Method for preparing supported metallocene catalyst and method for preparing polyolefin using the same

Abstract

The present invention relates to a method for preparing a supported metallocene catalyst, and a method for preparing polyolefin using the same, in which the supported metallocene catalyst prepared from the simple process according to the method for preparing the supported metallocene catalyst of the present invention can apply to the polymerization of the polyolefin that is polymerized at low pressure or high pressure; the molecular weight distribution of polyolefin prepared can be easily controlled; and there are effects such that its catalyst activity is significantly higher than that of the existed supported metallocene catalyst, and the molecular weight distribution can be easily controlled.

Claims

1. A method for preparing a supported metallocene catalyst, comprising: i) preparing a support supported with metallocene compounds 1 and 2 by reacting metallocene compounds 1 and 2 with a support; ii) preparing a support supported with the metallocene compounds 1 and 2, and a co-catalyst 1 by reacting the support supported with the metallocene compounds 1 and 2 with the co-catalyst 1; iii) preparing a catalyst precursor that is sequentially supported with the metallocene compounds 1 and 2, the co-catalyst 1 and further metallocene compounds in the support by reacting the metallocene compounds 1 and 2 with the support supported with the metallocene compounds 1 and 2 and the co-catalyst 1; and iv) preparing a metallocene catalyst by reacting the catalyst precursor and a co-catalyst 2, wherein the supported amount of the co-catalyst 2 is 0.2 to 10 mole, based on 1 mole of the transition metal that is supported in the metallocene compound, by the boron contained in the co-catalyst 2, and wherein the metallocene compound 1 is [A-O(CH.sub.2).sub.aC.sub.5H.sub.4].sub.2ZrCl.sub.2, in which a is an integer of 4-8, and A is one selected from the group consisting of methoxymethyl, t-bytixymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethyoxyethyl, 1-methyl-1-methoxyethyl and t-butyl, wherein the metallocene compound 2 is [(A-D-(CH.sub.2).sub.a)](CH.sub.3)X(C.sub.5Me.sub.4)(NCMe.sub.3)TiCl.sub.2, in which a is an integer of 4-8, X is methylene, ethylene or silicon, D is oxygen or nitrogen atom, and A is one selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl of carbon number 1-20, hydrogen, methoxymethyl, t-butoxymethyl, tetrahydropranyl, tetrahydrofuranyl, 1-ethoxyethyl, and 1-methyl-1-metoxyethyl and t-butyl, wherein the co-catalyst 2 is a borate compound represented by Formula 8;
T.sup.+[BQ.sub.4].sup.[Formula 8] wherein T.sup.+ is a polyatomic ion having a valency of +1; B is boron in an oxidation state of +3 form; and Q is independently selected from the group consisting of hydride, dialkylamido, alk oxide, aryloxide, hydrocarbyl, halocarbyl, and halo-substituted-hydrocarbyl radical, respectively, the above Q has below 20 carbons.

2. The method for preparing the supported metallocene catalyst according to claim 1, wherein the support is dried at 200 to 800 C.

3. The method for preparing the supported metallocene catalyst according to claim 1, wherein the support is one selected from the group consisting of silica, silica-alumina, and silica-magnesia.

4. The method for preparing the supported metallocene catalyst according to claim 1, wherein the co-catalyst 1 is the compound represented by Formula 7:
[Al(R.sup.3)O].sub.n[Formula 7] wherein, R.sup.3 is the same or different halogen radical, hydrocarbyl radical of carbon number 1 to 20 or hydrocarbyl radical of carbon number 1 to 20 substituted with halogen to each other, and n is an integer of above 2.

5. The method for preparing the supported metallocene catalyst according to claim 4, wherein the compound represented by Formula 7 is one selected from the group consisting of methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

6. The method for preparing the supported metallocene catalyst according to claim 1, wherein the co-catalyst 2 is one or more selected from the group consisting of trimethylammonium tetraphenylborate, methyloctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis (pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyloctadecylphosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate, and methyldi(tetradecyl)-ammonium tetrakis(pentafluorophenyl)borate.

7. A method for preparing a polyolefin, wherein an olefin-based monomer is polymerized under the presence of the supported metallocene catalyst prepared according to the method of claim 1.

8. The method for preparing the polyolefin according to claim 7, wherein the polymerization is performed in a slurry process or a gas-phase process.

9. The method for preparing the polyolefin according to claim 7, wherein the supported metallocene catalyst is injected to the olefin-based monomer, in which the supported metallocene catalyst is a type of slurry that is prepared by diluting in aliphatic hydrocarbon solvent of carbon number 5 to 12, aromatic hydrocarbon solvent, or hydrocarbon solvent substituted with Chlorine atom when it is injected.

