Method for preparing supported hybrid metallocene catalyst

Abstract

The present disclosure relates to a method for preparing a supported hybrid metallocene catalyst, and the catalyst is prepared by supporting a first metallocene compound, supporting a cocatalyst by a separate-input method in which primarily adding a part at 100° C. to 150° C. and secondarily adding the rest at −5° C. to 40° C., and then supporting a second metallocene compound, thereby improving a supporting rate of the cocatalyst in the supported catalyst and maintaining high catalytic activity. Therefore, the present disclosure can effectively prepare a polyolefin with improved processability which exhibits increased molecular weight distribution while having high morphology (reduced fine powder), high bulk density and improved settling efficiency.

Claims

1. A method for preparing a supported hybrid metallocene catalyst, comprising the steps of: supporting at least one first metallocene compound on a silica support; supporting an aluminum-based cocatalyst by contacting the silica support on which the first metallocene compound is supported with at least one aluminum-based cocatalyst compound; and supporting at least one second metallocene compound on the silica support on which the aluminum-based cocatalyst is supported; wherein the aluminum-based cocatalyst is supported on the silica support on which the first metallocene compound is supported by a separate-input method in which 50% by weight to 90% by weight of a whole input of at least one aluminum-based cocatalyst compound is primarily added at a temperature of 100° C. to 150° C., and the rest of the whole input is secondarily added at a temperature of −5° C. to 40° C.

2. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein a supported amount of the first metallocene compound or the second metallocene compound is 0.01 mmol/g to 1 mmol/g based on 1 g of the silica support, respectively.

3. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein each of the first metallocene compound and the second metallocene compound is represented by one of the following Chemical Formulae 1 to 5: [Chemical Formula 1]
(Cp.sup.lR.sup.a)n(Cp.sup.2R.sup.b)M.sup.1Z.sup.3−n in Chemical Formula 1, M.sup.1 is a group 4 transition metal; Cp.sup.1 and Cp.sup.2 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and a fluorenyl radical, each of which is optionally substituted with a C1-C20 hydrocarbon; R.sup.a and R.sup.b are the same as or different from each other, and are each independently hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl, provided that at least one of R.sup.a or R.sup.b is not hydrogen; Z.sup.1 is each independently a halogen, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or unsubstituted C1-C20 alkylidene, a substituted or unsubstituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy; and n is 1 or 0; [Chemical Formula 2]
(Cp.sup.3R.sup.c).sub.mB.sup.1(Cp.sup.4R.sup.d)M.sup.2Z.sup.2.sub.3−m in Chemical Formula 2, M.sup.2 is a group 4 transition metal; Cp.sup.3 and Cp.sup.4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and a fluorenyl radical, each of which is optionally substituted with a C1-C20 hydrocarbon; R.sup.c and R.sup.d are the same as or different from each other, and are each independently hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl; Z.sup.2 is each independently a halogen, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or unsubstituted C1-C20 alkylidene, a substituted or unsubstituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy; B.sup.1 is at least one radical comprising a carbon, germanium, silicon, phosphorus, or nitrogen atom, which cross-links the Cp.sup.3R.sup.c ring and the Cp.sup.4R.sup.d ring or cross-links the Cp.sup.4R.sup.d ring and M.sup.2; and m is 1 or 0; [Chemical Formula 3]
(Cp.sup.5R.sup.e)B.sup.2(J)M.sup.3Z.sup.3.sub.2 in Chemical Formula 3, M.sup.3 is a group 4 transition metal; Cp.sup.5 is selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and a fluorenyl radical, each of which is optionally substituted with a C1-C20 hydrocarbon; R.sup.e is hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl; Z.sup.3 is each independently a halogen, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or unsubstituted C1-C20 alkylidene, a substituted or unsubstituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy; B.sup.2 is at least one radical comprising a carbon, germanium, silicon, phosphorus, or nitrogen atom, which cross-links the Cp.sup.5R.sup.e ring and J; and J is selected from the group consisting of NR.sup.f, 0, PR.sup.f and S, where R.sup.f are each independently a C1-C20 alkyl, an aryl, a substituted alkyl, or a substituted aryl; ##STR00017## in Chemical Formula 4, R.sup.1 to R.sup.4 and R.sup.1□to R.sup.4□are the same as or different from each other, and are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C6-C20 aryl group, a C7-C20 alkylaryl group, a C7-C20 arylalkyl group, or a C1-C20 amine group, and two or more adjacent groups of R.sup.1 to R.sup.4 and R.sup.1□to R.sup.4□are optionally connected with each other to form one or more aliphatic rings, aromatic rings, or hetero rings; Q.sup.1 and Q.sup.2 are the same as or different from each other, and are each independently hydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C20 alkenyl group, a C7-C40 alkylaryl group, or a C7-C40 arylalkyl group; B.sup.3 is a C2-C20 alkylene group, a C3-C20 cycloalkylene group, a C6-C20 arylene group, a C7-C40 alkylarylene group, or a C7-C40 arylalkylene group; M.sup.4 is a group 4 transition metal; and Z.sup.4 and Z.sup.5 are the same as or different from each other, and are each independently a halogen, a C1-C20 alkyl group, a C2-C10 alkenyl group, a C6-C20 aryl group, a nitro group, an amido group, a C1-C20 alkylsilyl group, a C1-C20 alkoxy group, or a C1-C20 sulfonate group; ##STR00018## in Chemical Formula 5, R.sup.5 and R.sup.5□are the same as or different from each other, and are each independently hydrogen, a C1-C20 alkyl, a C2-C20 alkenyl, a C6-C20 aryl, a C6-C20 silyl, a C7-C20 alkylaryl, a C7-C20 arylalkyl, or a metalloid of a group 4 metal substituted with a hydrocarbyl, and R.sup.5 and R.sup.5□, or two R.sup.5□s are optionally connected with each other by an alkylene comprising a C1-C20 alkyl or a C6-C20 aryl to form a ring; R.sup.6 are is each independently hydrogen, a halogen, a C1-C20 alkyl, a C2-C20 alkenyl, a C6-C20 aryl, a C7-C20 alkylaryl, a C7-C20 arylalkyl, a C1-C20 alkoxy, a C6-C20 aryloxy, or an amido, and two or more groups of R.sup.6s are optionally connected with each other to form an aliphatic ring or an aromatic ring; CY.sup.1 together with N form a substituted or unsubstituted aliphatic or aromatic ring, and a substituent of CY.sup.1 is a halogen, a C1-C20 alkyl, a C2-C20 alkenyl, a C6-C20 aryl, a C7-C20 alkylaryl, a C7-C20 arylalkyl, a C1-C20 alkoxy, a C6-C20 aryloxy, or an amido, wherein two or more substituents are optionally connected with each other to form an aliphatic ring or an aromatic ring; M.sup.5 is a group 4 transition metal; and Q.sup.3 and Q.sup.4 are the same as or different from each other, and are independently a halogen, a C1-C20 alkyl, a C2-C20 alkenyl, a C6-C20 aryl, a C7-C20 alkylaryl, a C7-C20 arylalkyl, a C1-C20 alkylamido, a C6-C20 arylamido, or a C1-C20 alkylidene.

