Hybrid supported metallocene catalyst and polyolefin preparation method using same

Abstract

The present invention relates to a hybrid supported metallocene catalyst and a polyolefin preparation method using the same. Using the hybrid supported metallocene catalyst can not only significantly reduce the amount of wax produced when polymerizing olefin monomers, but can also enhance the stress cracking resistance of the polyolefin that is prepared.

Claims

1. A hybrid supported metallocene catalyst for the preparation of a polyolefin comprising ethylene, the hybrid supported metallocene catalyst comprising a combination of three metallocene compounds, the combination of three metallocene compounds being selected from: ##STR00026## ##STR00027## ##STR00028## a cocatalyst compound; and a support.

2. The hybrid supported metallocene catalyst of claim 1, wherein the cocatalyst compound includes at least one selected from the group consisting of a first cocatalyst of the following Chemical Formula 5 and a second cocatalyst of the following Chemical Formula 6,
—[Al(R.sub.27)—O—].sub.k—  [Chemical Formula 5] in Chemical Formula 5, each R.sub.28 is independently a halogen, a halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more,
T.sup.+[BG.sub.4].sup.−  [Chemical Formula 6] in Chemical Formula 6, T.sup.+ is a +1 valent polyatomic ion, B is boron in an oxidation state of +3, and G is each independently selected from the group consisting of a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbyl group and a halo-substituted hydrocarbyl, wherein the G has or less carbon atoms, provided that G is halide at one or less position.

3. The hybrid supported metallocene catalyst of claim 1, wherein the weight ratio of the transition metals of the first metallocene compound, the second metallocene compound and the third metallocene compound to the support is 1:10 to 1:1000.

4. The hybrid supported metallocene catalyst of claim 1, wherein the weight ratio of the cocatalyst compound to the support is 1:1 to 1:100.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The FIG. 1s a process diagram schematically showing a method of producing a polyolefin according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) Hereinafter, the invention will be described in more detail by way of examples. However, these examples are given for illustrative purposes only and the scope of the present invention is not limited by the examples.

Preparation Example of First Metallocene Compound

Preparation Example 1

(3) ##STR00020##

1-1. Preparation of Ligand Compound

(4) 2 g of fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred at room temperature overnight. 3.6 g of (6-(tert-butoxy)hexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane, and fluorene-Li slurry was transferred thereto under a dry ice/acetone bath for 30 minutes and the solution was stirred at room temperature overnight. At the same time, 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (12 mmol, 2.8 g) was dissolved in 60 mL of THF, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, and the solution was stirred at room temperature overnight. After confirming the completion of the reaction by NMR sampling of a reaction solution of fluorene and (6-(tert-butoxy)hexyl)dichloro(methyl)silane, 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole-Li solution was transferred under dry ice/acetone bath and then stirred at room temperature overnight. After the reaction, the solution was extracted with ether/water and residual moisture of the organic layer was removed with MgSO.sub.4, thereby obtaining two ligands (Mw 597.90, 12 mmol). It was confirmed by 1H-NMR that two isomers were produced.

(5) .sup.1H NMR (500 MHz, d6-benzene): −0.30˜-0.18 (3H, d), 0.40 (2H, m), 0.65˜1.45 (8H, m), 1.12 (9H, d), 2.36˜2.40 (3H, d), 3.17 (2H, m), 3.41˜3.43 (3H, d), 4.17˜4.21 (1H, d), 4.34˜4.38 (1H, d), 6.90˜7.80 (15H, m)

1-2. Preparation of Metallocene Compound

(6) 7.2 g (12 mmol) of the ligand compound synthesized in 1-1 above was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise thereto in a dry ice/acetone bath and stirred at room temperature overnight. The solution was dried under vacuum to obtain a brown-colored sticky oil, which was then dissolved in toluene to obtain a slurry. ZrCl.sub.4(THF).sub.2 was prepared and 50 mL of toluene was added thereto to prepare a slurry. 50 mL toluene slurry of ZrCl.sub.4(THF).sub.2 was transferred in a dry ice/acetone bath. It was changed to violet color by stirring at room temperature overnight. The reaction solution was filtered to remove LiCl. The filtrate was dried under vacuum to remove toluene, to which hexane was added and subjected to sonication for 1 hour. The slurry was filtered to obtain 6 g of a dark violet-colored metallocene compound as a filtered solid (Mw 758.02, 7.92 mmol, yield 66 mol %). Two isomers were observed by 1H-NMR.

