CATALYST SYSTEM FOR ETHYLENE OLIGOMERIZATION AND METHOD FOR PRODUCING ETHYLENE OLIGOMERIZATION USING THE SAME

Abstract

The present disclosure relates to a catalyst system for ethylene oligomerization and a method for producing ethylene oligomerization using the same and more particularly, to a catalyst system for ethylene oligomerization including a transition metal or transition metal precursor with a new structure, a ligand with a backbone structure expressed by the following Chemical Formula 1 or Chemical Formula 2, and a co-catalyst for providing an ethylene oligomer and a method for producing ethylene oligomerization using the same. [Chemical Formula 1] R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 Herein, R.sup.1, R.sup.2 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, and Y.sup.1 represents a group connecting CO(O). [Chemical Formula 2] R.sup.1OY.sup.2OR.sup.2 Herein, R.sup.1, R.sup.2 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, and Y.sup.2 represents a group connecting O and is a linear, branched, or cyclic alkyl group having 3 or more carbon atoms, or hetero hydrocarbyl, or substituted heterohydrocarbyl. The catalyst system of the present disclosure has an excellent catalytic activity and in the distribution of the produced -olefins, C8-C18 -olefins are highly distributed.

Claims

1. A catalyst system for ethylene oligomerization comprising: a transition metal or transition metal precursor; a ligand with a backbone structure expressed by the following Chemical Formula 1 or Chemical Formula 2; and a co-catalyst:
R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 [Chemical Formula 1] (wherein R.sup.1, R.sup.2 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, and Y.sup.1 represents a group connecting CO(O)), and
R.sup.1OY.sup.2OR.sup.2 [Chemical Formula 2] (wherein R.sup.1, R.sup.2 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, and Y.sup.2 represents a group connecting O and is a linear, branched, or cyclic alkyl group having 3 or more carbon atoms, or hetero hydrocarbyl, or substituted heterohydrocarbyl).

2. The catalyst system for ethylene oligomerization of claim 1, wherein the ligand with a backbone structure expressed by Chemical Formula 1 or Chemical Formula 2 is a diether compound represented by the following General Formula 1,
R.sup.1R.sup.2C(CH.sub.2OR.sup.3)(CH.sub.2OR.sup.4) (1) (wherein R.sup.1 and R.sup.2 are identical or different and represent C 1-C18 alkyl groups, C3-C18 cycloalkyl groups, or C7-C18 aryl radical groups; and R.sup.3 and R.sup.4 are identical or different and represent C1-C4 alkyl radical groups or cyclic or polycyclic groups in which the carbon atom at position 2 contains 2 or 3 unsaturated bonds and which have 5, 6, or 7 carbon atoms), or any one selected from dicarboxylic acid ester compounds represented by the following General Formula 2 to General Formula 6: ##STR00003## (wherein R.sup.1 and R.sup.2 are each independently hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group or alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group or alkyl aryl group having 7 to 20 carbon atoms and are combined to form a cycle, and R.sup.3 and R.sup.4 are each independently a linear or branched alkyl group having 1 to 20 carbon atoms), ##STR00004## (wherein R.sub.1 and R.sub.2 are identical to or different from each other and represent linear, branched, or cyclic alkyl groups or alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or arylalkyl groups or alkylaryl groups having 7 to 20 carbon atoms; and R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are identical to or different from each other and represent hydrogen, linear, branched, or cyclic alkyl groups or alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or arylalkyl groups or alkylaryl groups having 7 to 20 carbon atoms).

3. The catalyst system for ethylene oligomerization of claim 2, wherein the dicarboxylic acid ester of General Formula 2 is any one selected from malonate, succinate, glutarate, pivalate, adipate, sebacate, malate, naphthalene dicarboxylate, trimellitate, benzene-1,2,3-tricarboxylate, pyromellitate, and carbonate.

