Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst using the same

Abstract

The present disclosure provides a method for preparing a supported hybrid metallocene catalyst which can be used to prepare a polyolefin, a supported hybrid metallocene catalyst prepared by using the method, and a method for preparing a polyolefin using the supported hybrid metallocene catalyst.

Claims

1. A method for preparing a supported hybrid metallocene catalyst, comprising the steps of supporting at least one first metallocene compound represented by the following Chemical Formula 1 or 2 on a support; and supporting a cocatalyst on the support on which the first metallocene compound is supported: ##STR00021## in Chemical Formula 1, R.sub.1, R.sub.2, R.sub.5, and R.sub.6 are the same as or different from each other, and are each independently hydrogen or a C1 to C20 alkyl group, R.sub.3, R.sub.4, R.sub.7, and R.sub.8 are the same as or different from each other, and are each independently hydrogen or a C1 to C20 alkyl group, or adjacent R.sub.3 and R.sub.4 and adjacent R.sub.7 and R.sub.8, respectively, are optionally connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring, Q is a Group 4 transition metal, and R.sub.9 and R.sub.10 are pivalate, ##STR00022## in Chemical Formula 2, M is a Group 4 transition metal, B is carbon, silicon, or germanium, Q.sub.1 and Q.sub.2 are the same as or different from each other, and are each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group, X.sub.1 and X.sub.2 are pivalate, and C.sub.1 and C.sub.2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 3a, Chemical Formula 3b, Chemical Formula 3c, or Chemical Formula 3d, provided that at least one of C.sub.1 and C.sub.2 is represented by Chemical Formula 3a, ##STR00023## in Chemical Formulae 3a, 3b, 3c, and 3d, R.sub.1 to R.sub.28 are the same as or different from each other, and are each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 ether group, a C1 to C20 silylether group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, R.sub.1 to R.sub.3 are the same as or different from each other, and are each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group, and two or more neighboring groups of R.sub.1 to R.sub.28 are optionally connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring.

2. The method of claim 1, further comprising a step of supporting a second metallocene compound on the support on which the cocatalyst is supported, wherein the second metallocene compound is represented by the same Chemical Formula 1 or 2 of claim 1 except R.sub.9, R.sub.10, X.sub.1 and X.sub.2 are each independently pivalate, halogen, or a C1 to C20 alkyl group.

3. The method of claim 1, wherein the first metallocene compound is selected from the group consisting of the following structural formulae: ##STR00024##

4. The method of claim 2, wherein the second metallocene compound is selected from the group consisting of the following structural formulae: ##STR00025##

5. The method of claim 2, wherein the first metallocene compound and the second metallocene compound are supported at a weight ratio of 1:99 to 99:1.

6. The method of claim 1, wherein the cocatalyst comprises one or more selected from the group of compounds represented by the following Chemical Formula 4, Chemical Formula 5, and Chemical Formula 6:
[Al(R.sub.29)O].sub.n[Chemical Formula 4] in Chemical Formula 4, R.sub.29 are the same as or different from each other, and each independently halogen; C1 to C20 hydrocarbon; or halogen-substituted C1 to C20 hydrocarbon; and
J(R.sub.30).sub.3[Chemical Formula 5] in Chemical Formula 5, R.sub.30 are the same as R.sub.29 defined in Chemical Formula 4; and J is aluminum or boron;
[E-H].sup.+[ZA.sub.4].sup. or [E].sup.+[ZA.sub.4].sup.[Chemical Formula 6] in Chemical Formula 6, E is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; and A are the same as or different from each other, and each independently a C6 to C20 aryl group or a C1 to C20 alkyl group, of which one or more hydrogen atoms are unsubstituted or substituted with halogen, C1 to C20 hydrocarbon, alkoxy, or phenoxy.

7. The method of claim 1, wherein the cocatalyst comprises one or more compounds selected from the group consisting of methyl aluminoxane(MAO), ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

8. The method of claim 1, wherein the support comprises one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia.

9. The method of claim 1, wherein the support is previously dried at 200 to 1000 C.

10. The method of claim 2, wherein the first and second metallocene compound are each supported in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the support.

11. The method of claim 1, wherein the cocatalyst is supported in an amount of 1 to 1,000 parts by weight based on 100 parts by weight of the support.

12. A supported hybrid metallocene catalyst prepared by the method according to claim 1.

13. A method for preparing a polyolefin, comprising the step of polymerizing olinic monomers in the presence of the supported hybrid metallocene catalyst of claim 12.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only, and the invention is not intended to be limited by these examples.