(7) .sup.1H NMR (500 MHz, CDCl.sub.3): 1.19 (9H, d), 1.71 (3H, d), 1.50˜1.70 (4H, m), 1.79 (2H, m), 1.98˜2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66˜7.88 (15H, m)

Preparation Example 2

(8) ##STR00021##

2-1. Preparation of Ligand Compound

(9) 2.63 g (12 mmol) of 5-methyl-5,1 hydroindeno [1,2-b]indole was added to a 250 mL flask and dissolved in in 50 mL of THF. Then, 6 mL of 2.5 M n-BuLi hexane solution was added dropwise to dry ice/acetone bath, and the mixture was stirred at room temperature overnight. In another 250 mL flask, 1.62 g (6 mmol) of (6-(tert-butoxy)hexyl)dichloro(methyl)silane was dissolved in 100 mL of hexane, and then the solution was slowly added dropwise to a lithiated solution of 5-methyl-5,10-dihydroindeno[1,2-b]indole and the solution was stirred at room temperature overnight. After the reaction, the solution was extracted with ether/water and residual moisture of the organic layer was removed with MgSO.sub.4, and dried under vacuum to obtain 3.82 g (6 mmol) of a ligand compound, which was confirmed by 1H-NMR.

(10) .sup.1H NMR (500 MHz, CDCl.sub.3): −0.33 (3H, m), 0.86˜1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 (3H, d), 4.17 (1H, d), 4.25 (1H, d), 6.95˜7.92 (16H, m)

2-2. Preparation of Metallocene Compound

(11) 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 above was dissolved in 100 mL of toluene and 5 mL of MTBE, and then 5.6 mL (14 mmol) of 2.5 M n-BuLi hexane solution was added dropwise thereto in a dry ice/acetone bath and stirred at room temperature overnight. In another flask, 22.26 g (6 mmol) of ZrCl.sub.4(THF).sub.2 was prepared and 100 ml of toluene was added to prepare a slurry. The toluene slurry of ZrCl.sub.4(THF).sub.2 was transferred to the lithiated ligand under a dry ice/acetone bath. The mixture was stirred at room temperature overnight and changed to violet color.

(12) After filtering the reaction solution to remove LiCl, the resulting filtrate was dried under vacuum and hexane was added and subjected to sonication. The slurry was filtered to obtain 3.40 g (yield 71.1 mol %) of dark violet metallocene compound as a filtered solid.

(13) .sup.1H NMR (500 MHz, CDCl.sub.3): 1.74 (3H, d), 0.85˜2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H, m), 6.48˜8.10 (16H, m)

Preparation Example of Second Metallocene Compound

Preparation Example 3

(14) ##STR00022##

(15) t-Butyl-O—(CH.sub.2).sub.6-Cl was prepared using 6-chlorohexanol by a method described in Tetrahedron Lett. 2951 (1988), and NaCp was reacted therewith to obtain t-Butyl-O—(CH.sub.2).sub.6—C.sub.5H.sub.5 (yield 60%, b.p. 80° C./0.1 mmHg).

(16) Further, t-Butyl-O—(CH.sub.2).sub.6—C.sub.5H.sub.5 was dissolved in THF at −78° C., and normal butyllithium (n-BuLi) was slowly added thereto. The temperature was raised to room temperature, and the solution was reacted for 8 hours. The previously synthesized lithium salt solution was slowly added again to a suspension of ZrCl.sub.4(THF).sub.2 (1.70 g, 4.50 mmol)/THF (30 ml) at −78° C. and then further reacted at room temperature for 6 hours.

(17) All volatile materials were dried under vacuum, and hexane solvent was added to the obtained oily liquid material and filtered. The filtered solution was dried under vacuum, and then hexane was added thereto to induce precipitation at a low temperature (−20° C.). The obtained precipitate was filtered off at a low temperature to obtain a compound [tBu-O—(CH.sub.2).sub.6—C.sub.5H.sub.4].sub.2ZrCl.sub.2 in the form of a white solid (yield: 92%).