4. The catalyst system for ethylene oligomerization of claim 3, wherein the dicarboxylic acid ester of General Formula 2 is any one selected from diethyl malonate, dibutyl malonate, dimethyl succinate, diethyl succinate, dinormalpropyl succinate, diisopropyl succinate, 1,1-dimethyl-dimethylsuccinate, 1,1-dimethyl-diethylsuccinate, 1,1-dimethyl-dinormalpropylsuccinate, 1,1-dimethyl-diisopropylsuccinate, 1,2-dimethyl-dimethylsuccinate, 1,2-dimethyl-diethylsuccinate, ethyl-dimethylsuccinate, ethyl-diethylsuccinate, ethyl-dinormalpropylsuccinate, ethyl-diisopropylsuccinate, 1,1-diethyl-dimethylsuccinate, 1,1-diethyl-diethylsuccinate, 1,1-diethyl-dimethylsuccinate, 1,2-diethyl-dimethylsuccinate, 1,2-diethyl-diethylsuccinate, 1,2-diethyl-dinormalpropylsuccinate, 1,2-diethyl-diisopropylsuccinate, normalpropyl-dimethylsuccinate, normalpropyl-diethylsuccinate, normalpropyl-dinormalpropylsuccinate, normalpropyl-diisopropylsuccinate, isopropyl-dimethylsuccinate, isopropyl-diethylsuccinate, isopropyl-dinormalpropylsuccinate, isopropyl-diisopropylsuccinate, 1,2-diisopropyl-dimethylsuccinate, 1,2-diisopropyl-diethylsuccinate, 1,2-diisopropyl-dinormalpropylsuccinate, 1,2-diisopropyl-diisopropylsuccinate, normalbutyl-dimethylsuccinate, normalbutyl-diethylsuccinate, normalbutyl-dinormalpropylsuccinate, normalbutyl-diisopropylsuccinate, isobutyl-dimethyl succinate, isobutyl-diethylsuccinate, isobutyl-dinormalpropylsuccinate, isobutyl-diisopropylsuccinate, 1,2-dinormalbutyl-dimethylsuccinate, 1,2-dinormalbutyl-diethylsuccinate, 1,2-dinormalbutyl-dinormalpropylsuccinate, 1,2-dinormalbutyl-diisopropylsuccinate, 1,2-dinormalbutyl-dimethylsuccinate, 1,2-diisobutyl-dimethylsuccinate, 1,2-diisobutyl-diethylsuccinate, 1,2-diisobutyl-dinormalpropylsuccinate, 1,2-diisobutyl-diisopropylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl malate, di-n-butyl malate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl benzene-1,2,3-tricarboxylate, tributyl benzene-1,2,3-tricarboxylate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

5. The catalyst system for ethylene oligomerization of claim 1, wherein the transition metal or transition metal precursor is chromium or a chromium precursor.

6. The catalyst system for ethylene oligomerization of claim 5, wherein the chromium or chromium precursor is selected from the group consisting of chromium(III)acetylacetonate, chromium trichloride tristetrahydrofuran, and chromium(III)2-ethylhexanoate.

7. The catalyst system for ethylene oligomerization of claim 1, wherein the co-catalyst is methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, or a mixture thereof.

8. The catalyst system for ethylene oligomerization of claim 1, wherein the co-catalyst is a combination of trialkylaluminum and the following borate or boron compound: dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammoniumtetra(pentafluorophenyl)borate, sodiumtetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, H.sup.+(0Et.sub.2)2[(bis-3,5-trifluoromethyl)phenyl]borate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl)boron, trimethylammoniumtetraphenylborate, triethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate, tributylammoniumtetraphenylborate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, aniliniumtetraphenylborate, aniliniumtetrakis(pentafluorophenyl)borate, pyridiniumtetraphenylborate, pyridiniumtetrakis(pentafluorophenyl)borate, ferrocenium tetrakis(pentafluorophenyl)borate, silvertetraphenylborate, silver tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetraphenylphenyl)borane, and tris(3,4,5-trifluorophenyl)borane.

9. A method for producing ethylene oligomerization by bringing an ethylene monomer into contact with a catalyst system for ethylene oligomerization including a transition metal or transition metal precursor, a ligand with a backbone structure expressed by the following Chemical Formula 1 or Chemical Formula 2, and a co-catalyst:
R.sup.1R.sup.2C(CH.sub.2OR.sup.3)(CH.sub.2OR.sup.4) (1) (wherein R.sup.1, R.sup.2 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, and Y.sup.1 represents a group connecting CO(O)), and
R.sup.1OY.sup.2OR.sup.2 [Chemical Formula 2] (wherein R.sup.1, R.sup.2 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, and Y.sup.2 represents a group connecting O and is a linear, branched, or cyclic alkyl group having 3 or more carbon atoms, or hetero hydrocarbyl, or substituted heterohydrocarbyl).

