Transition Metal Compound, Catalyst Composition and Method for Preparing Polypropylene Using the Same

Abstract

The present disclosure relates to a novel transition metal compound of the following Chemical Formula 1, which exhibits high hydrogen reactivity with excellent catalytic activity for propylene polymerization, and is useful in the preparation of a polypropylene having a narrow molecular weight distribution and a low melting point, a catalyst composition including the same, and a method for preparing a polypropylene using the same,

##STR00001## wherein M, X.sup.1, X.sup.2, R.sup.1 to R.sup.9 are described herein.

Claims

1. A transition metal compound represented by the following Chemical Formula 1: ##STR00046## in Chemical Formula 1, M is a Group 4 transition metal, X.sup.1 and X.sup.2 are the same as or different from each other, and are each independently halogen, R.sup.1 and R.sup.2 are the same as or different from each other, and are each independently C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.7-40 alkylaryl, or C.sub.7-40 arylalkyl, R.sup.3 to R.sup.6 are the same as or different from each other, and are each independently C.sub.1-20 alkyl, R.sup.7 is C.sub.6-20 aryl substituted with at least one selected from the group consisting of hydrogen, C.sub.1-20 alkyl, and C.sub.1-20 alkylsilyl, and R.sup.8 and R.sup.9 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 the M is zirconium (Zr) or hafnium (Hf).

3. The transition metal compound of claim 1, wherein the R.sup.1 and R.sup.2 are each independently C.sub.1-8 linear or branched alkyl, C.sub.2-12 linear or branched alkoxyalkyl, or C.sub.6-12 aryl.

4. The transition metal compound of claim 1, wherein the R.sup.3 to R.sup.6 are each independently C.sub.1-6 linear or branched alkyl.

5. The transition metal compound of claim 1, wherein the R.sup.7 is phenyl, phenyl substituted with C.sub.1-6 linear or branched alkyl, phenyl substituted with C.sub.1-6 linear or branched alkylsilyl, naphthyl, naphthyl substituted with C.sub.1-6 linear or branched alkyl, or naphthyl substituted with C.sub.1-6 linear or branched alkylsilyl.

6. The transition metal compound of claim 1, wherein the R.sup.8 and R.sup.9 are each independently C.sub.1-6 linear or branched alkyl.

7. The transition metal compound of claim 1, which is represented by the following Chemical Formula 1-1 or Chemical Formula 1-2: ##STR00047## in Chemical Formulae 1-1 and 1-2, M, X.sup.1, X.sup.2, R.sup.1, and R.sup.2 are as defined in claim 1, and R.sup.10 to R.sup.14 and R.sup.15 to R.sup.21 are the same as or different from each other, and are each independently hydrogen, C.sub.1-20 alkyl, or C.sub.1-20 alkylsilyl.

8. The transition metal compound of claim 1, which is any one of compounds represented by the following structural formulae: ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052##

9. A catalyst composition comprising the transition metal compound of claim 1.

10. The catalyst composition of claim 9, comprising the transition metal compound and a support.

11. The catalyst composition of claim 9, further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulae 2 to 4:
—[Al(R.sup.22)—O].sub.m—  [Chemical Formula 2] in Chemical Formula 2, R.sup.22 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.23).sub.3  [Chemical Formula 3] in Chemical Formula 3, R.sup.23 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.−  [Chemical Formula 4] in Chemical Formula 4, E is a neutral or cationic Lewis base; 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 unsubstituted or substituted with a substituent selected from the group consisting of halogen, C.sub.1-20 alkyl, C.sub.1-20 alkoxy, and C.sub.6-20 phenoxy.

12. A method for preparing a polypropylene, comprising a step of polymerizing propylene monomers in the presence of the catalyst composition of claim 9.

13. The method for preparing a polypropylene of claim 12, wherein the polymerization step is performed while introducing 1500 ppm or less of hydrogen gas based on the propylene monomers.

14. The method for preparing a polypropylene of claim 12, wherein the polypropylene is a homopolymer.

15. The method for preparing a polypropylene of claim 14, wherein the polypropylene has a molecular weight distribution (Mw/Mn) of 2.35 or less, a melt index (MI.sub.2.16, measured at 230° C. under a load of 2.16 kg) of 1000 g/10 min to 1500 g/10 min, and a melting point (Tm) of 148° C. or less.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0141] Hereinafter, the function and effect of the present invention will be described in more detail through specific examples. However, these examples are for illustrative purposes only, and the invention is not intended to be limited by these examples.

EXAMPLES

[0142] <Preparation of Transition Metal Compound>

Example 1

[0143] ##STR00019##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-isopropyl-4-phenyl) Indenyl Silane

[0144] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-phenyl)indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-phenyl)indenyl Zirconium Dichloride

[0145] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0146] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (6H, s), 0.86 (6H, d), 1.79 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.36 (1H, s), 7.41-7.51 (7H, m), 8.29 (1H, m).

