Catalyst composition for synthesizing olefin copolymer and method for preparing olefin copolymer

Abstract

The present invention relates to a catalyst composition for synthesizing an olefin copolymer, including a first metallocene catalyst, a second metallocene catalyst, and a third metallocene catalyst, each having a specific structure, and a method for preparing an olefin copolymer using the catalyst composition for synthesizing an olefin copolymer.

Claims

1. A catalyst composition for synthesizing an olefin copolymer, comprising: a first metallocene catalyst containing a transition metal compound represented by the following Chemical Formula 1; a second metallocene catalyst containing a transition metal compound represented by the following Chemical Formula 2; and a third metallocene catalyst containing a transition metal compound represented by the following Chemical Formula 3: ##STR00022## wherein, in the above Chemical Formula 1, R.sub.1 to R.sub.4 are the same as or different from each other and each independently represents hydrogen, a halogen, a C1-C20 linear or branched alkyl group, a C2-C20 linear or branched alkenyl group, a C1-C20 linear or branched alkylsilyl group, a C1-C20 linear or branched silylalkyl group, a C1-C20 linear or branched alkoxysilyl group, a C1-C20 linear or branched alkoxy group, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20 arylalkyl group, Q.sub.1 represents a C4-C20 alkylene group, a C4-C20 alkenylene group, a C6-C20 arylene group, a C4-C20 cycloalkylene group, a C7-C22 arylalkylene group, or a C5-C22 cycloalkyl alkylene group, R.sub.5 to R.sub.11 are the same as or different from each other and each independently represents hydrogen, a halogen, a C1-C20 linear or branched alkyl group, a C2-C20 linear or branched alkenyl group, a C1-C20 linear or branched alkylsilyl group, a C1-C20 linear or branched silylalkyl group, a C1-C20 linear or branched alkoxysilyl group, a C1-C20 linear or branched alkoxy group, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20 arylalkyl group, two or more adjacent substituents on a benzene ring among R.sub.5 to R.sub.11 can be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, M.sub.1 is a Group 4 transition metal, and Y.sub.1 and Y.sub.2 are the same as or different from each other and each independently represents a halogen, a C1-C20 alkyl group, a C2-C20 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: ##STR00023## wherein, in the above Chemical Formula 2, M.sub.2 is a Group 4 transition metal, X.sub.21 and X.sub.22 are the same as or different from each other and each independently represents a halogen, a C1-C20 alkyl group, a C2-C20 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, Q.sub.2 is carbon, silicon, or germanium, R.sub.21 and R.sub.22 are the same as or different from each other and each independently represents hydrogen, a halogen, 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, a C1-C20 alkoxy group, a C2-C20 alkoxyalkyl group, a C3-C20 heterocycloalkyl group, or a C5-C20 heteroaryl group, and one of C.sub.21 and C.sub.22 is represented by the following Chemical Formula 2a and the other is represented by the following Chemical Formula 2b: ##STR00024## wherein, in the above Chemical Formula 2a, Z.sub.1 to Z.sub.9 are the same as or different from each other and each independently represents a hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C1-C20 alkoxy group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20 arylalkyl group, and in the above Chemical Formula 2b, Z.sub.10 and Z.sub.12 to Z.sub.15 are hydrogen, a halogen, and a C1-C3 alkyl group, and Z.sub.11 is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C1-C20 alkoxysilyl group, a C1-C20 ether group, a C1-C20 silyl ether group, a C1-C20 silyloxy group, a C1-C20 alkoxy group, a C2-C20 alkoxyalkyl group, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20 arylalkyl group: ##STR00025## wherein, in the above Chemical Formula 3, M.sub.3 is a Group 4 transition metal, X.sub.31 and X.sub.32 are the same as or different from each other and each independently represents a halogen, a C1-C20 alkyl group, a C2-C20 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, Q.sub.3 is carbon, silicon, or germanium, R.sub.31 and R.sub.32 are the same as or different from each other and each independently represents hydrogen, a halogen, 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, a C1-C20 alkoxy group, a C2-C20 alkoxyalkyl group, a C3-C20 heterocycloalkyl group, or a C5-C20 heteroaryl group, and one of C.sub.31 and C.sub.32 is represented by the following Chemical Formula 3a or Chemical Formula 3b, and the other of C31 and C32 is represented by the following Chemical Formula 3c, Chemical Formula 3d, or Chemical Formula 3e: ##STR00026## wherein, in the above Chemical Formula 2a, 2b, 3a, 3b, and 3c, J.sub.1 to J.sub.31 and J.sub.1 to J.sub.13 are the same as or different from each other and each independently represents hydrogen, a halogen, a C1-C20 alkyl group, a C1-C20 haloalkyl group, a C2-C20 alkenyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C1-C20 alkoxysilyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20 arylalkyl group, one or more of J.sub.9 to J.sub.13 and J.sub.9 to J.sub.13 is a C1-C20 haloalkyl group, and two or more adjacent substituents on a benzene ring among J.sub.1 to J.sub.31 and J.sub.1 to J.sub.13 can be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

