Ligand compound, transition metal compound, and catalyst composition including the same

Abstract

The present invention relates to a novel ligand compound, a transition metal compound and a catalyst composition including the same. The novel ligand compound and the transition metal compound of the present invention may be useful as a catalyst of polymerization reaction for preparing an olefin-based polymer having a low density. In addition, an olefin polymer which is polymerized using the catalyst composition including the transition metal compound may be used for the manufacture of a product having low melt index (MI) and high molecular weight.

Claims

1. A transition metal compound represented by the following Formula 1: ##STR00041## in Formula 1, R.sub.1 is hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, arylalkoxy having 7 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R.sub.2a to R.sub.2e are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; R.sub.3 is hydrogen, halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, alkylidene having 1 to 20 carbon atoms, or phenyl which is substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms; R.sub.4 to R.sub.9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or a metalloid radical of a metal in group 14 which is substituted with hydrocarbyl having 1 to 20 carbon atoms; wherein adjacent two or more of R.sub.6 to R.sub.9 are optionally connected to form a ring, Q is Si, C, N, P or S; M is a transition metal in group 4; and X.sub.1 and X.sub.2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkylamino having 1 to 20 carbon atoms, arylamino having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms.

2. The transition metal compound of claim 1, wherein R.sub.1 is hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, arylalkoxy having 7 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R.sub.2a to R.sub.2e are each independently hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or phenyl; R.sub.3 is hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 13 carbon atoms, arylalkyl having 7 to 13 carbon atoms, or phenyl which is substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms and phenyl; R.sub.4 to R.sub.9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; wherein adjacent two or more of R.sub.6 to R.sub.9 are optionally connected to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; wherein the aliphatic ring or the aromatic ring is optionally substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms; Q is Si; M is Ti: and X.sub.1 and X.sub.2 are each independently hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 12 carbon atoms, alkylaryl having 7 to 13 carbon atoms, arylalkyl having 7 to 13 carbon atoms, alkylamino having 1 to 13 carbon atoms, or arylamino having 6 to 12 carbon atoms.

3. The transition metal compound of claim 1, wherein R.sub.1 is hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, aryl having 6 to 12 carbon atoms, arylalkoxy having 7 to 13 carbon atoms, alkylaryl having 7 to 13 carbon atoms, or arylalkyl having 7 to 13 carbon atoms; R.sub.2a to R.sub.2e are each independently hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or phenyl; R.sub.3 is hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkylaryl having 7 to 13 carbon atoms, arylalkyl having 7 to 13 carbon atoms, phenyl, or phenyl which is substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms and phenyl; R.sub.4 to R.sub.9 are each independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aryl having 6 to 12 carbon atoms, alkylaryl having 7 to 13 carbon atoms, or arylalkyl having 7 to 13 carbon atoms; wherein adjacent two or more of R.sub.6 to R.sub.9 are optionally connected to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms; wherein the aliphatic ring or the aromatic ring is optionally substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms, Q is Si; M is Ti; and X.sub.1 and X.sub.2 are each independently hydrogen, halogen, alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms.

4. The transition metal compound of claim 1, wherein R.sub.1 is hydrogen or alkyl having 1 to 12 carbon atoms; R.sub.2a to R.sub.2e are each independently hydrogen, halogen, alkyl having 1 to 12 carbon atoms, or alkoxy having 1 to 12 carbon atoms; R.sub.3 is hydrogen, alkyl having 1 to 12 carbon atoms, or phenyl; R.sub.4 and R.sub.5 are each independently hydrogen, or alkyl having 1 to 12 carbon atoms; R.sub.6 to R.sub.9 are each independently hydrogen or methyl; Q is Si; M is Ti; and X.sub.1 and X.sub.2 are each independently hydrogen or alkyl having 1 to 12 carbon atoms.