(18) .sup.1H NMR (300 MHz, CDCl.sub.3): 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J=8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H).

(19) .sup.13C NMR (CDCl.sub.3): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

Preparation Example of Third Metallocene Compound

Preparation Example 4

(20) ##STR00023##

4-1. Preparation of Ligand Compound

(21) 102.54 g (376.69 mmol) of 3-tether indene was added to a dried 1 L Schlenk flask and 450 ml of THF was introduced thereto under argon. The solution was cooled to −30° C., and then 173.3 ml (119.56 g, d=0.690 g/ml) of 2.5 M nBuLi hexane solution was added dropwise. The reaction mixture was slowly warmed up to room temperature and stirred until the next day. After this lithiated 3-thether indene solution was cooled to −78° C., 24.3 g (188.3 mmol) of dimethyldichlorosilicone was prepared and added dropwise to the Schlenk flask. The added mixture was slowly warmed up to room temperature and stirred for one day, and 200 ml of water was added to a flask and quenched. The organic layer was separated and dried with MgSO.sub.4. Thereby, 115 g (191.4 mmol, 101.6%) of a yellow oil was obtained.

(22) NMR standard purity (wt %)=100%. Mw=600.99. 1H NMR (500 MHz, CDCl.sub.3): −0.53, −0.35, −0.09 (6H, t), 1.18 (18H, m), 1.41 (8H, m), 1.54 (4H, m), 1.68 (4H, m), 2.58 (4H, m), 3.32 (4H, m), 6.04 (1H, s), 6.26 (1H, s), 7.16 (2H, m), 7.28 (3H, m), 7.41 (3H, m).

4-2. Preparation of Metallocene Compound

(23) 191.35 mmol of the ligand compound synthesized in 3-1 above was added to a 2 L Schlenk flask dried in an oven, and 4 equivalents of MTBE (67.5 g, d=0.7404 g/ml) and 696 g of toluene (d=0.87 g/ml) solution were dissolved in a solvent. Then, 2.1 equivalents of nBuLi solution (160.7 ml) was added and was subjected to lithiation until the next day. 72.187 g (191.35 mmol) of ZrCl.sub.4(THF).sub.2 was taken in a glove box and put in a 2 L Schlenk flask and a toluene-containing suspension was prepared. The above two flasks were cooled to −78° C. and then ligand anion was slowly added to a Zr suspension. After the addition was completed, the temperature of the reaction mixture was slowly increased to room temperature. After stirring overnight, the slurry was filtered under argon. Both the filtered solid and the filtrate were evaporated under vacuum-pressure. From 115 g (191.35 mmol) of the ligand, 150.0 g (198 mmol, >99%) of the catalyst precursor was obtained as filtrate and stored in toluene solution (1.9446 g/mmol).

(24) NMR standard purity (wt %)=100%. Mw=641.05. 1H NMR (500 MHz, CDCl.sub.3): 0.87 (6H, m), 1.14 (18H, m), 1.11-1.59 (16H, m), 2.61, 2.81 (4H, m), 3.30 (4H, m), 5.54 (1H, s), 5.74 (1H, s), 6.88 (1H, m), 7.02 (1H, m), 7.28 (1H, m), 7.39 (1H, d), 7.47 (1H, t), 7.60-7.71 (1H, m).

Preparation Example 5

(25) ##STR00024##

5-1. Preparation of Ligand Compound

(26) (1) Synthesis of Chlorodimethyl(TMCp)Silane (CDMTS)

(27) 6.0 ml (40 mmol) of TMCP was dissolved in 60 ml of dry THF (60 ml) in a dried 250 ml Schlenk flask and then the solution was cooled to −78° C. 17 ml (42 mmol) of n-BuLi 2.5M hexane solution was slowly added dropwise, and the mixture was stirred at room temperature overnight. 4.8 m (140 mmol) of dichlorodimethylsilane was dissolved in n-hexane in another 250-mL Schlenk flask and cooled to −78° C., and then the TMCP-lithiation solution previously reacted was slowly added. It was stirred at room temperature overnight, and the solvent was removed under reduced pressure. The resulting product was dissolved in toluene and filtered to remove the remaining LiCl, thereby obtaining 7.0 g (33 mmol) of a yellow liquid (yield 83%).