2. The catalyst composition for synthesizing an olefin copolymer of claim 1, wherein, in Chemical Formula 1: R.sub.1 and R.sub.2 are a C1-C20 alkylsilyl group or a C1-C20 silylalkyl group, R.sub.3 and R.sub.4 are a C6-C20 arylene group or a C8-C22 aryl dialkylene group, R.sub.5 to R.sub.11 are each independently hydrogen, a halogen, or a C1-C20 linear or branched alkyl group, M.sub.1 is titanium, zirconium, or hafnium, and Y.sub.1 and Y.sub.2 are independently a halogen.

3. The catalyst composition for synthesizing an olefin copolymer of claim 1, wherein Z.sub.1 to Z.sub.9 in Chemical Formula 2a are each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylene group, a propylene group, a butenyl group, a phenyl group, a benzyl group, a naphthyl group, a methoxy group, an ethoxy group, or a tert-butoxyhexyl group, Z.sub.11 in Chemical Formula 2b is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylene group, a propylene group, a butenyl group, a phenyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a tert-butyldimethylsilyl ether group, a methoxy group, an ethoxy group, or a tert-butoxyhexyl group, and R.sub.21 and R.sub.22 in Chemical Formula 2 are independently a methyl group or a tert-butoxyhexyl group.

4. The catalyst composition for synthesizing an olefin copolymer of claim 1, wherein J.sub.1 to J.sub.31 and J.sub.1to J.sub.13in Chemical Formulae 3a, 3b, 3c, 3d, and 3e are each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a halogen group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a methoxy group, or an ethoxy group, and at least one of J.sub.9 to J.sub.13 and J.sub.9to J.sub.13is a perfluoroalkyl having 1 to 3 carbon atoms, and R.sub.31 and R.sub.32 in Chemical Formula 3 are each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, a tert-butoxymethyl group, a tert-butoxyhexyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.

5. The catalyst composition for synthesizing an olefin copolymer of claim 1, wherein a molar ratio of a first metallocene catalyst containing a transition metal compound of Chemical Formula 1 and a third metallocene catalyst containing a transition metal compound of Chemical Formula 3 relative to a second metallocene catalyst containing a transition metal compound of Chemical Formula 2 is 1:0.5 to 2:1 to 5.

6. The catalyst composition for synthesizing an olefin copolymer of claim 1, wherein the catalyst composition for synthesizing an olefin copolymer further includes a cocatalyst and an optional support.

7. The catalyst composition for synthesizing an olefin copolymer of claim 6, wherein the cocatalyst includes at least one selected from the group consisting of the compounds of the following Chemical Formulae 6 and 7:
[Al(X)O].sub.k[Chemical Formula 6] wherein, in Chemical Formula 6, each X is independently a halogen, or a halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more, and
T.sup.+[BG.sub.4].sup.[Chemical Formula 7] wherein, in Chemical Formula 7, T.sup.+ is a +1 charge polyatomic ion, B is boron in an oxidation state of +3, and G is each independently selected from the group consisting of hydride, dialkylamido group, halide group, alkoxide group, aryloxide group, hydrocarbyl group, halocarbyl group and halo-substituted hydrocarbyl group, wherein the G has 20 or less carbon atoms, provided that G is halide at one or less position.