5. The transition metal of claim 1, wherein the compound represented by Formula 1 is a compound represented by one of the following formulae: ##STR00042## ##STR00043##

6. A ligand compound represented by the following Formula 2: ##STR00044## in Formula 2, R.sub.1, and R.sub.10 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, arylalkoxy having 7 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R.sub.2a to R.sub.2e are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; R.sub.3 is hydrogen, halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, alkylidene having 1 to 20 carbon atoms, or phenyl which is substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms; R.sub.4 to R.sub.9 are each independently, hydrogen, silyl, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or a metalloid radical of a metal in group 14, which is substituted with hydrocarbyl having 1 to 20 carbon atoms; wherein adjacent two or more of R.sub.6 to R.sub.9 are optionally connected to form a ring; and Q is Si, C, N, P or S.

7. The ligand compound of claim 6, wherein R.sub.1, R.sub.10 and R.sub.11 are each independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, aryl having 6 to 12 carbon atoms, arylalkoxy having 7 to 13 carbon atoms, alkylaryl having 7 to 13 carbon atoms, or arylalkyl having 7 to 13 carbon atoms; R.sub.2a to R.sub.2e are each independently hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or phenyl; R.sub.3 is hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkylaryl having 7 to 13 carbon atoms, arylalkyl having 7 to 13 carbon atoms, phenyl, or phenyl which is substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms and phenyl; R.sub.4 to R.sub.9 are each independently, hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aryl having 6 to 12 carbon atoms, alkylaryl having 7 to 13 carbon atoms, or arylalkyl having 7 to 13 carbon atoms; wherein adjacent two or more of R.sub.6 to R.sub.9 are optionally connected to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms; wherein the aliphatic ring or the aromatic ring is optionally substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms; and Q is Si.

8. The ligand compound of claim 6, wherein the compound represented by Formula 2 is a compound represented by one of the following formulae: ##STR00045## ##STR00046##

9. A method for preparing the ligand compound according to claim 6, the method comprising: a) reacting a compound represented by Formula 4 below with a compound represented by the following Formula 5 below to prepare a compound represented by Formula 3 below; and b) reacting the compound represented by Formula 3 with a compound represented by Formula 6 below to prepare the ligand compound represented by Formula 2: ##STR00047## in the above formulae, R.sub.1 and R.sub.10, R.sub.2a to R.sub.2e, and Q are the same as defined in Formula 2.

10. A method for preparing the transition metal compound according to claim 1, by reacting a compound represented by Formula 2 below with a compound represented by Formula 7 below and an organolithium compound: ##STR00048## [Formula 7] M(X.sub.1X.sub.2).sub.2 in the above formulae, R.sub.10 is hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, arylalkoxy having 7 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; and R.sub.1 to R.sub.9, R.sub.2a to R.sub.2e, Q, M, X.sub.1, and X.sub.2 are the same as defined in Formula 1.

11. A catalyst composition comprising the transition metal compound according to claim 1, wherein the catalyst composition is a polyethylene polymerization catalyst.

12. The catalyst composition of claim 11, which further comprises one or more cocatalysts.

13. The catalyst composition of claim 12, wherein the cocatalyst comprises one or more compounds selected from the following Formulae 8 to 10:
[Al(R.sub.13)O].sub.a[Formula 8] where each R.sub.13 is independently a halogen radical, a hydrocarbyl radical of 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl radical of 1 to 20 carbon atoms, and a is an integer of 2 or more;
D(R.sub.13).sub.3[Formula 9] where D is aluminum or boron, and each R.sub.13 is independently a halogen radical, a hydrocarbyl radical of 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl radical of 1 to 20 carbon atoms,
[L-H].sup.+[Z(A).sub.4].sup.
or
[L].sup.+[Z(A).sub.4].sup.[Formula 10] where L is a neutral or a cationic Lewis acid; H is a hydrogen atom; Z is an element in group 13; and each A is independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms, where one or more hydrogen atoms is optionally independently substituted with a substituent; wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.

14. The catalyst composition of claim 12, wherein the catalyst composition further comprises a reaction solvent.

15. A method for preparing a polymer using the catalyst composition according to claim 11, comprising contacting the transition metal compound according to Formula 1 and one or more olefin monomers.