10. The catalyst system for ethylene oligomerization of claim 2, wherein the transition metal or transition metal precursor is chromium or a chromium precursor.

11. The catalyst system for ethylene oligomerization of claim 2, wherein the co-catalyst is methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, or a mixture thereof.

12. The catalyst system for ethylene oligomerization of claim 2, wherein the co-catalyst is a combination of trialkylaluminum and the following borate or boron compound: dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammoniumtetra(pentafluorophenyl)borate, sodiumtetrakis [(bis-3,5-trifluoromethyl)phenyl]borate, H.sup.+(0Et.sub.2)2[(bis-3,5-trifluoromethyl)phenyl]borate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl)boron, trimethylammoniumtetraphenylborate, triethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate, tributylammoniumtetraphenylborate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, aniliniumtetraphenylborate, aniliniumtetrakis(pentafluorophenyl)borate, pyridiniumtetraphenylborate, pyridiniumtetrakis(pentafluorophenyl)borate, ferrocenium tetrakis(pentafluorophenyl)borate, silvertetraphenylborate, silver tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetraphenylphenyl)borane, and tris(3,4,5-trifluorophenyl)borane.

Description

DETAILED DESCRIPTION

[0041] Example embodiments will now be described more fully.

[0042] The illustrative embodiments described in the detailed description and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here.

[0043] [Method for Producing Ethylene Oligomerization]

[0044] The present disclosure provides a method for producing an ethylene oligomer by adding the catalyst for ethylene oligomerization into oligomerization.

[0045] In order for the catalyst system of the present disclosure to express a higher catalytic activity when ethylene oligomerization is carried out, it is preferable to use an appropriate reaction solvent and use components, i.e., procatalyst, co-catalyst, and other additives, required for the catalyst system, under the selected reaction conditions with a composition ratio in a predetermined range. Herein, trimerization may be performed in the slurry phase, liquid phase, gas phase, or bulk phase. If the trimerization is performed in the liquid or slurry phase, a reaction solvent may be used as a medium. As a preferable example of the method for producing an ethylene oligomer, the above-described catalyst (for example, procatalyst, co-catalyst) for ethylene oligomer, ethylene, and a solvent may be added into a reactor to react ethylene in ethylene oligomerization, and, thus, an ethylene oligomer can be produced.

[0046] In preparing the catalyst used in the present disclosure, the amount of the co-catalyst is in the range of generally 0.1 to 20,000, preferably 1 to 4,000, aluminum or boron atoms per chromium atom. If the concentration of each component is out of the above-described range, the catalytic activity may become too low or an undesirable side reaction such as the production of polymer may occur. In the catalyst system used in the present disclosure, the transition metal or transition metal precursor, the R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 or R.sup.1OY.sup.2OR.sup.2 backbone structure ligand and the co-catalyst are added simultaneously or sequentially in arbitrary order into an arbitrary proper solvent in the presence or absence of a monomer, and, thus, an active catalyst can be obtained. For example, the transition metal precursor, the R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 or R.sup.1OY.sup.2OR.sup.2 backbone structure ligand, the co-catalyst, and the monomer may be brought into contact with each other simultaneously, or the transition metal precursor, the R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 or R.sup.1OY.sup.2OR.sup.2 backbone structure ligand and the co-catalyst may be added simultaneously or sequentially in arbitrary order and then brought into contact with the monomer, or the transition metal precursor and the R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 or R.sup.1OY.sup.2OR.sup.2 backbone structure ligand may be added together to form a metal-ligand complex which can be separated and then added to the co-catalyst so as to be brought into contact with the monomer, or the transition metal precursor, the R.sup.1OC(O)Y.sup.1C(O)OR.sup.2 or R.sup.1OY.sup.2OR.sup.2 backbone structure ligand and the co-catalyst may be added together to form a metal-ligand complex which can be separated and then brought into contact with the monomer. Examples of a solvent proper for contact between the components of the catalyst or catalyst system may include hydrocarbon solvents, such as heptane, toluene, 1-hexene, and the like, and polar solvents, such as diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like, but may not be limited thereto.