(28) 1H NMR (500 MHz, CDCl.sub.3): 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08 (1H, s).

(29) (2) After 2.72 g (10 mmol) of 3-(6-(tert-butoxy) hexyl)-1H-indene (T-Ind) was dissolved in 50 mL of THE in a dried 250 mL Schlenk flask, 8.2 ml (20.4 mmol) of n-BuLi 2.5 M hexane solution was slowly added dropwise in a dry ice/acetone bath. The solution was reacted at room temperature overnight to obtain a red solution. 2.15 g (10 mmol) of CDMTS previously synthesized was dissolved in THF in another 250 mL Schlenk flask, and then the T-Ind-Li solution was subjected to dropwise feeding in a dry ice/acetone bath. After the solution was reacted at room temperature overnight, a dark brown slurry was confirmed, which was quenched with water and extracted with ether to obtain 4.18 g (9.27 mmol) of a desired compound (yield 92.7%).

(30) 1H NMR (500 MHz, CDCl.sub.3): 0.43 (3H, s), −0.15 (3H, s), 1.21 (9H, s), 1.42-2.08 (22H, m), 2.61 (1H, s), 3.35-3.38 (2H, m), 3.52 (1H, s), 6.21 (1H, s), 7.17-7.43 (4H, m).

(31) 4-2. Preparation of Metallocene Compound

(32) 4.18 g (9.27 mmol) of the ligand compound synthesized in 5-1 above was dissolved in 100 ml of toluene, and 4.4 ml (4 equivalents) of MTBE was further added thereto. To the obtained solution was added dropwise 8.2 ml (20.4 mmol) of n-BuLi 2.5 M hexane solution in a dry ice/acetone bath. The solution was reacted at room temperature overnight to obtain a reddish slurry. 3.50 g (9.27 mmol) of ZrCl.sub.4(THF).sub.2 was prepared in a glove box and 50 ml of toluene solution was prepared, to which the ligand-Li solution was subjected to dropwise feeding in in a dry ice/acetone bath. After the solution was reacted at room temperature overnight, a reddish slurry was identified. The slurry was filtered to remove LiCl, which toluene was vacuum dried to about 90% and recrystallized with hexane. The slurry was filtered to obtain 2.5 g (4.1 mmol) of a yellow filter cake (yield 44.1%).

(33) 1H NMR (500 MHz, CDCl.sub.3): 0.93 (3H, s), 1.17 (12H, s), 1.37-1.63 (8H, m), 2.81-2.87 (1H, m), 2.93-2.97 (1H, m), 3.29-3.31 (2H, t), 5.55 (1H, s), 7.02-7.57 (4H, m)

Preparation Example 6

(34) ##STR00025##

6-1. Preparation of Ligand Compound

(35) 27.88 g (240 mmol) of Indene was added to a dried 250 mL Schlenk flask and 800 mL of MTBE was added under argon. After the solution was cooled to 0° C., 115.2 ml (288 mmol, d=0.690 g/ml) of 2.5 M nBuLi hexane solution was added dropwise. The reaction mixture was slowly warmed up to room temperature and stirred until the next day. Since the remaining nBuLi with increased purity may affect the next reaction, all the solvent MTBE was evaporated and Indene Li salt was added using a Schlenk filter under argon and then dissolved in 600 ml of THE solvent. A solution of 25.09 g (92.48 mmol) of Silicon Tether and 700 ml of THF was prepared in another 2 L Schlenk flask, and the Schlenk flask was cooled to −78° C., and then the lithiated solution was added dropwise. The added mixture was stirred at room temperature for one day, quenched by adding 400 ml of water into the flask, and the organic layer was separated and dried over MgSO.sub.4. Thereby, 35.41 g (82.2 mmol, 88.9%) of a yellow oil was obtained.