Example 2

[0147] ##STR00020##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-isopropyl-4-(4′-tertbutylphenyl))indenyl Silane

[0148] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(4′-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-(4′-tertbutylphenyl))indenyl Zirconium Dichloride

[0149] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0150] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (6H, s), 0.86 (6H, d), 1.33 (9H, s), 1.79 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.36 (1H, s), 7.30 (2H, d), 7.38-7.49 (4H, m), 8.29 (1H, m).

Example 3

[0151] ##STR00021##

[0152] Preparation of ligand compound 2,3,4,5-tetramethylcyclopentadienyl dimethyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl silane 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0153] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0154] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (6H, s), 0.86 (6H, d), 1.32 (18H, s), 1.79 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.36 (1H, s), 7.42-7.49 (2H, m), 7.73 (2H, s), 8.29 (1H, m).

Example 4

[0155] ##STR00022##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-isopropyl-4-naphthyl)indenyl Silane

[0156] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-naphthyl)indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-naphthyl)indenyl Zirconium Dichloride

[0157] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0158] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (6H, s), 0.86 (6H, d), 1.79 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.36 (1H, s), 6.36-7.46 (4H, m), 7.77 (1H, t), 8.09 (1H, m), 8.20 (1H, d), 8.29 (1H, d), 8.50 (1H, d), 8.95 (1H, d).

Example 5

[0159] ##STR00023##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-isopropyl-4-(2,5-dimethylphenyl))indenyl Silane

[0160] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(2,5-dimethylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-(2,5-dimethylphenyl))indenyl Zirconium Dichloride

[0161] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0162] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (6H, s), 0.86 (6H, d), 1.79 (6H, s), 2.12 (6H, s), 2.33 (3H, s), 2.39 (1H, m), 2.46 (3H, s), 6.36 (1H, s), 7.11 (1H, d), 7.30 (1H, d), 7.42-7.49 (2H, m), 7.73 (1H, s), 8.29 (1H, d).

Example 6

[0163] ##STR00024##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Diethyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0164] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, diethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Diethylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0165] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0166] .sup.1H-NMR (500 MHz, CDCl.sub.3):0.66 (4H, q), 0.86 (6H, d), 0.94 (6H, t), 1.32 (18H, s), 1.79 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.36 (1H, s), 7.42-7.49 (2H, m), 7.73 (2H, s), 8.29 (1H, d).

Example 7

[0167] ##STR00025##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dihexyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0168] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dihexylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dihexylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0169] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0170] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.60 (4H, t), 0.86 (6H, d), 0.88 (6H, t), 1.23-1.28 (16H, m), 1.32 (18H, s), 1.79 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.36 (1H, s), 7.42-7.50 (2H, m), 7.73 (2H, s), 8.25 (1H, d).

Example 8

[0171] ##STR00026##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl 6-(tert-butoxy)hexyl)methyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0172] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, 6-(tert-butoxy)hexyl)methyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl 6-(tert-butoxy)hexyl)methylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0173] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0174] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.19 (3H, s), 0.62 (2H, t), 0.84 (6H, d), 1.29-1.31 (4H, m), 1.35 (18H, s), 1.43 (2H, t), 1.50 (2H, t), 1.70 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 3.35 (2H, t), 6.36 (1H, s), 7.40-7.51 (2H, m), 7.80 (2H, m), 8.31 (1H, d).

Example 9

[0175] ##STR00027##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Methylphenyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0176] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, methylphenyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Methylphenyl Silyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0177] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0178] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.26 (3H, s), 0.84 (6H, d), 1.35 (18H, s), 1.74 (6H, s), 2.15 (6H, s), 2.42 (1H, m), 6.29 (1H, s), 7.25-7.42 (7H, m), 7.85 (2H, s), 8.25 (1H, d).

Example 10

[0179] ##STR00028##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Methylhexyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0180] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, methylhexyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Methylhexyl Silyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0181] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0182] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.25 (3H, s), 0.62 (2H, t), 0.84 (6H, d), 0.88 (3H, t), 1.29-1.30 (8H, m), 1.38 (18H, s), 1.72 (6H, s), 2.18 (6H, s), 2.42 (1H, m), 6.40 (1H, s), 7.32-7.35 (2H, m), 7.70 (2H, s), 8.15 (1H, m).