[0047] The reaction conditions for ethylene oligomerization in the presence of the catalyst of the present disclosure are not particularly limited. For example, a reaction temperature may be in the range of 0 C. to 200 C. and preferably 20 C. to 100 C. and a reaction pressure may be in the range of 1 bar to 100 bar and preferably 5 bar to 70 bar. The duration of the reaction may vary depending on the activity of the catalyst system, and a reaction time of 5 minutes to 3 hours may be applied. Thus, the reaction can be completed effectively.

[0048] Hereinafter, examples of the present disclosure will be described in more detail. However, the following examples are provided to aid in the understanding of the present disclosure, but shall not be construed as limiting the scope of the present disclosure, and various modifications and changes can be made from the following examples without departing from the spirit of the present disclosure.

[0049] [Materials and Analysis Instrument]

[0050] The synthesis reactions described below were performed under an inert atmosphere such as nitrogen or argon using Standard Schlenk and Glove Box techniques.

[0051] Solvents for synthesis such as tetrahydrofuran (THF), normalhexane (n-Hexane), normalpentane (n-Pentane), diethylether, and methylene chloride (CH.sub.2Cl.sub.2) were passed through an activated alumina column to remove moisture and then used as being preserved on an activated molecular sieve.

[0052] Gas chromatography (GC) analysis was performed using an Agilent technologies 7890A GC system under the conditions including a carrier gas of N.sub.2, a carrier gas flow of 2.0 mL/min, a split ratio of 20/l, an initial oven temperature of 50 C., an initial time of 2 min, a ramp of 10 C./min, and a final temperature of 280 C. A column used herein was an HP-5, and ethanol or nonane was quantified to be used as internal standard.

EXAMPLES

[0053] 2,2-diisobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (EP 361,493, page 4), 9,9-bis(methoxymethyl)fluorene (EP728,769, page 12), and diethyl-2,3-diisobutylsuccinate (WO 00/63261) were synthesized by the processes disclosed in the corresponding documents, respectively. Methyl aluminoxane, a 10% w/w solution in toluene, was purchased from Albemarle and the other reagents such as trityl(tetrafluorophenyl)borate and triethyl aluminum were purchased from Aldrich chemical company or Strem chemical company unless otherwise noted.

Example 1

[0054] A 300-ml stainless steel reactor was washed with nitrogen in a vacuum and then 50 ml of toluene was added thereto, and 10.0 mmol-Al MAO was added thereto. Then, the temperature was increased to 65 C.

[0055] CrCl.sub.3(THF).sub.3 (0.02 mmol) and 9,9-bis(methoxymethyl)fluorene (0.02 mmol) were introduced into a Schlenk flask, and 10 ml of methylenechloride was added thereto, and the solution was stirred for 4 hours. Then, the solvent was removed under reduced pressure and the resultant solid was suspended in 20 ml of toluene. A 0.01 mmol toluene solution was taken out and then introduced into the reactor.

[0056] Ethylene was fed into a pressure reactor under a pressure of 32 bar and then stirred at a stirring speed of 600 rpm. After 30 minutes, the supply of ethylene into the reactor was stopped and the stirring was stopped to stop the reaction. The reactor was cooled to lower than 10 C. After the unreacted ethylene within the reactor was discharged, ethanol mixed with 10 vol % of hydrochloric acid was added to the liquid present in the reactor. A small amount of an organic layer sample was passed through anhydrous magnesium sulfate and dried and then analyzed using GC-FID. The remaining organic layer was filtered to separate a solid wax/polymer product therefrom. After the solid product was dried in an oven at a temperature of 100 C. overnight, a polymer was obtained and the weight of the polymer was checked. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Example 2

[0057] The process of Example 1 was performed in the same manner except that 2,2-diisobutyl-1,3-dimethoxy propane (0.02 mmol) was used instead of 9,9-bis(methoxymethyl)fluorene, and the result of GC analysis and the weight of a polymer are given in Table 1.