16. The method for preparing a polymer of claim 15, wherein the polymer is a homopolymer or a copolymer of polyolefin.

17. The method for preparing a polymer of claim 15, wherein the polymer has melt index (Mi) of 3.5 g/10 min or less, and a density of less than 0.90 g/cc.

Description

Preparation of Transition Metal Compound

Example 1

Preparation of Compound of Formula 1-1

(1) ##STR00029##

(2) Under a glove box, the ligand compound of Formula 2-1 (467 mg, 1.1 mmol/1.0 eq) and 5.5 ml (0.2 M) of toluene were added to a 50 ml vial, and stirred first. n-BuLi (0.924 ml, 2.31 mmol/2.1 eq, 2.5 M in hexane) was added thereto at 40 C., and then reacted at room temperature overnight. Then, MeMgBr (1.1 ml, 3.3 mmol/3 eq, 3.0 M in diethyl ether) was slowly added thereto dropwisely at 40 C., and TiCl.sub.4DME (0.307 mg, 1.1 mmol/1.0 eq) was added in order, followed by stirring at room temperature overnight. After drying solvents, the reaction mixture was filtered using hexane. Then, to a filtrate, DME (0.343 ml, 3.3 mmol/3 eq) was added and stirred at room temperature overnight. After drying solvents, filtering was performed using hexane to obtain 144 mg of a yellow solid (26%, dr=1:1).

(3) .sup.1H-NMR (CDCl.sub.3, 500 MHz): 7.79 (d, 1H), 7.74 (d, 1H), 7.55 (d, 1H), 7.39 (d, 1H), 7.32 (d, 1H), 7.20 (d, 1H), 7.18 (d, 1H), 7.12-7.04 (m, 5H), 7.00 (t, 1H), 6.97 (t, 1H), 6.93 (t, 1H), 6.53 (d, 1H), 3.38 (S, 3H), 2.25 (s, 3H), 2.25 (s, 3H), 2.02 (s, 3H), 1.77 (s, 3H), 1.69 (s, 9H), 1.68 (s, 9H), 1.53 (s, 3H), 1.22 (s, 6H), 1.04 (s, 6H), 0.86 (s, 3H), 0.02 (s, 3H)

Example 2

Preparation of Compound of Formula 1-2

(4) ##STR00030##

(5) To a 250 ml round-bottom flask, the ligand compound of Formula 2-2 (4.2 g, 10.8 mmol/1.0 eq) and 54 ml (0.2 M) of toluene were added and stirred. n-BuLi (4.3 ml, 9.1 mmol/2.1 eq, 2.5 M in hexane) was added thereto at 40 C., and then stirred at room temperature overnight. Then, MeMgBr (10.8 ml, 32.4 mmol/3.0 eq, 3.0 M in diethyl ether) was slowly added thereto dropwisely at 40 C., and TiCl.sub.4DME (3 g, 10.8 mmol/1 eq) was added in order, followed by stirring at room temperature overnight. Then, the reaction mixture was filtered using hexane.

(6) To a filtrate, DME (5.6 ml, 54 mmol/5 eq) was added and the solution thus obtained was filtered in hexane and concentrated to obtain 1.1 g of a yellow solid (20%, dr=1:0.9).

(7) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.88 (d, 1H), 7.83 (d, 1H), 7.74 (d, 1H), 7.70 (d, 1H), 7.39 (d, 2H), 7.34 (d, 1H), 7.23 (m, 3H), 7.17 (d, 1H), 7.12 (d, 1H), 7.07 (d, 1H), 7.04 (d, 1H), 7.00 (t, 1H), 6.86 (t, 1H), 3.58-3.48 (m, 2H), 2.32 (s, 3H), 2.22 (s, 3H), 1.97 (s, 3H), 1.69 (s, 9H), 1.68 (s, 9H), 1.43 (s, 3H), 1.40 (d, 3H), 1.31 (d, 3H), 1.25 (d, 6H), 1.13 (s, 3H), 0.88 (t, 3H), 0.85 (s, 3H), 0.72 (s, 3H), 0.19 (s, 3H), 0.01 (s, 3H)

Example 3

Synthesis of Compound of Formula 1-3

(8) ##STR00031##

(9) To a 250 ml round-bottom flask, the ligand compound of Formula 2-3 (4.26 g, 10.501 mmol) and 53 ml (0.2 M) of MTBE were added and stirred. n-BuLi (8.6 ml, 21.52 mmol, 2.05 eq, 2.5 M in hexane) was added thereto at 40 C., and then stirred at room temperature overnight.

