TRANSITION METAL COMPOUND AND CATALYST COMPOSITION COMPRISING THE SAME

Abstract

Disclosed is a novel transition metal compound that exhibits excellent catalytic activity in polyethylene polymerization and is useful for preparing polyethylene having a high intramolecular short-chain branch content without deteriorating physical properties such as molecular weight, melting point, and density; a catalyst composition comprising the same; and a method for preparing polyethylene using the same.

Claims

1. A transition metal compound represented by Chemical Formula 1: ##STR00027## wherein in Chemical Formula 1, A is a Group 14 element, M is a Group 4 transition metal, R.sup.1 and R.sup.2 are the same as or different from each other, and are each independently hydrogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.1-20 alkylsilyl, C.sub.1-20 silylalkyl, C.sub.1-20 alkoxysilyl, C.sub.1-20 alkoxy, C.sub.6-20 aryl, C.sub.7-20 alkylaryl, or C.sub.7-20 arylalkyl, X.sup.1 and X.sup.2 are the same or different from each other, and are each independently halogen, and Q.sup.1 and Q.sup.2 are the same as or different from each other, and are each independently C.sub.1-20 alkyl.

2. The transition metal compound of claim 1, wherein: A is silicon, and M is zirconium.

3. The transition metal compound of claim 1, wherein: R.sup.1 and R.sup.2 are each hydrogen, phenyl, or phenyl substituted with C.sub.1-6 straight-chain or branched alkyl.

4. The transition metal compound of claim 1, wherein the transition metal compound represented by Chemical Formula 1 is a transition metal compound represented by Chemical Formula 1-1: ##STR00028## wherein in Chemical Formula 1-1, A, M, X.sup.1, X.sup.2, Q.sup.1, and Q.sup.2 are as defined in claim 1; R is the same as or different from each other, and are each independently hydrogen or C.sub.1-6 straight-chain or branched alkyl; and a and b are each independently 0 or 1.

5. The transition metal compound of claim 4, wherein: at least one of R in the Chemical Formula 1-1 is C.sub.3-6 branched alkyl, and the remaining R are each is hydrogen.

6. The transition metal compound of claim 1, wherein: Q.sup.1 and Q.sup.2 are each independently C.sub.1-6 straight-chain or branched alkyl.

7. The transition metal compound of claim 1, wherein: the compound represented by the Chemical Formula 1 is any one selected from the group consisting of the following: ##STR00029## ##STR00030## ##STR00031##

8. A catalyst composition comprising the transition metal compound according to claim 1.

9. The catalyst composition of claim 8, further comprising a support.

10. The catalyst composition of claim 8, which further comprises at least one cocatalyst selected from the group consisting of compounds represented by Chemical Formulas 2 to 4:
[Al(R.sup.21)O].sub.m[Chemical Formula 2] wherein in Chemical Formula 2, R.sup.21 are the same as or different from each other, and are each independently halogen, C.sub.1-20 alkyl or C.sub.1-20 haloalkyl; and m is an integer of 2 or more;
J(R.sup.31).sub.3 [Chemical Formula 3] wherein in Chemical Formula 3, R.sup.31 are the same as or different from each other, and are each independently halogen, C.sub.1-20 alkyl or C.sub.1-20 haloalkyl; and J is aluminum or boron;
[E-H].sup.+[ZQ.sub.4].sup.? or [E].sup.+[ZQ.sub.4].sup.?[Chemical Formula 4] wherein in Chemical Formula 4, E is a neutral or cationic Lewis base, [E-H].sup.+ and [E].sup.+ are each a Bronsted acid; H is a hydrogen atom; Z is a Group 13 element; and Q are the same as or different from each other, and are each independently C.sub.6-20 aryl or C.sub.1-20 alkyl, wherein said C.sub.6-20 aryl or C.sub.1-20 alkyl is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, C.sub.1-20 alkyl, C.sub.1-20 alkoxy and C.sub.6-20 phenoxy.

11. The catalyst composition of claim 8, which further comprises at least one antistatic agent represented by the following Chemical Formula 5:
R.sup.51N(CH.sub.2CH.sub.2OH).sub.2 [Chemical Formula 5] wherein in Chemical Formula 5, R.sup.51 is C.sub.8-30 straight-chain alkyl.

12. A method for preparing polyethylene comprising copolymerizing ethylene and an alpha-olefin in the presence of the catalyst composition of claim 8.

13. The method of claim 12, wherein: the alpha-olefin is at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and mixtures thereof.

14. The method of claim 12, wherein: the ethylene copolymerization has a catalytic activity of 4.0 kg PE/g.Math.cat.Math.hr or more, and the catalytic activity is a value obtained by measuring the weight (kg PE) of polyethylene produced per the weight (g) of the catalyst composition used based on the unit time (h).

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0159] Hereinafter, the actions and effects of the present disclosure will be described in more detail by way of specific examples invention. However, these examples are for illustrative purposes only, and the scope of the present disclosure is not limited thereby.

PREPARATION OF METALLOCENE COMPOUND

SYNTHESIS EXAMPLE 1

[0160] ##STR00008##

[0161] Step 1-1. Preparation of Ligand Compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl indene) Silane

[0162] 15.24 mmol of 2-methyl indene was added to a reactor, and then dried under reduced pressure for 30 minutes. 70 mL of n-hexane and 10 mL of methyl tert-butyl ether (MTBE) were added thereto, and the mixture was stirred and allowed to completely dissolve. The reactor was cooled to ?25? C., and then 6.4 mL (16 mmol) of n-butyllithium (n-BuLi, 2.5 M n-hexane solution) was slowly added dropwise with stirring. The mixture was stirred at 25? C. for 12 hours, and dichlorodimethyl silane (15.24 mmol) was then added thereto.

