Ethylene/1-hexene or ethylene/1-butene copolymer having excellent processibility and environmetal stress crack resistance

Abstract

The present invention relates to an ethylene/1-hexene or ethylene/1-butene copolymer having excellent processibility. The ethylene/1-hexene or ethylene/1-butene copolymer according to the present invention has high molecular weight and wide molecular weight distribution, and thus excellent processibility, and has excellent environmental stress crack resistance, and thus, may be applied for a high inner pressure heating pipe, a mining pipe, or a large-diameter pipe, and the like.

Claims

1. An ethylene/1-butene copolymer having: weight average molecular weight(g/mol) of 10,000 to 400,000, molecular weight distribution (Mw/Mn, PDI) of 2 to 30, density (g/cm.sup.3) of 0.930 to 0.950, MFR.sub.5(g/10 min, measured at 190° C. by ASTM 1238) of 0.1 to 5, melt flow rate ratio (MFR.sub.21.6/MFR.sub.5, measured at 190° C. by ASTM 1238) of 10 to 200, and an environmental stress crack resistance (ESCR) of 400 hours to 20,000 hours, as measure by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80° C.

2. The copolymer according to claim 1, wherein the environmental stress crack resistance (ESCR) measured by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80° C. is 600 hours to 8,760 hours.

3. The copolymer according to claim 1, wherein the weight average molecular weight is 50,000 to 350,000 g/mol.

4. The copolymer according to claim 1, wherein the molecular weight distribution is 7 to 28.

5. The copolymer according to claim 1, wherein the MFR.sub.5 is 0.1 to 3.

6. The copolymer according to claim 1, wherein the melt flow rate ratio is 15 to 180.

7. The copolymer according to claim 1, wherein the ethylene/1-butene copolymer is prepared by polymerizing ethylene and 1 butene, in the presence of at least one first metallocene compound represented by the following Chemical Formula 1; and at least one second metallocene compound selected from the compounds represented by the following Chemical Formulae 3 to 5: ##STR00024## in the Chemical Formula 1, A is hydrogen, halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, C.sub.7-20 alkylaryl, C.sub.7-20 arylalkyl, C.sub.1-20 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.3-20 heterocycloalkyl, or C.sub.5-20 heteroaryl; D is —O—, —S—, —N(R)—or —Si(R)(R′)—, wherein R and R′ are identical to or different from each other, and are each independently hydrogen, halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, or C.sub.6-.sub.20 aryl; L is C.sub.1-10 linear or branched alkylene; B is carbon, silicon or germanium; Q is hydrogen, halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, C.sub.7-20 alkylaryl, or C.sub.7-20 arylalkyl; M is Group 4 transition metal; X.sup.1 and X.sup.2 are identical to or different from each other, and are each independently halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, nitro, amido, C.sub.1-20 alkylsilyl, C.sub.1-20 alkoxy, C.sub.1-20 , or C.sub.1-20 sulfonate; C.sup.1 and C.sup.2 are identical to or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b or Chemical Formula 2c, provided that both C.sup.1 and C.sup.2 are not Chemical Formula 2c; [Chemical Formula 2a] ##STR00025## in the Chemical Formulae 2a, 2b and 2c, R.sub.1 to R.sub.17 and R.sub.1′ to R.sub.9′ are identical to or different from each other, and are each independently hydrogen, halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.1-20 alkylsilyl, C.sub.1-20 silylalkyl, C.sub.1-20 alkoxysilyl, C.sub.1-20 alkoxy, C.sub.6-20 aryl, C.sub.7-20 alkylaryl, or C.sub.7-20 arylalkyl, and two or more neighboring groups of R.sub.10 to R.sub.17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
(Cp.sup.1R.sup.a).sub.n(Cp.sup.2R.sup.b)M.sup.1Z.sup.1.sub.3-n   [Chemical Formula 3] in the Chemical Formula 3, M.sup.1 is Group 4 transition metal; Cp.sup.1 and Cp.sup.2 are identical to or different from each other, and are each independently one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which may be substituted with hydrocarbon having a carbon number of 1 to 20; R.sup.a and R.sup.b are identical to or different from each other, and are each independently hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl; Z.sup.1 is a halogen atom, C.sub.1-20 alkyl, C.sub.2-10 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.6-20 aryl, substituted or unsubstituted C.sub.1-20 alkylidene, or substituted or unsubstituted amino, C.sub.2-20 alkylalkoxy, or C.sub.7-40 arylalkoxy; n is 1 or 0;
(Cp.sup.3R.sup.c).sub.mB.sup.1(Cp.sup.4R.sup.d)M.sup.2Z.sup.2.sub.3-m  [Chemical Formula 4] in the Chemical Formula 4, M.sup.2 is Group 4 transition metal; Cp.sup.3 and Cp.sup.4 are identical to or different from each other, and are each independently one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbon having a carbon number of 1 to 20; R.sup.c and R.sup.d are identical to or different from each other, and are each independently hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl; Z.sup.2 is a halogen atom, C.sub.1-20 alkyl, C.sub.2-10 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.6-20 aryl, substituted or unsubstituted C.sub.1-20 alkylidene, or substituted or unsubstituted amino, C.sub.2-20 alkylalkoxy, or C.sub.7-40 arylalkoxy; B.sup.1 is one or more of carbon, germanium, silicon, phosphorus or nitrogen-containing radical, or a combination thereof, which crosslinks a Cp.sup.3R.sup.c ring with a Cp.sup.4R.sup.d ring, or crosslinks one Cp.sup.4R.sup.d ring to M.sup.2; m is 1 or 0;
(Cp.sup.5R.sup.e)B.sup.2(J)M.sup.3Z.sup.3.sub.2  [Chemical Formula 5] in the Chemical Formula 5, M.sup.3 is Group 4 transition metal; Cp.sup.5 is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbon having a carbon number of 1 to 20; R.sup.e is hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl; Z.sup.3 is a halogen atom, C.sub.1-20 alkyl, C.sub.2-10 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.6-20 aryl, substituted or unsubstituted C.sub.1-20 alkylidene, substituted or unsubstituted amino, C.sub.2-20 alkylalkoxy, or C.sub.7-40 arylalkoxy; B.sup.2 is one or more of carbon, germanium, silicon, phosphorus or nitrogen-containing radicals or a combination thereof, which crosslinks a Cp.sup.5R.sup.e ring with J; and J is one selected from the group consisting of NR.sup.f, O, PR.sup.f and S, wherein R.sup.f is C.sub.1-20 alkyl, aryl, substituted alkyl, or substituted aryl.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows the GPC curve of the polymers prepared in Comparative Examples and Examples of the present invention.