8. The catalyst composition for synthesizing an olefin copolymer of claim 6, wherein the mass ratio of the support relative to the total weight of the transition metals contained in the first metallocene compound and the second metallocene compound is 10 to 10,000.

9. The catalyst composition for synthesizing an olefin copolymer of claim 6, wherein the mass ratio of the cocatalyst compound relative to the support is 1 to 100.

10. A method for preparing an olefin copolymer, the method comprising a step of copolymerizing ethylene and an alpha-olefin in the presence of the catalyst composition for synthesizing an olefin copolymer of claim 1.

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 given for illustrative purposes only, and the scope of the invention is not intended to be limited thereto.

Preparation Example

Preparation Example of First Metallocene Compound

Preparation Example 1

(2) ##STR00019##

(3) 6.3 g (20 mmol) of 1,8-bis(bromomethyl)naphthalene and 8.3 g (40 mmol) of methyl TMS-indene lithium salt were dissolved in 80 mL of THF, respectively, then combined dropwise in a dry ice/acetone bath, and the mixture was stirred overnight at room temperature. After completion of the stirring, the reaction product was extracted with ether/water, the organic layer was treated with MgSO.sub.4 to remove residual moisture, and the solvent was removed under vacuum and reduced pressure to obtain 11.1 g of a liquid ligand compound (20 mmol, Mw 556.93).

(4) 11 g of the obtained ligand compound was dissolved in a mixed solvent of 80 mL of toluene and 5 mL of methyl tertiary butyl ether (MTBE), 16.7 mL (41.6 mmol) of a 2.5 M n-butyllithium hexane solution was added dropwise thereto, and the mixture was stirred at room temperature. Then, 7.5 g (19.8 mmol) of ZrCl.sub.4(THF).sub.2 was added to 80 mL of toluene to prepare a slurry, which was then transferred in a dry ice/acetone bath and stirred overnight at room temperature.

(5) After completion of the stirring, the slurry was filtered to remove LiCl, the filtrate was dried under vacuum to remove toluene, and 100 mL of hexane was added thereto and the mixture was sonicated for 1 hour. Thereafter, the slurry was filtered to obtain 4.5 g of a metallocene compound as a filtered solid (yield 62.3 mol %, yellow solid).

(6) .sup.1H NMR (500 MHz, CDCl.sub.3): 8.16-6.95 (14H, m), 5.99 (2H, d), 3.99 (2H, m), 3.83 (2H, m), 3.39 (2H, m), 0.15 (18H, d)

Preparation Example of Second Metallocene Compound

Preparation Example 2

(7) ##STR00020##

(8) 1) Preparation of Ligand Compound

(9) 3 g (10 mmol) of indenoindole was added to a first dry 250 mL Schlenk flask, and was then dissolved in 100 mL of hexane. Then, 4.4 mL (11 mmol) of a 2.5 M nBuLi hexane solution was slowly added dropwise thereto, and the reaction mixture was slowly warmed to room temperature and then stirred until the next day. 2.7 g (10 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was added to a second 250 mL Schlenk flask, and was then dissolved in 50 mL of hexene. Then, the moisture was cooled to 78 C., and then a solution of first 250 mL Schlenk flask was injected through a cannula.

(10) After completion of the injection, the temperature of the Schlenk flask was raised to room temperature and stirred for one day. 2.1 g (10 mmol) of methyl TMS-indene lithium salt was dissolved in 100 mL of THF, added dropwise thereto, and stirred overnight at room temperature. After completion of the stirring, the reaction product was extracted with ether/water, the organic layer was treated with MgSO.sub.4 to remove residual moisture, and the solvent was removed under vacuum and reduced pressure to obtain 7 g of a liquid ligand compound (10 mmol, Mw: 696.1).