[0163] 15.24 mmol of 2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene was added to another reactor and then dried under reduced pressure for 30 minutes. 35 mL of MTBE was added thereto, and the mixture was stirred and allowed to completely dissolve. The reactor was cooled to ?25? C., and then 6.4 mL (16 mmol) of n-BuLi (2.5 M n-hexane solution) was slowly added dropwise with stirring. The mixture was stirred at 25? C. for 12 hours, and then CuCN was added and allowed to react for 30 minutes.

[0164] The two reactant products prepared in this way were mixed, and then allowed to react at 25? C. for 12 hours. After adding water and stirring for 1 hour, the reactor was left and then the aqueous layer was separated. Then, water and toluene were again added to the reactor, and stirred and left for 5 minutes, and then the aqueous layer was separated and removed. The organic layer was dehydrated with MgSO.sub.4, filtered again, and added to the reactor, and then dried.

##STR00009##

Step 1-2. Preparation of Transition Metal Compound Dimethyl Silanediyl (2-methyl-1H-inden-1-yl)(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Zirconium Chloride

[0165] The ligand prepared in step 1-1 was dissolved in a mixed solvent (Toluene/Ether, volume ratio 10/1) of 21 mL of toluene and 2.1 mL of diethylether (Et.sub.2O), and cooled to ?25? C., and then 12.8 mL (32 mmol) of n-BuLi (2.5 M n-hexane solution) was slowly added dropwise and stirred. Then, the mixture was stirred at 25? C. for 12 hours, cooled to ?20? C., and then ZrCl.sub.4 (15.24 mmol) was mixed with toluene (0.17 M), and the resulting slurry was added thereto. Then, after stirring at 25? C. for 12 hours, the solvent was completely dried and removed. The reaction mixture was filtered and dried using dichloromethane (DCM), then dichloromethane/hexane was added, and recrystallized at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound as a yellow powder (only racemic) in 20% (molar basis).

[0166] For the transition metal compound thus obtained, NMR data were measured using Bruker AVANCE III HD 500 MHz NMR/PABBO(.sup.1H/.sup.19F/Broad band) probe: .sup.1H, solvent: CDCl.sub.3.

[0167] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.21 (s, 6H), 1.79 (S, 6H), 1.95 (m, 2H), 2.80 (m, 4H), 6.36 (s, 2H), 7.18-7.51 (m, 10H).

SYNTHESIS EXAMPLE 2

[0168] ##STR00010##

Step 2-1. Preparation of Ligand Compound, (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Dimethyl (2-methyl-4-phenyl-indene) Silane

[0169] The ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl-4-phenyl-indene)silane was prepared in the same manner as in step 1-1 of Synthesis Example 1, except that in step 1-1 of Synthesis Example 1, 2-methyl-4-phenyl indene was used instead of 2-methyl indene as a reactant.

Step 2-2. Preparation of Transition Metal Compound Dimethyl Silanediyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(2-methyl-4-phenyl-1H-inden-1-yl) Zirconium Chloride

[0170] The transition metal compound having the above structure, dimethyl silanediyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(2-methyl-4-phenyl-1H-inden-1-yl)zirconium chloride (Synthesis Example 2) was prepared in the same manner as in step 1-2 of Synthesis Example 1, except that the ligand obtained in step 2-1 was used.

[0171] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.22 (s, 6H), 1.81 (S, 6H), 1.98 (m, 2H), 2.81 (m, 4H), 6.35 (s, 2H), 7.18-7.49 (m, 13H), 8.29 (d, 1H).

SYNTHESIS EXAMPLE 3

[0172] ##STR00011##

Step 3-1. Preparation of Ligand Compound (4-(4-(tert-butyl)phenyl)-2-methyl-inden-1-yl)dimethyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene) Silane

[0173] The ligand compound (4-(4-(tert-butyl)phenyl)-2-methyl-inden-1-yl)dimethyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene) silane was prepared in the same manner as in step 1-1 of Synthesis Example 1, except that in step 1-1 of Synthesis Example 1, 4-(4-(tertbutyl)phenyl)-2methyl indene was used instead of 2-methyl indene as a reactant.

Step 3-2. Preparation of Transition Metal Compound Dimethyl Silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Zirconium Chloride

[0174] The transition metal compound having the above structure, dimethyl silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) zirconium chloride (Synthesis Example 3) was prepared in the same manner as in step 1-2 of Synthesis Example 1, except that the ligand obtained in step 3-1 was used.

[0175] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.25 (s, 6H), 1.33 (s, 9H), 1.75 (S, 6H), 1.81 (m, 2H), 2.81 (m, 4H), 6.36 (s, 2H), 7.18-7.39 (m, 12H), 8.21 (d, 1H).

SYNTHESIS EXAMPLE 4

[0176] ##STR00012##

Step 4-1. Preparation of Ligand Compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) Silane

[0177] The ligand compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) silane was prepared in the same manner as in step 3-1 of Synthesis Example 3, except that in step 3-1 of Synthesis Example 3, 2-methyl-4-(4-(tert-butyl)-phenyl)-1,5,6,7-tetrahydro-s-indacene was used instead of 2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene as a reactant.

Step 4-2. Preparation of Transition Metal Compound Dimethyl Silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) Zirconium Chloride

[0178] The transition metal compound having the above structure, dimethyl silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 4) was prepared in the same manner as in step 1-2 of Synthesis Example 1, except that the ligand obtained in step 4-1 was used.

[0179] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.22 (s, 6H), 1.29 (s,18H), 1.75 (S, 6H), 1.81 (m, 2H), 2.81 (m, 4H), 6.36 (s, 2H), 7.18-7.39 (m,11H), 8.21 (d, 1H).