PREPARATION EXAMPLE OF METALLOCENE COMPOUND

Preparation Example 1: Precursor A

(2) ##STR00013##

(3) 1-1 Synthesis of Ligand Compound

(4) 4.05 g (20 mmol) of ((1H-inden-3-yl)methyl)trimethylsilane was placed into a dried 250 mL Schlenk flask and dissolved in 40 mL of diethylether under argon gas. After cooling the solution to 0 C., 1.2 equivalent weights (9.6 mL, 24 mmol) of 2.5 M n-BuLi (hexane solution) dissolved in hexane was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 hours. A solution of 2.713 g (10 mmol) of silicone tether in 30 ml of hexane was prepared in another 250 ml Schlenk flask, cooled down to 78 C., and the above prepared mixture was slowly added dropwise thereto. After the dropwise addition, the mixture was slowly warmed to room temperature and stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO.sub.4 was added to the extracted organic layer and stirred for a while. And then, it was filtered and the solvent was dried under reduced pressure to obtain 6.1 g (molecular weight: 603.11, 10.05 mmol, yield: 100.5%) of a yellow oil-type ligand compound. The obtained ligand compound was used for the synthesis of the metallocene compound without a separation process.

(5) .sup.1H NMR (500 MHz, CDCl.sub.3): 0.02 (18H, m), 0.82 (3H, m), 1.15 (3H, m), 1.17 (9H, m), 1.42 (H, m), 1.96 (2H, m), 2.02 (2H, m), 3.21 (2H, m), 3.31 (1H, s), 5.86 (1H, m), 6.10 (1H, m), 7.14 (3H, m), 7.14 (2H, m) 7.32 (3H, m).

(6) 1-2 Synthesis of Metallocene Compound Precursor

(7) ##STR00014##

(8) The ligand compound synthesized in 1-1 was added to a 250 mL Schlenk flask dried in an oven, and then dissolved in 4 equivalent weights of methyl tert-butyl ether and 60 mL of toluene, to which 2 equivalent weights of n-BuLi hexane solution was added for lithiation. After one day, all solvent in the flask was removed under a vacuum condition, and the resultant was dissolved in an equal amount of toluene. In a glove box, one equivalent weight of ZrCl.sub.4(THF).sub.2 was added in a 250 mL Schlenk flask, and then toluene was injected into the flask to prepare a suspension. The above two flasks were cooled down to 78 C., and then the lithiated ligand compound was slowly added to the toluene suspension of ZrCl.sub.4(THF).sub.2. After completion of the injection, the reaction mixture was slowly warmed up to room temperature, stirred for one day and allowed to react. Then, toluene in the mixture was removed to a volume of about through vacuum/reduced pressure. Hexane of about 5 times the volume of the remaining toluene was added thereto and the mixture was recrystallized. The resultant was filtered without contacting with the outside air to obtain a metallocene compound. The resulting filter cake in the upper portion of the filter was washed using a small amount of hexane, and then weighed in the glove box to identify the synthesis, yield, and purity.

(9) 7.3 g (9.56 mmol, 95.6%) of a purple oil was obtained from 6.1 g (10 mmol) of the ligand compound, and was stored in a toluene solution (purity: 100%, molecular weight: 763.23).

(10) .sup.1H NMR (500 MHz, CDCl.sub.3): 0.03 (18H, m), 0.98, 1.28 (3H, d), 1.40 (9H, m), 1.45 (4H, m), 1.66 (6H, m), 2.43 (4H, s), 3.47 (2H, m), 5.34 (1H, m), 5.56 (1H, m), 6.95 (1H, m), 6.97 (1H, m), 6.98 (1H, m), 7.22 (1H, m), 7.36 (2H, m), 7.43 (1H, m), 7.57 (1H, m)

(11) 1-3 Synthesis of Metallocene Compound

(12) ##STR00015##

(13) 1.52 g (2 mmol) of the metallocene compound precursor prepared in 1-2 was added to a 250 mL Schlenk flask dried in an oven, and then diluted with 40 mL of dry toluene. This solution was cooled down to 78 C., and then 840 mg (6 mmol, 3 equivalent weights) of potassium pivalate was added thereto under an argon atmosphere. When this reaction mixture was gradually warmed up to room temperature, the color of the solution changed from red to yellow as the reaction proceeded. This reaction mixture was further stirred for about 2 hours, and then passed through a celite pad under an argon atmosphere to remove the residual potassium pivalate and inorganic materials. A solvent was removed from a filtrate under reduced pressure to obtain a light yellow compound with a yield of 80%.