Example 11

[0183] ##STR00029##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Methylpropyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0184] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, methylpropyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Methylpropyl Silyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Zirconium Dichloride

[0185] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0186] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.22 (3H, s), 0.64 (2H, t), 0.90 (3H, d), 0.94 (3H, t), 1.29 (2H, m), 1.34 (18H, s), 1.75 (6H, s), 2.14 (6H, s), 2.42 (1H, m), 6.43 (1H, s), 7.38-7.41 (2H, m), 7.72 (2H, s), 8.22 (1H, m).

Example 12

[0187] ##STR00030##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0188] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0189] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0190] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.24 (6H, s), 0.96 (6H, d), 1.42 (18H, s), 1.82 (6H, s), 2.24 (6H, s), 2.49 (1H, m), 6.42 (1H, s), 7.52-7.56 (2H, m), 7.78 (2H, s), 8.33 (1H, m).

Example 13

[0191] ##STR00031##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Diethyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0192] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, diethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Diethylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0193] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0194] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.68 (4H, q), 091 (6H, d), 0.98 (6H, t), 1.52 (18H, s), 1.85 (6H, s), 2.33 (6H, s), 2.46 (1H, m), 6.42 (1H, s), 7.47-7.51 (2H, m), 7.83 (2H, s), 8.39 (1H, d).

Example 14

[0195] ##STR00032##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dihexyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0196] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dihexylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dihexylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0197] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0198] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.70 (4H, t), 0.93 (6H, d), 1.08 (6H, t), 1.53-1.58 (16H, m), 1.72 (18H, s), 1.89 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.46 (1H, s), 7.42-7.50 (2H, m), 7.73 (2H, s), 8.36 (1H, d).

Example 15

[0199] ##STR00033##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl 6-(tert-butoxy)hexyl)methyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0200] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, 6-(tert-butoxy)hexyl)methyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl 6-(tert-butoxy)hexyl)methylsilyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0201] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0202] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (3H, s), 0.68 (2H, t), 0.92 (6H, d), 1.39-1.41 (4H, m), 1.45 (18H, s), 1.51 (2H, t), 1.60 (2H, t), 1.82 (6H, s), 2.42 (6H, s), 2.59 (1H, m), 3.48 (2H, t), 6.44 (1H, s), 7.52-7.59 (2H, m), 7.83 (2H, m), 8.35 (1H, d).

Example 16

[0203] ##STR00034##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Methylphenyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0204] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, methylphenyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Methylphenyl Silyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0205] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0206] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.31 (3H, s), 0.94 (6H, d), 1.54 (18H, s), 1.74 (6H, s), 2.15 (6H, s), 2.72 (1H, m), 6.33 (1H, s), 7.28-7.32 (7H, m), 775 (2H, s), 8.48 (1H, d).

Example 17

[0207] ##STR00035##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Methylhexyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0208] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, methylhexyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Methylhexyl Silyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0209] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0210] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.27 (3H, s), 0.71 (2H, t), 0.85 (6H, d), 0.92 (3H, t), 1.39-1.44 (8H, m), 1.48 (18H, s), 1.72 (6H, s), 2.18 (6H, s), 2.42 (1H, m), 6.58 (1H, s), 7.47-7.51 (2H, m), 7.78 (2H, s), 8.18 (1H, m).

Example 18

[0211] ##STR00036##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Methylpropyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Silane

[0212] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, methylpropyl silane (1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Methylpropyl Silyl (2-isopropyl-4-(3′,5′-di-tertbutylphenyl))indenyl Hafnium Dichloride

[0213] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing HfCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0214] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.33 (3H, s), 0.84 (2H, t), 1.10 (3H, d), 1.24 (3H, t), 1.89 (2H, m), 1.94 (18H, s), 1.99 (6H, s), 2.25 (6H, s), 2.51 (1H, m), 6.43 (1H, s), 7.41-7.48 (2H, m), 7.78 (2H, s), 8.02 (1H, m).

Example 19

[0215] ##STR00037##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-isopropyl-4-(4′-trimethylsilanyl-phenyl))indenyl Silane

[0216] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-isopropyl-4-(4′-trimethylsilanyl-phenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-isopropyl-4-(4′-trimethylsilanyl-phenyl))indenyl Zirconium Dichloride

[0217] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0218] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (6H, s), 0.29 (9H, s), 0.88 (6H, d), 1.81 (6H, s), 2.12 (6H, s), 2.39 (1H, m), 6.41 (1H, s), 7.38-7.49 (2H, m), 7.62 (1H, s), 7.75 (2H, d), 8.29 (1H, m).