(36) NMR standard purity (wt %)=100%. Mw=430.70. 1H NMR (500 MHz, CDCl.sub.3): −0.45, −0.22, −0.07, 0.54 (total 3H, s), 0.87 (1H, m), 1.13 (9H, m), 1.16-1.46 (10H, m), 3.25 (2H, m), 3.57 (1H, m), 6.75, 6.85, 6.90, 7.11, 7.12, 7.19 (total 4H, m), 7.22-7.45 (4H, m), 7.48-7.51 (4H, m).

6-2. Preparation of Metallocene Compound

(37) The ligand compound synthesized in 6-1 above was added a 1 L Schlenk flask dried in an oven and then dissolved in diethylether. Then, 2.1 equivalents of nBuLi solution was added and subjected lithiation until the next day. 2.1 equivalents of ZrCl.sub.4(THF).sub.2 was taken in a glove box and added to a 2 L Schlenk flask and a diethylether-containing suspension was prepared. The above two flasks were cooled to −78° C. and ligand anion was slowly added to the Zr suspension. After the addition was completed, the temperature of the reaction mixture was slowly increased to room temperature. After stirring overnight, the ether in the mixture was subjected to a vacuum-reduced pressure to remove the solvent. Hexane was added in volume as much as the previous solvent. In this case, the reason for adding hexane is that the synthesized catalyst precursor has reduced solubility in hexane and promotes crystallization. The hexane slurry was filtered under argon. Then, both the filtered solid and the filtrate were evaporated under vacuum-pressure. The filter cake and the filtrate each were confirmed by NMR whether to synthesize the catalyst, respectively, and the yield and purity were confirmed by weighing and sampling in the glove box. From 35.41 g (82.2 mmol) of a ligand, 36.28 g (77.1 mmol, 93.8%) of a red solid was obtained as a filter cake.

(38) NMR purity standard (wt %)=100%. Mw=470.76. 1H NMR (500 MHz, CDCl.sub.3): 0.88 (3H, m), 1.15 (9H, m), 1.17-1.47 (10H, m), 1.53 (4H, d), 1.63 (3H, m), 1.81 (1H, m), 6.12 (2H, m), 7.15 (2H, m), 7.22-7.59 (8H, m)

Preparation Example of Hybrid Supported Catalyst

Example 1

(39) 1-1. Driving of Support

(40) Silica (SYLOPOL 948, manufactured by Grace Davison) was dehydrated in a vacuum state at a temperature of 400° C. for 12 hours.

(41) 1-2. Preparation of Supported Catalyst

(42) 100 ml of a toluene solution was added to a glass reactor at room temperature to which 10 g of the prepared silica was added, and then stirred while raising the temperature of the reactor to 40° C. After sufficiently dispersing the silica, 60.6 ml of a 10 wt % methylaluminoxane (MAO)/toluene solution was added, the temperature was raised to 80° C., and then the mixture was stirred at 200 rpm for 16 hours. After that, the temperature was again lowered to 40° C., followed by washing with a sufficient amount of toluene to remove unreacted aluminum compound. After 100 mL of toluene was again added, 0.5 mmol of the metallocene catalyst prepared in Preparation Example 4 was added and stirred for 1 hour. After completion of the reaction, 0.5 mmol of the metallocene catalyst prepared in Preparation Example 3 was added thereto and stirred for 1 hour. After completion of the reaction, 0.5 mmol of the metallocene catalyst prepared in Preparation Example 1 was added thereto and the mixture was stirred for 2 hours. After completion of the reaction, the stirring was stopped, the toluene layer was separated and removed, and the remaining toluene was removed by subjecting to a reduced pressure at 40° C. to prepare a supported catalyst.

Example 2

(43) A supported catalyst was prepared in the same manner as in Example 1, except that 0.5 mmol of the metallocene catalyst prepared in Preparation Example 2 was used instead of the metallocene catalyst prepared in Preparation Example 1.

Example 3

(44) A supported catalyst was prepared in the same manner as in Example 2, except that 0.5 mmol of the metallocene catalyst prepared in Preparation Example 5 was used instead of the metallocene catalyst prepared in Preparation Example 4.