(11) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.86-7.11 (17H, m), 5.11-5.64 (3H, d), 4.16 (1H, m), 3.20 (2H, m), 1.61-1.47 (6H, m), 1.15 (9H, s), 0.34 (3H, m)

(12) 2) Preparation of Metallocene Compound

(13) 5.5 g (7.9 mmol) of the obtained ligand compound was dissolved in 80 mL of toluene, 6.6 mL (16.6 mmol) of a 2.5 M n-butyllithium hexane solution was added dropwise thereto, and the mixture was stirred at room temperature. Then, 3 g (7.9 mmol) of ZrCl.sub.4(THF).sub.2 was added to 80 mL of toluene to prepare a slurry, which was then transferred in a dry ice/acetone bath and stirred overnight at room temperature.

(14) After completion of the stirring, the slurry was filtered to remove LiCl, and the filtrate was dried under vacuum to remove toluene, and 100 mL of hexane was added thereto and the mixture was sonicated for 1 hour. Thereafter, the slurry was filtered to obtain 1.5 g of metallocene compound as a filtered solid (yield 23 mol %, red solid).

(15) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.66-7.20 (17H, m), 6.15-5.71 (1H, d), 5.65 (2H, m), 3.76 (2H, m), 3.20 (2H, m), 1.51-1.29 (4H, m), 1.15 (3H, s), 0.01 (9H, s)

Preparation Example of Third Metallocene Compound

Preparation Example 3

(16) ##STR00021##

(17) 1) Preparation of Ligand Compound

(18) A solution of 2.9 g (7.4 mmol) of 8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole was dissolved in 100 mL of hexane and 2 mL (16.8 mmol) of MTBE tertiary butyl ether), and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise thereto in a dry ice/acetone bath and stirred overnight at room temperature. In another 250 mL Schlenk flask, 2 g (7.4 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane and then added dropwise in a dry ice/acetone bath, and a lithiated slurry of (2-trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole was added dropwise via a cannula. After the injection was completed, the mixture was slowly raised to room temperature and stirred at room temperature overnight. At the same time, 1.2 g (7.4 mmol) of fluorene was dissolved in 100 mL of THF, and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred overnight at room temperature.

(19) The reaction solution (Si solution) of 8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole and (6-(tert-butoxy)hexyl)dichloro(methyl)silane was subjected to NMR sampling to confirm the completion of the reaction.

(20) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.74-6.49 (11H, m), 5.87 (2H, s), 4.05 (1H, d), 3.32 (2H, m), 3.49 (3H, s), 1.50-1.25 (8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17 (3H, d)

(21) After the synthesis was confirmed, a lithiated solution of fluorene was slowly added dropwise to the Si solution in a dry ice/acetone bath, and the mixture was stirred overnight at room temperature. After the reaction, the residue was extracted with ether/water, and the organic layer was treated with MgSO.sub.4 to remove residual moisture. The solvent was removed under vacuum and reduced pressure to obtain 5.5 g (7.4 mmol) of an oily ligand compound, which was confirmed by 1H-NMR.

(22) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.89-6.53 (19H, m), 5.82 (2H, s), 4.26 (1H, d), 4.14-4.10 (1H, m), 3.19 (3H, s), 2.40 (3H, m), 1.35-1.21 (6H, m), 1.14 (9H, s), 0.97-0.9 (4H, m), 0.34 (3H, t).

(23) 2) Preparation of Metallocene Compound

(24) 5.4 g (Mw 742.00, 7.4 mmol) of the synthesized ligand compound was dissolved in 80 mL of toluene and 3 mL (25.2 mmol) of MTBE, and 7.1 mL (17.8 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred overnight at room temperature. 3.0 g (8.0 mmol) of ZrCl.sub.4(THF).sub.2 was added to 80 mL of toluene to prepare a slurry. 80 mL of ZrCl.sub.4(THF).sub.2 as a toluene slurry was transferred to a ligand-Li solution in a dry ice/acetone bath and stirred overnight at room temperature.

(25) The reaction mixture was filtered to remove LiCl, the filtrate was dried under vacuum to remove toluene, and 100 mL of hexane was added thereto and sonicated for 1 hour. This was filtered to obtain 3.5 g of a purple metallocene compound as a filtered solid (yield 52 mol %).