Comparative Example 1

[0219] ##STR00038##

Preparation of Transition Metal Compound Dimethylsilanediylbis(2-methyl-4-(4′-tert-butyl-phenyl)indenyl) Zirconium Dichloride

[0220] At room temperature, 143 g (0.54 mol) of 2-methyl-4-(4′-tert-butylphenyl)-1-indene was added to 2.4 L of toluene, followed by 143 mL of tetrahydrofuran and 234 mL of n-butyllithium solution (2.5 M toluene). Thereafter, the mixture was heated to 80° C. and stirred at that temperature for 1 hour. After cooling down to 40° C., 33.6 g (0.26 mmol) of dimethyldichlorosilane was added dropwise to the reaction solution. The reaction solution was stirred at 60° C. for 3 hours. After cooling down to room temperature, 218 mL of n-butyllithium solution (2.5 M toluene) was added dropwise. Thereafter, this solution was heated to 80° C. and stirred at that temperature for 1 hour. After cooling down to room temperature, 71.1 g (0.305 mol) of zirconium tetrachloride was slowly added. This solution was stirred at 45° C. for 2 hours, and the formed precipitate was separated by filtration through a G3 sintered glass filter and washed carefully with 700 mL of THF. The residue was then dried in an oil vacuum pump, and a product with a racemic:meso ratio of 1:1 was obtained in a yield of 155 g (80%).

Comparative Example 2

[0221] ##STR00039##

Preparation of Ligand Compound Dimethyl Tetramethylramethylcyclopentadienyl 2-methyl-4-(4′-tert-butylphenyl)indenyl Silane

[0222] Tetrahydrofuran (600 mL) and tetramethylcyclopentadiene (50 g) were added to a 2 L flask, and n-BuLi (2.5 M hexane solution, 170 mL) was slowly added dropwise at −10° C. under a nitrogen atmosphere, followed by stirring at room temperature for 12 hours. The temperature of the reaction solution was lowered to −10° C. again, and then dimethyl dichlorosilane (170 g) was added thereto. Thereafter, it was stirred at room temperature for 12 hours to react, and the reaction product was dried under vacuum. Thereafter, n-hexane (500 mL) was added thereto to dissolve the reaction product, and the product was filtered through a celite filter. Then, the filtered solution was dried under vacuum to obtain 70 g of dimethyl tetramethylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 80%).

[0223] A flask into which toluene (200 mL), tetrahydrofuran (40 mL) and 2-methyl-4-(4′-t-butylphenyl)indene (50 g) were added was cooled down to −10° C., and then n-BuLi (2.5M hexane solution, 76 mL) was slowly added dropwise, followed by stirring at room temperature for 12 hours. The temperature of the reaction product was lowered to −10° C. again, and then dimethyl tetramethylcyclopentadienyl chlorosilane (38 g) synthesized above was added and reacted by stirring at room temperature for 12 hours. When the reaction was completed, water (400 mL) was added, followed by stirring at room temperature for 1.5 hours. Thereafter, the resulting solution was extracted with toluene, and dried under vacuum to obtain 80 g of dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4′-t-butylphenyl)indenyl silane in the form of yellow oil (yield 95%).

Preparation of Transition Metal Compound Tetramethylcyclopentadienyl Dimethylsilyl 2-methyl-4-(4′-tert-butylphenyl)indenyl Zr Dichloride

[0224] Dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4′-t-butylphenyl) indenyl silane (50 g), which is the ligand compound prepared above, toluene (300 mL) and diethyl ether (100 mL) were added to a flask, and cooled down to −10° C. Then, n-BuLi (2.5 M hexane solution, 90 mL) was slowly added dropwise. After the dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was dried under vacuum to obtain 40 g of tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl dilithium salt in the form of solid (yield 80%), which was used directly in the next reaction without purification. The tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl dilithium salt (40 g), toluene (40 mL) and ether (10 mL) were added to a flask and stirred. In a separate flask, a mixture of toluene (30 mL) and ZrCl.sub.4 (20 g) was prepared. The mixture in the flask containing ZrCl.sub.4 was slowly added dropwise to the flask containing the dilithium salt of the ligand compound with a cannula, and stirred at room temperature for 24 hours. After stirring, the mixture was dried under vacuum, extracted with methylene chloride (500 mL), filtered through a celite filter, and the filtrate was dried under vacuum. The obtained solid was washed with a 1:3 mixture of methylene chloride and n-hexane (50 mL), and then dried under vacuum to obtain 32 g of tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl zirconium dichloride in the form of yellow solid (yield 60%).

Comparative Example 3

[0225] ##STR00040##

Preparation of Ligand Compound 2,4-dimethylramethylcyclopentadienyl 2-methyl-4-(4′-tert-butylphenyl)indenyl Silane

[0226] Tetrahydrofuran (600 mL) and 1,3-dimethylcyclopentadiene (50 g) were added to a 2 L flask, and n-BuLi (2.5 M hexane solution, 170 mL) was slowly added dropwise at −10° C. under a nitrogen atmosphere, followed by stirring at room temperature for 12 hours. The temperature of the reaction solution was lowered to −10° C. again, and then dimethyl dichlorosilane (170 g) was added thereto. Thereafter, it was stirred at room temperature for 12 hours to react, and the reaction product was dried under vacuum. Thereafter, n-hexane (500 mL) was added thereto to dissolve the reaction product, and the product was filtered through a celite filter. Then, the filtered solution was dried under vacuum to obtain 70 g of dimethyl 2,4-dimethylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 70%).