SYNTHESIS EXAMPLE 5

[0180] ##STR00013##

Step 5-1. Preparation of Ligand Compound (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) Silane

[0181] The ligand compound 2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene was prepared in the same manner as in step 3-1 of Synthesis Example 3, except that in step 3-1 of Synthesis Example 3, 2-methyl-1,5,6,7-tetrahydro-s-indacene was used instead of 2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene as a reactant.

Step 5-2. Preparation of Transition Metal Compound Dimethyl Silanediyl (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) Zirconium Chloride

[0182] The transition metal compound having the above structure, dimethyl silanediyl (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 5) was prepared in the same manner as in step 3-2 of Synthesis Example 3, except that the ligand obtained in step 5-1 was used.

[0183] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.22 (s, 6H), 1.23 (s,9H), 1.79 (S, 6H), 2.07 (m, 2H), 2.85 (t,4H), 6.36 (s, 2H), 7.24-7.49 (m, 8H), 8.29 (d, 1H).

SYNTHESIS EXAMPLE 6

[0184] ##STR00014##

Step 6-1. Preparation of Ligand Compound (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Dimethyl (2-methyl indene) Silane

[0185] The ligand compound (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl indene) silane was prepared in the same manner as in step 1-1 of Synthesis Example 1, except that in step 1-1 of Synthesis Example 1, 2-methyl-1,5,6,7-tetrahydro-s-indacene was used instead of 2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene as a reactant.

Step 6-2. Preparation of Transition Metal Compound Dimethyl Silanediyl (2-methyl-1H-inden-1-yl)(2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Zirconium Chloride

[0186] The transition metal compound having the above structure, dimethyl silanediyl (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 6) was prepared in the same manner as in step 1-2 of Synthesis Example 1, except that the ligand obtained in step 6-1 was used.

[0187] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.24 (s, 6H), 1.76 (S, 6H), 2.17 (m, 2H), 2.89 (t,4H), 6.42 (s, 2H), 7.24-7.35 (m,6H).

SYNTHESIS EXAMPLE 7

[0188] ##STR00015##

Step 7-1. Preparation of Ligand Compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) Silane

[0189] The ligand compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) silane was prepared in the same manner as in step 3-1 of Synthesis Example 3, except that in step 4-1 of Synthesis Example 4, dichloro diethyl silane was used instead of dichloro dimethyl silane as a reactant.

Step 7-2. Preparation of Transition Metal Compound Diethyl Silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) Zirconium Chloride

[0190] The transition metal compound having the above structure, Diethyl silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 7) was prepared in the same manner as in step 4-2 of Synthesis Example 4, except that the ligand obtained in step 7-1 was used.

[0191] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.66 (m, 4H), 0.94 (t, 9H), 1.33 (s, 18H), 1.79 (s, 6H), 1.95(m, 2H), 2.83 (m, 4H), 3.36 (s, 2H), 7.3-7.40 (m, 11H), 8.29 (d, 1H).

SYNTHESIS EXAMPLE 8

[0192] ##STR00016##

Step 8-1. Preparation of Ligand Compound (4-(3,5-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(3,5-di-tert-butylphenyl)-2-methyl indene) Silane

[0193] The ligand compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) silane was prepared in the same manner as in step 7-1 of Synthesis Example 7, except that in step 7-1 of Synthesis Example 7, (4-(3,5-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene was used instead of 2-methyl-4-(4-(tert-butyl)-phenyl) -1,5,6,7-tetrahydro-s-indacene as a reactant, and 4-(3,5-di-tert-butylphenyl)-2-methyl-1H-indene was used instead of 4-(4-(tert-butyl)phenyl)-2-methyl indene.

Step 8-2. Preparation of Transition Metal Compound Diethyl Silanediyl (4-(3,5-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(3,5-di-ter-butylphenyl)-2-methyl-1H-inden-1-yl) Zirconium Chloride

[0194] The transition metal compound having the above structure, diethyl silanediyl (4-(3,5-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 8) was prepared in the same manner as in step 7-2 of Synthesis Example 7, except that the ligand obtained in step 8-1 was used.

[0195] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.68 (m, 4H), 0.90 (t, 9H), 1.37 (s, 36H), 1.82 (s, 6H), 1.98 (m, 2H), 2.81 (m, 4H), 3.36 (s, 2H), 7.35 (m, 4H), 7.73 (s,4H), 8.29 (d,1H).

SYNTHESIS EXAMPLE 9

[0196] ##STR00017##

Step 9-1. Preparation of Ligand Compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)methylpropyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) Silane

[0197] The ligand compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)methylpropyl(4-(4-(tert-butyl)phenyl)-2-methyl indene) silane was prepared in the same manner as in step 4-1 of Synthesis Example 4, except that in step 4-1 of Synthesis Example 4, dichloromethylpropylsilane was used instead of dichlorodimethylsilane as a reactant.

Step 9-2. Preparation of Transition Metal Compound Methylpropyl Silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) Zirconium Chloride

[0198] The transition metal compound having the above structure, methylpropyl silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 9) was prepared in the same manner as in step 4-2 of Synthesis Example 4, except that the ligand obtained in step 9-1 was used.

[0199] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.21 (s, 3H), 0.60 (t, 2H), 0.94 (t, 3H), 1.29 (m, 20H), 1.79 (S, 6H), 1.94 (m, 2H), 2.84 (m, 4H), 6.34 (s,1H), 6.36 (s,1H), 7.28-7.39 (m,11H), 7.91 (d, 1H).

COMPARATIVE SYNTHESIS EXAMPLE 1

[0200] ##STR00018##

Step 10-1. Preparation of Ligand Compound

[0201] 0.83 g (5 mmol) of fluorene was added to a dried 250 mL schlenk flask, and 30 mL of diethyl ether was injected under reduced pressure. The ether solution was cooled to ?78? C., the inside of the flask was replaced with argon, and 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. Another 250 mL schlenk flask was filled with 30 mL of ether, and then 2.4 mL (20 mmol) of dichlorodimethylsilane was injected. The flask was cooled to ?78? C., and then a lithiated solution of 2-hexyl-fluorene was injected thereto through a cannula. After the injection was completed, the mixture was slowly raised to room temperature, stirred for about 5 hours, and then ether used as a solvent and the remaining excess dichlorodimethylsilane were removed under vacuum under reduced pressure. A dark red brown solid chloro(9H-fluoren-9-yl)dimethylsilane was obtained in the flask.