(26) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.90-6.69 (9H, m), 5.67 (2H, s), 3.37 (2H, m), 2.56 (3H, s), 2.13-1.51 (11H, m), 1.17 (9H, s).

Preparation Example of Hybrid Supported Catalyst

Example 1

(27) 3.0 kg of a toluene solution was added to a 20 L SUS autoclave, and the reactor temperature was maintained at 40 C. 1000 g of silica (manufactured by Grace Davison, SYLOPOL 948) was dehydrated by applying vacuum for 12 hours at a temperature of 600 C., and then added to a reactor to sufficiently disperse the silica. The metallocene compound of Preparation Example 1 was then dissolved in toluene at a ratio of 0.1 mmol per 1 g of SiO.sub.2 and then added thereto. The mixture was allowed to react at 40 C. for 2 hours while stirring. Then, the stirring was stopped, followed by settling for 30 minutes and decantation of the reaction solution.

(28) Then, 3 kg of a 10 wt % methylaluminoxane (MAO)/toluene solution was added to the reactor, and the mixture was stirred at 200 rpm at 40 C. for 12 hours. The metallocene compound of Preparation Example 2 was then dissolved in toluene at a ratio of 0.05 mmol per 1 g of SiO.sub.2 and added thereto. The mixture was allowed to react while stirring at 200 rpm at 40 C. for 12 hours. Then, the metallocene compound of Preparation Example 3 was dissolved in toluene at a ratio of 0.15 mmol per 1 g of SiO.sub.2 and added thereto. The mixture was allowed to react while stirring at 200 rpm at 40 C. for 12 hours.

(29) Thereafter, 3.0 kg of hexane was added to the reactor, a hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. The filtrate was dried under reduced pressure at 40 C. for 4 hours to prepare 1 kg of a SiO.sub.2 hybrid supported catalyst.

Example 2

(30) A supported catalyst was prepared in the same manner as in Example 1, except that the addition amount of the metallocene compound of Preparation Examples 1 to 3 was changed.

Comparative Example 1

(31) A polyethylene copolymer (ME1000, manufactured by LG Chem Ltd) prepared with a Ziegler-Natta catalyst was used as Comparative Example 1.

Experimental Example

Ethylene-1-Hexene Copolymerization

(32) The respective hybrid supported metallocene catalysts prepared in each of the examples were respectively fed into a CSTR continuous polymerization reactor (reactor volume: 50 L, reaction flow rate: 7 m/s) to prepare an olefin polymer. 1-hexene was used as the comonomer, the reactor pressure was set to 10 bar, and the polymerization temperature was maintained at 90 C.

(33) The polymerization conditions using the respective hybrid supported metallocene catalysts of Examples 1 to 3 are summarized in Table 1 below.

(34) TABLE-US-00001 TABLE 1 Polymerization condition Pressure (bar)/ Hydro- 1- temperature gen hexene Catalyst ( C.) (g/hr) (cc/min) Example 1 Preparation Example 1 10/90 3.0 6 0.10 mmol/g SiO.sub.2 Preparation Example 2 0.05 mmol/g SiO.sub.2 Preparation Example 3 0.15 mmol/g SiO.sub.2 Example 2 Preparation Example 1 10/90 3.0 6 0.07 mmol/g SiO.sub.2 Preparation Example 2 0.07 mmol/g SiO.sub.2 Preparation Example 2 0.15 mmol/g SiO.sub.2

(35) Evaluation of Physical Properties of Polymer

(36) 1) Melt Index (MFR, 2.16 kg/21.6 kg): Measurement temperature 190 C., ASTM 1238

(37) 2) MFRR (MFR.sub.21.6/MFR.sub.2.16): the ratio where MFR.sub.21.6 melt index (MI, load: 21.6 kg) is divided by MFR.sub.2.16 (MI, load: 2.16 kg).

(38) 3) Molecular weight and molecular weight distribution: 1,2,4-trichlorobenzene containing 0.0125% of BHT was dissolved using a PL-SP260 system at 160 C. for 10 hours and subjected to pretreatment. The number average molecular weight and the weight average molecular weight were measured at a temperature of 160 C. using a PL-GPC220 system.