Description

BEST MODE

(1) Hereinafter, the present invention will be described in more detail with reference to the preferable examples, but is not limited thereto.

(2) Hereinafter, the preferable example will be described in order to understand the present invention, but the following examples are only for describing the example of the present invention, and it is apparently understood by the person who is skilled in the art that various modifications and amendments within the range of the technique spirit and the scope of the present invention can be possible and the modifications and amendments belong in the attached claims.

MODE FOR INVENTION

Example

(3) The organic reagents and solvents that were required for the polymerization and the producing of the catalyst in the following Examples were the products obtained from Aldrich Company, which were purified through the standard method, ethylene having a high purity obtained from Applied Gas Technology Company was used, it was polymerized after passing through water and oxygen filtering machine, and the contact with air and water was blocked all of the catalyst synthesis, supporting and polymerizing so that the reproducibility of experiment was increased.

Synthesis of Metallocene Compound

Synthesis of [t-Bu-O(CH2)6C5H4]2ZrCl2

(4) t-Butyl-O(CH.sub.2).sub.6Cl was produced by using 6-chlorohexanol in a method disclosed in the document that is Tetrahedron Lett. 2951 (1988), and was reacted with NaCp to obtain t-Butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 (Yield: 60%, b.p. 80 C./0.1 mmHg). In addition, t-Butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 was dissolved in THF at 78 C.; normal butyl lithium (n-BuLi) was slowly added, and then its temperature was increased to a room temperature; and then reacted for 8 hours. The above solution was again reacted at a room temperature for further 6 hours after slowly adding a pre-synthesized lithium salt in a suspension solution of ZrCl.sub.4(THF).sub.2 (1.70 g, 4.50 m mol)/THF (30 ml) at 78 C. All of volatile materials were dried in a vacuum, and then the oil liquid material obtained was filtered by adding hexane solvent. After drying the filtered solution in a vacuum, hexane was added to precipitate at a low temperature (20 C.). The precipitate obtained was filtered to obtain [tBu-O(CH.sub.2).sub.6C.sub.5H.sub.4].sup.2ZrCl.sub.2 compound in a type of white solid material (Yield: 92%).

(5) 1 H NMR (300 MHz, CDCl3): 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).

(6) 13 C 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.

Synthesis of [methyl(6-t-buthoxyhexyl)silyl(5-tetramethylCp)(t-Butylamido)TiCl2

(7) After 50 g of Mg (s) was added to 10 L reactor at a room temperature, 300 mL of THF was added. After 0.5 g of I.sub.2 was added, the temperature of the reactor was maintained at 50 C. After stabilizing the temperature of the reactor, 250 g of 6-t-buthoxyhexyl chloride was added in a rate of 5 mL/min by using a feeding pump to the reactor. According to the adding of 6-t-buthoxyhexylchloride, it could be observed that the temperature of the reactor was increased to about 45 C. While 6-t-buthoxyhexylchloride was continually added, the stirring was maintained for 12 hours. After 12 hours of the reaction, the black reaction solution could be obtained. After taking 2 mL of the prepared black solution, water was added to obtain an organic layer so that it could be known that 6-t-buthoxyhexane could be confirmed through 1H-NMR and Grignard reaction was satisfactorily progressed from 6-t-buthoxyhexane. And then, 6-t-buthoxyhexyl magnesium chloride was synthesized. 500 g of MeSiCl.sub.3 and 1 L of THF were added to the reactor, and then the temperature was cooled to 20 C. 560 g of the synthesized 6-t-buthoxyhexyl magnesium chloride was added in a rate of 5 mL/min by using the feeding pump. After finishing the injection of Grignard reagent, the stirring was performed for 12 hours while the temperature of the reactor was gradually increased to a room temperature. After 12 hours of the reaction, it could be observed that MgCl.sub.2 salt having a white color was produced. A filter solution could be obtained by removing salt through Press dewatering Filtration machine for experiment (labdori, HanKang Engineering Co.) by adding 4 L of hexane. After adding the obtained filter solution to the reactor, the liquid having a light yellow color could be obtained by adding hexane at 70 C. It could be confirmed that the obtained liquid was a required methyl(6-t-toxyhexyl)dichlorosilane compound through 1H-NMR.

(8) 1 H-NMR (CDCl.sub.3): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H).