(14) .sup.1H NMR (500 MHz, CDCl.sub.3): 0.05-0.24 (18H, m), 0.89-0.92 (3H, m), 1.28-1.43 (31H, m), 1.50-1.62 (4H, m), 2.17-2.23 (2H, m), 2.46 (4H, s), 3.34 (2H, m), 6.32 (2H, m), 6.67 (2H, m), 7.14-7.38 (8H, m)

Preparation Example 2: Precursor B

(15) ##STR00016##

(16) As a metallocene compound precursor, Dichloro[rac-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)]zirconium(IV) was procured (purchased from Sigma-Aldrich, Cas Number 100163-29-9). 2.13 g (5 mmol) of the metallocene compound precursor was added to a 250 mL Schlenk flask dried in an oven. Under an argon atmosphere, 1.02 g (10 mmol) of pivalic acid was added thereto, and dissolved in 50 mL of dichloromethane. This reaction mixture was cooled down to 0 C., and then 1.4 mL (10 mmol) of triethylamine was slowly injected thereto. A bath was removed, and the reaction mixture was gradually warmed up to room temperature. Within 30 minutes, a yellow color disappeared and it turned to a white color. After about 1 hr, the reaction solvent was completely removed under reduced pressure, and 100 mL of ether was added to completely dissolve a white solid by sonication. The mixture in the flask was filtered under an argon atmosphere to obtain a colorless ether filtrate. This filtrate was completely dried to obtain 2.65 g (yield of about 90%) of a white solid.

(17) .sup.1H NMR (500 MHz, CDCl.sub.3): 1.19 (18H, s), 1.41-1.58 (4H, m), 1.72-1.79 (2H, m), 1.81-1.88 (2H, m), 2.21-2.25 (2H, m), 2.33-2.39 (2H, m), 2.52-2.60 (2H, m), 2.82-2.88 (2H, m), 3.03-3.16 (4H, m), 5.57 (2H, s), 5.92 (2H, s)

(18) Preparation Example 3: Precursor C

(19) ##STR00017##

(20) As a metallocene compound precursor, Dichloro[rac-ethylene bis(indenyl)]zirconium(IV) was procured (purchased from Sigma-Aldrich, CAS Number 100080-82-8). 2.05 g (5 mmol) of the metallocene compound precursor was added to a 250 mL Schlenk flask dried in an oven, and then 60 mL of dry toluene was added thereto to prepare a suspension. Under an argon atmosphere, 2.11 g (15 mmol, 3 equivalent weights) of potassium pivalate was thereto, and within about 2 hrs, floating materials disappeared, and the solution turned clear yellow. This reaction mixture was further stirred for about 3 hours, and then passed through a celite pad under an argon atmosphere to remove residual potassium pivalate and inorganic materials. A solvent was removed from a resulting filtrate under reduced pressure and recrystallized with pentane to obtain a light yellow compound with a yield of 50% to 60%.

(21) .sup.1H NMR (500 MHz, CDCl.sub.3): 0.98-1.22 (18H, m), 3.34 (4H, s), 6.61 (2H, m), 6.83 (2H, m), 7.26-7.35 (4H, m), 7.37-7.41 (2H, m), 7.43-7.48 (1H, m), 7.54-7.58 (1H, m)

Comparative Preparation Example 1: Precursor D

(22) ##STR00018##

(23) The metallocene compound precursor of the above structural formula synthesized in 1-2 of Preparation Example 1 was used.

Comparative Preparation Example 2: Precursor E

(24) ##STR00019##

(25) A metallocene compound having the above structural formula, Dichloro [rac-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)]zirconium(IV) was procured (purchased from Sigma-Aldrich, Cas Number 100163-29-9).

Comparative Preparation Example 3: Precursor F

(26) ##STR00020##

(27) A metallocene compound having the above structural formula, Dichloro[rac-ethylene bis(indenyl)]zirconium(IV) was procured (purchased from Sigma-Aldrich, Cas Number 100080-82-8).