(2) FIG. 2 shows the GPC curve of the polymers prepared in Comparative Examples and Examples of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) Hereinafter, preferable examples are presented to aid in understanding of the invention. However, these examples are provided only to aid in understanding of the invention, and the scope of the invention is not limited thereto.

A First Metallocene Compound

Preparation Example 1

(4) ##STR00023##

(5) 1-1) Preparation of a Ligand Compound

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

(7) .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)

(8) 1-2) Preparation of a Metallocene Compound

(9) 7.2 g (12 mmol) of the ligand compound synthesized in 1-1 was dissolved in 50 mL of diethylether, and 11.5 mL of a 2.5 M n-BuLi solution in hexane was added dropwise thereto in a dry ice/acetone bath, and the solution was stirred at room temperature overnight. The solution was vacuum dried to obtain brown sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl.sub.4(THF).sub.2 was prepared and 50 mL of toluene was added to prepare a slurry. The 50 mL toluene slurry of ZrCl.sub.4(THF).sub.2 was transferred under a dry ice/acetone bath. After stirring at room temperature overnight, it turned to violet color. The reaction solution was filtered to remove LiCl. The filtrate was vacuum dried to remove toluene, and then, hexane was introduced and sonication was conducted for 1 hour. The slurry was filtered to obtain filtered solid of 6 g of dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol %). Two isomers were observed in 1H-NMR.

(10) .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)

A Second Metallocene Compound

Preparation Example 2

Preparation of [tBu-O—(CH2)6—C5H4]2ZrCl2]

(11) t-Butyl-O—(CH.sub.2).sub.6—Cl was prepared using 6-chlorohexanol by the method suggested in the document (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).