(10) Then, MeMgBr (8.8 ml, 26.25 mmol, 2.5 eq, 3.0 M in diethyl ether) was slowly added thereto dropwisely at 40 C., and TiCl.sub.4 (10.50 ml, 10.50 mmol) was added in order, followed by stirring at room temperature overnight. Then, the reaction mixture was filtered using hexane.

(11) To a filtrate, DME (3.3 ml, 31.50 mmol) was added and the solution thus obtained was filtered in hexane and concentrated to obtain 3.42 g of a yellow solid (68%, dr=1:0.68).

(12) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.83 (d, 1H), 7.80 (d, 1H), 7.74 (d, 1H), 7.71 (d, 1H), 7.68 (d, 1H), 7.37 (d, 1H), 7.31-6.90 (m, 9H), 6.84 (t, 1H), 2.54 (s, 3H), 2.47 (s, 3H), 2.31 (s, 3H), 2.20 (s, 3H), 1.65 (s, 9H), 1.63 (s, 9H), 1.34 (s, 3H), 1.00 (s, 3H), 0.98 (s, 3H), 0.81 (s, 3H), 0.79 (s, 3H), 0.68 (s, 3H), 0.14 (s, 3H), 0.03 (s, 3H)

Example 4

Preparation of Compound of Formula 1-4

(13) ##STR00032##

(14) To a 100 ml schlenk flask, 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 ml (0.2 M) of toluene were added, and 10.3 ml (25.779 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added thereto dropwisely at 30 C., and then stirred at room temperature overnight. After stirring, 12.6 ml (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added thereto dropwisely, and 13.2 ml (13.204 mmol, 1.05 eq, 1.0 M in toluene) of TiCl.sub.4 was added in order, followed by stirring at room temperature overnight. After stirring, the reaction mixture was vacuum dried and extracted with 150 ml of hexane. After removing solvents to 50 ml, 4 ml (37.725 mmol, 3.0 eq) of DME was added dropwisely and stirred at room temperature overnight. After vacuum drying again, extraction with 150 ml of hexane was performed. After drying solvents, 2.23 g of a brown solid was obtained (38%, dr=1:0.5).

(15) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.507.30 (10H), 2.66 (s, 3H), 2.61 (s, 3H), 2.15 (s, 3H), 1.62 (s, 9H), 1.56 (s, 9H), 1.53 (s, 3H), 0.93 (s, 3H), 0.31 (s, 3H), 0.58 (s, 3H), 0.51 (s, 3H), 0.26 (s, 3H), 0.39 (s, 3H)

Example 5

Preparation of Compound of Formula 1-5

(16) ##STR00033##

(17) The ligand compound of Formula 2-5 (1.74 g, 4.14 mmol/1.0 eq) and 20.7 ml (0.2 M) of toluene were added to a 50 ml vial and stirred. n-BuLi (3.48 ml, 8.7 mmol/2.1 eq, 2.5 M in hexane) was added thereto at 40 C., and then stirred at room temperature overnight. Then, MeMgBr (4.14 ml, 12.42 mmol/3.0 eq, 3.0 M in diethyl ether) was slowly added thereto dropwisely at 40 C., and TiCl.sub.4DME (1.1 g, 4.14 mmol/1.0 eq) was added in order, followed by stirring at room temperature overnight. After drying solvents, the reaction mixture was filtered using hexane. Then, to a filtrate, DME (1.29 ml, 12.42 mmol/3 eq) was added and stirred at room temperature overnight. After drying solvents, filtering was performed using hexane to obtain 335 mg of a yellow solid (16.3%, dr=1:0.8).