4. The method for preparing a supported hybrid metallocene catalyst according to claim 3, wherein the metallocene compound represented by the Chemical Formula 1 is any one of the following structural formulae: ##STR00019## ##STR00020## ##STR00021##

5. The method for preparing a supported hybrid metallocene catalyst according to claim 3, wherein the metallocene compound represented by the Chemical Formula 2 is any one of the following structural formulae: ##STR00022## ##STR00023## ##STR00024##

6. The method for preparing a supported hybrid metallocene catalyst according to claim 3, wherein the metallocene compound represented by the Chemical Formula 3 is any one of the following structural formulae: ##STR00025## ##STR00026##

7. The method for preparing a supported hybrid metallocene catalyst according to claim 3, wherein the metallocene compound represented by the Chemical Formula 4 is any one of the following structural formulae: ##STR00027## ##STR00028##

8. The method for preparing a supported hybrid metallocene catalyst according to claim 3, wherein the metallocene compound represented by the Chemical Formula 5 is any one of the following structural formulae: ##STR00029## ##STR00030## in the above structural formulae, R.sup.7 are each independently hydrogen or methyl; and Q.sup.5 and Q.sup.6 are the same as or different from each other, and are are each independently methyl, dimethylamido or chloride.

9. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein the aluminum-based cocatalyst is supported on the silica support on which the first metallocene compound is supported by the separate-input method in which 60 wt % to 90 wt % of a whole input of the at least one aluminum-based cocatalyst compound is primarily added at a temperature of 110° C. to 130° C., and the rest of the whole input is secondarily added at a temperature of 0° C. to 40° C.

10. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein the at least one aluminum-based cocatalyst compound is represented by the following Chemical Formula 6: [Chemical Formula 6]
R.sup.8—[Al(R.sup.9)—(O).sub.l].sub.x—R.sup.10  [Chemical Formula 6] in Chemical Formula 6, R.sup.8, R.sup.9, and R.sup.10 are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 hydrocarbyl group, or a C1 to C20 hydrocarbyl group substituted with a halogen; l is 0 or 1; and x is an integer of 2 or more.

11. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein the at least one aluminum-based cocatalyst compound is an alkylaluminoxane-based compound selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane; or trialkylaluminum selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and isoprenylaluminum, or combination thereof.

12. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein a supported amount of the aluminum-based cocatalyst is 5 mmol/g to 15 mmol/g based on 1 g of the silica support.

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

14. The method for preparing a supported hybrid metallocene catalyst according to claim 1, further comprising a step of supporting at least one borate-based cocatalyst compound on the silica support on which the aluminum-based cocatalyst is supported.

15. The method for preparing a supported hybrid metallocene catalyst according to claim 14, wherein the at least one borate-based cocatalyst compound is a borate-based compound in the form of tri-substituted ammonium salts, dialkyl ammonium salts, or tri-substituted phosphonium salts.

16. A method for preparing a polyolefin, comprising the step of polymerizing olefinic monomers in the presence of the supported hybrid metallocene catalyst prepared according to claim 1.

17. The method for preparing a polyolefin according to claim 16, wherein the polyolefin has a bulk density of 0.38 g/mL or more, and a molecular weight distribution (Mw/Mn) or 3.5 or more.

18. The method for preparing a polyolefin according to claim 16, wherein the olefinic monomers are ethylene monomers, and the polyolefine has a settling efficiency defined by the following Equation 1 of 20 to 80%: [Equation 1]
Settling efficiency(%)=an amount of the ethylene monomers used/(an amount of ethylene monomers used used+an solvent content)×100.

19. The method for preparing a supported hybrid metallocene catalyst according to claim 3, wherein the first metallocene compound is the compound represented by the Chemical Formula 1, 2 or 4, and the second metallocene compound is the compound represented by the Chemical Formula 3 or 5.

20. The method for preparing a supported hybrid metallocene catalyst according to claim 1, wherein the first metallocene compound and the second metallocenc compound are used in a ratio of 1:0.5 to 1:2.5 or 1:1 to 1:1.5.

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.

EXAMPLES

Synthesis Examples of Metallocene Compound

Synthesis Example 1: First Metallocene Compound

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

(3) 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. Thereafter, it was heated to room temperature and reacted for 8 hours. The lithium salt solution synthesized as described above was slowly added to a suspension solution of ZrCl.sub.4(THF).sub.2 (1.70 g, 4.50 mmol)/THF (30 mL) at −78° C., and further reacted for about 6 hours at room temperature.

(4) All volatiles were dried in vacuum and the resulting oily liquid material was filtered by adding a hexane solvent. The filtered solution was dried in vacuum, and hexane was added to obtain a precipitate at a low temperature (−20° C.). The obtained precipitate was filtered at a low temperature to obtain bis(3-(6-(tert-butoxy)hexyl)cyclopenta-2,4-dien-1-yl)-zirconiumdichloride ([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%).

(5) .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).

(6) .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.

Synthesis Example 2: Second Metallocene Compound

(7) 50 g of Mg (s) was added to a 10 L reactor at room temperature, followed by 300 mL of THF. 0.5 g of I.sub.2 was added, and the reactor temperature was maintained at 50° C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. As the 6-t-butoxyhexyl chloride was added, it was observed that the temperature of the reactor was elevated by about 4° C. to 5° C. It was stirred for 12 hours while continuously adding 6-t-butoxyhexyl chloride. After the reaction for 12 hours, a black reaction solution was produced. 2 mL of the black solution was taken to which water was added to obtain an organic layer. The organic layer was confirmed to be 6-t-butoxyhexane through .sup.1H-NMR. It could be seen from the above 6-t-butoxyhexane that Grignard reaction was well performed. Consequently, 6-t-buthoxyhexyl magnesium chloride was synthesized.

(8) 500 g of MeSiCl.sub.3 and 1 L of THF were introduced to a reactor, and then the reactor temperature was cooled down to −20° C. 560 g of the 6-t-butoxyhexyl magnesium chloride synthesized above was added to the reactor at a rate of 5 mL/min using a feeding pump. After completion of the feeding of Grignard reagent, the mixture was stirred for 12 hours while slowly raising the reactor temperature to room temperature. After the reaction for 12 hours, it was confirmed that white MgCl.sub.2 salt was produced. 4 L of hexane was added thereto and the salt was removed through a labdori to obtain a filtered solution. After the filtered solution was added to the reactor, hexane was removed at 70° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired compound, methyl(6-t-buthoxy hexyl)dichlorosilane, through 1H-NMR.

(9) 1H-NMR (CDCl3): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H).