Example of Supported Catalyst

Catalyst Example 1

(28) 0.95 g of the catalyst precursor structure A prepared in Preparation Example 1 and 30 mL of toluene were added to a 50 mL Schlenk flask to prepare a precursor solution. 100 mL of toluene was added to a 300 mL high pressure glass reactor, 10 g of silica (Grace Davison, SP952X calcined at 650 C.) was added thereto at 40 C., and stirred for 30 min, and then allowed to stand. The solution prepared in the 50 mL flask was added to a glass reactor, warmed to 60 C., and allowed to react for 6 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, 70 g of 10 wt % MAO was added thereto, warmed to 80 C., and allowed to react for 12 hrs while stirring. The reactor was cooled down to room temperature, and then stirring was stopped, followed by settling for 10 min and then decantation. 100 mL of hexane was added into the reactor, the hexane slurry was transferred to a Schlenk flask, and the hexane solution was subjected to decantation. The resultant was dried at room temperature under reduced pressure for 3 hrs.

Catalyst Example 2

(29) A supported catalyst was prepared in the same manner as in Catalyst Example 1, except that 0.76 g of the catalyst precursor structure B was used instead of the catalyst precursor structure A.

Catalyst Example 3

(30) A supported catalyst was prepared in the same manner as in Catalyst Example 1, except that 0.70 g of the catalyst precursor structure C was used instead of the catalyst precursor structure A.

Catalyst Example 4

(31) 0.76 g of the catalyst precursor structure A prepared in Preparation Example 1 and 30 mL of toluene were added to a 50 mL Schlenk flask to prepare a precursor solution. 100 mL of toluene was added to a 300 mL high pressure glass reactor, 10 g of silica (Grace Davison, SP952X calcined at 650 C.) was added thereto at 40 C., and stirred for 30 min, and then allowed to stand. The solution prepared in the 50 mL flask was added to a glass reactor, warmed to 80 C., and allowed to react for 6 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, 70 g of 10 wt % MAO was added thereto, warmed to 80 C., and allowed to react for 12 hrs while stirring. The reactor was cooled down to room temperature, and then stirring was stopped, followed by settling for 10 min and then decantation. 100 mL of hexane was added into the reactor, the hexane slurry was transferred to a Schlenk flask, and the hexane solution was subjected to decantation. The resultant was dried at room temperature under reduced pressure for 3 hrs.

Catalyst Example 5

(32) A supported catalyst was prepared in the same manner as in Catalyst Example 4, except that 0.61 g of the catalyst precursor structure B was used instead of the catalyst precursor structure A.

Catalyst Example 6

(33) 0.50 g of the catalyst precursor structure A prepared in Preparation Example 1 and 30 mL of toluene were added to a 50 mL Schlenk flask to prepare a precursor solution. 100 mL of toluene was added to a 300 mL high pressure glass reactor, 7 g of silica (Grace Davison, SP952X calcined at 650 C.) was added thereto at 40 C., and stirred for 30 min, and then allowed to stand. The solution prepared in the 50 mL flask was added to a glass reactor, warmed to 60 C., and allowed to react for 6 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, 54 g of 10 wt % MAO was added thereto, warmed to 80 C., and allowed to react for 12 hrs while stirring. The reactor was cooled down to room temperature, and then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, warmed to 80 C., 0.25 g of the catalyst precursor structure B prepared in Preparation Example 2 was added thereto, and allowed to react for 4 hrs. The reactor was cooled down to room temperature, and then stirring was stopped, followed by settling for 10 min and then decantation. 100 mL of hexane was added into the reactor, the hexane slurry was transferred to a Schlenk flask, and the hexane solution was subjected to decantation. The resultant was dried at room temperature under reduced pressure for 3 hrs.

Catalyst Example 7

(34) A supported catalyst was prepared in the same manner as in Catalyst Example 6, except that 0.77 g of the catalyst precursor structure A was used instead of 0.50 g, and 0.52 g of the catalyst precursor structure C was used instead of the catalyst precursor structure B.

Catalyst Example 8

(35) A supported catalyst was prepared in the same manner as in Catalyst Example 6, except that 0.35 g of the catalyst precursor structure A was used instead of 0.50 g, and 0.24 g of the catalyst precursor structure E was used instead of the catalyst precursor structure B.