(9) After 1.2 mole (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, the temperature was cooled to 20 C. 480 mL of n-BuLi was added in a rate of 5 mL/min to the reactor by using the feeding pump. After adding n-BuLi, the stirring was maintained for 12 hours while the temperature of the reactor was gradually increased to a room temperature. After 12 hours of the reaction, an equivalent Methyl(6-t-buthoxyhexyl)dichlorosilane (326 g, 350 mL) was quickly added to the reactor. While the temperature of the reactor was gradually increased to a room temperature, the stirring was maintained for 12 hours; the temperature of the reactor was again cooled to 0 C.; and then 2 equivalent t-BuNH.sub.2 was added. The reactor was stirred for 12 hours while the temperature of the reactor was gradually increased to a room temperature. After 12 hours of the reaction, THF was removed; and then the filter solution without salt could be obtained through Labdori by adding 4 L of hexane. After the filter solution was again added to the reactor, the solution having a yellow color could be obtained by removing hexane at 70 C. It could be confirmed that the obtained solution having a yellow color was Methyl(6-t-buthoxyhexyl)(tetramethylCpH)t-Butylaminosilane compound through 1H-NMR.

(10) TiCl.sub.3(THF).sub.3 (10 mmol) was quickly added to dilithium salt of ligand of 78 C. that is synthesized in THF solution from n-BuLi and ligand Dimethyl(tetramethylCpH)t-Butylaminosilane. While the reaction solution was gradually increased from 78 C. to a room temperature, the stirring was maintained for 12 hours. After stirring for 12 hours, the stirring was maintained for 12 hours after adding an equivalent PbCl.sub.2 (10 mmol) to the reactor at a room temperature. After stirring for 12 hours, the solution having a greenish heavy black color could be obtained. After THF was removed from the produced reaction solution, the product was filtered by adding hexane. After removing hexane from the obtained filter solution, it could be confirmed as the required [methyl(6-t-buthoxyhexyl)silyl(.sup.5-tetramethylCp)(t-Butylamido)]TiCl.sub.2 compound through 1H-NMR.

(11) 1H-NMR (CDCl.sub.3): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.80.8 (m), 1.4 (s, 9H), 1.2 <136> (s, 9H), 0.7 (s, 3H)

Preparation of [(CH2)4C5H4]2ZrCl2

(12) It purchased from Aldrich Company was used.

Synthesis of 6-t-butoxyhexylmethylsilylbisindenyl zirconium dichloride

(13) After 17.5 ml of 2.5M n-BuLi solution was injected in 5 ml of indene that is dissolved in 20 ml of ether for 20 minutes at 0 C., the stirring was maintained for 2 hours at a room temperature. After 5.25 g of t-buthoxyhexylmethyldichlorosilane was dissolved in 10 ml of hexane, it was added to a indenyllithium solution over 10 minutes at 78 C. After the reaction solution was stirred for 3 hours at a room temperature, lithium chloride was removed by filtering and the solvent was dried in a vacuum thereby obtaining the product that is mixed with a structural isomer. The structural isomer was confirmed through 1H NMR.

(14) .sup.1H NMR (500 MHz, CDCl.sub.3): 1.17 (t-BuO, 9H, s), 3.59 (Indene, 2H, m), 0.21 (MeSi, 3H, s), 0.47 (CH.sub.2, 2H, m), 0.89 (CH.sub.2, 2H, m), 1.28 (CH.sub.2, 2H, m), 1.56 (CH.sub.2, 4H, m), 3.26 (OCH.sub.2, t, JHH=0.014), 7.48 (ArH, 2H, m), 7.38 (ArH, 2H, m), 7.26 (ArH, 2H, m), 7.16 (ArH, 2H, m), 6.90 (indene, H, m), 6.60 (ArH, 2H, m).

(15) The material that was confirmed through .sup.1H NMR as mentioned above was dissolved in 40 ml of ether, and then injected to 17.5 ml of 2.5 M n-BuLi solution for 20 minutes at 78 C. After stirring for 3 hours at a room temperature, the product was obtained by filtering after solidifying by adding hexane. 1 g of zirconium chloride was added to 20 ml of toluene, and then stirred. 30 ml of toluene/ether 1:2 solution was added to 2.3 g of the ligand solid that was obtained from the above process, and then was injected to the zirconium chloride mix solution for 20 minutes at 78 C. After stirring for 16 hours at a room temperature, it was filtered. The final catalyst was obtained by the re-crystallization of the material with hexane.