(10) 1.2 mol of tetramethylcyclopentadiene (150 g) and 2.4 L of THF were added to the reactor, and then the reactor temperature was cooled down to −20° C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL/min using a feeding pump. After n-BuLi was added, the mixture was stirred for 12 hours while slowly raising the reactor temperature to room temperature. After the reaction for 12 hours, an equivalent of methyl(6-t-buthoxy hexyl)dichlorosilane) (326 g, 350 mL) was rapidly added to the reactor. The mixture was stirred for 12 hours while slowly raising the reactor temperature to room temperature. Then, the reactor temperature was cooled to 0° C. again, and 2 equivalents of t-BuNH.sub.2 was added. The mixture was stirred for 12 hours while slowly raising the reactor temperature to room temperature. After the reaction for 12 hours, THF was removed. Thereafter, 4 L of hexane was added and the salt was removed through a labdori to obtain a filtered solution. The filtered solution was added to the reactor again, and hexane was removed at 70° C. to obtain a yellow solution. The yellow solution obtained above was confirmed to be methyl(6-t-buthoxyhexyl)(tetramethylCpH)t-Butylaminosilane through .sup.1H-NMR.

(11) TiCl.sub.3(THF).sub.3 (10 mmol) was rapidly added to a dilithium salt of a ligand at −78° C., which was synthesized from n-BuLi and the ligand of dimethyl(tetramethylCpH)t-butylaminosilane in THF solution. While slowly heating the reaction solution from −78° C. to room temperature, it was stirred for 12 hours. After stirring for 12 hours, an equivalent of PbCl.sub.2 (10 mmol) was added to the reaction solution at room temperature, and then stirred for 12 hours. After stirring for 12 hours, a dark black solution having a blue color was obtained. THF was removed from the reaction solution thus obtained before hexane was added and the product was filtered. Hexane was removed from the filtered solution, and then the product was confirmed to be the desired (tBu-O—(CH.sub.2).sub.6)(CH.sub.3)Si(C.sub.5(CH.sub.3).sub.4)(tBu-N)TiCl.sub.2, which is (t-butoxyhexylmethylsilyl(N-t-butylamido)(2,3,4,5-tetramethylcyclopentadienyl)-titaniumdichloride through 1H-NMR.

(12) 1H-NMR (CDCl3): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8-0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3H).

Preparation Examples of Supported Hybrid Metallocene Catalyst

Example 1: Supported Hybrid Metallocene Catalyst

(13) (1) Preparation of Support

(14) Silica (SP 952, manufactured by Grace Davison Co.) was dehydrated and dried at a temperature of 600° C. for 12 hours under vacuum.

(15) (2) Preparation of Supported Hybrid Metallocene Catalyst

(16) About 3.0 kg of toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and about 1000 g of the silica support prepared in step (1) was added thereto, followed by stirring while raising the reactor temperature to about 40° C. After sufficient dispersion of the silica for about 60 minutes, about 0.1 mol of the first metallocene compound prepared in Synthesis Example 1 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution.

(17) Thereafter, 5.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added to the reactor, and the temperature was raised to 110° C., followed by stirring at about 200 rpm for about 12 hours. After lowering the temperature to 40° C. again, 2.0 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added and stirred for about 4 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution.

(18) About 3.0 kg of toluene was added to the reaction solution thus recovered, and stirred for about 10 minutes. Thereafter, about 0.1 mol of the second metallocene compound prepared in Synthesis Example 2 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution. About 3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered out. The supported hybrid metallocene catalyst was prepared by drying under reduced pressure at about 50° C. for about 4 hours.

Example 2: Supported Hybrid Metallocene Catalyst

(19) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 1, except that the temperature at which 5.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added was changed from 110° C. to 130° C. in Example 1.

Example 3: Supported Hybrid Metallocene Catalyst

(20) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 2, except that 6.8 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added at 130° C. and 1.5 kg of the same was added at 40° C.

Comparative Example 1: Supported Hybrid Metallocene Catalyst

(21) (1) Preparation of Support

(22) Silica (SP 952, manufactured by Grace Davison Co.) was dehydrated and dried at a temperature of 600° C. for 12 hours under vacuum.

(23) (2) Preparation of Supported Hybrid Metallocene Catalyst

(24) About 3.0 kg of toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and about 1000 g of the silica support prepared in step (1) was added thereto, followed by stirring while raising the reactor temperature to about 40° C. After sufficient dispersion of the silica for about 60 minutes, about 0.1 mol of the first metallocene compound prepared in Synthesis Example 1 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution.

(25) Thereafter, 7.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added to the reactor, and the temperature was raised to 60° C., followed by stirring at about 200 rpm for about 12 hours. After lowering the temperature to 40° C. again, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution.

(26) About 3.0 kg of toluene was added to the reaction solution thus recovered, and stirred for about 10 minutes. Thereafter, about 0.1 mol of the second metallocene compound prepared in Synthesis Example 2 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution. About 3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered out. The supported hybrid metallocene catalyst was prepared by drying under reduced pressure at about 50° C. for about 4 hours.

