uniformly, and heated to 70 ° C. with stirring for 4 hours. The temperature was lowered again to remove the filtrate, and then washed five times with 100 ml of toluene. The obtained solid was dried in vacuo to obtain a silica-supported PNP ligand substance of microuniform powder with free flowability. The material was analyzed by an elemental analyzer and found to have a chromium content of 0.097 wt%.

Production Example 18

Calcined Silica Supported Chrome Precursors

3.0 g of the silica-supported chromium precursor obtained in Preparation Example 17 was placed in a quartz tube connected with a sintered sintered glass frit and calcined by heating at 700 ° C. for 2 hours. Analysis of the material by an elemental analyzer showed a chromium content of 0.108 wt%.

Production Example 19

Silica-fixed PNP Ligand

In a 250 ml round bottom flask, which had been sufficiently dried and replaced with nitrogen, 9.0 g of a powder of silica (Davison Grace, XPO2412) dried at 200 ° C. and vacuum for 24 hours, dispersed in 60 ml of toluene, and then dimethyl obtained in Preparation Example 9 0.47 g (1.0 mmol) of vinylsilyl-ene, ene-bis (diphenylphosphino) amide ligands were added and mixed uniformly, and then the treatment was the same as in Preparation Example 10. Analysis of the obtained material showed a PNP ligand content of 0.070 mmol / g.

Comparative Preparation Example 1

Synthesis of isopropyl-N, N-bis (diphenylphosphino) amide

(a) Ewart et al, J. Chem. Soc. 1964, 1543; (b) Dossett, SJ et. al, Chem. Comm., 2001, 8, 699; (c) Balakrishna, MS et al, J. Organomet. Chem. A mixed heteroatom PNP ligand was prepared by reacting amine with phosphine R ₂ PCl as disclosed in 1990, 390, 2, 203. Reactive phosphine chloride R ₂ PCl was prepared as described in the literature.

(Casalnuovo, A. L. et al, J. Am. Chem. Soc. 1994, 116, 22, 9869; Rajanbabu, T. V. et al, J. Org. Chem. 1997, 62, 17, 6012).

28 mmol of Chlorodiphenylphosphine was dissolved in 15 ml of Triethylamine in 80 ml of DMC, and 1.11 ml (13 mmol) of Isopoypylamin was added at 0 ° C. The reaction was stirred for 30 minutes and then the ice bath was removed. After stirring for a total of 24 hours, the solution was filtered to remove the triethylammonium salt formed. After crystallization, the product was separated and obtained in 85% yield.

Example 1

Ethylene tetramerization using PNP ligands containing functional groups, chromium (III) acetylacetonoate and MAO

The 300 ml stainless steel reactor was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, followed by addition of MAO 3.0 mmol-Al, and the temperature was raised to 45 ° C. In a glove box, 5.3 mg (0.015 mmol) of chromium (III) acetylacetonoate in 10 ml of toluene was taken in a 50 ml Schlenk container, and (5.8) (phenyl) ₂ PN (hydrogen) P (phenyl) ₂ of Preparation Example 1 0.015 mmol) was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, the liquid contained in the reactor was injected with ethanol mixed with 10 vol% hydrochloric acid. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by FD-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried overnight in a 100 ° C. oven and weighed to yield 0.9 g of polyethylene. GC analysis confirmed that the reaction mixture contained 4.2 g oligomer.

Table 2 shows the results of preparing the ligands of Preparation Examples 3 to 9 instead of the ligand of Preparation Example 1 as described above.

Ethylene tetramerization with PNP ligands containing functional groups Yes Total output
(g) Activity
(Kg / g-Cr) 1-C6
(%) 1-C8
(%) Etc
(%) polymer
(%) Preparation Example 1 (PPh ₂ ) ₂ NH 5.1 3.5 11.0 47.3 24.3 17.5 Preparation Example 3 (PPh ₂ ) ₂ N-SiMe ₃ 25.4 32.6 18.0 58.3 14.0 15.0 Preparation Example 4 (PPh ₂ ) ₂ N-SiPh ₂ H 48.4 62.1 15.0 73.0 4.1 7.9 Preparation Example 5 (PPh ₂ ) ₂ N-SiMe ₂ H 8.5 10.9 5.8 50.7 0.0 36.8 Preparation Example 6 (PPh ₂ ) ₂ N-SiPh ₃ 58.7 75.3 13.6 68.1 16.5 1.4 Preparation Example 7 (PPh ₂ ) ₂ N-SiMe ₃ -N (PPh ₂ ) ₂ 7.1 9.1 5.2 56.3 5.6 32.9 Preparation Example 8 PNP-SiMe ₂ -O-SiMe ₂ -PNP 14.5 18.6 11.5 68.8 4.3 15.4 Preparation Example 9 (PPh ₂ ) ₂ N-SiMe ₂ (C ₂ H ₃ ) 11.2 14.4 5.9 60.0 0.0 10.3 Comparative Production Example 3 (PPh ₂ ) ₂ N-iPr 20.5 26.3 12.3 69.5 13.9 4.5

Example 2

Ethylene tetramerization using silica-impregnated PNP ligand with chromium (III) acetylacetonoate and MAO

The ligand was carried out in the same manner as in Example 1, except that 0.3 g (0.015 mmol) of silica-impregnated PNP ligand of Preparation Example 10 was mixed instead of (phenyl) ₂ PN (hydrogen) P (phenyl) ₂ . Thereafter 0.5 g of polyethylene was obtained and found to contain 9.3 g of oligomer in the reaction mixture. The content of each component in the oligomer was summarized in Table 3 as a result of using the silica impregnated functional ligands of Preparation Examples 11 to 16 in the same manner for the ethylene tetramerization reaction.