(39) The molecular weight distribution was represented by the ratio between the weight average molecular weight and the number average molecular weight.

(40) Then, using the measured GPC data, a GPC curve graph in which the x axis was log Mw and the y axis was dw/dlog Mw was derived.

(41) 5) Environmental Stress Crack Resistance (ESCR): The time to F50 (50% failure or cracking) was measured using a 10% Igepal CO-630 Solution at a temperature of 50 C. according to ASTM D 1693.

(42) 6) Spiral flow length (SF): An ENGEL 150-ton injection machine was used. The SF was measured under conditions in which the mold thickness was 1.5 mm, the injection temperature was 190 C., the mold temperature was 50 C., and the injection pressure was 90 bar.

(43) 7) Dimensional change ratio: A test specimen was prepared from each of the olefin copolymers obtained in the examples and comparative examples, and the dimensional change rate was measured using Dynamic Mechanical Analysis (DMA).

(44) Specifically, the respective olefin copolymers obtained in the examples and comparative examples were pressed with a pressure of 20 MPa at 200 C. for about 5 minutes to prepare a test specimen (width: 6 mm, thickness: 0.3 mm). A step of maintaining the test specimen at a temperature of 32 C. and a pressure of 0.5 MPa for 20 minutes and a step of raising the temperature and maintaining it at a temperature of 60 C. and a pressure of 0.5 MPa for 10 minutes were set to one cycle, and four cycles were repeated.

(45) Strain was recorded under the condition of 32 C. for each cycle, and finally the dimensional change rate was determined by the value obtained by dividing the difference between the strain of the first cycle and the strain of the fourth cycle by the strain value of the first cycle*100(%).

(46) TABLE-US-00002 TABLE 2 Dimensional MWD Density change Catalyst (Kg/mol) MWD MI MFRR (g/cm.sup.3) rate (%) ESCR Spiral Example 1 141.941 7.3 0.31 3.35 0.949 2.02 360 15 Example 2 137.144 9.2 0.32 3.56 0.951 1.53 320 17 Comparative 138.940 12.2 0.9 4.0 0.952 4.35 50 13 Example 1

(47) As shown in Table 2, it was confirmed the olefin copolymer obtained using the hybrid metallocene catalysts of Examples 1 and 2 had an environmental stress crack resistance of 300 hours or more, exhibited a relatively high spiral flow length, and further exhibited a dimensional change rate of about 2% or less even under the conditions of high temperature and high pressure, thus providing high dimensional stability.

(48) Meanwhile, as confirmed in FIG. 1, the olefin copolymer obtained in each of Examples 1 and 2 showed that in a GPC curve graph in which the x axis was log Mw and the y axis was dw/dlog Mw, the integration value in a region where the log Mw was 5.0 or more and less than 5.5 was about 23% and 21% of the total x-axis integration value, and compared to the total x-axis integration value, the difference of the ratio of the integration value in a region where the log Mw was 5.0 or more and less than 5.5 and the ratio of the integration value in a region where the log Mw was 4.5 or more and less than 5.0 were 6.36% and 5.24%, respectively.

(49) As described above, as the olefin copolymer prepared in each of Examples 1 and 2 showed the above-mentioned numerical values in a GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw, the olefin copolymer can have a characteristics such that it is not easily broken while having high stiffness required for polymer injection products, high pressure resistance and chemical resistance, and excellent dimensional stability, thereby exhibiting a very low strain due to a change in temperature and pressure.

(50) That is, the olefin copolymer obtained using the hybrid metallocene catalysts of Examples 1 and 2 can not only have a wide range of melt flow index and melt flow rate ratio, and thus excellent processability, and can have a high molecular weight, a broad molecular weight distribution, and a high long-chain branch content, but can also have excellent environmental stress crack resistance and processability, and exhibit excellent stability in a high temperature and high pressure environment, whereby it is applied to food containers, bottle caps, or the like, thereby achieving excellent performance.