(16) .sup.1H NMR (500 MHz, C.sub.6D.sub.6): 1.15 (t-BuO, 9H, s), 1.12 (MeSi, 3H, s), 1.34 (CH.sub.2, 6H, m), 1.47 (CH.sub.2, 2H, m), 1.60 (CH.sub.2, 2H, m), 3.26 (OCH.sub.2, t, JHH=0.014, 7.40 (ArH, 2H, m), 7.33 (ArH, 2H, m), 7.28 (ArH, 2H, m), 7.16 (ArH, 2H, m), 6.90 (indene, H, m), 5.83 (ArH, 2H, m)

Synthesis of [t-Bu-O(CH2)6C5H4]2HfCl2

(17) t-Butyl-O(CH.sub.2).sub.6Cl was prepared from the method disclosed in the document (Tetrahedron Lett. 2951 (1988)) by using 6-chlorohexanol, and was reacted with NaCp to obtain t-Butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 (Yield: 60%, b.p. 80 C./0.1 mmHg). In addition, t-Butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 was dissolved in THF at 78 C.; a normal butylilthium (n-BuLi) was gradually added; the temperature was increased to a room temperature; and then was reacted for 8 hours. The above solution was again reacted at a room temperature for further 6 hours after slowly adding a pre-synthesized lithium salt in a suspension solution of HfCl4 (1.44 g, 4.50 m mol)/THF (30 ml) at 78 C. All of volatile materials were dried in a vacuum, and then the oil liquid material obtained was filtered by adding hexane solvent. After drying the filtered solution in a vacuum, hexane was added to precipitate at a low temperature (20 C.). The precipitate obtained was filtered to obtain [tBu-O(CH.sub.2).sub.6C.sub.5H.sub.4].sub.2HfCl.sub.2 compound in a type of white solid material (Yield: 88%).

(18) .sup.1H-NMR (300 MHz, CDCl3): 6.19 (t, J=2.6 Hz, 2H), 6.08 (t, J=2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2 H), 2.65 (t, J=8 Hz), 1.56-1.48 (m, 4H), 1.34 (m, 4H), 1.17 (s, 9H).

(19) .sup.13C-NMR (CDCl.sub.3): 134.09, 116.06, 111.428, 72.42, 61.33, 30.42, 30.67, 30.14, 29.20, 27.52, 26.01.

Production Example of Preparation of Catalyst that is Composed of Co-Catalyst 1 Layer+Metallocene Catalyst Layer+Co-Catalyst 2 Layer

Production Example 1

(20) 10 ml of Toluene was added to 3 g of silica (Sylopol 2212, Grace Davison) having 280 m.sup.2/g surface area and 1.47 ml/g pore volume that is plasticized; was reacted with MAO 15 ml (10 wt % Toluene solution) for 2 hours at 70 C.; and then removed with non-reacted MAO solution by washing with toluene. After it was reacted with 0.72 mmole of metallocene compound having tert butoxy-group obtained from Synthetic Example 1 for 1 hour at 50 C., it was washed with toluene. And then, it was reacted with 1.2 mmole of trityl tetrakis (penta-fluoro-phenyl)borate (TB) for 1 hour at 50 C.; and then the catalyst in a state of solid was prepared by drying under the reduced pressure at 50 C. The mole ratio of boron (B)/transition metal (Zr) was 1.3.

Production Example 2

(21) The same method with Production Example 1 was used except treating 0.6 mmole of treating trityl tetrakis (penta-fluoro-phenyl)borate (TB). The mole ratio of boron (B)/transition metal (Zr) was 0.7.

Production Example 3

(22) The same method with Production Example 1 was used except treating 0.15 mmole of treating trityl tetrakis (penta-fluoro-phenyl)borate (TB). The mole ratio of boron (B)/transition metal (Zr) was 0.2.

Production Example 4

(23) The same method with Production Example 1 was used except using Dimethylanilinium Tetrakis(pentafluorophenyl)borate Trityl (AB) instead of TB.

Production Example 5

(24) The same method with Production Example 1 was used except using the metallocene compound having tert butoxy-group obtained from Synthetic Example 2 instead of the metallocene compound obtained from Synthetic Example 1.

Production Example 6

(25) The same method with Production Example 1 was used except using Bis indenyl-based metallocene compound obtained from Synthetic Example 4 instead of the metallocene compound obtained from Synthetic Example 1.

Production Comparative Example 1

(26) The same method with Production Example 1 was used except 30 ml of MAO instead of 15 ml of MAO and not treating TB.

Production Comparative Example 2

(27) The same method with Production Example 1 was used except that 15 ml of MAO (10 wt % of toluene solution) was reacted for 1 hour at 50 C.; was washed with toluene to remove non-reacted MAO; was decompressed at 50 C.; and then dried, instead of trityl tetrakis (penta-fluoro-phenyl)borate (TB).

Production Comparative Example 3

(28) The same method with Production Example 5 was used except not treating TB.

Production Comparative Example 4

(29) The same method with Production Example 1 was used except using the metallocene compound obtained from Synthetic Example 3.