Comparative Example 1

(45) 100 ml of a toluene solution was added to a glass reactor at room temperature, 10 g of the prepared silica was added, and the mixture was stirred while raising the temperature of the reactor to 40° C. After sufficiently dispersing the silica, 60.6 ml of 10 wt % methylaluminoxane (MAO)/toluene solution was added, the temperature was raised to 80° C., and then the mixture was stirred at 200 rpm for 16 hours. After that, the temperature was lowered again to 40° C., and the unreacted aluminum compound was removed by washing with a sufficient amount of toluene. After 100 mL of toluene was again added, 0.5 mmol of the metallocene catalyst prepared in Preparation Example 3 was added thereto, and the mixture was stirred for 1 hour. After completion of the reaction, 0.5 mmol of the metallocene catalyst prepared in Preparation Example 1 was added thereto and stirred for 2 hours. After completion of the reaction, the stirring was stopped, and the toluene layer was separated and removed. Thereafter, the remaining toluene was removed by subjecting to a reduced pressure at 40° C. to prepare a supported catalyst.

Comparative Example 2

(46) A supported catalyst was prepared in the same manner as in Comparative Example 1, except that 0.5 mmol of the metallocene catalyst prepared in Preparation Example 2 was used instead of the metallocene catalyst prepared in Preparation Example 1.

Comparative Example 3

(47) A supported catalyst was prepared in the same manner as in Comparative Example 2, except that 0.5 mmol of the metallocene catalyst prepared in Preparation Example 6 was used instead of the metallocene catalyst prepared in Preparation Example 3.

Comparative Example 4

(48) A supported catalyst was prepared in the same manner as in Comparative Example 2, except that 0.5 mmol of the metallocene catalyst prepared in Preparation Example 4 was used instead of the metallocene catalyst prepared in Preparation Example 3.

Comparative Example 5

(49) A supported catalyst was prepared in the same manner as in Comparative Example 2, except that 0.5 mmol of the metallocene catalyst prepared in Preparation Example 5 was used instead of the metallocene catalyst prepared in Preparation Example 3.

Test Example 1: Hydrogen/Ethylene Blending Polymerization (Semi-Batch Type)

(50) 30 mg of each of the supported catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were weighed in a dry box and placed in a 50-mL glass bottle. The bottle was sealed with a rubber diaphragm, taken out of the dry box to prepare a catalyst for injection. Polymerization was performed in a 600 mL temperature-controllable metal alloy reactor which was equipped with a mechanical stirrer and used under a high pressure.

(51) To this reactor, 1 L of hexane including 1.0 mmol triethylaluminum was injected, and the respective supported catalysts prepared above were introduced without contact with air. Then, polymerization was carried out for 1 hour at 80° C., while continuously providing a gaseous ethylene monomer at a pressure of Kgf/cm.sup.2 and hydrogen gas at 0.7 vol % relative to ethylene monomer. The termination of the polymerization was completed by first stopping the stirring and then removing the ethylene by evacuation.

(52) Most of the polymerization solvent was removed from the resulting polymer by filtration, and the polymer was dried in a vacuum oven at 80° C. for 4 hours.

(53) The polymerization activity, MI, MFRR, and amount of wax produced of the polyolefin prepared above were measured according to the following criteria and the results are shown in Table 1 below.

(54) 1) MI (5): The weight of the melted polymer resin passing through a 2.1 mm orifice at 190° C. for 10 minutes under the condition of applying a force of 5 kg vertically to the gravity direction was measured according to ASTM D1238 standard.

(55) 2) MFRR (21.6/5): MFRR was measured by dividing the weight of the melted polymer resin passing through a 2.1 mm orifice at 190° C. for 10 minutes under the condition of applying a force of 21.6 kg vertically to the gravity direction by the weight of the melted polymer resin passing through a 2.1 mm orifice at 190° C. for 10 minutes under the condition of applying a force of 5 kg vertically to the gravity direction in the same way as in 1) above.

(56) 3) Amount of wax produced: The content of wax volume sunk by settling 100 cc of hexane in the process for 24 hours was measured.