[0202] 0.83 g (5 mmol) of fluorene was injected into a dried 100 mL schlenk flask and dissolved in 30 mL of ether. Then, 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise at ?78? C., and the solution was stirred for one day. The previously synthesized chloro(9H-fluoren-9-yl)dimethylsilane was dissolved in 40 mL of ether, and then a lithiated solution of fluorene was added dropwise at ?78? C. The mixture was reacted overnight, and then 50 mL of water was added to the flask and quenched. The organic layer was separated and dried over MgSO.sub.4. The mixture obtained through filtration was carried out by completely removing a solvent under vacuum and reduced pressure conditions, and then recrystallized from hexane to obtain a ligand compound.

[0203] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): ?0.52 (6H, s), 4.26 (2H, s), 7.29 (4H, m), 7.36 (4H, m), 7.53 (4H, m), 7.89 (4H, m)

Step 10-2. Preparation of Transition Metal Compound

[0204] 1.94 g (5 mmol) of the ligand compound synthesized in step 10-1 was added to a dry 250 mL schlenk flask, dissolved in ether, and then 4.4 mL (11 mmol) of 2.5 M nBuLi hexane solution was added and subjected to lithiation. After one day, 1.88 g (5 mmol) of ZrCl.sub.4(THF).sub.2 was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension containing ether.

[0205] After both flasks were cooled to ?78? C., the lithiated ligand compound was slowly added to Zr suspension. After the injection was completed, the reaction mixture was slowly raised to room temperature. After the reaction was allowed to proceed for one day, the mixture was filtered in a filter system that was not in contact with an external air to obtain a metallocene compound.

[0206] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 1.46 (6H, s), 6.99 (4H, m), 7.29 (4H, m), 7.68 (4H, m), 7.9 (4H, m).

COMPARATIVE SYNTHESIS EXAMPLE 2

[0207] ##STR00019##

Step 11-1. Preparation of Ligand Compound

[0208] 1.0 mol of tert-BuO(CH.sub.2).sub.6MgCl solution as a Grignard reagent was obtained from the reaction between the compound tert-BuO(CH.sub.2).sub.6Cl and Mg(0) in a THF solvent. The prepared Grignard compound was added to a flask containing methyl-SiCl.sub.3 compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at ?30? C., and the mixture was stirred at room temperature for at least 8 hours. The filtered solution was vacuum dried to obtain a compound of tert-BuO(CH.sub.2).sub.6SiMeCl.sub.2 (yield 92%).

[0209] Fluorene (3.33 g, 20 mmol), hexane (100 mL) and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) were added to a reactor at ?20? C., and 8 ml of n-BuLi (2.5 M in Hexane) was slowly added thereto and stirred at room temperature for 6 hours to obtain a fluorenyl lithium solution. After completion of the stirring, the reactor temperature was cooled to ?30? C., and the prepared fluorenyl lithium solution was added to a solution of tert-BuO(CH.sub.2).sub.6SiMeCl.sub.2 (2.7 g, 10 mmol) in hexane (100 mL) at ?30? C. over 1 hour. After stirring at room temperature for 8 hours or more, water was added for extraction, and the mixture was evaporated and dried to obtain a compound of (tert-BuO(CH.sub.2).sub.6)MeSi(9-C.sub.13H.sub.10).sub.2 (5.3 g, yield: 100%).

[0210] .sup.1H-NMR(500 MHz, CDCl.sub.3, ppm): ?0.35 (MeSi, 3H, s), 0.26 (SiCH.sub.2, 2H, m), 0.58 (CH.sub.2, 2H, m), 0.95 (CH.sub.2, 4H, m), 1.17 (tert-BuO, 9H, s), 1.29 (CH.sub.2, 2H, m), 3.21 (tert-BuOCH.sub.2, 2H, t), 4.10 (Flu-9H, 2H, s), 7.25 (Flu-H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

Step 11-2. Preparation of Transition Metal Compound

[0211] 4.8 mL of n-BuLi(2.5 M in Hexane) was slowly added to (tert-BuO(CH.sub.2).sub.6)MeSi(9-C.sub.13H.sub.10).sub.2 (3.18 g, 6 mmol)/MTBE(20 mL) solution prepared in step 11-1 at ?20? C., and the mixture was reacted for at least 8 hours while raising to room temperature to prepare a slurry solution of dilithium salts. The prepared dilithium salt slurry solution was slowly added to a slurry solution of ZrCl.sub.4(THF).sub.2 (2.26 g, 6 mmol)/hexane (20 mL) at ?20? C., and then further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to obtain (tert-BuO(CH.sub.2).sub.6)MeSi(9-C.sub.13H.sub.9).sub.2ZrCl.sub.2 compound as a red solid (4.3 g, yield: 94.5%).

[0212] .sup.1H-NMR(500 MHz, C.sub.6D.sub.6, ppm): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH.sub.2, 2H, m), 1.66 (CH.sub.2, 4H, m), 1.91 (CH.sub.2, 4H, m), 3.32 (tert-BuOCH.sub.2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15 (Flu-H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64 (Flu-H, 2H, d), 7.77 (Flu-H, 2H, d).