[0227] A flask into which toluene (200 mL), tetrahydrofuran (40 mL) and 2-methyl-4-(4′-t-butylphenyl)indene (50 g) were added was cooled down to −10° C., and then n-BuLi (2.5M hexane solution, 76 mL) was slowly added dropwise, followed by stirring at room temperature for 12 hours. The temperature of the reaction product was lowered to −10° C. again, and then dimethyl 2,4-dimethylcyclopentadienyl chlorosilane (38 g) was added and reacted by stirring at room temperature for 12 hours. When the reaction was completed, water (400 mL) was added, followed by stirring at room temperature for 1.5 hours. Thereafter, the resulting solution was extracted with toluene, and dried under vacuum to obtain 80 g of dimethyl 2,4-dimethylcyclopentadienyl 2-methyl-4-(4′-t-butylphenyl) indenyl silane in the form of yellow oil (yield 95%).

Preparation of Transition Metal Compound 2,4-dimethylcyclopentadienyl Dimethylsilyl 2-methyl-4-(4′-tert-butylphenyl)indenyl Zr Dichloride

[0228] Dimethyl 2,4-dimethylcyclopentadienyl 2-methyl-4-(4′-t-butylphenyl) indenyl silane (50 g), which is the ligand compound prepared above, toluene (300 mL) and diethyl ether (100 mL) were added to a flask, and cooled down to −10° C. Then, n-BuLi (2.5 M hexane solution, 90 mL) was slowly added dropwise. After the dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was dried under vacuum to obtain 40 g of 2,4-dimethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl dilithium salt in the form of solid (yield 80%), which was used directly in the next reaction without purification. The 2,4-dimethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl dilithium salt (40 g), toluene (40 mL) and ether (10 mL) were added to a flask and stirred. In a separate flask, a mixture of toluene (30 mL) and ZrCl.sub.4 (20 g) was prepared. The mixture in the flask containing ZrCl.sub.4 was slowly added dropwise to the flask containing the dilithium salt of the ligand compound with a cannula, and stirred at room temperature for 24 hours. After stirring, the mixture was dried under vacuum, extracted with methylene chloride (500 mL), filtered through a celite filter, and the filtrate was dried under vacuum. The obtained solid was washed with a 1:3 mixture of methylene chloride and n-hexane (50 mL), and then dried under vacuum to obtain 32 g of 2,4-dimethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl zirconium dichloride in the form of yellow solid (yield 60%).

Comparative Example 4

[0229] ##STR00041##

Preparation of Ligand Compound Dimethyl 4-butyl-2-methylcyclopentadienyl 2-methyl-4-(4′-tert-butylphenyl)indenyl Silane

[0230] Tetrahydrofuran (600 mL) and 1-butyl-3-methylcyclopentadiene (50 g) were added to a 2 L flask, and n-BuLi (2.5 M hexane solution, 170 mL) was slowly added dropwise at −10° C. under a nitrogen atmosphere, followed by stirring at room temperature for 12 hours. The temperature of the reaction solution was lowered to −10° C. again, and then dimethyl dichlorosilane (170 g) was added thereto. Thereafter, it was stirred at room temperature for 12 hours to react, and the reaction product was dried under vacuum. Thereafter, n-hexane (500 mL) was added thereto to dissolve the reaction product, and the product was filtered through a celite filter. Then, the filtered solution was dried under vacuum to obtain 70 g of dimethyl 4-butyl-2-methylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 70%).

[0231] A flask into which toluene (200 mL), tetrahydrofuran (40 mL) and 2-methyl-4-(4′-t-butylphenyl) indene (50 g) were added was cooled down to −10° C., and then n-BuLi (2.5M hexane solution, 76 mL) was slowly added dropwise, followed by stirring at room temperature for 12 hours. The temperature of the reaction product was lowered to −10° C. again, and then dimethyl 4-butyl-2-methylcyclopentadienyl chlorosilane (38 g) was added and reacted by stirring at room temperature for 12 hours. When the reaction was completed, water (400 mL) was added, followed by stirring at room temperature for 1.5 hours. Thereafter, the resulting solution was extracted with toluene, and dried under vacuum to obtain 80 g of dimethyl 4-butyl-2-methylcyclopentadienyl 2-methyl-4-(4′-t-butylphenyl) indenyl silane in the form of yellow oil (yield 95%).