Comparative Example 2: Supported Hybrid Metallocene Catalyst

(27) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 1, except that the temperature at which 5.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added was changed from 110° C. to 60° C. in Example 1.

Comparative Example 3: Supported Hybrid Metallocene Catalyst

(28) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 1, except that the temperature at which 5.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added was changed from 110° C. to 80° C. in Example 1.

Comparative Example 4: Supported Hybrid Metallocene Catalyst

(29) A supported hybrid metallocene catalyst was prepared in the same manner as in Comparative Example 1, except that the temperature at which 7.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added was changed from 60° C. to 110° C. in Comparative Example 1.

Comparative Example 5: Supported Hybrid Metallocene Catalyst

(30) (1) Preparation of Support

(31) Silica (SP 952, manufactured by Grace Davison Co.) was dehydrated and dried at a temperature of 180° C. for 12 hours under vacuum.

(32) (2) Preparation of Supported Hybrid Metallocene Catalyst

(33) About 3.0 kg of toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and about 1000 g of the silica support prepared in step (1) was added thereto, followed by stirring while raising the reactor temperature to about 40° C.

(34) After sufficient dispersion of the silica for about 60 minutes, 7.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added to the reactor, and the temperature was raised to 110° C., followed by stirring at about 200 rpm for about 12 hours. After lowering the temperature to 40° C. again, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution.

(35) About 3.0 kg of toluene was added to the reaction solution thus recovered, and stirred for about 10 minutes. Thereafter, about 0.1 mol of the first metallocene compound prepared in Synthesis Example 1 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, about 0.1 mol of the second metallocene compound prepared in Synthesis Example 2 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution. About 3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered out. The supported hybrid metallocene catalyst was prepared by drying under reduced pressure at about 50° C. for about 4 hours.

Comparative Example 6: Supported Hybrid Metallocene Catalyst

(36) (1) Preparation of Support

(37) Silica (SP 952, manufactured by Grace Davison Co.) was dehydrated and dried at a temperature of 180° C. for 12 hours under vacuum.

(38) (2) Preparation of Supported Hybrid Metallocene Catalyst

(39) About 3.0 kg of toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and about 1000 g of the silica support prepared in step (1) was added thereto, followed by stirring while raising the reactor temperature to about 40° C.

(40) After sufficient dispersion of the silica for about 60 minutes, 5.4 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added to the reactor, and the temperature was raised to 110° C., followed by stirring at about 200 rpm for about 12 hours. After lowering the temperature to 40° C. again, 2.0 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was added and stirred for about 4 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution.

(41) About 3.0 kg of toluene was added to the reaction solution thus recovered, and stirred for about 10 minutes. Thereafter, about 0.1 mol of the first metallocene compound prepared in Synthesis Example 1 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, about 0.1 mol of the second metallocene compound prepared in Synthesis Example 2 was dissolved to become a solution state, added thereto and then reacted while stirring for about 2 hours. Thereafter, the stirring was stopped, followed by settling for about 30 minutes and then decantation of the reaction solution. About 3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered out. The supported hybrid metallocene catalyst was prepared by drying under reduced pressure at about 50° C. for about 4 hours.

(42) In the supported hybrid catalyst preparation process according to Examples 1 to 3 and Comparative Examples 1 to 6, a supporting content, a supporting temperature, and a supporting order of the first metallocene compound, the second metallocene compound, and the cocatalyst are shown in Table 1 below.

(43) TABLE-US-00001 TABLE 1 First metallocene Second metallocene Cocatalyst compound compound Primary Primary Secondary Secondary Content Temp. Content Temp. content temp. content temp. Separate Supporting (mmol/gSiO.sub.2) (° C.) (mmol/gSiO.sub.2) (° C.) (mmol/gSiO.sub.2) (° C.) (mmol/gSiO.sub.2) (° C.) input order Ex. 1 0.1 40 0.1 40 8 110 3 40 ◯ Precursor 1/MAO/ Precursor 2 Ex. 2 0.1 40 0.1 40 8 130 3 40 ◯ Precursor 1/MAO/ Precursor 2 Ex. 3 0.1 40 0.1 40 9 130 2 40 ◯ Precursor 1/MAO/ Precursor 2 Comp. 0.1 40 0.1 40 11 60 none none X Precursor 1/MAO/ Ex. 1 Precursor 2 Comp. 0.1 40 0.1 40 8 60 3 40 ◯ Precursor 1/MAO/ Ex. 2 Precursor 2 Comp. 0.1 40 0.1 40 8 80 3 40 ◯ Precursor 1/MAO/ Ex. 3 Precursor 2 Comp. 0.1 40 0.1 40 11 110 none none X Precursor 1/MAO/ Ex. 4 Precursor 2 Comp. 0.1 40 0.1 40 11 110 none none X MAO/Precursor 1/ Ex. 5 Precursor 2 Comp. 0.1 40 0.1 40 8 110 3 40 ◯ MAO/Precursor 1/ Ex. 6 Precursor 2

(44) In the preparation of the supported catalyst in Table 1, the supporting order of the first metallocene compound (precursor 1), the second metallocene compound (precursor 2), and the cocatalyst (MAO) was expressed as “I”.