Catalyst Example 9

(36) 0.50 g of the catalyst precursor structure A prepared in Preparation Example 1 and 30 mL of toluene were added to a 50 mL Schlenk flask to prepare a precursor solution. 100 mL of toluene was added to a 300 mL high pressure glass reactor, 8 g of silica (Grace Davison, SP952X calcined at 650 C.) was added thereto at 40 C., and stirred for 30 min, and then allowed to stand. The solution prepared in the 50 mL flask was added to a glass reactor, warmed to 60 C., and allowed to react for 3 hrs while stirring. 0.25 g of the catalyst precursor structure B prepared in Preparation Example 2 was added to the reactor, and allowed to react for 5 hrs. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, 54 g of 10 wt % MAO was added thereto, warmed to 80 C., and allowed to react for 12 hrs while stirring. The reactor was cooled down to room temperature, and then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, warmed to 80 C., 0.17 g of the catalyst precursor structure F prepared in Comparative Preparation Example 3 was added thereto, and allowed to react for 4 hrs. The reactor was cooled down to room temperature, and then stirring was stopped, followed by settling for 10 min and then decantation. 100 mL of hexane was added into the reactor, the hexane slurry was transferred to a Schlenk flask, and the hexane solution was subjected to decantation. The resultant was dried at room temperature under reduced pressure for 3 hrs.

Catalyst Example 10

(37) A supported catalyst was prepared in the same manner as in Catalyst Example 6, except that 0.41 g of the catalyst precursor structure B was used instead of the catalyst precursor structure A, and 0.50 g of the catalyst precursor structure C was used instead of the catalyst precursor structure B.

Catalyst Comparative Example 1

(38) A supported catalyst was prepared in the same manner as in Catalyst Example 1, except that 0.85 g of the catalyst precursor structure D prepared in Comparative Preparation Example 1 was used instead of the catalyst precursor structure A.

Catalyst Comparative Example 2

(39) A supported catalyst was prepared in the same manner as in Catalyst Example 5, except that 0.51 g of the catalyst precursor structure E prepared in Comparative Preparation Example 1 was used instead of the catalyst precursor structure B.

Catalyst Comparative Example 3

(40) 100 mL of toluene was added to a 300 mL high pressure glass reactor, 10 g of silica (Grace Davison, SP952X calcined at 650 C.) was added thereto at 40 C., and stirred for 30 min, and then allowed to stand. 70 g of 10 wt % MAO was added thereto, warmed to 80 C., and allowed to react for 12 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. 50 mL of toluene was added to the reactor and stirred for 5 min. And then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, 0.68 g of the catalyst precursor structure A prepared in Preparation Example 1 and 30 mL of toluene were added thereto. The temperature was warmed to 60 C., and allowed to react for 4 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. 100 mL of hexane was added into the reactor, the hexane slurry was transferred to a Schlenk flask, and the hexane solution was subjected to decantation. The resultant was dried at room temperature under reduced pressure for 3 hrs.

Catalyst Comparative Example 4

(41) A supported catalyst was prepared in the same manner as in Catalyst Comparative Example 3, except that 0.61 g of the catalyst precursor structure C prepared in Preparation Example 3 was used instead of the catalyst precursor structure A.

Catalyst Comparative Example 5

(42) 100 mL of toluene was added to a 300 mL high pressure glass reactor, 10 g of silica (Grace Davison, SP952X calcined at 650 C.) was added thereto at 40 C., and stirred for 30 min, and then allowed to stand. 70 g of 10 wt % MAO was added thereto, warmed to 80 C., and allowed to react for 12 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. 50 mL of toluene was added to the reactor and stirred for 5 min. And then stirring was stopped, followed by settling for 10 min and then decantation. After 30 mL of toluene was added to the reactor, 0.33 g of the catalyst precursor structure A prepared in Preparation Example 1 and 30 mL of toluene were added thereto. The temperature was warmed to 60 C., and allowed to react for 2 hrs while stirring. And then, 0.45 g of the catalyst precursor structure B prepared in Preparation Example 2 and 30 mL of toluene were added to the reactor, and allowed to react for 2 hrs while stirring. The reactor was cooled down to 40 C., and then stirring was stopped, followed by settling for 10 min and then decantation. 100 mL of hexane was added into the reactor, the hexane slurry was transferred to a Schlenk flask, and the hexane solution was subjected to decantation. The resultant was dried at room temperature under reduced pressure for 3 hrs.

