Polyethylene copolymer and method for preparing same

Abstract

The present invention relates to a polyethylene copolymer which has excellent processability and long-term durability, and thus is useful for hollow molding of a pipe or the like.

Claims

1. A polyethylene copolymer comprising an ethylene-derived repeating unit and an alpha-olefin-derived repeating unit having 3 or more carbon atoms, and satisfying the following Equation 1 and Equation 2:
slow crack growth (SCG) index≤(carbon number of the alpha olefin).sup.1/2×5  [Equation 1] wherein, in the above Equation 1, the SCG index is a value (p/q) obtained by dividing melt index (p) of the polyethylene copolymer measured according to ASTM 1238 (load of 21.6 kg, 190° C.) by comonomer distribution index (q) of the polyethylene copolymer, and
comonomer distribution index (CDI)=c/d  [Equation 2] wherein, in the above Equation 2, the comonomer distribution index (CDI) is calculated by the above Equation 2 based on a molecular weight distribution curve graph, measured by gel permeation chromatography with respect to the polyethylene copolymer, where x-axis represents the molecular weight of the polymer chain and y-axis represents a content of the polymer chain, c is short chain branch (SCB) content (measured by FT-IR) of 2 to 7 carbon atoms per 1000 carbon atoms of the polymer chain, which is a molecular weight value m in which an area (s1) between a molecular weight distribution curve and the x-axis in a section of a≤x≤m is 80% of an area (s2) between the molecular weight distribution curve and the x-axis in a section of a≤x≤b, d is short chain branch (SCB) content (measured by FT-IR) of 2 to 7 carbon atoms per 1000 carbon atoms of the polymer chain, which is a molecular weight value n in which an area (s3) between the molecular weight distribution curve and the x-axis in a section of a≤x≤n is 20% of an area (s4) between the molecular weight distribution curve and the x-axis in a section of a≤x≤b, and a is a minimum value of molecular weight which is represented by the x-axis in the molecular weight distribution curve graph, and b is a maximum value of molecular weight which is represented by the x-axis in the molecular weight distribution graph, wherein the polyethylene copolymer has a comonomer distribution index (CDI) of 1.2 to 3.0.

2. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a strain hardening (S.H.) modulus (measured at 80° C.) of 0.85 MPa or more.

3. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a stress crack resistance (FNCT, measured at 4 MPa) of 1000 h or more.

4. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a melt index (measured at 190° C. under a load of 2.16 kg according to ASTM D1238) of 0.01 g/10 min to 0.65 g/10 min.

5. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a melt index (measured at 190° C. under a load of 21.6 kg according to ASTM D1238) of 2 g/10 min to 30 g/10 min.

6. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has an SCG index of 11 or less.

7. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a density (ASTM 1505) of 0.930 g/cm.sup.3 to 0.945 g/cm.sup.3.

8. The polyethylene copolymer according to claim 1, wherein an average value of the short chain branch content (measured by FT-IR) of 2 to 7 carbon atoms per 1000 carbon atoms that each of a plurality of polymer chains contained in the polyethylene copolymer has is 7/1000 C or more and 15/1,000 C or less.