Production Comparative Example 5

(30) The same method with Production Example 4 was used except not treating TB.

Production Comparative Example 6

(31) The same method with Production Example 6 was used except not treating TB.

(32) <Preparation and Evaluation of Physical Property of Polyethylene>

Example 1

(33) 3 L of normal hexane was injected to high-pressure reactor having 5 L volume while not contacting with air and oxygen; triethylaluminium was injected to be 0.6 mmol/L triethylaluminum concentration about normal hexane; and then 30 mg of the catalyst in a state of solid obtained from Production Example 1 was injected. And then, ethylene was continuously injected at 80 C. to polymerize for 2 hours while maintaining 9 bar of pressure. And then, the supply of ethylene was stopped and the pressure was removed to finish the reaction. The suspension obtained from the above process was isolated and dried to prepare the polyethylene particle.

Example 2

(34) The same method with Example 1 was used except using the catalyst obtained from Production Example 2 instead of the catalyst obtained from Production Example 1.

Example 3

(35) The same method with Example 1 was used except using the catalyst obtained from Production Example 3 instead of the catalyst obtained from Production Example 1.

Example 4

(36) The same method with Example 1 was used except using the catalyst obtained from Production Example 4 instead of the catalyst obtained from Production Example 1.

Example 5

(37) The same method with Example 1 was used except using the catalyst obtained from Production Example 5 instead of the catalyst obtained from Production Example 1.

Example 6

(38) The same method with Example 1 was used except using the catalyst obtained from Production Example 6 instead of the catalyst obtained from Production Example 1.

Example 7

(39) The same method with Example 1 was used except injecting 30 mg the catalyst in a state of solid obtained from Production Comparative Example 1 instead of the catalyst obtained from Production Example 1, and then further injecting TB having an amount corresponding to B/Zr=2 as a mole ratio.

Example 8

(40) The same method with Example 1 was used except the ethylene polymerization at 40 bar.

Example 9

(41) The same method with Example 1 was used except using AB instead of TB.

Comparative Example 1

(42) The same method with Example 1 was used except using the catalyst obtained from Production Comparative Example 1 instead of the catalyst obtained from Production Example 1.

Comparative Example 2

(43) The same method with Example 1 was used except using the catalyst obtained from Production Comparative Example 4 instead of the catalyst obtained from Production Example 1.

Comparative Example 3

(44) The same method with Example 1 was used except using the catalyst obtained from Production Comparative Example 3 instead of the catalyst obtained from Production Example 1.

Comparative Example 4

(45) The same method with Example 1 was used except using the catalyst obtained from Production Comparative Example 5 instead of the catalyst obtained from Production Example 1.

Comparative Example 5

(46) The same method with Example 1 was used except using the catalyst obtained from Production Comparative Example 6 instead of the catalyst obtained from Production Example 1.

Comparative Example 6

(47) The same method with Example 1 was used except using the catalyst obtained from Production Comparative Example 2 instead of the catalyst obtained from Production Example 1.

Comparative Example 7

(48) The same method with Comparative Example 1 was used except the ethylene polymerization at 40 bar.

(49) Evaluation of Physical Property

(50) 1) Melt Index (MI, 2.16 kg): Evaluation Temperature 190 C., Evaluation based on ASTM 1238.

(51) 2) High Load Melt Index (HLMI, 21.16 kg): Evaluation Temperature 190 C., Evaluation based on ASTM 1238.

(52) 3) MFR (HLMI/MI): The ratio is divided HLMI Melt Index (MI, 21.6 kg Load) by MI (MI, 2.16 kg Load).

(53) Table 1 is a low-pressure polymerization property, in which the pressure was 9 bar on ethylene polymerizing, and Table 2 is a high-pressure polymerization property, in which the pressure was 40 bar on ethylene polymerizing.

(54) TABLE-US-00001 TABLE 1 Borate Supported Activity MI Co- Metallocene (KgPE/ (2.16 Kg) Section catalyst Catalyst gCat) (g/10 min) MFR Example 1 TB Pro. Ex. 1 39 1.2 17 Example 2 TB Pro. Ex. 2 36 0.85 18 Example 3 TB Pro. Ex. 3 7 0.69 19 Example 4 AB Pro. Ex. 4 31 1.1 17 Example 5 TB Pro. Ex. 5 3.5 <0.1 Example 6 TB Pro. Ex. 6 4.5 0.68 35 Example 7 after TB Pro. Com. Ex. 1 9.4 0.4 22 Com. Ex. 1 Pro. Com. Ex. 1 3.1 0.78 17 Com. Ex. 2 TB Pro. Com. Ex. 4 0.3 1.1 18 Com. Ex. 3 Pro. Com. Ex. 3 0.9 <0.1 Com. Ex. 4 Pro. Com. Ex. 5 0.7 1.2 17 Com. Ex. 5 Pro. Com. Ex. 6 0.5 0.16 49 Com. Ex. 6 Pro. Com. Ex. 2 10 0.75 23

(55) For Table 1, TB is trityl tetrakis (penta-fluoro-phenyl)borate, and AB is Dimethylanilinium Tetrakis(pentafluorophenyl)borate Trityl.