Example of Polyethylene Polymerization

Polymerization Examples 1 to 10 and Comparative Polymerization Examples 1 to 6: Preparation of a Polyolefin

(43) Ethylene Polymerization

(44) 2 mL of TEAL (1 M in hexane) and 70 g of 1-hexene were injected into a 2 L autoclave high pressure reactor, and 0.6 kg of hexene was added thereto, and then warmed to 85 C. while stirring at 500 rpm. And then, 30 to 45 mg of the supported catalysts (Catalyst Examples 1 to 10 and Comparative Catalyst Examples 1 to 5) and hexane were added to the reactor in vials. When the internal temperature of the reactor reached 85 C., the solution was reacted under an ethylene pressure of 30 bar for 1 hr while stirring at 500 rpm. Hydrogen was injected at a rate (0.005-0.001%) determined according to a flow rate of ethylene. After completion of the reaction, a resulting polymer was filtered to primarily remove hexane, and then dried in an oven at 80 C. for 3 hrs.

(45) The reaction conditions and results of Polymerization Examples 1 to 10 and Comparative Polymerization Examples 1 to 6 are shown in the following Tables 1 and 2.

(46) TABLE-US-00001 TABLE 1 Content of BD(Bulk Catalyst catalyst Activity Mw(*10.sup.4) density) (structure) (mg) (kgPE/gCat) (g/mol) PDI (g/mL) Example 1 Preparation 35 4.7 12.5 3.9 0.32 Example 1 Example 2 Preparation 45 3.4 30.2 2.9 0.31 Example 2 Example 3 Preparation 45 3.9 13.7 3.1 0.31 Example 3 Example 4 Preparation 40 4.2 12.7 4.0 0.33 Example 4 Example 5 Preparation 45 3.0 30.8 3.0 0.32 Example 5 Comparative Comparative 40 4.0 12.8 3.6 0.30 Example 1 Preparation Example 1 Comparative Comparative 100 1.5 35.1 2.7 0.28 Example 2 Preparation Example 2 Comparative Comparative 40 3.8 12.3 3.4 0.28 Example 3 Preparation Example 3 Comparative Comparative 40 3.5 13.8 3.1 0.24 Example 4 Preparation Example 4

(47) Referring to Table 1, it was confirmed that the supported hybrid metallocene catalyst prepared by first supporting the metallocene compound having pivalate, and then supporting the cocatalyst, as in Examples 1 to 5, had the catalytic activity of the same as or higher than that of Comparative Examples 1 to 4 prepared by using the metallocene compound prepared by using the metallocene compound having no pivalate or first supporting the cocatalyst.

(48) In addition, the polyolefin prepared using the metallocene catalysts of Examples 1 to 5 is predicted to have excellent processability, because the PDI is larger than that of the polyolefin prepared using the metallocene catalysts of Comparative Examples 1 to 4, and bulk density was also improved.

(49) TABLE-US-00002 TABLE 2 Content of BD(Bulk Catalyst catalyst Activity H.sub.2 feed MI_2.16 MFRR Tm density) (structure) (mg) (kgPE/gCat) (mol %) (g/10 mim) (2/10) ( C.) (g/mL) Example 6 Preparation 35 5.2 0.05 0.72 10.5 120.0 0.32 Example 6 Example 7 Preparation 30 6.3 0.03 0.28 15.2 120.5 0.31 Example 7 Example 8 Preparation 35 4.8 0.04 0.40 13.1 120.1 0.30 Example 8 Example 9 Preparation 35 5.5 0.04 0.48 13.9 120.9 0.32 Example 9 Example 10 Preparation 35 5.0 0.03 0.65 11.1 121.1 0.29 Example 10 Comparative Comparative 40 4.0 0.01 1.1 9.5 119.5 0.29 Example 5 Preparation Example 3 Comparative Comparative 40 3.9 0.03 0.76 10.0 120.6 0.28 Example 6 Preparation Example 5

(50) Referring to Table 2, it was confirmed that the supported hybrid metallocene catalyst prepared by first supporting the metallocene compound having pivalate, and then supporting the cocatalyst and the metallocene compound having or not having pivalate, as in Examples 6 to 10, had the catalytic activity of the same as or higher than that of Comparative Examples 5 to 6 prepared by using the metallocene compound prepared by using the metallocene compound having no pivalate or first supporting the cocatalyst.

(51) Moreover, the polyolefin prepared using the metallocene catalysts of Examples 6 to 10 is predicted that its processability and physical properties can be easily controlled, because it has excellent bulk density and thus can improve productivity, and the MFRR value can be finely adjusted to a desired level compared with to the polyolefin prepared using the metallocene catalysts of Comparative Examples 5 to 6.