KR101471156B1 - Ethylene oligomerization catalyst systems having enhanced selectivity - Google Patents

Abstract

The present invention relates to a method for improving activity and selectivity of an oligomerization reaction using a terminal functional group-introduced ligand in a catalyst system for ethylene oligomerization comprising a ligand structure having an X-Y-X skeleton and a chromium source.

Description

[0002] Ethylene oligomerization catalyst systems having enhanced selectivity

The present invention relates to a catalyst system for use in the oligomerization reaction of ethylene, such as trimerization of ethylene.

Linear alpha-olefins are widely used commercially as important materials for comonomers, detergents, lubricants, and plasticizers. Especially, 1-hexene and 1-octene are used in the production of linear low density polyethylene (LLDPE) It is widely used as a comonomer for controlling density.

Conventional production processes of LLDPE (linear low-density polyethylene) include forming alpha-olefins, such as alpha-olefins, for example, by forming branches in the polymer backbone with ethylene to control the density 1-hexene, and 1-octene.

Therefore, there is a problem that the cost of the comonomer is a large part of the manufacturing cost for the production of the LLDPE having a high comonomer content. Various attempts have been made to solve these problems.

In addition, since the application fields and the market sizes of the alpha-olefins are different depending on the type, the technology capable of selectively producing a specific olefin is commercially important. However, the conventional ethylene oligomerization reaction has the ineffectiveness of producing a large amount of butene, high-grade oligomer and polyethylene together with 1-hexene and 1-octene. Therefore, recent researches on chromium catalyst technology for producing 1-hexene or 1-octene with high selectivity through selective ethylene oligomerization have been conducted.

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

In addition, a (o- _{ethylphenyl) 2 PN (Me) P (} o- ethyl does not have a polar substituent on at least one of R1, R2, R3 and R4 compound as a ligand which does not exhibit catalytic activity for 1-hexene under catalytic conditions Phenyl) ₂ has been studied ( Chem . Commun . , 2002, 858 ).

However, the ligand of the PNP type skeleton containing the hetero atom of the prior art described above still has a continuing demand for a consistently long-lasting polymerization activity and high selectivity during 1-octene or 1-hexene production.

In order to solve the problems of the prior art as described above, the present invention aims to provide a catalyst system for ethylene oligomerization comprising a ligand in which a functional group is introduced into an atom of X-Y-X skeleton, a chromium source, and a cocatalyst.

Further, an attempt to provide an oligomerization method of ethylene with high polymerization activity and reaction selectivity by using the above catalyst system.

In order to achieve the above object, the present invention provides a ligand represented by the following general formula (1):

Chromium supply; And

The present invention provides a catalyst system for ethylene oligomerization comprising a cocatalyst.

[Chemical Formula 1]

Wherein X is phosphorus, arsenic or antimony,

W is a carbon chain having 0 to 10 carbon atoms,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

Z is nitrogen, oxygen or sulfur,

R ₅ is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group except for hydrogen, and

n is 1 or 2;

The present invention also provides an oligomerization method of ethylene having improved activity and selectivity of the reaction using the catalyst system.

Hereinafter, a catalyst system for oligomerization of selective ethylene according to a specific embodiment of the present invention, a method for producing the same, and a method for oligomerizing ethylene using the catalyst system will be described in detail.

The term "catalyst system" as used herein refers to a catalyst system in which a transition metal, a ligand and a cocatalyst are simultaneously or sequentially added in any order, in any suitable solvent, in the presence or absence of monomers, .

The present invention provides, in one embodiment, a ligand represented by the following general formula (1):

Chromium supply; And

The present invention provides a catalyst system for ethylene oligomerization comprising a cocatalyst.

[Chemical Formula 1]

Wherein X is phosphorus, arsenic or antimony,

W is a carbon chain having 0 to 10 carbon atoms,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

Z is nitrogen, oxygen or sulfur,

R ₅ is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group except for hydrogen, and

n is 1 or 2;

The present inventors have found that the addition of a -WZ (R ₅ ) n group having a terminal functional group to the N atom of the existing (R ₁ ) (R ₂ ) XNX (R ₃ ) (R ₄ ) structure can increase the solubility of the catalyst And thus the polymerization activity was increased in the polymerization reaction and the selectivity was also increased. Thus, the present invention was completed.