(56) For Table 1, in the case of Example 5 and Comparative Example 3, HLMI as well as MI were not evaluated due to the very high molecular weight of polyethylene produced.

(57) TABLE-US-00002 TABLE 2 Borate Supported Activity HLMI Co- Metallocene (KgPE/ (21.6 kg) Section catalyst Catalyst gCat) (g/10 min) MFR Example 8 TB Pro. Ex. 1 78 1.8 18 Example 9 AB Pro. Ex. 4 102 1.5 18 Com. Ex. 7 Pro. Com. Ex. 1 12 0.61 21

(58) As shown in Table 1, in the case of polymerizing using Example 1 to 4 that were the supported catalyst supported with further 0.2 to 1.3 of Borate (AB, TB) as a mole ratio as compared to Zr using Synthetic Example 1, its activity was increased in 2 to 13 times, as compared with in the case of polymerizing using Comparative Example 1 that was the catalyst not applied with Borate. As compared with Comparative Example 6, in which its activity was increased by further treating MAO, the activity in Example 1 was increased in about 4 times.

(59) As compared with Comparative Example 2 that was not applied with Borate, the activity of Example 1 that was further not supported with 1.3 of TB as a mole ratio as compared to Zr using Synthetic Example 5 was increased in about 4 times. However, the activity of Comparative Example 2 that was polymerized by using the supported catalyst using Synthetic Example 3 without alkoxy alkyl ligand was decreased than the activity of Comparative Example 4.

(60) It could be confirmed that Example 7 was prepared through the method for injecting Borate on polymerizing, not applying to the catalyst, and the activity was increased in about 3 times as compared with Comparative Example 1.

(61) As shown in Table 2, it could be confirmed that the activity of the high pressure polymerization was increased in 6 to 9 times as compared with Comparative Example 7, as the above results in the case of the supported catalyst applied with Borate, like Example 8 and Example 9.

Production Example of Preparation of Catalyst that is Composed of Co-Catalyst 1 Layer+Metallocene Catalyst 1 Layer+Metallocene Catalyst 2 Layer+Co-Catalyst 2 Layer

Production Example 7

(62) 10 ml of Toluene was added to 3 g of silica (Sylopol 2212, Grace Davison) having 280 m.sup.2/g surface area and 1.47 ml/g pore volume that is plasticized; was reacted with MAO 15 ml (10 wt % Toluene solution) for 2 hours at 70 C.; and then removed with non-reacted MAO solution by washing with toluene. After it was reacted with 0.48 mmole of metallocene compound having tert butoxy-group obtained from Synthetic Example 1 and 0.24 mmole of metallocene compound obtained from Synthetic Example 2 for 1 hour at 50 C., it was washed with toluene. And then, it was reacted with 1.2 mmole of trityl tetrakis (penta-fluoro-phenyl)borate (TB) for 1 hour at 50 C.; and then the catalyst in a state of solid was prepared by drying under the reduced pressure at 50 C.

Production Comparative Example 7

(63) The same method with Example 7 was used except using 0.72 mmole of metallocene compound having tert butoxy-group obtained from only Synthetic Example 1 instead of the metallocene compound obtained from Synthetic Example 1 and the metallocene compound obtained from Synthetic Example 2.

Production Comparative Example 8

(64) The same method with Example 7 was used except using 0.72 mmole of metallocene compound having tert butoxy-group obtained from only Synthetic Example 2 instead of the metallocene compound obtained from Synthetic Example 1 and the metallocene compound obtained from Synthetic Example 2.

Production Comparative Example 9

(65) The same method with Example 7 was used except not treating TB.

(66) <Preparation and Evaluation of Physical Property of Polyethylene>

Example 10

(67) 3 L of normal hexane was injected to high-pressure reactor having 5 L volume while not contacting with air and oxygen; triethylaluminium was injected to be 0.6 mmol/L triethylaluminum concentration about normal hexane; and then 30 mg of the catalyst in a state of solid obtained from Production Example 7 was injected. And then, ethylene was continuously injected at 80 C. to polymerize for 2 hours while maintaining 9 bar of pressure. And then, the supply of ethylene was stopped and the pressure was removed to finish the reaction. The suspension obtained from the above process was isolated and dried to prepare the polyethylene particle.