COMPARATIVE SYNTHESIS EXAMPLE 3

[0213] ##STR00020##

Step 12-1. Preparation of Ligand 8-(4-(tert-butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

[0214] 8-Bromo-6-methyl-1,2,3,5-tetrahydro-s-indacene (35 mmol, 9.8 g), (4-(tert-butyl)phenyl)boronic acid (70 mmol, 12.5 g), sodium carbonate (87.50 mmol, 9.3 g), and tetrakistriphenylphosphine palladium(1.80 mmol, 2 g) were added to 250 mL RBF, to which toluene (35 mL), ethanol (18 mL), and water (1 mL) were added. Then, the mixture was stirred in an oil bath preheated to 90? C. for 16 hours. The extent to which the reaction proceeded was confirmed by NMR, and if the reaction was less proceeded, the reaction was further carried out for 16 hours, or the reactants excluding indacene and the solvent were additionally formulated according to the amount of the remaining indacene, and then reacted for 16 hours. When the reaction is completed, all ethanol was removed from the rotary evaporator, and worked up with water and hexane. The organic layer was collected and dried over MgSO.sub.4, and all solvents were removed. The crude mixture from which the solvent was removed was subjected to silica gel short column to remove black impurities. Again, all solvents were removed and methanol was added to form a solid. The resulting solid was filtered and washed with methanol to obtain a ligand of the following structure, 8-(4-(tent-butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (8.5 g, 80% , white solid).

##STR00021##

[0215] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 7.44?7.31 (m, 4H), 7.12 (s, 1H), 6.47 (s, 1H), 3.19 (s, 2H), 2.97 (t, 2H), 2.09?2.02 (m, 5H), 1.38 (s, 9H).

Step 12-2. Preparation of Ligand Compound (6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)Silane

[0216] 4-(4-(tent-butyl)phenyl)-2-methyl-1H-indene (19 mmol, 5 g) was added to a 100 mL Schlenk flask to make an argon atmosphere. When the argon atmosphere was made, anhydrous hexane (66 mL) and anhydrous MTBE (13 mL) were added, and the mixture was cooled to ?25? C. n-BuLi (2.5 M in Hexane, 21 mmol, 8.4 mL) was slowly injected, and after the injection was completed, the temperature was raised to room temperature and the mixture was stirred for 3 hours. After completion of the stirring, the mixture was cooled to ?25? C. again, and tether silane (15.20 mmol, 4.1 g) was injected into the flask with one shot, and slowly filtered at room temperature to remove LiCl, and then the solvent was dried to prepare (6-(tert-butoxy) hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)chloro(methyl)silane

[0217] Then, 8-(4-(tent-butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (19 mmol, 5.75 g) obtained in step 12-1 and CuCN (0.95 mmol, 0.09 g) were added to another 100 mL Schlenk flask to made an argon atmosphere. When the argon atmosphere was made, anhydrous MTBE (48 mL) was added thereto, and the mixture was cooled to ?25? C. n-BuLi (2.5 M in Hexane, 21 mmol, 8.4 mL) was slowly injected, and when the injection was completed, the temperature was raised to room temperature and the mixture was stirred for 3 hours. After completion of the stirring, the mixture was cooled to ?25? C. again, and the previously synthesized (6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)chloro(methyl)silane was injected into the flask with one shot. Then, the temperature was slowly raised to room temperature and the mixture was stirred for 16 hours. The resultant was purified by silica gel column to obtain a ligand compound of the following structure, (6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)silane (10.87 mmol, 8.30 g, 57%, light yellow solid).

##STR00022##

[0218] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 7.78?7.41 (m, 6H), 7.34?7.31 (m, 3H), 7.28?7.12 (m, 2H), 6.84?6.80 (m, 1H), 6.56?6.54 (m, 1H), 3.77?3.60 (m, 2H), 3.27?3.23 (t, 2H), 2.97?2.81 (m, 4H), 2.20?2.09 (m, 6H), 2.04?2.02 (m, 2H), 1.39?1.38 (m, 18H), 1.15 (s, 9H), 1.52?0.43 (m, 10H), 0.02?0.15 (m, 3H).

Step 12-3. Preparation of Transition Metal Compound (6-(tert-butoxy)hexyl)(methyl)silanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)Zirconium Dichloride

[0219] (6-(Tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methypsilane ligand (2.62 mmol, 2 g) obtained in step 12-2 was added to a 50 mL Schlenk flask to make an argon atmosphere. When the argon atmosphere was made, anhydrous diethyl ether (52.4 mL) was added and cooled to ?25? C. n-BuLi (2.5 M in Hexane, 5.76 mmol, 2.3 mL) was slowly injected, and when the injection was completed, the temperature was raised to room temperature and the mixture was stirred for 3 hours. After completion of the stirring, the Schlenk flask under argon containing this solution and ZrCl.sub.42(THF) (2.62 mmol, 1.0 g) was cooled to ?78? C., and the ligand solution was transferred to a flask containing zirconium at low temperature. After slowly raising the temperature to room temperature, the mixture was stirred for 16 hours. After completion of the stirring, the resulting solid was filtered off under argon atmosphere, and the solvent was dried to obtain a crude mixture. This was dissolved in a minimum amount of anhydrous toluene and stored at ?25? C. to ?30? C. to form a solid. The resulting solid was liberated by adding an excess of hexane when it was in a low temperature state, and then filtered and collected. Then, the obtained solid was dried and purified to obtain a catalyst compound, that is, a transition metal compound (6-(tert-butoxy)hexyl)(methypsilanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium dichloride (0.49 mmol, 0.45 g, 19%, yellow solid).

[0220] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 7.48?7.46 (m, 3H), 7.42?7.40 (m, 5H), 7.25?7.23 (m, 2H), 7.18?7.16 (m, 2H), 6.69 (s, 1H), 3.38?3.35 (t, 2H), 3.01?2.79 (m, 4H), 2.35 (s, 3H), 2.21 (s, 3H), 2.03?1.94 (m, 2H), 1.88?1.35 (m, 10H), 1.15 (s, 9H), 1.33 (s, 18H), 1.19 (s, 9H), 1.16?1.12 (m, 3H).