Hereinafter, the constituent components of the catalyst system for ethylene oligomerization will be described.

In the ligand having a terminal functional group represented by the general formula (1), X is phosphorus, arsenic, or antimony, preferably phosphorus.

W is a carbon chain having 0 to 10 carbon atoms, preferably a carbon chain having 0 to 5 carbon atoms.

Z is nitrogen, oxygen or sulfur, preferably nitrogen.

R ₁ , R ₂ , R ₃ And R < ₄ > are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group and non-electron donor. These can be non-polar groups. Propyl, propyl, propyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl isopropylphenyl, o-isopropoxyphenyl, cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxyphenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, , Ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, and the like, but are not limited thereto. Preferred are cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot- , o-isopropoxyphenyl. < / RTI >

R ₁ , R ₂ , R ₃ And R < ₄ > may all be aromatic or substituted aromatic groups.

R ₅ is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group except for hydrogen. Selected from the group consisting of alkyl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino or derivatives thereof and optionally substituted aryl .

An example of such a preferable ligand is one having a PNP-type skeleton structure in which an end functional group is introduced as described below, and can be prepared by a conventional method for preparing a ligand.

Preferably, the chromium source according to the above embodiment is a chromium or chromium precursor. Preferably, the chromium or chromium precursor is selected from the group consisting of chromium (III) acetylacetonate, chromium trithiothreitrifluoride, and chromium (III) -2-ethylhexanoate.

And, the ethylene oligomerization catalyst system according to the above embodiment includes a cocatalyst, which is an organometallic compound comprising a Group 13 metal, which can be generally used to polymerize olefins under the catalyst of a transition metal compound Is not particularly limited.

Specifically, the cocatalyst is selected from the group consisting of trimethylaluminum (TMA), triethylaluminum (TEA), tri-isobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride There may be mentioned ethyl aluminum chloride, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, alumoxane, tetrafluoroborate etherate, silver tetrafluoroborate, sodium hexafluoroantimonate, boroxine, NaBH4, trimethylboron, triethyl (Phenyl) borate, triethyltetra (phenyl) borate, triphenylboron, dimethylphenylammonium tetra (pentafluorophenyl) borate, sodium tetrakis [(bis-3,5-trifluoromethyl ) Phenyl] borate, H ⁺ (OEt ₂ ) ₂ [(bis-3,5-trifluoromethyl) phenyl] borate, trityltetra (pentafluorophenyl ) Borate and tris (pentafluorophenyl) boron, and mixtures thereof, but the present invention is not limited thereto. Preferably alumoxane, more preferably methylalumoxane (MAO), which is alkylalumoxane.

The chromium compound and methylalumoxane, which are transition metals, can be used in a blend ratio of aluminum: metal of about 1: 1 to 10,000: 1, preferably about 1: 1 to 3,000: 1.

In order to increase the selectivity to the linear alpha olefin and increase the polymerization activity in the catalyst system comprising the ligand, the organic chromium source, and the cocatalyst represented by the above-mentioned Formula 1 as described above, the ligand: organic chromium Source: The cocatalyst can be present in any ratio from 1: 1: 1 to 10: 1: 10,000, preferably 1: 1: 100 to 5: 1: 3,000. However, the present invention is not limited thereto.

In the catalyst system comprising the ligand, organic chromium source, and cocatalyst represented by the above formula (1), the three components of the catalyst system are added simultaneously or in any order, sequentially in any suitable solvent, with or without a monomer Lt; / RTI > catalyst. Suitable solvents include, but are not limited to, heptane, toluene, 1-hexene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone and the like.

The three components of the catalyst system may be used without being supported, or may be supported on a support material such as silica and alumina. As described above, the present invention is characterized in that the addition of a -WZ (R ₅ ) n group having a terminal functional group to a Y atom having a structure of (R ₁ ) (R ₂ ) XYX (R ₃ ) (R ₄ ) Can be improved. The improvement of the solubility of the catalyst is advantageous in that the supporting efficiency can be enhanced even when the catalyst system is supported on the support.