Preparation Examples of Polymerization of Olefinic Monomer

Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 6: Homopolymerization of Ethylene

(45) Under the conditions as shown in Table 2 below, an ethylene homopolymerization reaction of Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 6 was performed using the supported hybrid metallocene catalyst of Examples 1 to 3 and Comparative Examples 1 to 6.

(46) 2 mL (1 M in hexane) of triethylaluminum (TEAL) was added to a 2 L autoclave high pressure reactor, 0.6 kg of hexane was added thereto, and the temperature was raised to 80° C. while stirring at 500 rpm. The supported hybrid catalyst and hexane were injected to a vial and added to the reactor, followed by additional 0.2 kg of hexane. When the temperature inside the reactor reached 80° C., the reaction was carried out for 1 hour while stirring at 500 rpm under an ethylene pressure of 30 bar. After the completion of the reaction, the obtained polymer was first filtered to remove hexane, and dried in an oven at 80° C. for 3 hours.

(47) In the polymerization process of Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 6, the catalytic activity and physical properties of the prepared polyolefin were measured as follows, and the results are shown in Table 2 below.

(48) (1) Catalytic activity (kgPE/gSiO.sub.2): The catalytic activity of the catalyst used in each of Examples and Comparative Examples was calculated by measuring a weight of the catalyst used in the polymerization reaction and a weight of the polymer prepared through the polymerization reaction.

(49) Specifically, the weight (kg) of the polyethylene obtained after the polymerization process and the drying process was measured to be a kgPE value, and the weight (g) of the supported catalyst used in the polymerization process was measured to be gSiO.sub.2. And, the catalytic activity was calculated by dividing the weight (kg) of the obtained polyethylene (kgPE) by the weight (g) of the supported catalyst (gSiO.sub.2).

(50) (2) Weight average molecular weight (Mw) and molecular weight distribution (MWD, polydispersity index): The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC, manufactured by Water). The MWD (Mw/Mn) was calculated by dividing the weight average molecular weight by the number average molecular weight.

(51) Specifically, PL-GPC220 manufactured by Waters was used as the gel permeation chromatography (GPC) instrument, and a Polymer Laboratories PLgel MIX-B 300 mm length column was used. An evaluation temperature was 160° C., and 1,2,4-trichlorobenzene was used for a solvent at a flow rate of 1 mL/min. Each polyethylene sample was pretreated by dissolving in 1,2,4-trichlorobenzene containing 0.0125% of BHT for 10 hours using a GPC analyzer (PL-GP220), and the sample with a concentration of 10 mg/10 mL was supplied in an amount of 200 μL. Mw and Mn were obtained using a calibration curve formed using a polystyrene standard. 9 kinds of the polystyrene standard were used with the molecular weight (g/mol) of 2000/10000/30000/70000/200000/700000/2000000/4000000/10000000.

(52) (3) Particle size distribution (PSD): Polymers were separated by a particle size using sieves (size: 850 μm, 500 μm, 300 μm, 180 μm).

(53) Specifically, the polymer was separated according to the particle size using the above-described sieves as follows: in case of the particle size of the polymer is larger than 850 μm (>850), in case of larger than 500 μm and 850 μm or less (>500), in case of larger than 300 μm and 500 μm or less (>300), in case of larger than 180 μm and 300 μm or less (>180), and in case of 180 μm or less (fine). And the weights of the polymers separated by the corresponding particle size were measured and expressed as a percentage (wt %), respectively, based on a total weight of the polymer.

(54) The particle size distribution (PSD) result was expressed as PSD with the weight values that were simply separated using sieves in the laboratory, without using a specific instrument or specific criteria.

(55) (4) Bulk density (BD): It was measured in accordance with ASTM D 1895 Method A. Specifically, after filling a 100 mL SUS container with a polymer, a weight (g) of the polymer was measured and the bulk density was expressed as a weight per unit volume (g/mL).

(56) (5) Al supporting rate (%): The Al supporting rate in the supported catalyst was measured by an inductively coupled plasma spectrometer (ICP) analysis method. At this time, the Al supporting rate (%) represents an amount of the actually supported cocatalyst relative to an amount of the cocatalyst (Al) added in the preparation of the supported catalyst as a percentage value.