(18) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.90 (d, 1H), 7.85 (d, 1H), 7.74 (d, 1H), 7.71 (d, 1H), 7.40 (d, 1H), 7.37 (d, 1H), 7.27 (d, 1H), 7.23 (t, 2H), 7.17 (t, 2H), 7.13 (t, 2H), 7.06 (t, 1H), 7.01 (t, 1H), 6.86 (t, 1H), 2.97-2.91 (m, 2H), 2.90-2.82 (m, 2H), 2.33 (s, 3H), 2.22 (s, 3H), 1.96 (s, 3H), 1.68 (s, 9H), 1.66 (s, 9H), 1.38 (s, 3H), 1.32 (t, 3H), 1.24 (t, 3H), 1.07 (s, 3H), 0.88 (s, 3H), 0.85 (s, 3H), 0.72 (s, 3H), 0.19 (s, 3H), 0.01 (s, 3H)

Example 6

Preparation of Compound of Formula 1-6

(19) ##STR00034##

(20) The ligand compound of Formula 2-6 (1.06 g, 2.45 mmol/1.0 eq) and 12.25 ml (0.2 M) of toluene were added to a 50 ml vial and stirred. n-BuLi (2.06 ml, 5.15 mmol/2.1 eq, 2.5 M in hexane) was added thereto at 40 C., and then stirred at room temperature overnight. Then, MeMgBr (2.45 ml, 7.35 mmol/3.0 eq, 3.0 M in diethyl ether) was slowly added thereto dropwisely at 40 C., and TiCl.sub.4DME (686 mg, 2.45 mmol/1.0 eq) was added in order, followed by stirring at room temperature overnight. After drying solvents, the reaction mixture was filtered using hexane. Then, to a filtrate, DME (1.29 ml, 12.42 mmol/3 eq) was added and stirred at room temperature overnight. After drying solvents, filtering was performed using hexane to obtain 400 mg of a yellow solid (32%, dr=1:1).

(21) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.55 (d, 2H), 7.32 (d, 2h), 7.08 (t, 2H), 6.95 (t, 2H), 6.89 (s, 2H), 6.79 (s, 2H), 2.73 (s, 3H), 2.65 (s, 3H), 2.55 (s, 3H), 2.33 (s, 3H), 2.21 (s, 3H), 2.02 (s, 6H), 1.94 (s, 3H), 1.77 (s, 6H), 1.67 (s, 3H), 1.64 (s, 3H), 1.28 (s, 3H), 1.07 (s, 3H), 1.04 (s, 18H), 0.72 (s, 3H), 0.22 (s, 3H)

Example 7

Preparation of Compound of Formula 1-7

(22) ##STR00035##

(23) To a 100 ml schlenk flask, 1 g (2.347 mmol, 1.0 eq) of the ligand compound of Formula 2-7 and 10 ml (0.2 M) of toluene were added, and 2.0 ml (4.811 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added thereto dropwisely at 30 C., and then stirred at room temperature overnight. After stirring, 2.4 ml (7.041 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added thereto dropwisely, and 2.5 ml (2.464 mmol, 1.05 eq, 1.0 M in toluene) of TiCl.sub.4 was added in order, followed by stirring at room temperature overnight. After stirring, the reaction mixture was vacuum dried and extracted with 30 ml of hexane. After removing solvents to 10 ml, 1 ml (7.041 mmol, 3.0 eq) of DME was added dropwisely and stirred at room temperature overnight. After vacuum drying again, extraction with 10 ml of hexane was performed. After drying solvents, 0.63 g of a brown solid was obtained (53%, dr=1:0.38).