Preparation of Transition Metal Compound 4-butyl-2-methylcyclopentadienyl Dimethylsilyl 2-methyl-4-(4′-tert-butylphenyl)indenyl Zr Dichloride

[0232] Dimethyl 4-butyl-2-methylcyclopentadienyl 2-methyl-4-(4′-t-butylphenyl) indenyl silane (50 g), which is the ligand compound prepared above, toluene (300 mL) and diethyl ether (100 mL) were added to a flask, and cooled down to −10° C. Then, n-BuLi (2.5 M hexane solution, 90 mL) was slowly added dropwise. After the dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was dried under vacuum to obtain 40 g of 4-butyl-2-methylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl dilithium salt in the form of solid (yield 80%), which was used directly in the next reaction without purification. The 4-butyl-2-methylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl dilithium salt (40 g), toluene (40 mL) and ether (10 mL) were added to a flask and stirred. In a separate flask, a mixture of toluene (30 mL) and ZrCl.sub.4 (20 g) was prepared. The mixture in the flask containing ZrCl.sub.4 was slowly added dropwise to the flask containing the dilithium salt of the ligand compound with a cannula, and stirred at room temperature for 24 hours. After stirring, the mixture was dried under vacuum, extracted with methylene chloride (500 mL), filtered through a celite filter, and the filtrate was dried under vacuum. The obtained solid was washed with a 1:3 mixture of methylene chloride and n-hexane (50 mL), and then dried under vacuum to obtain 32 g of 4-butyl-2-methylcyclopentadienyl dimethylsilyl 2-methyl-4-(4′-t-butylphenyl) indenyl zirconium dichloride in the form of yellow solid (yield 60%).

Comparative Example 5

[0233] ##STR00042##

Preparation of Ligand Compound Cyclopentadienyl Dimethyl (2-isopropyl-4-(4′-tertbutylphenyl))indenyl Silane

[0234] After dissolving indene in THF, n-BuLi (1.05 eq) was slowly added dropwise at −25° C., followed by stirring at room temperature for 3 hours. Then, silane (2 eq) was added at −10° C., followed by stirring overnight at room temperature. After vacuum drying, it was dissolved in THF. CPNa/THF solution (1 eq.) was slowly added dropwise at −25° C. After stirring at room temperature overnight, it was worked up with water and dried. A ligand was obtained by using a silica gel column.

Preparation of Transition Metal Compound Cyclopentadienyl Dimethylsilyl (2-isopropyl-4-(4′-tertbutylphenyl))indenyl Zirconium Dichloride

[0235] The ligand was dissolved in toluene/ether (2/1) and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene and added to a flask, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and DCM was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. A catalyst precursor was obtained in the form of yellow solid.

[0236] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.40 (s, 6H), 0.86 (d, 6H), 1.33 (s, 9H), 2.38 (m, 1H), 6.40-6.51 (m, 4H), 7.31-7.49 (m, 6H), 8.29 (d, 1H).

Comparative Example 6

[0237] ##STR00043##

[0238] The above transition metal compound (2,3,4,5-tetramethylcyclopentadienyl dimethylsilyl (2-isopropyl)indenyl zirconium dichloride) was prepared according to the method disclosed in International Patent Publication WO 2018-185176 A1.

[0239] .sup.1H-NMR (500 MHz, CDCl.sub.3):1.10 (s, 3H), 1.16 (d, 3H), 1.20 (s, 3H), 1.38 (d, 3H), 1.87 (s, 6H), 1.97 (s, 3H), 1.99 (s, 3H), 3.02 (m, 1H), 6.96 (m, 1H), 7.05 (s, 1H), 7.31 (m, 1H), 7.58 (1H, d), 7.61 (1H, d).

Comparative Example 7

[0240] ##STR00044##

Preparation of Ligand Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethyl (2-phenyl-4-(4′-tertbutylphenyl))indenyl Silane

[0241] 2,3,4,5-tetramethylcyclopentadien (TMCP) was dissolved in tetrahydrofuran (THF), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, dimethylsilane (Silane, 1.05 eq) was added thereto at −10° C., and stirred overnight at room temperature. In another reactor, (2-phenyl-4-(4′-tertbutylphenyl))indene was dissolved in a mixed solution of toluene/THF (5/1 by volume, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at −25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol %) was added and stirred for 30 minutes, and then the first reaction product, a mono-Si solution, was added thereto. Thereafter, it was stirred overnight at room temperature, worked up with water and dried to obtain a ligand.