COMPARATIVE SYNTHESIS EXAMPLE 4

[0221] ##STR00023##

Step 13-1. Preparation of Ligand Compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4-(tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl indene) Silane

[0222] The ligand compound (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4-(tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl indene) silane was prepared in the same manner as in step 3-1 of Synthesis Example 3, except that in step 4-1 of Synthesis Example 4, 4-(4-(tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl indene was used instead of 4-(4-(tert-butyl)phenyl)-2-methyl indene as a reactant.

Step 13-2. Preparation of Transition Metal Compound Dimethyl Silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl-1H-inden-1-yl) Zirconium Chloride

[0223] The transition metal compound having the above structure, dimethyl silanediyl (4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Comparative Synthesis Example 4) was prepared in the same manner as in step 4-2 of Synthesis Example 4, except that the ligand obtained in step 13-1 was used.

[0224] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.23 (s, 6H), 1.29 (s,18H), 1.41 (s, 9H), 1.76 (S, 6H), 1.92 (m, 2H), 2.80 (m, 4H), 3.85 (s, 3H), 6.36 (s, 2H), 7.28-7.36 (m,9H), 7.58 (s, 1H).

COMPARATIVE SYNTHESIS EXAMPLE 5

[0225] ##STR00024##

Step 14-1. Preparation of Ligand Compound (4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Dimethyl Indene Silane

[0226] The ligand compound (4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl indene silane was prepared in the same manner as in step 1-1 of Synthesis Example 1, except that in step 1-1 of Synthesis Example 1, indene was used instead of 2-methyl indene as a reactant, and 4-phenyl-1,5,6,7-tetrahydro-s-indacene was used instead of 2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene.

Step 14-2. Preparation of Transition Metal Compound Dimethyl Silanediyl(4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1H-inden-1-yl) Zirconium Chloride

[0227] The transition metal compound having the above structure, Dimethyl Silanediyl(4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1H-inden-1-yl) zirconium chloride (Comparative Synthesis Example 5) was prepared in the same manner as in step 1-2 of Synthesis Example 1, except that the ligand obtained in step 14-1 was used.

[0228] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.22 (s, 6H), 1.96 (m, 2H), 2.83 (m, 4H), 6.36 (d, 2H), 6.58 (d, 2H), 7.18-7.50 (m, 10H).

COMPARATIVE SYNTHESIS EXAMPLE 6

[0229] ##STR00025##

[0230] The transition metal compound having the above structure, 1,1-dimethylsilylene-bis[2-methyl-4-(4-tert-butylphenyl)-5,6,7-trihydro-s-indacen-1-yl]} zirconium dichloride (Comparative Synthesis Example 6) was prepared as disclosed in PCT Patent Application Publication WO 2006-097497 A1.

COMPARATIVE SYNTHESIS EXAMPLE 7

[0231] ##STR00026##

Step 15-1. Preparation of Ligand Compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Dimethyl Cyclopentadienyl Silane

[0232] The ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl cyclopentadienyl silane was prepared in the same manner as in step 1-1 of Synthesis Example 1, except that in step 1-1 of Synthesis Example 1, sodium cyclopentadienyl (sodium Cp, Na cyclopentadiene) in THF (1.0 M) was used instead of 2-methyl indene Li Salt solution as a reactant.

Step 15-2. Preparation of Transition Metal Compound Dimethyl Silanediyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclopentadienyl) Zirconium Chloride

[0233] The transition metal compound having the above structure, dimethyl Silanediyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclopentadienyl) zirconium chloride (Comparative Synthesis Example 7) was prepared in the same manner as in step 1-2 of Synthesis Example 1, except that the ligand obtained in step 15-1 was used.

[0234] .sup.1H-NMR (500 MHz, CDCl.sub.3, ppm): 0.22 (s, 6H), 1.80 (S, 3H), 1.98 (m, 2H), 2.80 (m, 4H), 6.35 (d, 2H), 6.41 (s, 1H), 6.50 (d, 2H), 7.41-7.46 (m, 6H).

Preparation Of Supported Catalyst

Preparation Example 1

[0235] 50 mL of toluene was added to a pico reactor, to which 7 g of silica gel (SYLOPOL 952X, calcinated under 250? C.) was added under Ar, and 10 mmol of methylaluminoxane (MAO) was slowly injected at room temperature, and the mixture was reacted with stirring at 95? C. for 24 hours. After completion of the reaction, the mixture was cooled to room temperature and left for 15 minutes, and the solvent was decanted using a cannula. Toluene (400 mL) was added thereto, and the mixture was stirred for 1 minute and left for 15 minutes, and the solvent was decanted using a cannula.

[0236] 60 ?mol of the metallocene compound of Synthesis Example 1 was dissolved in 30 mL of toluene, and then transferred to a reactor using a cannula. The mixture was reacted with stirring at 80? C. for 2 hours. After the reaction was completed and the precipitation was completed, the reaction mixture was cooled to room temperature and left for 15 minutes. The upper layer solution was removed and the remaining reaction product was washed with toluene. After washing again with hexane, 2 wt % of an antistatic agent, N,N-bis(2-hydroxyethyl)pentadecylamine (Atmer 163), based on silica weight (g), was dissolved in 3 mL of hexane based on silica weight (g), and added thereto, and then the mixture was stirred at room temperature for 10 minutes. After the reaction was completed and the precipitation was completed, the upper layer was removed and transferred to a glass filter to remove the solvent.

[0237] The resultant was subjected to a primary drying at room temperature for 5 hours under vacuum, and to a secondary drying at 45? C. for 4 hours under vacuum to obtain a silica-supported metallocene catalyst in the form of solid particles.