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

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

(14) .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)

(15) .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

Precipitation 3

Preparation of [(tBu-O—(CH2)6)(CH3)Si(C5(CH3)4)(tBu-N)TiCl2]

(16) 50 g of Mg(s) was introduced into a 10 L reactor at room temperature, and then, THF 300 mL was added thereto. About 0.5 g of 12 was added, and then, the temperature of the reactor was maintained at 50° C. After the temperature of the reactor was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a speed of 5 mL/min using a feeding pump. It was observed that as 6-t-butoxyhexyl chloride was added, the temperature of the reactor increased by about 4 to 5° C. While continuously adding 6-t-butoxyhexyl chloride, the solution was stirred for 12 hours. After reaction for 12 hours, a black reaction solution was obtained. 2 mL of the produced black solution was taken, water was added thereto to obtain an organic layer, and 6-t-butoxyhexane was confirmed through 1H-NMR. From the 6-t-butoxyhexane, it could be seen that a Gringanrd reaction progressed well. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

(17) 500 g of MeSiCl.sub.3 and 1 L of THF were added to a reactor, and the reactor was cooled to −20° C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a speed of 5 mL/min using a feeding pump. After the feeding of a Grignard reagent was completed, the solution was stirred for 12 hours while slowly raising the temperature of the reactor to room temperature. After reaction for 12 hours, it was confirmed that white MgCl.sub.2 salts were produced. 4 L of hexane was added and salts were removed through Labdori to obtain a filtered solution. The filtered solution was added to the reactor, and then, hexane was removed at 70° C. to obtain light yellow liquid. It was confirmed through 1H-NMR that the obtained liquid is desired compound methyl(6-t-butoxyhexyl)dichlorosilane.

(18) .sup.1H-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)

(19) 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and then, the reactor was cooled to −20° C. 480 mL of n-BuLi was added to the reactor at a speed of 5 mL/min using a feeding pump. After n-BuLi was added, the solution was stirred for 12 hours while slowly raising the temperature of the reactor. After reaction for 12 hours, an equivalent of methyl(6-t-butoxyhexyl)dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. The solution was stirred for 12 hours while slowly raising the temperature of the reactor to room temperature, and then, the reactor was cooled to 0° C. again, and 2 equivalents of t-BuNH.sub.2 was added. While slowly raising the temperature of the reactor to room temperature, the solution was stirred for 12 hours. After reaction for 12 hours, THF was removed, 4 L of hexane was added, and salts were removed through Labdori to obtain a filtered solution. The filtered solution was added to the reactor again, and then, hexane was removed at 70° C. to obtain a yellow solution. It was confirmed through 1H-NMR that the obtained yellow solution is methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane).

(20) To the dilithium salt of ligand of −78° C. synthesized from n-BuLi and ligand dimethyl(tetramethylCpH)t-butylaminosilane in a THF solution, TiCl.sub.3(THF).sub.3(10 mmol) was rapidly added. The reaction solution was stirred for 12 hours while slowly raising the temperature from −78° C. to room temperature. After stirring for 12 hours, an equivalent of PbCl.sub.2(10 mmol) was added to the reaction solution at room temperature, and the solution was stirred for 12 hours. After stirring for 12 hours, a bluish black solution was obtained. THF was removed in the produced reaction solution, and then, hexane was added to filter the product. After removing hexane in the obtained filtered solution, it was confirmed through 1H-NMR that desired methyl(6-t-butoxyhexyl)silyl(η5-tetramethylCp)(t-butylamido)]TiCl.sub.2 of tBu-O—(CH.sub.2).sub.6)(CH.sub.3)Si(C.sub.5(CH.sub.3).sub.4)(tBu-N)TiCl.sub.2 was obtained.

(21) .sup.1H-NMR (CDCl.sub.3): 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)

Hybrid Supported Catalyst

Comparative Examples 1-1 and 1-2

(22) Into a 20 L sus high pressure reactor, 5.0 kg of a toluene solution was introduced and the temperature of the reactor was maintained at 40° C. 1,000 g of silica dehydrated by adding vacuum at 600° C. for 12 hours (manufactured by Grace Davison Company, SYLOPOL 948) was introduced into the reactor, the silica was sufficiently dispersed, and then, 80 g of the metallocene compound of the Preparation Example 2 was dissolved in toluene and introduced, and the solution was stirred at 200 rpm for 2 hours and reacted. Thereafter, the stirring was discontinued, and the solution was settled for 30 minutes, and then, the reaction solution was decanted.

(23) 2.5 kg of toluene was introduced into the reactor, 9.4 kg of a 10 wt % methylaluminoxane (MAO)/toluene solution was introduced, and then, the solution was stirred at 40° C., 200 rpm for 12 hours. After the reaction, stirring was discontinued, and the solution was settled for 30 minutes, and then, the reaction solution was decanted. 3.0 kg of toluene was introduced, and the solution was stirred for 10 minutes, and then, stirring was discontinued, the solution was settled for 30 minutes, and the toluene solution was decanted.