(24) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.98 (d, 1H), 7.95 (d, 1H), 7.70 (d, 1H), 7.64 (d, 2H), 7.61 (d, 2H), 7.58 (d, 1H) 7.457.30 (m, 8H), 2.66 (s, 3H), 2.61 (s, 3H), 2.14 (s, 3H), 1.59 (s, 3H), 1.55 (s, 9H), 1.54 (s, 9H), 0.83 (s, 3H), 0.80 (s, 3H), 0.58 (s, 3H), 0.52 (s, 3H), 0.25 (s, 3H), 0.37 (s, 3H)

Example 8

Preparation of Compound of Formula 1-8

(25) ##STR00036##

(26) To a 100 ml schlenk flask, 1 g (2.347 mmol, 1.0 eq) of the ligand compound of Formula 2-8 and 10 ml (0.2 M) of toluene were added, and 2.0 ml (4.811 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added thereto dropwisely at 30 C., followed by stirring at room temperature overnight.

(27) After stirring, 2.4 ml (7.041 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added thereto dropwisely, and 2.5 ml (2.464 mmol, 1.05 eq, 1.0 M in toluene) of TiCl.sub.4 was added in order, followed by stirring at room temperature overnight. After stirring, the reaction mixture was vacuum dried and extracted with 30 ml of hexane. After removing solvents to 10 ml, 1 ml (7.041 mmol, 3.0 eq) of DME was added dropwisely and stirred at room temperature overnight. After vacuum drying again, extraction with 10 ml of hexane was performed. After drying solvents, 0.79 g of a brown moist solid was obtained (53%, dr=1:0.35).

(28) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.98 (d, 1H), 7.94 (d, 1H), 7.70 (d, 2H), 7.67 (s, 1H), 7.64 (s, 1H), 7.58 (d, 1H), 7.56 (d, 1H), 7.457.30 (m, 8H), 2.66 (s, 3H), 2.61 (s, 3H), 2.14 (s, 3H), 1.60 (s, 3H), 1.55 (s, 18H), 0.92 (s, 3H), 0.91 (s, 3H), 0.60 (s, 3H), 0.53 (s, 3H), 0.22 (s, 3H), 0.36 (s, 3H)

Example 9

Preparation of Compound of Formula 1-9

(29) ##STR00037##

(30) To a 100 ml schlenk flask, 0.56 g (1.371 mmol, 1.0 eq) of the ligand compound of Formula 2-9 and 7 ml (0.2 M) of toluene were added, and 1.2 ml (2.810 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added thereto dropwisely at 30 C., followed by stirring at room temperature overnight. After stirring, 1.4 ml (4.113 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added thereto dropwisely, and 1.4 ml (1.440 mmol, 1.05 eq, 1.0 M in toluene) of TiCl.sub.4 was added in order, followed by stirring at room temperature overnight. After stirring, the reaction mixture was vacuum dried and extracted with 20 ml of hexane. After removing solvents to 10 ml, 0.5 ml (4.113 mmol, 3.0 eq) of DME was added dropwisely and stirred at room temperature overnight. After vacuum drying again, extraction with 20 ml of hexane was performed. After drying solvents, 0.48 g of a red brown solid was obtained (72%, dr=1:0.36).

(31) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.98 (d, 1H), 7.95 (d, 1H), 7.657.75 (m, 5H), 7.56 (d, 1H), 7.40 (t, 2H), 7.387.10 (m, 6H), 2.70 (s, 3H), 2.66 (s, 3H), 2.14 (s, 3H), 1.60 (s, 3H), 1.54 (s, 18H), 0.92 (s, 3H), 0.90 (s, 3H), 0.58 (s, 3H), 0.52 (s, 3H), 0.25 (s, 3H), 0.38 (s, 3H)

Example 10

Preparation of Compound of Formula 1-10

(32) ##STR00038##

(33) To a 100 ml schlenk flask, 0.6 g (1.322 mmol, 1.0 eq) of the ligand compound of Formula 2-10 and 8 ml (0.2 M) of toluene were added, and 1.1 ml (2.711 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added thereto dropwisely at 30 C., followed by stirring at room temperature overnight. After stirring, 1.4 ml (3.967 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added thereto dropwisely, and 1.4 ml (1.322 mmol, 1.0 eq, 1.0 M in toluene) of TiCl.sub.4 was added in order, followed by stirring at room temperature overnight. After stirring, the reaction mixture was vacuum dried and extracted with 40 ml of hexane. After removing solvents to 10 ml, 0.4 ml (3.967 mmol, 3.0 eq) of DME was added dropwisely and stirred at room temperature overnight. After vacuum drying again, extraction with 10 ml of hexane was performed. After drying solvents, 0.5 g of a yellow solid was obtained (72%, dr=1:1).