Comparative Example 8

(68) The same method with Example 10 was used except using the catalyst having tert-butoxy group obtained from Production Comparative Example 7 instead of the catalyst obtained from Production Example 7.

Comparative Example 9

(69) The same method with Example 10 was used except using the catalyst having tert-butoxy group obtained from Production Comparative Example 8 instead of the catalyst obtained from Production Example 7.

Comparative Example 10

(70) The same method with Example 10 was used except using the catalyst having tert-butoxy group obtained from Production Comparative Example 9 instead of the catalyst obtained from Production Example 7.

Example 11

(71) The same method with Example 10 was used except the ethylene polymerization at 40 bar.

Comparative Example 11

(72) The same method with Comparative Example 8 was used except the ethylene polymerization at 40 bar.

Comparative Example 12

(73) The same method with Comparative Example 10 was used except the ethylene polymerization at 40 bar.

(74) Table 3 is a low-pressure polymerization property, in which the pressure was 9 bar on ethylene polymerizing, and Table 4 is a high-pressure polymerization property, in which the pressure was 40 bar on ethylene polymerizing.

(75) TABLE-US-00003 TABLE 3 Metal- Supported locene Borate Metal- Activity MI Catalyst Co- locene (KgPE/ (2.16 Kg) Section (Syn. Ex.) catalyst Catalyst gCat) (g/10 min) MFR Example 1 and 2 TB Pro. 36 1.1 21 10 Ex. 7 Com. 1 TB Pro. Com. 39 1.2 17 Ex. 8 Ex. 7 Com. 2 TB Pro. Com. 3.5 <0.1 Ex. 9 Ex. 8 Com. 1 and 2 Pro. Com. 2.7 0.74 23 Ex. 10 Ex. 9

(76) For Table 3, TB is trityl tetrakis (penta-fluoro-phenyl)borate. For Table 3, HLMI as well as MI were not exactly evaluated in the case of Comparative Example 9 due to the very high molecular weight of polyethylene produced.

(77) TABLE-US-00004 TABLE 4 Metal- Supported locene Borate Metal- Activity HLMI Catalyst Co- locene (KgPE/ (21.6 kg) Section (Syn. Ex.) catalyst Catalyst gCat) g/10 min MFR Example 1 and 2 TB Pro. 87 1.2 22 11 Ex. 7 Com. 1 TB Pro. Com. 78 1.8 18 Ex. 11 Ex. 8 Com. 1 and 2 Pro. Com. 10 0.35 23 Ex. 12 Ex. 10

(78) Referring with Table 3 and Table 4, the activity of the catalyst in the case of further supporting Borate like Example 10 and Example 11 was increased as compared with the case of using only MAO like Comparative Example 10 and Comparative Example 12 for preparing the supported metallocene catalyst.

(79) Meanwhile, there was a disadvantage such that MFR of polymer using the supported catalyst supported with the single metallocene compound like Comparative Example 8 and Comparative Example 11 was small. However, MFR of polymer in the case of polymerizing ethylene using the hybrid supported metallocene catalyst supported with two or more metallocene compound at the same time like Example 10 and Example 11 could be made to be large, and also MFR of polymer in the case of using the supported catalyst supported with various two or more metallocene compounds at the same time could be controlled.

(80) Therefore, the activity of the catalyst can be controlled by adjusting the component ratio of each metallocene catalyst in the hybrid supported metallocene catalyst according to the present invention, the polymer having various physical properties and molecular weight distributions can be prepared, and finally it means that the metallocene supported catalyst that can control the distribution of molecular weight can be prepared in a single reactor.

Production Example of Preparation of Catalyst that is Composed of Metallocene Catalyst 1 Layer+Co-Catalyst 1 Layer+Metallocene Catalyst 2 Layer+Co-Catalyst 2 Layer

Production Example 8

(81) 10 ml of Toluene was added to 3 g of silica (Sylopol 2212, Grace Davison) having 280 m.sup.2/g surface area and 1.47 ml/g pore volume that is plasticized; was added and reacted with 0.36 mmole of the metallocene compound having tert butoxy-group obtained from Synthetic Example 1 for 1 hours at 70 C.; and then washed by using toluene. It was reacted with 15 ml of MAO (10 wt % toluene solution) for 2 hours at 70 C., and was removed with non-reacted MAO solution by washing with toluene. After it was reacted with 0.36 mmole of metallocene compound obtained from Synthetic Example 2 for 1 hour at 50 C., it was washed with toluene. And then, it was reacted with 1.2 mmole of trityl tetrakis (penta-fluoro-phenyl)borate (TB) for 1 hour at 50 C.; and then the catalyst in a state of solid was prepared by drying under the reduced pressure at 50 C.