(24) 3.0 kg of toluene was introduced into the reactor, 236 mL of 29.2 wt % metallocene compound of Preparation Example 3/toluene solution was introduced, and the solution was stirred at 40° C., 200 rpm for 2 hours and reacted. The temperature of the reactor was lowered to room temperature, and then, stirring was discontinued, the solution was settled for 30 minutes, and the reaction solution was decanted.

(25) 2.0 kg of toluene was introduced in the reactor, and the solution was stirred for 10 minutes, and then, stirring was discontinued, the solution was settled for 30 minutes, and the reaction solution was decanted.

(26) 3.0 kg of hexane was introduced into the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. By drying at 40° C. for 4 hours under reduced pressure, 910 g-SiO.sub.2 hybrid supported catalyst was prepared.

Examples 1-1 and 1-2

(27) Supported catalysts were prepared by the same methods as Comparative Examples 1-1 and 1-2, except that 314 mL of the metallocene compound of Preparation Example 3/toluene solution was introduced.

Example 1-3

(28) Into a 20 L sus high pressure reactor, 6.0 kg of a toluene solution was introduced and the temperature of the reactor was maintained at 40° C. 1,000 g of silica dehydrated by adding vacuum at 600° C. for 12 hours (manufactured by Grace Davison Company, SYLOPOL 948) was introduced into the reactor, the silica was sufficiently dispersed, and then, 80 g of the metallocene compound of the Preparation Example 2 was dissolved in toluene and introduced, and the solution was stirred at 40° C. for 2 hours and reacted. Thereafter, the stirring was discontinued, and the solution was settled for 30 minutes, and then, the reaction solution was decanted.

(29) 2.5 kg of toluene was introduced into the reactor, 9.4 kg of a 10 wt % methylaluminoxane (MAO)/toluene solution was introduced, and then, the solution was stirred at 40° C., 200 rpm for 12 hours. After the reaction, stirring was discontinued, and the solution was settled for 30 minutes, and then, the reaction solution was decanted. 3.0 kg of toluene was introduced, and the solution was stirred for 10 minutes, and then, stirring was discontinued, the solution was settled for 30 minutes, and the toluene solution was decanted.

(30) 3.0 kg of toluene was introduced into the reactor, 314 mL of the 29.2 wt % metallocene compound of Preparation Example 3/toluene solution was introduced, and the solution was stirred at 40° C., 200 rpm for 2 hours and reacted.

(31) 80 g of the metallocene compound of Preparation Example 1 and 1,000 mL of toluene were put in a flask to prepare a solution, and sonication was conducted for 30 minutes. The prepared metallocene compound of Preparation Example 1/toluene solution was introduced into the reactor, and the solution was stirred at 40° C., 200 rpm for 2 hours and reacted. The temperature of the reactor was lowered to room temperature, and then, stirring was discontinued, the solution was settled for 30 minutes, and the reaction solution was decanted.

(32) 2.0 kg of toluene was introduced in the reactor, and the solution was stirred for 10 minutes, and then, stirring was discontinued, the solution was settled for 30 minutes, and the reaction solution was decanted.

(33) 3.0 kg of hexane was introduced into the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. By drying at 40° C. for 4 hours under reduced pressure, 890 g-SiO.sub.2 hybrid supported catalyst was prepared.

Comparative Example 2-1

(34) Into a 20 L sus high pressure reactor, 3.0 kg of a toluene solution was introduced and the temperature of the reactor was maintained at 40° C. 500 g of silica (Grace Davison, SP2212) was introduced into the reactor, the silica was sufficiently dispersed, and then, 3.00 kg of a 10 wt % methylaluminoxane (MAO)/toluene solution was introduced, the temperature was raised to 80° C., and the solution was stirred at 200 rpm for 15 hours or more. The temperature of the reactor was lowered to 40° C. again, and then, 144 g of 7.5 wt % catalyst of Preparation Example 2/toluene solution was introduced into the reactor, and the solution was stirred at 200 rpm for 1 hour. 240 g of 8.8 wt % catalyst of Preparation Example 1/toluene solution was introduced into the reactor, and the solution was stirred at 200 rpm for 1 hour. The catalyst of Preparation Example 3 (18 g) was dissolved in toluene and introduced into the reactor, and the solution was stirred at 200 rpm for 2 hours. 70 g of a cocatalyst(anilinium tetrakis(pentafluorophenyl)borate) was diluted in toluene and introduced into the reactor, and the solution was stirred at 200 rpm for 15 hours or more. The temperature of the reactor was lowered to room temperature, and then, the stirring was discontinued, the solution was settled for 30 minutes, and the reaction solution was decanted. The toluene slurry was transferred to a filter dryer and filtered. 3.0 kg of toluene was introduced and the solution was stirred for 10 minutes, and then, stirring was discontinued and the solution was filtered. 3.0 kg of hexane was introduced into the reactor, and the solution was stirred for 10 minutes, and then, stirring was discontinued and the solution was filtered. By drying at 50° C. for 4 hours under reduced pressure, a 500 g-SiO.sub.2 supported catalyst was prepared.