(34) .sup.1H NMR (CDCl.sub.3, 500 MHz): 7.98 (d, 1H), 7.79 (d, 2H), 7.76 (d, 2H), 7.55 (d, 1H), 7.50 (d, 1H), 7.447.35 (m, 6H), 7.25 (t, 1H), 2.66 (s, 3H), 1.75 (s, 3H), 1.72 (s, 9H), 0.60 (s, 3H), 0.26 (s, 3H)

Comparative Example 1

Preparation of Ligand Compound

(35) ##STR00039##

Synthesis of N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-dimethylsilaneamine

(36) To a 100 ml schlenk flask, 4.65 g (15.88 mmol) of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-dimethylsilane was weighed and added, and 80 ml of THF was added thereto. At room temperature, tBuNH.sub.2 (4 eq, 6.68 mmol) was added thereto, followed by reacting at room temperature for 3 days. After finishing the reaction, THF was removed, and filtering using hexane was performed. After drying solvents, 4.50 g of a yellow liquid was obtained (86%).

(37) .sup.1H-NMR (in CDCl.sub.3, 500 MHz): 7.99 (d, 1H), 7.83 (d, 1H), 7.35 (dd, 1H), 7.24 (dd, 1H), 3.49 (s, 1H), 2.37 (s, 3H), 2.17 (s, 3H), 1.27 (s, 9H), 0.19 (s, 3H), 0.17 (s, 3H)

(38) ##STR00040##

(39) To a 50 ml schlenk flask, N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-dimethylsilaneamine (1.06 g, 3.22 mmol/1.0 eq) and 16.0 ml (0.2 M) of MTBE were added and stirred first. n-BuLi (2.64 ml, 6.60 mmol/2.05 eq, 2.5 M in THF) was added thereto at 40 C., and then stirred at room temperature overnight. Then, MeMgBr (2.68 ml, 8.05 mmol/2.5 eq, 3.0 M in diethyl ether) was slowly added thereto dropwisely at 40 C., and TiCl.sub.4 (2.68 ml, 3.22 mmol/1.0 eq, 1.0 M in toluene) was added in order, followed by stirring at room temperature overnight. Then, the reaction mixture was filtered by passing through Celite using hexane. After drying solvents, 1.07 g of a brown solid was obtained (82%).

(40) .sup.1H-NMR (CDCl.sub.3, 500 MHz): 7.99 (d, 1H), 7.68 (d, 1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 (s, 3H), 2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40 (s, 3H), 0.45 (s, 3H)

Preparation Example of Polymers

Experimental Examples 1 to 10, and Comparative Experimental Examples 1 to 4

(41) To a 2 L autoclave reactor, a hexane solvent (1.0 L) and 1-octene (in an amount shown in Table 1 below) were added, and the reactor was pre-heated to 150 C. At the same time, the pressure of the reactor was charged with ethylene (35 bars) in advance. A dimethylanilinium tetrakis(pentafluorophenyl) borate (AB) cocatalyst (9 mol) and a compound (3 mol) of the third column in Table 1 below, which was treated with a triisobutylaluminum (Tibal) compound (0.25 mmol) were injected to the reactor in order by applying argon with high pressure. Then, a copolymerization reaction was performed for 8 minutes. After that, the remaining ethylene gas was exhausted out, and a polymer solution was added to an excessive amount of ethanol to induce precipitation. The precipitated polymer was washed with ethanol twice or three times, and dried in a vacuum oven at 90 C. for 12 hours or more, and the physical properties thereof were measured.

(42) Various polymers were prepared in accordance with the polymerization temperature, a main catalyst and a catalyst listed in Table 1 below, and the results are shown in Table 1 below.