Using the catalyst system according to the above-described embodiment, it is possible to provide a method of oligomerization of ethylene with improved activity and selectivity of the reaction.

According to another embodiment of the invention there is provided a process for the oligomerization of ethylene which polymerizes ethylene in the presence of a catalyst system comprising a ligand, a chromium source and a cocatalyst,

[Chemical Formula 1]

Wherein X is phosphorus, arsenic or antimony,

W is a carbon chain having 0 to 10 carbon atoms,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

Z is nitrogen, oxygen or sulfur,

R ₅ is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group except for hydrogen, and

n is 1 or 2;

Specific examples and preferred examples of X, W, Z, R ₁ , R ₂ , R ₃ , R ₄ and R _{5 in} the above formula (1) are the same as those described in the catalyst system for ethylene oligomerization according to the above embodiment.

Further, specific examples and preferred examples of the chromium source and the cocatalyst are the same as those described in the catalyst system for ethylene oligomerization according to the above embodiment.

Oligomerization of ethylene can be carried out in the presence of an inert solvent in the presence or absence of an inert solvent using a catalyst system according to the above described embodiments and conventional equipment and contact techniques, a slurry reaction in which the catalyst system is partially or completely dissolved, Phase liquid / liquid reaction, or a bulk phase reaction or gas phase reaction in which the product olefin acts as the main medium.

The oligomerization reaction of ethylene can be carried out in any inert solvent that does not react with the catalyst compound and the activator. Suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene and 1-octene.

The oligomerization reaction of ethylene can be carried out at a temperature of 0 to 150 ° C, preferably 40 to 100 ° C, particularly preferably 50 to 90 ° C. The process according to the invention may also be carried out at a pressure of from 15 to 1500 psig, preferably from 15 to 700 psig.

In the above-described embodiment, 1-hexene or 1-octene can be produced in high activity and high selectivity by oligomerizing ethylene according to the above-described embodiment using another catalyst system.

The present invention provides a chromium catalyst system using the existing _{(R 1) (R 2)} XNX (R 3) (R 4) structure -WZ (R ₅₎ n ligands further introduced into a group with a terminal functionality on the N atom of the Thus, ethylene can be oligomerized with high polymerization activity and selectivity compared to existing catalyst systems.

1 is a photograph showing the dissolution state of a catalyst system containing a ligand prepared according to Comparative Synthesis Example 1 and Synthesis Example 2 of the present invention in toluene.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

Ligand  synthesis

[ Synthetic example  One]

_{PNP2: (C 6 H 5)} 2 PN (NMe 2) P (C 6 H 5) 2

1,1-Dimethylindrazine HCl (1.10 g, 13.5 mmol) and triethylamine (18.75 mL) were added to a flask having 62.5 mL of dichloromethane. Chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added and stirred for 30 min, then chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added again and stirred overnight. The trimethylammonium salt was filtered off and the solvent was removed to give a white solid. And recrystallized with methanol / dichloromethane to finally obtain transparent crystals.

_{1H NMR (CDCl 3): δ} 2.50 (6H, s, N (CH 3) 2), 7.24-7.47 (20H, m, ArH)

13C NMR (CDCl ₃ ): 隆 47.48, 47.55, 47.62 (N (CH ₃ ) ₂ ), 128.87, 127.93, 128.68, 133.19, 133.41, 139.56, 139.70

[ Synthetic example  2]

_{PNP3: (C 6 H 5)} 2 PN (CH 2 CH 2 NMe 2) P (C 6 H 5) 2

N, N-dimethylethylenediamine (1.47 mL, 13.5 mmol) and triethylamine (18.75 mL) were added to a flask having 62.5 mL of dichloromethane. Chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added and stirred for 30 min, then chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added again and stirred overnight. The trimethylammonium salt was filtered off and the solvent was removed. The resulting material was separated via column chromatography (silica gel, ethyl acetate). Finally, it was obtained in liquid form with strong viscosity.