Preparation of Transition Metal Compound 2,3,4,5-tetramethylcyclopentadienyl Dimethylsilyl (2-phenyl-4-(4′-tertbutylphenyl))indenyl Zirconium Dichloride

[0242] The ligand prepared above was dissolved in a mixed solution of toluene/ether (2/1 by volume, 0.7 M), and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene (0.17 M) in a separate flask, and added to the ligand solution, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and vacuum-dried to obtain the above metallocene compound.

[0243] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.21 (s, 6H), 1.42 (s, 9H), 1.72 (s, 6H), 2.08 (s, 6H), 6.92 (s, 1H), 7.01 (d, 2H), 7.19 (m, 3H), 7.31 (d, 2H), 7.39 (d, 2H), 7.54 (d, 1H), 8.32 (d, 1H).

Comparative Example 8

[0244] ##STR00045##

Preparation of Ligand Compound Cyclopentadienyl Dimethyl (2-isopropyl-4-(4′-trimethylsilanyl-phenyl))indenyl Silane

[0245] After dissolving indene in THF, n-BuLi (1.05 eq) was slowly added dropwise at −25° C., followed by stirring at room temperature for 3 hours. Then, silane (2 eq) was added at −10° C., followed by stirring overnight at room temperature. After vacuum drying, it was dissolved in THF. Cyclopentadienyl sodium/THF solution (CPNa/THF solution, 1 eq.) was slowly added dropwise at −25° C. After stirring at room temperature overnight, it was worked up with water and dried. Thereafter, separation and purification were performed using a silica gel column to obtain a ligand.

Preparation of Transition Metal Compound Cyclopentadienyl Dimethylsilyl Dimethyl (2-isopropyl-4-(4′-trimethylsilanyl-phenyl))indenyl Zirconium Dichloride

[0246] The ligand was dissolved in toluene/ether (2/1 by volume) and n-BuLi (2.05 eq) was added at −25° C., followed by stirring at room temperature for 5 hours. A slurry was prepared by mixing ZrCl.sub.4 (1 eq) with toluene and added to a flask, followed by stirring overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, and dichloromethane was added again. Then, LiCl was removed through a filter, the filtrate was vacuum-dried, and toluene was added thereto, followed by recrystallization at room temperature. A catalyst precursor was obtained in the form of yellow solid.

[0247] .sup.1H-NMR (500 MHz, CDCl.sub.3): 0.20 (s, 6H), 0.23 (s, 9H), 0.85 (d, 6H), 2.38 (m, 1H), 6.40-6.50 (m, 5H), 7.42-7.49 (m, 2H), 7.62 (d, 2H), 7.82 (d, 2H), 8.30 (d, 2H).

[0248] <Preparation of Supported Catalyst>

[0249] 3 g of a silica support (SP2410) was placed in a 2 L reactor under an argon (Ar) atmosphere, and 766 mL (13 mmol) of a 10 wt % methylaluminoxane (MAO) toluene solution was slowly added at room temperature, followed by stirring at 95° C. for 24 hours. After completion of the reaction, the mixture was cooled down to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. 400 mL of toluene was added, stirred for 1 minute, and allowed to stand for 15 minutes to decant the solvent using a cannula.

[0250] 70 μmol of each of the transition metal compounds prepared in Examples and Comparative Examples was dissolved in 40 mL of toluene, and transferred to the reactor using a cannula. After stirring at 75° C. for 5 hours, the mixture was cooled down to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. 400 mL of toluene was added, stirred for 1 minute, and allowed to stand for 15 minutes to decant the solvent using a cannula. This process was repeated twice. In the same manner, 400 mL of hexane was added thereto, stirred for 1 minute, and then allowed to stand for 15 minutes to decant the solvent using a cannula.

[0251] It was dried at room temperature under vacuum for 5 hours, and then dried at 45° C. under vacuum for 4 hours to obtain a supported catalyst.

[0252] <Polypropylene Polymerization>

[0253] A 2 L stainless steel reactor was vacuum-dried at 65° C., and cooled down. Then, 1.5 mmol of triethylaluminum, 2 bar of hydrogen, and 770 g of propylene were sequentially added at room temperature.

[0254] After stirring for 10 minutes, the temperature was raised to 70° C., and the supported metallocene catalyst was dissolved in 20 mL of hexane and added to the reactor at a nitrogen pressure. After performing the polymerization for 1 hour, unreacted propylene was ventilated.

[0255] The activity of the supported metallocene catalysts using one of the transition metal compounds prepared in Examples and Comparative Examples, and physical properties of the homo polypropylenes prepared using one of the supported metallocene catalysts were evaluated in the following manner. The results are shown in Table 1 below.

[0256] (1) Melt Index (MI)

[0257] The melt index was measured at 230° C. under a load of 2.16 kg according to the American Society for Testing and Materials ASTM D1238, and expressed as the weight (g) of the polymer that has been melted for 10 minutes.