Evaluation of Physical Properties

Melt Index of Polymer

(43) The melt index (MI) of each polymer was measured according to ASTM D-1238 (condition E, 190 C., 2.16 kg load)

Melting Temperature of Polymer

(44) The melting temperature (Tm) of each polymer was obtained using a differential scanning calorimeter 6000 (DSC) manufactured by PerkinElmer Co, and the melting temperature of a polymer may be measured as follows. About 0.5 mg to 10 mg of each specimen was charged in a container for measurement, and a nitrogen gas flow rate was controlled to 20 ml/min. In order to synchronize the thermal hysteresis of a polyolefin resin, the temperature of each specimen was increased from 0 C. to 150 C. with a rate of 20 C./min, decreased from 150 C. to 100 C. with a rate of 10 C./min and then, increased from 100 C. to 150 C. with a rate of 10 C./min, and the temperature of the peak of a heating curve on heat flow measured by DSC, that is, heat absorption peak during heating was set as the melting temperature.

Density of Polymer

(45) The density of each polymer was obtained by manufacturing a sheet having a thickness of 3 mm and a radius of 2 cm using a press mold at 190 C., annealing thereof at room temperature for 24 hours, and conducting measurement using a Mettler balance.

Measurement of Availability of a Product Having Low Density and High Molecular Weight in Accordance with Temperature

(46) TABLE-US-00001 TABLE 1 1-octene Poly- Melt injection merization index amount Cat. temp Density (MI) Tm Cat. (ml) (compound) ( C.) Cocat (g/cc) (g/10 min) ( C.) Comparative 140 Formula 11-1 150 AB 0.888 0.6 Experimental (Comparative Example 1 Example 1) Experimental 140 Formula 1-1 150 AB 0.884 0.2 Example 1 (Example 1) Comparative 310 Formula 11-1 150 AB 0.871 2.7 (56.9)/ Experimental (Comparative 66.8 Example 2 Example 1) Experimental 310 Formula 1-2 150 AB 0.865 3.2 (47.8)/ Example 2 (Example 2) 62.1 Experimental 310 Formula 1-3 150 AB 0.866 2.6 (49.8)/ Example 3 (Example 3) 61.8 Experimental 310 Formula 1-4 150 AB 0.866 1.4 (43.0)/ Example 4 (Example 4) 60.3 Comparative 330 Formula 11-1 150 AB 0.873 7.9 (60.5)/ Experimental (Comparative 68.7 Example 3 Example 1) Experimental 280 Formula 1-5 150 AB 0.868 1.0 (52.5)/ Example 5 (Example 5) 62.3 Experimental 280 Formula 1-6 150 AB 0.865 1.9 23.3/ Example 6 (Example 6) 54.4 Comparative 270 Formula 11-1 150 AB 0.879 4.1 74.0 Experimental (Comparative Example 4 Example 1) Experimental 270 Formula 1-7 150 AB 0.870 2.9 64.0 Example 7 (Example 7) Experimental 270 Formula 1-8 150 AB 0.872 2.2 64.0 Example 8 (Example 8) Experimental 270 Formula 1-9 150 AB 0.867 2.5 Example 9 (Example 9) Experimental 260 Formula 1-10 150 AB 0.873 1.4 64.1 Example 10 (Example 10) AB: dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst

(47) As verified in Table 1, if the compounds of Examples 1 to 10 were used as the catalysts, polymers having lower density could be prepared when compared to a case where the compound of Comparative Example 1 was used as the catalyst, if the injection amount of 1-octene were the same. In addition, irrespective of the injection amount of 1-octene, a certain trend was shown.

(48) Meanwhile, if the compounds of Examples 1 to 10 were used as the catalysts, low density and low melt index (MI) were shown, and the preparation of a polymer having high molecular weight could be secured.

(49) Accordingly, if a polymer is prepared using the transition metal compounds prepared in Examples 1 to 10 of the present invention, excellent copolymerization degree could be achieved, and a polymer in a low density region and a polymer having high molecular weight could be prepared.