1 H NMR (CDCl ₃ ):? 1.96 (8H, m, CH ₂ N (CH ₃ ) ₂ ), 7.24-7.47 (20H, m, ArH)

_{13C NMR (CDCl 3): δ} 46.58 (N (CH 3) 2), 50.682 (NCH 2), 59.51 (CH 2 NMe 2), 128.03, 128.06, 128.09, 128.75, 132.59, 132.70, 132.81, 139.33, 139.39, 139.45 (ArC)

31 P NMR (CDCl ₃ ): 隆 63.7 (s)

[ Synthetic example  3]

PNP4: ???????? (C ₆ H ₅ ) ₂ PN (CH ₂ CH ₂ NEt ₂ ) P (C ₆ H ₅ ) ₂

N, N-diethylethylenediamine (1.91 mL, 13.5 mmol) and triethylamine (18.75 mL) were added to a flask having 62.5 mL of dichloromethane. Chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added and stirred for 30 min, then chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added again and stirred overnight. The trimethylammonium salt was filtered off and the solvent was removed. The resulting material was dissolved in diethylether, passed through alumina, and then dried to obtain a viscous liquid.

_{1H NMR (CDCl 3): δ} 0.78 (6H, t, N (CH 2 CH 3) 2), 2.12 (2H, t, NCH 2 CH 2 NEt 2), 2.25 (4H, q, N (CH 2 CH 3 _{) 2), 3.42 (2H,} m, N (CH 2), 7.24-7.42 (20H, m, ArH)

_{13C NMR (CDCl 3): δ} 11.88 (N (CH 2 CH 3) 2), 47.34 (N (CH 2 CH 3) 2), 50.91 (NCH 2), 53.33 (CH 2 NMe 2), 128.01, 128.04, 128.07, 128.69, 132.59, 132.70, 132.81, 139.41, 139.54 (ArC)

31 P NMR (CDCl ₃ ): 隆 63.1 (s)

[ Synthetic example  4]

_{PNP5: (C 6 H 5)} 2 PN (CH 2 CH 2 N (iPr) 2) P (C 6 H 5) 2

N, N-Diisopropylethylenediamine (2.24 mL, 12.9 mmol) and triethylamine (18.75 mL) were added to a flask having 62.5 mL of dichloromethane. Chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added and stirred for 30 min, then chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added again and stirred overnight. The trimethylammonium salt was filtered off and the solvent was removed. The resulting material was dissolved in diethyl ether, passed through alumina, and subjected to column chromatography (silica gel, ethyl acetate) to obtain a ligand. The product was obtained in the form of a viscous liquid.

_{1H NMR (CDCl 3): δ} 0.74 (12H, d, N (CH 2 CH 3) 2), 2.18 (2H, t, CH 2 N (iPr) 2), 2.25 (4H, sept, N (CH (CH _{3) 2) 2), 3.30} (2H, m, NCH 2), 7.24-7.42 (20H, m, ArH)

_{13C NMR (CDCl 3): δ} 20.79 (N (CH (CH 3) 2) 2), 46.25 (NCH 2), 48.80 (N (CH (CH 3) 2) 2), 54.12 (CH 2 N (iPr) ₂ ), 127.99, 128.02, 128.05, 128.69, 132.59, 132.70, 132.81, 139.41, 139.54 (ArC)

31 P NMR (CDCl ₃ ): 隆 61.9 (s)

[ Synthetic example  5]

PNP ₆ : (C ₆ H ₅ ) ₂ PN (CH ₂ CH ₂ CH ₂ NMe ₂ ) P (C ₆ H ₅ ) ₂

N, N-dimethyl-1,3-propanediamine (0.65 mL, 5.15 mmol) and 7.5 mL of triethylamine were added to a flask having 30 mL of dichloromethane. Chlorodiphenylphosphine (1 mL, 5.4 mmol) was added and stirred for 30 min, then chlorodiphenylphosphine (1 mL, 5.4 mmol) was added again and stirred overnight. The trimethylammonium salt was filtered off and the solvent was removed. The resulting material was subjected to column chromatography (silica gel, ethyl acetate) to obtain a ligand. The product was obtained in the form of a viscous liquid.