Example 3

[0058] The process of Example 1 was performed in the same manner except that 2-isobutyl-2-isopentyl-1,3-dimethoxy propane (0.02 mmol) was used instead of 9,9-bis(methoxymethyl)fluorene, and the result of GC analysis and the weight of a polymer are given in Table 1.

Comparative Example 1

[0059] Zirconium tetrachloride (ZrCl.sub.4) (2.5 mmol) was introduced into a Schlenk flask, and 50 ml of toluene was added thereto with stirring. An ethylaluminum sesquichloride solution (10.0 mmol) was added thereto for 30 minutes. Then, the temperature was increased to 80 C. and a reaction was carried out for 30 minutes. Then, the temperature was lowered to room temperature, and the entire solution was used as a catalyst stock solution. A 0.03 mmol toluene solution was taken out and then introduced into the reactor.

[0060] Ethylene was fed into a pressure reactor under a pressure of 32 bar and then stirred at a stirring speed of 600 rpm. After 30 minutes, the supply of ethylene into the reactor was stopped and the stirring was stopped to stop the reaction. The reactor was cooled to lower than 10 C. After the unreacted ethylene within the reactor was discharged, ethanol mixed with 10 vol % of hydrochloric acid was added to the liquid present in the reactor. A small amount of an organic layer sample was passed through anhydrous magnesium sulfate and dried and then analyzed using GC-FID. The remaining organic layer was filtered to separate a solid wax/polymer product therefrom. After the solid product was dried in an oven at a temperature of 100 C. overnight, a polymer was obtained and the weight of the polymer was checked. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Comparative Example 2

[0061] Zirconium tetrachloride (ZrCl.sub.4) (2.5 mmol) was introduced into a Schlenk flask, and 50 ml of toluene was added thereto with stirring. A triethyl aluminum solution (3.9 mmol) was added thereto for 30 minutes with stirring. Then, an ethylaluminum sesquichloride solution (13.6 mmol) was further added thereto for 30 minutes. Then, the temperature was increased to 70 C. and a reaction was carried out for 1 hour. Then, the temperature was lowered to room temperature, and the entire solution was used as a catalyst stock solution. A 0.03 mmol toluene solution was taken out and then introduced into the reactor. Then, oligomerization was carried out in the same manner as in Comparative Example 1. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Comparative Example 3

[0062] Zirconium tetrachloride (ZrCl.sub.4) (0.03 mmol) was introduced into a Schlenk flask, and 5 ml of toluene was added thereto with stirring. N-butanol (0.12 mmol) was added thereto. Then, the temperature was increased to 50 C. and a reaction was carried out for 30 minutes. Then, an ethylaluminum sesquichloride solution (0.12 mmol) was slowly added thereto and stirred for 15 minutes. Then, the temperature was lowered to room temperature, and the entire solution was introduced into the reactor. Then, oligomerization was carried out in the same manner as in Comparative Example 1. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Comparative Example 4

[0063] Tris(2-ethylhexanoate)chromium (Cr(EH).sub.3) (0.03 mmol) was dissolved in toluene (3 mL) and then, 2,5-dimethylpyrrole (0.09 mmol) was added thereto, and the temperature was lowered to 0 C. Then, a triethylaluminum (0.33 mmol) and diethylaluminum chloride (0.24 mmol) solution was slowly added thereto and a reaction was carried out for 1 hour. The entire solution was introduced into the reactor, and oligomerization was carried out in the same manner as in Comparative Example 1. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Comparative Example 5

[0064] Tris(2-ethylhexanoate)chromium (Cr(EH).sub.3) (0.03 mmol) was dissolved in toluene (3 mL) and then, 2,5-dimethylpyrrole (0.09 mmol) was added thereto, and the temperature was lowered to 0 C. Then, an ethylaluminum sesquichloride (0.60 mmol) solution was slowly added thereto and a reaction was carried out for 1 hour. The entire solution was introduced into the reactor, and oligomerization was carried out in the same manner as in Comparative Example 1. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Example 4

[0065] The process of Example 1 was performed in the same manner except that diethyl malonate (0.02 mmol) was used instead of 9,9-bis(methoxymethyl)fluorene, and the result of GC analysis and the weight of a polymer are given in Table 1.