Ethylene tetramerization with silica impregnated PNP ligands Yes Total output
(g) Activity
(Kg / g-Cr) 1-C ₆ (%) 1-C ₈ (%) Etc(%) polymer(%) Preparation Example 10 10.8 13.8 11.5 76.3 10.1 2.1 Preparation Example 11 16.3 20.9 23.6 70.3 1.9 4.2 Preparation Example 12 32.5 41.7 12.5 81.5 2.8 3.2 Preparation Example 13 4.3 5.5 7.5 62.3 4.8 25.4 Preparation Example 14 42.3 54.2 17.7 77.3 4.2 0.8 Preparation Example 15 3.2 4.1 10.7 65.0 5.0 19.3 Preparation Example 16 8.2 10.5 16.3 69.5 6.4 7.8

Example 3

Ethylene tetramerization using silica-fixed PNP ligand with chromium (III) acetylacetonoate and MAO

The ligand was carried out in the same manner as in Example 1, except that 0.21 g (0.015 mmol) of the silica-fixed PNP ligand of Preparation Example 19 was mixed instead of (phenyl) ₂ PN (hydrogen) P (phenyl) ₂ . Thereafter 0.5 g of polyethylene was obtained and found to contain 7.5 g of oligomer in the reaction mixture and the content of each component in the oligomer is summarized in Table 4.

Ethylene tetramerization with silica-fixed PNP ligands Yes  Total output (g) Activity (kg / g-Cr) 1-C ₆ (%) 1-C ₈ (%) Etc(%) polymer(%) Preparation Example 19 8.0 10.3 12.5 67.5 13.7 6.3

Example 4

Ethylene tetramerization using PNP ligand and silica-fixed chromium (III) precursor and MAO

The chromium precursor in Example 1 was processed in the same manner except that 0.80 g (0.015 mmol-Cr) of silica-fixed chromium precursor of Preparation Example 17 was mixed instead of chromium (III) acetylacetonoate. Thereafter, 1.13 g of polyethylene including a catalyst residue was obtained, and it was confirmed that the reaction mixture contained 6.32 g of oligomer. The calcined silica-supported chromium precursor of Preparation Example 18 was used for the ethylene tetramerization reaction in the same manner, and the content of each component in the oligomer was summarized in Table 5.

 Ethylene tetramerization with chromium (III) precursors fixed with PNP ligands and silica Yes Total output
(g) Activity
(Kg / g-Cr) 1-C ₆ (%) 1-C ₈ (%)  Etc(%) polymer(%) Production Example 17 6.65 8.5 14.7 70.6 9.7 5.0 Production Example 18 9.5 12.2 15.8 68.5 10.6 5.1

Ethylene tetramerization reaction catalyst according to the present invention is fixed to a porous support material by using a functional substituent to perform the ethylene tetramerization reaction in a homogeneous as well as heterogeneous reaction system of 1-octene under various reaction conditions industrially Makes it possible to obtain.

Claims (8)

A hetero atom ligand represented by one of the following Chemical Formulas 1 to 3, and having a substituent of one of X ¹ to X ³ capable of being firmly supported on the porous support material; And Transition metal or transition metal precursor; Supported ethylene tetramerization catalyst system comprising: [Formula 1]

[Formula 2]

(3)

Wherein X ¹ and X ² are the same or different from each other, halogen, halogen-containing alkyl, amide, alkylsilyl, halogen-containing silyl, diphenylsilyl or triphenylsilyl; X ³ is halogen-containing alkylene, alkylene-silylene, or halogen-containing silylene; And R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different from each other or are selected from alkyl substituents having 1 to 6 carbon atoms or are phenyl groups. The method of claim 1, wherein the porous support material is selected from the group consisting of dendrimers, silica, alumina, magnesium oxide, calcium oxide, titanium oxide, zinc oxide, iron oxide, copper oxide, zirconium oxide and mixtures thereof. Supported ethylene tetramerization catalyst system. The supported ethylene tetramerization catalyst system according to claim 1, wherein the transition metal or transition metal precursor is supported on the support material. The supported ethylene tetramerization catalyst system according to claim 1, wherein the transition metal or transition metal precursor is chromium or chromium precursor. The chromium precursor according to claim 4, wherein the chromium precursor is trichloride tritetrahydrofuran chromium complex, (benzene) samkacarbonyl chromium, chromoctanoate, chromium acetylacetonate, chromium hexacarbonyl or chromium (III) 2-ethylhexa Supported ethylene tetramerization catalyst system, characterized in that it is noate. 3. The supported ethylene tetramerization catalyst system according to claim 2, wherein the porous support material is silica. The ethylene tetramerization method according to any one of claims 1 to 6, wherein the ethylene tetramerization catalyst system according to any one of claims 1 to 6 is used to tetramerize ethylene under heterogeneous conditions using a supported catalyst fixed to the porous support. 8. The method according to claim 7, wherein the compound which tetramerized ethylene is 1-octene.