(57) Specifically, the equipment used for the analysis was ICP-OES (Perkin Elmer), the analysis conditions were set to Plasma Gas 12 L/min, Auxiliary Gas 0.2 L/min, and Nebulizer Gas 0.8 L/min, RF Power was 1300 WATTS, and a sample flow rate was 1.50 mL/min with Radial View.

(58) TABLE-US-00002 TABLE 2 Catalytic Particle size Al supporting activity distribution rate (kgPE/ BD (wt %, Sieve, μm) Catalyst (ICP analysis, %) gSiO.sub.2) (g/mL) MWD >850 >500 >300 >180 Fine Prep. Ex. 1 90 10.8 0.40 4.2 30.4 52.8 16.4 0.4 0 Ex. 1 Prep. Ex. 2 89 12 0.40 4.3 32.3 49.0 18.1 0.6 0 Ex. 2 Prep. Ex. 3 89 9.9 0.41 4.2 27.9 55.0 16.2 0.9 0 Ex. 3 Comp. Prep. Comp. 79 8.9 0.35 4.0 10.1 51.9 36.6 1.2 0.2 Ex. 1 Ex. 1 Comp. Prep. Comp. 81 9.2 0.35 4.0 14.0 54.3 30.3 1.2 0.2 Ex. 2 Ex. 2 Comp. Prep. Comp. 83 9.6 0.36 4.0 12.5 50.2 35.5 1.5 0.3 Ex. 3 Ex. 3 Comp. Prep. Comp. 85 9.9 0.37 4.1 11.3 52.8 34.3 1.3 0.3 Ex. 4 Ex. 4 Comp. Prep. Comp. 84 11.0 0.39 3.3 22.1 57.2 19.4 1.2 0.1 Ex. 5 Ex. 5 Comp. Prep. Comp. 88 12.2 0.37 3.0 28.3 58.5 11.7 1.3 0.2 Ex. 6 Ex. 6

(59) Referring to Table 2, it was confirmed that Preparation Examples 1 to 3 could prepare a polyethylene satisfying both the high bulk density of 0.40 g/mL to 0.41 g/mL and the broad molecular weight distribution of 4.2 to 4.3. In particular, Preparation Examples 1 to 3 have an advantage in that the bulk density was rather increased while the catalytic activity was maintained as high as 9.9 kgPE/gSiO.sub.2 to 12 kgPE/gSiO.sub.2 with the large particle size and the narrow distribution. As a result, it can be seen that each of the particles of the resulting polymer is densely produced, and productivity can be increased by improving the settling efficiency when applied to an actual pilot process or continuous process.

(60) The supported hybrid catalysts of Examples 1 to 3 used in the polyethylene polymerization process of Preparation Examples 1 to 3 can broaden MWD of the polymer and thus processability of the polymer can be improved by supporting the first metallocene precursor prior to the cocatalyst. In addition, the supported hybrid catalyst of Example 1 dividedly supported the cocatalyst sequentially at high temperatures in order to evenly support the cocatalyst to the inside of the support, thereby significantly increasing the bulk density of the resulting polymer.

(61) In particular, when the Al content in the supported catalyst was analyzed by ICP for the supported hybrid catalysts of Examples 1 to 3, Examples 1 to 3 in which the cocatalysts were dividedly supported at high temperatures showed significantly higher Al supporting rates of 89% and 90%, even though the same amount of cocatalyst as Comparative Examples 1 to 6 was added.

(62) On the other hand, Comparative Preparation Examples 1 to 6 did not obtain a polymer satisfying the bulk density (BD), molecular weight distribution (MWD) and particle size distribution at the same time.

(63) Specifically, in Comparative Preparation Examples 1 to 3, the bulk density of the polyethylene was lower than that of Preparation Examples 1 to 3 by applying the catalysts of Comparative Examples 1 to 3 in which the cocatalysts were all or partly supported at a low temperature of 60° C. to 80° C. Also, in Comparative Preparation Example 4, the bulk density of the polyethylene was lower than that of the case where the cocatalyst was dividedly added by applying the supported hybrid catalyst of Comparative Example 4 in which the cocatalyst was supported at a high temperature of 110° C. at once. In particular, in Comparative Preparation Examples 1 to 4, the first metallocene compound was supported prior to the cocatalyst, so that the molecular weight distribution (MWD) of the polymer was broad, but the particle size distribution of the polymer was broad and the bulk density (BD) was low. Thus, it was difficult to expect an increase in productivity.