Example 5

[0066] The process of Example 1 was performed in the same manner except that diethyl succinate (0.02 mmol) was used instead of 9,9-bis(methoxymethyl)fluorene, and the result of GC analysis and the weight of a polymer are given in Table 1.

Example 6

[0067] The process of Example 1 was performed in the same manner except that diethyl-2,3-diisobutyl-succinate (0.02 mmol) was used instead of 9,9-bis(methoxymethyl)fluorene, and the result of GC analysis and the weight of a polymer are given in Table 1.

Example 7

[0068] The process of Example 1 was performed in the same manner except that diethyl gultarate (0.02 mmol) was used instead of 9,9-bis(methoxymethyl)fluorene, and the result of GC analysis and the weight of a polymer are given in Table 1.

Example 8

[0069] A 300-ml stainless steel reactor was washed with nitrogen in a vacuum and then 40 ml of toluene was added thereto, and 0.2 mmol-Al triethylaluminum was added thereto. Then, the temperature was increased to 65 C.

[0070] The catalyst (0.01 mmol) of Example 6 was taken out and introduced into the reactor, and trityltetra(pentafluorophenyl)borate (0.05 mmol) was dissolved in 10 ml of toluene and then introduced into the reactor.

[0071] Ethylene was fed into a pressure reactor under a pressure of 32 bar and then stirred at a stirring speed of 600 rpm. After 30 minutes, the supply of ethylene into the reactor was stopped and the stirring was stopped to stop the reaction. The reactor was cooled to lower than 10 C. After the unreacted ethylene within the reactor was discharged, ethanol mixed with 10 vol % of hydrochloric acid was added to the liquid present in the reactor. A small amount of an organic layer sample was passed through anhydrous magnesium sulfate and dried and then analyzed using GC-FID. The remaining organic layer was filtered to separate a solid wax/polymer product therefrom. After the solid product was dried in an oven at a temperature of 100 C. overnight, a polymer was obtained and the weight of the polymer was checked. The oligomer distribution in the reaction mixture obtained via GC analysis is given in Table 1.

Example 9

[0072] The process of Example 7 was performed in the same manner except that trimethyl aluminum (0.2 mmol) was used instead of triethylaluminum, and the result of GC analysis and the weight of a polymer are given in Table 1.

TABLE-US-00001 TABLE 1 Result of oligomerization Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Example 4 Example 5 Activity 62.5 47.2 45 6.7 13.7 1.7 1.52 1.47 (Kg-Olefins/ g-[M]/hr) Oligomer C4 3.6 3.8 3.9 29.8 30.7 18.9 0.7 0.7 Distribution (wt %) C6 18.3 18.1 18.4 20.8 21.0 14.5 90.2 91.2 (wt %) C8 22.1 22.3 22.0 10.2 9.5 10.2 0.3 0.3 (wt %) C10- 40.2 39.8 39.6 28.7 29.3 31.3 4.6 2.6 C18 (wt %) C20+ 12.0 12.3 12.7 6.6 7.3 14.3 (wt %) Polymer (wt %) 3.5 3.3 3.1 3.6 2.1 10.5 3.8 5.1 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Activity 21.1 71.2 166.7 82.3 128.6 118.8 (Kg-Olefins/ g-[M]/hr) Oligomer C4 4.5 3.7 3.5 3.3 3.5 3.2 Distribution (wt %) C6 19.2 19.7 18.6 19.6 18.4 18.9 (wt %) C8 20.3 21.0 21.8 20.9 21.6 22.1 (wt %) C10- 38.9 39.7 41.7 38.9 41.5 40.3 C18 (wt %) C20+ 14.2 13.4 12.1 14.5 12.3 13.3 (wt %) Polymer (wt %) 2.7 2.3 2.1 2.3 2.4 1.9

[0073] As listed in Table 1, it can be seen from the results of oligomerization according to Example 1 to Example 9 of the present disclosure that the novel oligomerization catalyst system of the present disclosure has a high catalytic activity. Further, in the oligomer distribution, C8 (C8 olefin) and C10-C18 olefins are highly distributed. Thus, it can be seen that the novel oligomerization catalyst system of the present disclosure is very useful for C8-C18 -olefins.

[0074] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.