Preparation Examples 2 to 9

[0238] The silica-supported metallocene catalyst in the form of solid particles was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Synthesis Examples 2 to 9 were respectively used instead of the metallocene compound of Synthesis Example 1.

Comparative Preparation Examples 1 to 7

[0239] The silica-supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Examples 1 to 7 were respectively used instead of the metallocene compound of Synthesis Example 1.

Polyethylene Polymerization

Example 1

[0240] An ethylene-1-hexene copolymer was prepared in the presence of the supported catalyst obtained in Preparation Example 1, and the specific method is as follows.

[0241] A 600 mL stainless steel reactor was vacuum dried at 120? C. and then cooled. 1 g of trimethylaluminum (TMA) was added to 250 g of hexane at room temperature, and the mixture was stirred for 10 minutes. After removing all the reacted hexane, 250 g of hexane and 0.5 g of triisobutylaluminum (TIBAL) were added thereto, and the mixture was stirred for 5 minutes. Then, 7 mg of the supported catalyst obtained in Preparation Example 1 was added thereto and then stirred while raising the temperature to 70? C. After stopping the stirring at 70? C., 10 mL of 1-hexene (C6) as a comonomer was added, and ethylene (ethylene, C2) was filled up to 30 bar, and then stirring was started. After the polymerization for 30 minutes, unreacted C2 was vented.

Examples 2 to 9

[0242] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalysts of Preparation Examples 2 to 9 were respectively used instead of the supported catalyst of Preparation Example 1.

Comparative Example 1

[0243] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 1 was used instead of the supported catalyst of Preparation Example 1.

Comparative Examples 2 and 3

[0244] An ethylene-1-hexene copolymer was prepared in the same manner as in Comparative Example 1, except that the addition amount of 1-hexene (C6) as a comonomer was changed to 20 mL (Comparative Example 2) and 25 mL (Comparative Example 3), respectively.

Comparative Example 4

[0245] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 2 was used instead of the supported catalyst of Preparation Example 1.

[0246] Comparative Examples 5 and 6

[0247] An ethylene-1-hexene copolymer was prepared in the same manner as in Comparative Example 4, except that the addition amount of 1-hexene (C6) as a comonomer was changed to 20 mL (Comparative Example 5) and 25 mL (Comparative Example 6), respectively.

Comparative Example 7

[0248] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 3 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 8

[0249] An ethylene-1-hexene copolymer was prepared in the same manner as in Comparative Example 7, except that the addition amount of 1-hexene (C6) as a comonomer was changed to 20 mL.

Comparative Example 9

[0250] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 4 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 10

[0251] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 5 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 11

[0252] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 6 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 12

[0253] An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 7 was used instead of the supported catalyst of Preparation Example 1.

Test Example: Polyethylene Polymerization Process and Physical Property Evaluation

[0254] The catalytic activity, process stability and physical properties of the polyethylene copolymer of the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

(1) Catalytic Activity (kg PE/g cat.Math.hr)

[0255] It was calculated as the ratio of the weight (kg PE) of the polyethylene copolymer produced per unit time (h) per the supported catalyst content (g Cat) used per unit time (h).

(2) Melting Point (Tm, ? C.)

[0256] Tm was measured using a differential scanning calorimeter (DSC).

[0257] Specifically, the melting temperature of the polymer was measured using a DSC 2920 (TA instrument) as a differential scanning calorimeter (DSC). Specifically, the polymer was heated to 150? C. and held for 5 minutes, then and the temperature was lowered to ?100? C. and then increased again. At this time, the speed of a temperature rise and drop was adjusted to 10? C./min, respectively. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature rises.

(3) Weight Average Molecular Weight (Mw, g/mol)

[0258] The weight average molecular weight (Mw) of the polyethylene copolymer was measured using gel permeation chromatography (GPC, manufactured by Water).

[0259] Specifically, a Waters PL-GPC220 instrument was used as the gel permeation chromatography (GPC) instrument, and a Polymer Laboratories PLgel MIX-B 300 mm length column was used. In this case, an evaluation temperature was 160? C., and 1,2,4-trichlorobenzene was used for a solvent at a flow rate of 1 mL/min. Each polyethylene sample was pretreated by dissolving it in 1,2,4-trichlorobenzene containing 0.0125% of BHT at 160? C. for 10 hours using a GPC analyzer (PL-GP220), and the sample was prepared at a concentration of 10 mg/10 mL and then supplied in an amount of 200 ?L. The values of Mw and Mn were obtained using a calibration curve formed using a polystyrene standard. 9 kinds of the polystyrene standard were used with the molecular weight of 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g/mol.

(4) Number of Short Chain Branches (SCB, FT-IR)

[0260] With respect to the polyethylene copolymers of Examples and Comparative Examples, the number of short chain branches (SCB) (content of branches having 2 to 7 carbon atoms per 1000 carbons) was measured by infrared spectroscopy (FT-IR).

[0261] Specifically, the polyethylene copolymer sample was pretreated by dissolving it in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160? C. for 10 hours using PL-SP260VS, and then measured using PerkinElmer Spectrum 100 FT-IR connected with high temperature GPC (PL-GPC220) at 160? C.

(5) Evaluation of Morphology of Polymers

[0262] With respect to the polyethylene copolymers of Examples and Comparative Examples, the appearance and touch of the obtained copolymer powder were visually and tactilely confirmed, and the morphology of the polymer was evaluated.

[0263] Specifically, after drying all the obtained powders under the same conditions, the morphology of the polymer is evaluated as very good if particles are scattered like sand grains and the grains maintain their original shape. The morphology of the polymer is evaluated as good if particles are scattered like sand grains, but there are particles where the grains aggregate like a snowman. The morphology of the polymer is evaluated as bad if particles are entangled in a lump rather than sand grains. In particular, when the morphology of the polyethylene copolymer is poor, it may be difficult to put into the gas phase polymerization reaction for the production of linear low-density polyethylene.