Production Example 9

(82) The same method with Production Example 8 was used except using the metallocene compound obtained from Synthetic Example 2 instead of the metallocene compound obtained from Synthetic Example 1 and using the metallocene compound obtained from Synthetic Example 1 instead of the metallocene compound obtained from Synthetic Example 2.

Production Example 10

(83) The same method with Production Example 8 was used except using 0.18 mole of the metallocene compound obtained from Synthetic Example 1 and 0.18 mmole of the metallocene compound obtained from Synthetic Example 2 instead of 0.36 mmole of the metallocene compound obtained from Synthetic Example 1 and using 0.18 mole of the metallocene compound obtained from Synthetic Example 1 and 0.18 mmole of the metallocene compound obtained from Synthetic Example 2 instead of the metallocene compound obtained from Synthetic Example 2.

Production Comparative Example 10

(84) 10 ml of Toluene was added to 3 g of silica (Sylopol 2212, Grace Davison) having 280 m.sup.2/g surface area and 1.47 ml/g pore volume that is plasticized; was reacted with MAO 15 ml (10 wt % Toluene solution) for 2 hours at 70 C.; and then removed with non-reacted MAO solution by washing with toluene. After it was reacted with 0.36 mmole of metallocene compound having tert butoxy-group obtained from Synthetic Example 1 for 1 hour at 50 C., it was washed with toluene. And then, after it was reacted with 0.36 mmole of the metallocene compound obtained from Synthetic Example 2 for 1 hour at 50 C., it was washed with toluene. Since then, it was reacted with 1.2 mmole of trityl tetrakis (penta-fluoro-phenyl)borate (TB) for 1 hour at 50 C.; and then the catalyst in a state of solid was prepared by drying under the reduced pressure at 50 C.

(85) <Preparation and Evaluation of Physical Property of Polyethylene>

Example 12

(86) 3 L of normal hexane was injected to high-pressure reactor having 5 L volume while not contacting with air and oxygen; triethylaluminium was injected to be 0.6 mmol/L triethylaluminum concentration about normal hexane; and then 30 mg of the catalyst in a state of solid obtained from Production Example 8 was injected. And then, ethylene was continuously injected at 80 C. to polymerize for 2 hours while maintaining 9 bar of pressure. And then, the supply of ethylene was stopped and the pressure was removed to finish the reaction. The suspension obtained from the above process was isolated and dried to prepare the polyethylene particle.

Example 13

(87) The same method with Example 12 was used except using the catalyst prepared from Production Example 9.

Example 14

(88) The same method with Example 12 was used except using the catalyst prepared from Production Example 10.

Comparative Example 13

(89) The same method with Example 12 was used except using the catalyst prepared from Production Comparative Example 10.

(90) TABLE-US-00005 TABLE 5 Metal- Supported locene Borate Metal- Activity MI Catalyst Co- locene (KgPE/ (2.16 Kg) Section (Syn. Ex.) catalyst Catalyst gCat) (g/10 min) MFR Example 1 and 2 TB Pro. 45 0.2 38 12 Ex. 8 Example 1 and 2 TB Pro. 40 0.6 27 13 Ex. 9 Example 1 and 2 TB Pro. 42 0.9 32 14 Ex. 10 Com. 1 and 2 TB Pro. Com. 25 1.1 23 Ex. 13 Ex. 10

(91) For Table 5, TB is trityl tetrakis (penta-fluoro-phenyl)borate. Referring with Table 5, for preparing the metallocene supported catalyst using two metallocene compounds including alkoxide ligand, the polyethylene having high molecular weight and broad molecular weight distribution could be prepared like Example 12 to Example 14 in the case of the metallocene supported catalyst prepared by firstly supporting with one metallocene compound or a part of two metallocene compounds, secondly supporting with MAO, and then supporting with the remained metallocene compound, like Production Example 8 to Production Example 10, as compared with in the case of preparing the catalyst by firstly supporting with MAO and then supporting metallocene compound like Comparative Example 10. In addition, the activity could be increased to about 70 to 80%.

(92) Therefore, the polymer that can control the activity of the catalyst, has various physical properties and molecular weight distributions, as well as has an excellent catalyst activity can be prepared by adjusting the component ratio of each metallocene catalyst using the method for preparing the supported metallocene catalyst according to the present invention, and finally it means that the metallocene supported catalyst that can control the distribution of molecular weight and has an excellent activity can be prepared in a single reactor.