_{1H NMR (CDCl 3): δ} 1.26 (12H, quin, NCH 2 CH 2 CH 2 NMe 2), 1.82 (2H, t, CH 2 NMe 2), 1.84 (6H, s, N (CH 3) 2), _{3.29 (2H, m, NCH 2} ), 7.21-7.39 (20H, m, ArH)

(CDCl ₃ ): 隆 29.26 (NCH ₂ CH ₂ CH ₂ NMe ₂ ), 45.26 (N (CH ₃ ) ₂ ), 51.12 (NCH ₂ ), 57.15 (CH ₂ NMe ₂ ), 128.01, 128.04, 128.70, 132.60, 132.71, 132.82, 139.46, 139.52, 139.58 (ArC)

31 P NMR (CDCl ₃ ): 隆 63.0 (s)

[compare Synthetic example  One]

_{PNP1: (C 6 H 5)} 2 PN (iPr) P (C 6 H 5) 2

To a flask having 62.5 mL of dichloromethane was added isopropylamine (1.16 g, 13.5 mmol) and triethylamine (18.75 mL). Chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added and stirred for 30 min, then chlorodiphenylphosphine (2.5 mL, 13.5 mmol) was added again and stirred overnight. The trimethylammonium salt was filtered off and the solvent was removed to give a white solid. Methanol / dichloromethane to finally obtain a transparent crystal of the following formula (2).

(2)

FIG. 1 is a photograph showing the dissolution state of the catalyst system containing the ligand prepared in Synthesis Example 2 and Comparative Synthesis Example 1 in toluene as a solvent used for ethylene oligomerization. According to FIG. 1, the conventional PNP type catalyst system according to Comparative Synthesis Example 1 did not dissolve in aggregated and dispersed form at all (left image), and the PNP 3 of the present invention according to Synthesis Example 2 dissolves to exhibit a uniform property (Right picture).

Polymerization reaction Oligomerization )

[Example 1]

The Andrew glass was assembled and vacuumed, heated with a torch, and then cooled. Nitrogen was bubbled through and toluene (230 ml) and MAO were injected in succession. Then, 20 μmol (10 mmol of sulrry in toluene, 2 mL) of the ligand and the chromium source solution according to Synthetic Example 2 prepared separately was injected. At this time, the molar ratio of Al / Cr became 600 (10% MAO solution in toluene, 10 mL).

Ethylene was charged at 50 psig and stirred at a stirring speed of 600 rpm. After reacting at 90 DEG C for 1 hour, the ethylene feed was stopped and cooled in ice water. Excess ethylene in the reactor was released and 1 mL of nonene was added as an internal standard. A small sample was taken, water was added and the organic layer was separated. Anhydrous magnesium sulfate was added to remove water and the composition was analyzed by GC. Methanol was added to the remaining organic layer, followed by filtration to obtain a solid product. These solid products are dried in the oven overnight and weighed.

When measuring the activity by weight, the weight was measured before the start of the ethylene supply, and after the reaction, the ethylene was released and the weight was measured to convert the difference into the activity. In this case, only the composition was analyzed by GC without adding the internal standard substance.

[Example 2]

Ligand was used in the same manner as in Example 1, except that PNP2 of Synthesis Example 1 was used.

[Example 3]

Was carried out in the same manner as in Example 1 except that the ligand was the PNP6 of Synthesis Example 5. [

[Comparative Example 1]

Ligand was carried out in the same manner as in Example 1, except that PNP1 of Synthesis Example 1 was used.

The results of Examples 1 to 3 and Comparative Example 1 are shown in Table 1 below.

Ligand Activity
(g / mol Cr / hr) Polyethylene
(wt%) GC Area% 1-This 1-Hx 1-Oc 1-De Example 1 PNP3 520,000 0.60 3.3 24.5 55.9 1.4 Example 2 PNP2 335,000 0.70 3.1 23.7 55.6 1.2 Example 3 PNP6 610,000 0.65 2.4 27.1 50.7 1.9 Comparative Example 1 PNP1 198,000 0.86 16.4 7.7 8.5 12.6

[Example 4]

And the reaction was carried out at 60 ° C for 1 hour.

[Example 5]

Ligand was used in the same manner as in Example 4, except that PNP2 of Synthesis Example 1 was used.

[Example 6]

Ligand was used in the same manner as in Example 4 except that PNP6 of Synthesis Example 5 was used.

 [Comparative Example 2]

Ligand was carried out in the same manner as in Example 4, except that PNP1 of Synthesis Example 1 was used.