[0258] (2) Melting Point (Tm)

[0259] The melting temperature, and melting point (Tm) of the propylene polymer were measured using differential scanning calorimeter (DSC 2920, manufactured by TA instrument). Specifically, the temperature was increased to 220° C., and maintained at that temperature for 5 minutes. After that, the temperature was lowered to 20° C., and further increased. The temperature at the top of the DSC (Differential Scanning calorimeter, manufactured by TA) curve was referred to as the melting point. Herein, the temperature was increased and lowered at a rate of 10° C./min, respectively, and the melting point was confirmed at the second heating period.

[0260] (3) Molecular Weight Distribution (MWD, Polydispersity Index)

[0261] The molecular weight distribution (MWD) was determined by measuring a weight average molecular weight (Mw) and a number average molecular weight (Mn) of the polymer using gel permeation chromatography (GPC, manufactured by Water), and then dividing the weight average molecular weight by the number average molecular weight.

[0262] Specifically, PL-GPC220 manufactured by Waters was used as the gel permeation chromatography (GPC) instrument, and a Polymer Laboratories PLgel MIX-B 300 mm length column was used. 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 polymer sample of Examples and Comparative Examples was pretreated by dissolving 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 with a concentration of 10 mg/10 mL was supplied in an amount of 200 μL. 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.

TABLE-US-00001 TABLE 1 Poly- merization condition Physical properties of homo polypropylene H.sub.2 (ppm) MI (g/10 min) MWD Tm (° C.) Example 1 500 1258 2.21 143 Example 2 530 1325 2.23 143 Example 3 530 1247 2.15 144 Example 4 550 1365 2.28 143 Example 5 530 1354 2.27 143 Example 6 530 1275 2.28 144 Example 7 530 1354 2.21 144 Example 8 530 1293 2.26 144 Example 9 530 1257 2.23 144 Example 10 530 1345 2.26 144 Example 11 530 1409 2.21 144 Example 12 550 1387 2.22 145 Example 13 550 1228 2.27 145 Example 14 550 1236 2.29 145 Example 15 550 1245 2.25 145 Example 16 550 1402 2.26 145 Example 17 550 1396 2.19 145 Example 18 550 1258 2.19 145 Example 19 540 1258 2.30 142 Comparative 4000 1358 2.82 153 Example 1 Comparative 3000 1289 2.75 152 Example 2 Comparative 3000 1225 2.79 152 Example 3 Comparative 3000 1387 2.81 152 Example 4 Comparative — Unmeasurable 2.27 No Tm due to Example 5 due to low atactic activity (activity <0.3) Comparative — Unmeasurable 2.27 152 Example 6 due to low activity (activity <0.3) Comparative 2500 1375 2.43 150 Example 7 Comparative — Unmeasurable 3.20 No Tm due to Example 8 due to low atactic activity (activity <0.3)

[0263] Referring to Table 1, the metallocene compounds of Examples 1 to 19 according to an embodiment of the present disclosure provided a polypropylene having a high melt index (MI.sub.2.16) of 1228 g/10 min to 1409 g/10 min even with a small amount of hydrogen, thereby confirming very good hydrogen reactivity. In addition, it can be confirmed from Examples 1 to 19 that the molecular weight distribution (MWD) was kept as narrow as about 2.15 to 2.3 even though hydrogen was used a lot. Moreover, the melting point (Tm) of Examples 1 to 19 was lowered to 142° C. to 145° C. despite the same homo polymerization, and thus it can be confirmed that a polypropylene which is excellent for soft multifilaments could be produced.

[0264] On the other hand, in the case of Comparative Examples 1 to 8, an excessive amount of hydrogen had to be introduced in the polymerization process in order to achieve a high melt index, and in the case of Comparative Examples 5, 6, and 8, it was not possible to measure the melt index of the prepared polymer due to low activity even though the excessive amount of hydrogen was introduced. Specifically, in the case of Comparative Examples 1 to 4 and Comparative Example 7, hydrogen reactivity was significantly lowered and an excessive amount of hydrogen had to be introduced in the polymerization process, because the substituent at position 2 in the indenyl ligand was methyl or phenyl. Therefore, the molecular weight distribution (MWD) was as high as about 2.45 to 2.82 and 2.43, and the melting point (Tm) was as high as about 152° C. to 153° C. and 150° C. In particular, in the case of Comparative Examples 5 and 8, only a hydrogen substituent was included in the cyclopentadienyl ring, so that tacticity of the catalyst collapsed during propylene polymerization, thereby forming atactic PP. In addition, as in Comparative Example 6, when hydrogen was substituted at position 4 in the indenyl ligand, it was impossible to measure the melt index due to reduced activity.