Examples 2-1 to 2-3

(35) Into a 20 L sus high pressure reactor, 3.0 kg of a toluene solution was introduced and the temperature of the reactor was maintained at 40° C. 500 g of silica (Grace Davison, SP2212) was introduced into the reactor, the silica was sufficiently dispersed, and then, 2.78 kg of 10 wt % methylaluminoxane (MAO)/toluene solution was introduced, the temperature was raised to 80° C., and the solution was stirred at 200 rpm for 15 hours. The temperature of the reactor was lowered to 40° C. again, and then, 300 g of 7.5 wt % catalyst of Preparation Example 2/toluene solution was introduced into the reactor, and the solution was stirred at 200 rpm for 1 hour. 250 g of 8.8 wt % catalyst of Preparation Example 1/toluene solution was introduced into the reactor, and the solution was stirred at 200 rpm for 1 hour. The catalyst of Preparation Example 3 (20 g) was dissolved in toluene and introduced into the reactor, and the solution was stirred at 200 rpm for 2 hours. 70 g of a cocatalyst(anilinium tetrakis(pentafluorophenyl)borate) was diluted in toluene and introduced into the reactor, and the solution was stirred at 200 rpm for 15 hours or more. The temperature of the reactor was lowered to room temperature, and then, the stirring was discontinued, the solution was settled for 30 minutes, and the reaction solution was decanted. The toluene slurry was transferred to a filter dryer and filtered. 3.0 kg of toluene was introduced and the solution was stirred for 10 minutes, and then, stirring was discontinued and the solution was filtered. 3.0 kg of hexane was introduced into the reactor, and the solution was stirred for 10 minutes, and then, stirring was discontinued and the solution was filtered. By drying at 50° C. for 4 hours under reduced pressure, a 500 g-SiO.sub.2 supported catalyst was prepared.

(36) Ethylene/1-hexene copolymer

(37) Each hybrid supported metallocene catalyst prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2 was introduced into an isobutene slurry loop process continuous polymerization reactor (reactor volume 140 L, reactant flow rate 7 m/s) to prepare olefin polymer. As comonomer, 1-hexene was used, and the reaction pressure was maintained at 40 bar and the polymerization temperature was maintained at 90° C.

(38) The polymerization conditions using each hybrid supported metallocene catalyst of Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2 are summarized in the following Table 1.

(39) TABLE-US-00001 TABLE 1 Comparative Comparative Exam- Exam- Exam- Catalyst used Example 1-1 Example 1-2 ple 1-1 ple 1-2 ple 1-3 Ethylene 29.7 30.0 31.2 31.1 33.0 supply amount (kg/hr) 1-hexene 2.1 2.2 2.5 2.5 2.9 input (wt %) Hydrogen 53 53 55 56 177 input (ppm) Catalytic 3.9 3.8 3.9 4.0 3.9 activity (kgPE/kg cat./hr)

(40) Ethylene/1-butene copolymer

(41) With each hybrid supported metallocene catalyst prepared in Examples 2-1 to 2-3 and Comparative Example 2-1, two hexane slurry stirred tank process polymerization reactors were bimodally operated to prepare olefin polymer. As comonomer, 1-butene was used.

(42) The polymerization conditions using each hybrid supported metallocene catalyst of Examples 2-1 to 2-3 and Comparative Example 2-1 are summarized in the following Table 2.