The results of Examples 4 to 6 and Comparative Example 2 are shown in Table 2 below.

Ligand Activity
(g / mol Cr / hr) Polyethylene
(wt%) GC Area% 1-This 1-Hx 1-Oc 1-De Example 4 PNP3 463,000 0.90 4.7 25.9 59.8 1.8 Example 5 PNP2 335,000 1.05 5.6 26.3 53.3 1.5 Example 6 PNP6 880,000 1.34 3.1 30.8 55.9 2.5 Comparative Example 2 PNP1 198,000 2.91 10.8  9.4 13.3 15.1

According to the results shown in Tables 1 and 2, compared with Comparative Examples 1 and 2 using the ligands of the existing structure, Examples 1 to 6 exhibited very high polymerization activity and showed selectivity to 1-hexene and 1-octene .

Claims (10)

A ligand represented by the following formula (1);
Chromium supply; And
Catalyst for ethylene oligomerization comprising cocatalyst:
[Chemical Formula 1]

Wherein X is phosphorus, arsenic or antimony,
W is a carbon chain having 0 to 10 carbon atoms,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,
Substituents of the substituted hydrocarbyl group of the substituted hydrocarbyl group of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each methoxy, ethoxy, isopropoxy, alkoxy of 3 to 20 carbon atoms, Thiomorpholino, thiomorpholino, cyano, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, methoxymethoxy, hydroxyl, amino, ≪ RTI ID = 0.0 >
Z is nitrogen, oxygen or sulfur,
R ₅ is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group except for hydrogen, and
n is 1 or 2; The method according to claim 1,
Wherein the chromium source is selected from the group consisting of chromium (III) acetylacetonate, chromium trithrometetrahydrofuran and chromium (III) -2-ethylhexanoate. The method according to claim 1,
The cocatalyst is selected from the group consisting of trimethylaluminum (TMA), triethylaluminum (TEA), tri-isobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum There may be mentioned a metal salt such as chloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, alumoxane, tetrafluoroborate etherate, silver tetrafluoroborate, sodium hexafluoroantimonate, boroxine, NaBH4, trimethylboron, triethylboron, (Phenyl) borate, trimethyltetra (phenyl) borate, triphenylboron, dimethylphenylammoniumtetra (pentafluorophenyl) borate, sodium tetrakis [(bis-3,5-trifluoromethyl) phenyl ] Borate, H + (OEt2) 2 [(bis-3,5-trifluoromethyl) phenyl] borate, trityltetra (pentafluorophenyl) Switch (pentafluorophenyl) boron, and ethylene oligomers for Localization catalyst system is selected from the group consisting of mixtures thereof. The method according to claim 1,
The hydrocarbyl groups of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a methyl, ethyl, ethylenyl, propyl, butyl, cyclohexyl, benzyl, phenyl, tolyl, xylyl, mesityl, Naphthyl, and atarcenyl. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
The heterohydrocarbyl groups of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from the group consisting of methoxy, ethoxy, phenoxy, tolyloxy, xylyloxy, mesityloxy, dimethylamino, diethylamino, methyl Ethylamino, thiomethyl, thiophenyl, trimethylsilyl, and dimethylhydraquinone. delete The method according to claim 1,
Wherein the ligand is _{(C 6 H 5) 2 PN} (NMe 2) P (C 6 H 5) 2, (C 6 H 5) 2 PN (CH 2 CH 2 NMe 2) P (C 6 H 5) 2, ( _{C 6 H 5) 2 PN (} CH 2 CH 2 NEt 2) P (C 6 H 5) 2, (C 6 H 5) 2 PN (CH 2 CH 2 N (iPr) 2) P (C 6 H 5) ₂ , and (C ₆ H ₅ ) ₂ PN (CH ₂ CH ₂ CH ₂ NMe ₂ ) P (C ₆ H ₅ ) ₂ . A process for the oligomerization of ethylene wherein ethylene is polymerized in the presence of the catalyst system of any one of claims 1 to 5. 9. The method of claim 8,
Wherein the polymerization reaction temperature is 40 to 100 占 폚. 9. The method of claim 8,
Wherein the polymerization pressure is from 15 to 700 psig.

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