TABLE-US-00001 TABLE 1 Amount Activity of C6 (kg PE/g .Math. Mw Tm SCB Morphology Compound used (mL) cat .Math. hr) (?10.sup.3 g/mol) (? C.) (Number/1000 C) Evaluation Example 1 Synthesis 10 4.5 530 123.5 5.2 very Example 1 good Example 2 Synthesis 10 5.1 400 124.2 5.0 very Example 2 good Example 3 Synthesis 10 6.2 480 121.5 5.8 very Example 3 good Example 4 Synthesis 10 5.9 450 118.5 6.5 very Example 4 good Example 5 Synthesis 10 5.2 480 124.5 5.2 very Example 5 good Example 6 Synthesis 10 6.0 460 125.7 4.5 very Example 6 good Example 7 Synthesis 10 6.7 450 117.2 6.8 very Example 7 good Example 8 Synthesis 10 5.5 580 121.8 5.8 very Example 8 good Example 9 Synthesis 10 6.0 480 121.6 5.9 very Example 9 good Comparative Comparative 10 3.2 450 127.7 2.2 good Example 1 Synthesis Example 1 Comparative Comparative 20 2.9 380 124.1 3.9 bad Example 2 Synthesis Example 1 Comparative Comparative 25 unmeasurable unmeasurable unmeasurable unmeasurable Example 3 Synthesis (Fouling) Example 1 Comparative Comparative 10 2.7 400 128.4 1.9 good Example 4 Synthesis Example 2 Comparative Comparative 20 3.0 350 125.8 2.9 bad Example 5 Synthesis Example 2 Comparative Comparative 25 unmeasurable unmeasurable unmeasurable unmeasurable Example 6 Synthesis (Fouling) Example 2 Comparative Comparative 10 2.1 350 126.8 3.5 good Example 7 Synthesis Example 3 Comparative Comparative 20 1.5 300 123.5 4.1 bad Example 8 Synthesis Example 3 Comparative Comparative 10 0.7 350 124.8 3.8 good Example 9 Synthesis Example 4 Comparative Comparative 10 1.1 150 127.8 1.8 good Example 10 Synthesis Example 5 Comparative Comparative 10 5.1 500 128.1 1.1 bad Example 11 Synthesis Example 6 Comparative Comparative 10 1.1 330 129.2 1.3 good Example 12 Synthesis Example 7

[0264] As shown in Table 1, it can be confirmed that the polyethylene copolymers of Examples 1 to 9 according to the present disclosure employ a supported catalyst containing a metallocene compound having an asymmetric structure consisting of a specific bridge group and indacene and indene ligands, and thus, the number of short chain branches (SCB) per 1000 carbons appears at a very high level in the range of 4.5/1000 C to 6.8/1000 C.

[0265] On the other hand, in the case of Comparative Examples in which the copolymerization process is performed with different substituents and structures of the catalyst, it can be confirmed that even if the addition amount of 1-hexene (C6) as a comonomer is increased, there is a problem that it is difficult to increase the SCB content, or the catalytic activity decreases or the morphology of polyethylene is not good.

[0266] Specifically, in the case of Comparative Examples 1 and 4 in which 10 mL of comonomer 1-hexene (C6) is added in the same manner as in Examples, it can be confirmed that the number of short chain branches (SCB) per 1000 carbon atoms is significantly lowered to 2.2/1000 C and 1.9/1000 C. Further, even in the case of Comparative Examples 2 and 5 in which the amount of the comonomer 1-hexene (C6) is increased to 20 mL, it can be confirmed that the number of short chain branches (SCB) per 1000 carbons is only 3.9/1000 C and 2.9/1000 C, and even if the amount is doubled, it is difficult to secure more than 4/1000 C, and also the morphology is also deteriorated. Moreover, in the case of Comparative Examples 3 and 6 in which the amount of the comonomer 1-hexene (C6) is further increased to 25 mL, fouling occurs in the polymerization process and thus, it is impossible to evaluate the physical properties of the polymer.

[0267] On the other hand, even when using a catalyst containing a metallocene compound having an asymmetric ligand structure similar to the structure of the catalyst used in Examples, in the case of Comparative Example 7 in which 10 mL of comonomer 1-hexene (C6) is added in the same manner as in Examples, the number of short chain branches (SCB) per 1000 carbons is significantly reduced to 3.5/1000 C. In addition, in the case of Comparative Example 8 in which the amount of the comonomer 1-hexene (C6) is further increased to 20 mL using the same catalyst as in Comparative Example 7, the number of short chain branches (SCB) per 1000 carbons is increased to 4.1/1000 C, but the catalytic activity in the polymerization process is significantly decreased by 4 kg PE/g_cat_h or more, and also the weight average molecular weight of the obtained polyethylene copolymer is lowered, and the morphology is also poor.

[0268] Further, in the case of Comparative Example 9, which methoxy at position 5 and tert-butyl at position 6 of indene are contained in the metallocene compound of the catalyst, it has physical properties similar to those of Examples, but its activity is very low, which causes a drawback that the overall process cost and the synthetic unit price increase. Similarly, in the case of Comparative Example 10 in which there is no methyl group at position 2 of indene and indacene, it can be confirmed that not only the activity is low, but also the molecular weight is low and the copolymerizability is poor.

[0269] Further, in the case of Comparative Example 11 in which the ligand compound structure is a bis indacene structure rather than an indene-indacene combination, it can be confirmed that it maintains the activity and molecular weight similar to those of Examples, but the copolymerizability is significantly deteriorated, and the SCB content becomes very small. Furthermore, in the case of Comparative Example 12 in which the ligand compound structure is a cyclopentadiene-indacene structure rather than an indene-indacene combination, it can be confirmed that not only the activity is poor, but also the molecular weight is low and copolymerizability is poor.