(64) In Comparative Preparation Examples 5 and 6, the molecular weight distribution (MWD) of the polymer was significantly decreased and narrowed by applying a supported hybrid catalyst in which the cocatalyst was supported prior to the catalyst precursor.

Preparation Example 4 and Comparative Preparation Examples 7 to 9: Ethylene-1-Hexene Copolymerization

(65) Under the conditions as shown in Table 3 below, an ethylene-1-hexene copolymerization reaction of Preparation Example 4 and Comparative Preparation Examples 7 to 9 was performed using the supported hybrid metallocene catalyst of Example 1 and Comparative Examples 1, 4 and 5.

(66) At this time, the polymerization reactor was a continuous polymerization reactor of an isobutane slurry loop process, that is, a loop slurry reactor, the reactor volume was 140 L, and the reaction flow rate was operated at about 7 m/s. Gases (ethylene, hydrogen) and comonomer (1-hexene) required for the polymerization were constantly and continuously injected, and the individual flow rate was adjusted to the target product. The concentration of all gases and comonomer (1-hexene) was confirmed by on-line gas chromatograph. The supported catalyst was added to an isobutane slurry, the reactor pressure was maintained at about 40 bar, and the polymerization was performed at a temperature of about 93° C.

(67) In the polymerization process of Preparation Example 4 and Comparative Preparation Examples 7 to 9, the catalytic activity and physical properties of the prepared polyolefin were measured and the results are shown in Table 3 below. Among these, the catalytic activity, Mw, MWD, and BD were measured by the method as mentioned above.

(68) (6)Ethylene load (C2) weight (kg/h): When carrying out the ethylene-1-hexene copolymerization reaction under the polymerization conditions as described above, the ethylene consumption per hour (amount of polymer produced), that is, ethylene load weight per unit time (kg/h) was measured.

(69) (7) MI.sub.2.16 and MFRR (21.6/2.16): The melt index (MI.sub.2.16) was measured in accordance with ASTM D 1238 (condition E, 190° C., 2.16 kg load).

(70) The melt flow rate ratio (MFRR, 21.6/2.16) was calculated by dividing MFR.sub.21.6 by MFR.sub.2.16, and the MFR.sub.21.6 was measured in accordance with ISO 1133 at 190° C. under a load of 21.6 kg and the MFR.sub.2.16 was measured in accordance with ISO 1133 at 190° C. under a load of 2.16 kg.

(71) (8) Density (density): The density was measured in accordance with ASTM D 1505.

(72) (9) Slurry density (DI): The slurry density refers to an amount of polymer per unit volume in the slurry loop reactor, and was measured using radiation.

(73) (10) Settling efficiency (SE, %): The settling efficiency was measured by the following Equation 1.
Settling efficiency(%)=amount of ethylene used/(amount of ethylene used+solvent content)×100.  [Equation 1]

(74) TABLE-US-00003 TABLE 3 Prep. Comp. Prep. Comp. Prep. Comp. Prep. Ex. 4 Ex. 7 Ex. 8 Ex. 9 Catalyst Ex. 1 Comp. Ex. 1 Comp. Ex. 4 Comp. Ex. 5 C2 (kg/h) 40 33 34 32 MWD 4.5 4.3 4.3 3.0 MFRR 33.5 32.2 31.8 28.5 (MI.sub.21.6/MI.sub.2.16) BD (g/mL) 0.49 0.44 0.46 0.45 Density (g/cm.sup.3) 0.935 0.934 0.935 0.935 DI (kg/m.sup.3) 562 561 560 560 SE (%) 68 62 63 61 Activity 11.5 10.4 10.9 12.0 (kgPE/gSiO.sub.2)

(75) Referring to Table 3, it was confirmed that Preparation Example 4 could effectively prepare a polyolefin having a high bulk density and a broad molecular weight distribution by using the supported hybrid catalyst of Example 1 in which the first metallocene precursor was supported and then the cocatalyst was dividedly supported, followed by the second metallocene precursor.

(76) Particularly, in Preparation Example 4, the cocatalyst was first supported at a high temperature of 110° C. and then the rest was sequentially supported at 40° C. to evenly support the cocatalyst to the inside of the support. Therefore, when a continuous polymerization was performed under the same temperature, pressure and slurry density (DI), the settling efficiency (S. E) and the ethylene load were greatly increased while maintaining the high activity. Specifically, the settling efficiency (S. E) of Preparation Example 4 was further improved by about 7.9% to about 11.5% compared to Comparative Preparation Examples 7 to 9. As a result, it was confirmed that the ethylene load weight per hour of Preparation Example 4 was further increased by about 17.6% to about 25% compared to Comparative Preparation Examples 7 to 9, and thus productivity in the slurry loop polymerization process, which is a pilot continuous process, was significantly improved.