(57) TABLE-US-00001 TABLE 1 Amount of Activity MFRR wax produced (kgPE/gCat .Math. 2 hr) MI (5) (21.6/5) (cc) Example 1-1 6.8 18.2 — 5 Example 2-1 7.7 0.89 47 10 Example 3-1 7.0 0.89 32 10 Comparative 6.2 15.9 — 40 Example 1-1 Comparative 6.5 0.59 24 50 Example 2-1 Comparative 4.9 0.55 23 45 Example 3-1 Comparative 3.6 0.27 57 20 Example 4-1 Comparative 4.5 0.30 36 15 Example 5-1

Test Example 2: Hydrogen/Ethylene Blending Polymerization (Continuous Batch System)

(58) A multistage continuous CSTR reactor composed of two reactors with a capacity of 0.2 m.sup.3 as shown in FIG. 1 was prepared.

(59) The first reactor R1 was charged at a flow rate of 23 kg/hr of hexane, 7 kg/hr of ethylene, 2.0 g/hr of hydrogen, and 30 mmol/hr of triethylaluminum (TEAL), respectively. Also, the hybrid supported metallocene catalysts prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were injected at 2 g/hr (170 μmol/hr). In this case, the first reactor was maintained at 80° C., the pressure was maintained at 8 bar, the residence time of the reactant was maintained at 2.5 hours, and the slurry mixture containing the polymer was continuously supplied to the second reactor while maintaining a constant liquid level in the reactor.

(60) The second reactor (R2) was charged at a flow rate of 25 kg/hr of hexane, 6 kg/hr of ethylene, 15 cc/min of 1-butene and 30 mmol/hr of triethylaluminum (TEAL), and a hybrid supported metallocene catalyst according to Preparation Example 1 was injected at 2 g/hr (170 μmol/hr) and a molecular weight modifier (MwE) according to Preparation Example 2 were injected at 34 μmol/hr. The second reactor was maintained at 78° C., the pressure was maintained at 6 bar, the residence time of the reactants was maintained at 1.5 hours, and the polymer mixture was continuously supplied to a post reactor while maintaining a constant liquid level in the reactor.

(61) The post reactor was maintained at 75° C. and unreacted monomers were polymerized. The polymerization product was then prepared as a final polyethylene via a solvent removal unit and dryer. The prepared polyethylene was mixed with 1000 ppm of calcium stearate (manufactured by DOOBON INC.) and 2000 ppm of heat stabilizer 21B (manufactured by SONGWON Industrial) and then made into pellets.

(62) The polymerization activity, HLMI, density, amount of wax produced and FNCT of the polyolefin prepared above were measured according to the following criteria, and the results are shown in Table 2 below.

(63) 1) MI: The weight of the melted polymer resin which passed through a 2.1 mm orifice at 190° C. for 10 minutes under the condition of applying a force of 21.6 kg vertically to the gravity direction was measured according to ASTM D1238 standard.

(64) 2) Amount of wax produced: The content of wax volume sunk by settling 100 cc of hexane in the process for 24 hours was measured.

(65) 3) Stress cracking resistance (FNCT): Measured according to ASTM standard under the conditions of 80° C., 60 Mpa and IGEPAL CA-630 10% solution.

(66) TABLE-US-00002 TABLE 2 Amount of wax Activity produced FNCT (kgPE/gSilica) MI Density (cc) (hr) Example 1-2 18 16.0 0.942 5 326 Example 2-2 16 16.2 0.940 10 >1000 Example 3-2 16 15.8 0.941 10 804 Comparative 10 15.7 0.941 40 110 Example 1-2 Comparative 13 14.8 0.940 50 317 Example 2-2

(67) Referring to Tables 1 and 2, it was confirmed that in the case of Examples 1 to 3 using the catalysts prepared by hybrid-supporting three types of metallocene compounds, the amount of wax produced could be remarkably reduced and a very high stress cracking resistance (Full Notch Creep Test, FNCT) was exhibited, as compared with Comparative Examples 1 to 5 using the catalysts prepared by hybrid-supporting two types of metallocene compounds.

DESCRIPTION OF SYMBOLS

(68) R1: First reactor R2: Second reactor Rp: Post reactor C1: First hybrid supported metallocene catalyst C2: Second hybrid supported metallocene catalyst M1: First olefin monomer M2: Second olefin monomer MwE: Molecular weight regulator