(43) TABLE-US-00002 TABLE 2 Comparative Exam- Exam- Exam- Catalyst used Example 2-1 ple 2-1 ple 2-2 ple 2-3 R1 ethylene supply 7.0 7.0 7.0 7.0 amount (kg/hr) R1 pressure 7.1 7.5 7.2 7.9 (kg/cm.sup.2) R1 temperature 83.0 84.4 85.0 84.0 (° C.) R1 hydrogen input 3.00 3.10 2.44 1.70 (g/hr) R2 ethylene supply 6.0 6.0 6.0 6.0 amount (kg/hr) R2 pressure 4.9 4.7 4.8 4.8 (kg/cm.sup.2) R2 temperature 75.1 75.2 73.0 75.0 (° C.) R2 1-butene input 20.0 18.0 18.0 18.0 (g/hr) Catalytic activity 2.6 6.1 7.8 6.4 (kg PE/g SiO.sub.2)

(44) Assessment of Properties of Polymer

(45) The properties of the polymers prepared in Examples and Comparative Examples were assessed by the following method.

(46) 1) density: ASTM 1505

(47) 2) melt flow rate (MFR, 2.16 kg/21.6 kg): measurement temperature 190° C., ASTM 1238

(48) 3) MFRR (MFR.sub.21.6/MFR.sub.2.16): the ratio of MFR.sub.21.6 melt index (MI, 21.6 kg load) divided by MFR.sub.2.16 (MI, 2.16 kg load).

(49) 4) Mn, Mw, PDI, GPC curves: The sample was pretreated by dissolving in 1,2,4-trichlorobenzene containing 0.0125% BHT using PL-SP260 at 160° C. for 10 hours, and number average molecular weight and weight average molecular weight were measured at measurement temperature of 160° C. using PL-GPC220. The molecular weight distribution was expressed as the ratio of weight average molecular weight and number average molecular weight.

(50) 5) FNCT (Full Notch Creep Test): measured according to ISO 16770, as conducted until now and described in a document [M. Fleissner in Kunststoffe 77 (1987), pp. 45 et seq.]. At 10% concentration of IGEPAL CO-630 (Etoxilated Nonylphenol, Branched), a stress crack accelerating medium using tension of 4.0 MPa at 80° C., due to the shortening of stress initiation time by notch (1.5 mm/safety razor blade), damage time was shortened. The test specimens were manufactured by sawing three test specimens of width 10 mm, height 10 mm, length 100 mm from compression-moulded sheet of 10 mm thickness. In a notch device specifically prepared for this purpose, a center notch was provided to the sample using safety razor blade. The notch depth is 1.5 mm. The time taken until the specimen was cut was measured.

(51) The results are shown in the following Tables 3 and 4. Further, the GPC curves of each polymer are shown in FIGS. 1 and 2.

(52) TABLE-US-00003 TABLE 3 Comparative Comparative Unit Example 1-1 Example 1-2 Example 1-1 Example 1-2 Example 1-3 Density g/cm.sup.3 0.941 0.941 0.941 0.941 0.941 MFR.sub.2.16 g/10 min 0.63 0.56 0.55 0.56 0.41 HLMI — 20.7 18.9 17.4 18.2 49.1 MFRR.sub.21.6/2.16 — 33 34 32 33 120 Mn — 40,000 36,300 36,100 31,600 14,200 Mw — 150,000 137,000 145,000 132,000 128,000 MWD — 3.74 3.77 4.02 4.18 9.05 FNCT hr 300 400 2,000 2,000 3,000 GPC curve FIG. 1

(53) TABLE-US-00004 TABLE 4 Comparative Exam- Exam- Exam- Unit Example 2-1 ple 2-1 ple 2-2 ple 2-3 Density g/cm.sup.3 0.9432 0.9448 0.9457 0.9443 MFR.sub.5 g/10 min 0.31 0.23 0.17 0.24 HLMI — 10.1 7.5 5.3 7.1 MFRR.sub.21.6/5 — 33 33 31 29 Mn — 12,500 11,100 12,800 11,600 Mw — 219,000 239,000 245,000 242,000 MWD — 17.52 21.54 19.18 20.85 FNCT hr 380 3,000 650 2,000 GPC curve FIG. 2

(54) First, it was confirmed that the contents of polymer parts (log M=5˜6) of Examples increased compared to each Comparative Example, as shown in FIG. 1 and FIG. 2. Particularly, it was confirmed that in case GPC curves are similar, even slight change in the contents of polymer parts (log M=5˜6) has large influence on FNCT (Table 3 and Table 4).