9. A method for preparing the polyethylene copolymer of claim 1, comprising a step of polymerizing an ethylene monomer and an alpha olefin monomer in the presence of a hybrid supported catalyst which includes: a transition metal mixture including a first mixture including a first transition metal compound containing at least one compound represented by the following Chemical Formulas 2 or 3, and a second transition metal compound containing at least one compound represented by the following Chemical Formulas 4, 5, 6 or 7, or a second mixture including a first transition metal compound containing at least one compound represented by the following Chemical Formula 1, and a second transition metal compound containing at least one compound represented by select the following Chemical Formulas 4, 6 or 7; and a support on which the transition metal mixtures are supported: ##STR00042## wherein, in Chemical Formula 1, M.sub.1 is a Group 4 transition metal; R.sub.1 to R.sub.8 are the same as or different from each other and are each independently hydrogen, a C.sub.1-20 alkyl, a C.sub.2-20 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.6-20 aryl, a C.sub.7-20 alkylaryl, —(CH.sub.2).sub.n—OR.sub.a, or a C.sub.7-20 arylalkyl, or two or more adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that at least one of R.sub.1 to R.sub.8 is —(CH.sub.2).sub.n—OR.sub.a, where R.sub.a is a C.sub.1-6 linear or branched alkyl group, and n is an integer of 2 to 10; and X.sub.1 and X.sub.2 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-10 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy, ##STR00043## wherein, in Chemical Formula 2, M.sub.2 is a Group 4 transition metal; X.sub.3 and X.sub.4 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-10 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy; R.sub.11 to R.sub.14 are the same as or different from each other and are each independently hydrogen, a C.sub.1-20 alkyl, a C.sub.2-20 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.6-20 aryl, a C.sub.7-20 alkylaryl, —(CH.sub.2).sub.m—OR.sub.b, or a C.sub.7-20 arylalkyl, or two or more adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that at least one of R.sub.11 to R.sub.14 is —(CH.sub.2).sub.m—OR.sub.b, where R.sub.b is a C.sub.1-6 linear or branched alkyl group, and m is an integer of 2 to 10; and R.sub.15 and R.sub.16 are the same as or different from each other and are each independently hydrogen, a C.sub.1-20 alkyl, a C.sub.3-20 cycloalkyl, a C.sub.1-10 alkoxy, a C.sub.2-20 alkoxyalkyl, a C.sub.6-20 aryl, a C.sub.6-10 aryloxy, a C.sub.2-20 alkenyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.8-40 arylalkenyl, or a C.sub.2-10 alkynyl, ##STR00044## wherein, in Chemical Formula 3, M.sub.3 is a Group 4 transition metal; X.sub.5 and X.sub.6 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-10 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy; and R.sub.20 to R.sub.29 are the same as or different from each other and are each independently hydrogen, a C.sub.1-20 alkyl, a C.sub.3-20 cycloalkyl, a C.sub.1-10 alkoxy, a C.sub.2-20 alkoxyalkyl, a C.sub.6-20 aryl, a C.sub.6-10 aryloxy, a C.sub.2-20 alkenyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.8-40 arylalkenyl, or a C.sub.2-10 alkynyl, provided that at least one of R.sub.20 to R.sub.29 is —(CH.sub.2).sub.p—OR.sub.c, where R.sub.c is a C.sub.1-6 linear or branched alkyl group, and p is an integer of 2 to 10, ##STR00045## wherein, in Chemical Formula 4, A.sub.1 is hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, a C.sub.7-20 arylalkyl group, a C.sub.1-20 alkoxy group, a C.sub.2-20 alkoxyalkyl group, a C.sub.3-20 heterocycloalkyl group, or a C.sub.5-20 heteroaryl group; D.sub.1 is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, or a C.sub.6-20 aryl group; L.sub.1 is a C.sub.1-10 linear or branched alkylene group; Y.sub.1 is carbon, silicon, or germanium; Z.sub.1 is hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, or a C.sub.7-20 arylalkyl group; M.sub.4 is a Group 4 transition metal; X.sub.7 and X.sub.8 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-10 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy; C.sub.1 is represented by the following Chemical Formula 4a, ##STR00046## C.sub.2 is —NR.sub.36—; and R.sub.30 to R.sub.36 are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.1-20 alkylsilyl group, a C.sub.1-20 silylalkyl group, a C.sub.1-20 alkoxysilyl group, a C.sub.1-20 alkoxy group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, or a C.sub.7-20 arylalkyl group, or two or more adjacent groups of R.sub.30 to R.sub.35 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, ##STR00047## wherein, in Chemical Formula 5, A.sub.2 is hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, a C.sub.7-20 arylalkyl, a C.sub.1-20 alkoxy group, a C.sub.2-20 alkoxyalkyl group, a C.sub.3-20 heterocycloalkyl group, or a C.sub.5-20 heteroaryl group; D.sub.2 is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, or a C.sub.6-20 aryl group; L.sub.2 is a C.sub.1-10 linear or branched alkylene group; Y.sub.2 is carbon, silicon, or germanium; Z.sub.2 is hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, or C.sub.7-20 arylalkyl group; M.sub.5 is a Group 4 transition metal; X.sub.9 and X.sub.10 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-10 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy; C.sub.3 is represented by the following Chemical Formula 5a, ##STR00048## C.sub.4 is —NR.sub.44—; and R.sub.40 to R.sub.44 are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.1-20 alkylsilyl group, a C.sub.1-20 silylalkyl group, a C.sub.1-20 alkoxysilyl group, a C.sub.1-20 alkoxy group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, or a C.sub.7-20 arylalkyl group, or two or more adjacent groups of R.sub.40 to R.sub.43 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, ##STR00049## wherein, in Chemical Formula 6, A.sub.3 is hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, a C.sub.7-20 arylalkyl, a C.sub.1-20 alkoxy group, a C.sub.2-20 alkoxyalkyl group, a C.sub.3-20 heterocycloalkyl group, or a C.sub.5-20 heteroaryl group; D.sub.3 is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, or a C.sub.6-20 aryl group; L.sub.3 is a C.sub.1-10 linear or branched alkylene group; Y.sub.3 is carbon, silicon, or germanium; Z.sub.3 is hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, or a C.sub.7-20 arylalkyl group; M.sub.6 is a Group 4 transition metal; X.sub.11 and X.sub.12 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-20 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy; C.sub.5 and C.sub.6 are the same as or different from each other and are each independently represented by one of the following Chemical Formulas 6a to 6b, ##STR00050## and R.sub.50 to R.sub.58, and R.sub.60 to R.sub.68, are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.1-20 alkylsilyl group, a C.sub.1-20 silylalkyl group, a C.sub.1-20 alkoxysilyl group, a C.sub.1-20 alkoxy group, a C.sub.6-20 aryl group, a C.sub.7-20 alkylaryl group, or a C.sub.7-20 arylalkyl group, or two or more adjacent groups of R.sub.50 to R.sub.58 and R.sub.60 to R.sub.68 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, ##STR00051## wherein, in Chemical Formula 7, M.sub.7 is a Group 4 transition metal; X.sub.13 and X.sub.14 are the same as or different from each other and are each independently a halogen, a C.sub.1-20 alkyl, a C.sub.2-10 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.6-20 aryl, a C.sub.1-20 alkylidene, an amino, a C.sub.2-20 alkylalkoxy, or a C.sub.7-40 arylalkoxy; R.sub.71 to R.sub.74 are the same as or different from each other and are each independently hydrogen, a C.sub.1-20 alkyl, a C.sub.2-20 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.6-20 aryl, a C.sub.7-20 alkylaryl, —(CH.sub.2).sub.q—OR.sub.d, or a C.sub.7-20 arylalkyl, or two or more adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that at least one of R.sub.71 to R.sub.74 is —(CH.sub.2).sub.q—OR.sub.d, where R.sub.d is a C.sub.1-6 linear or branched alkyl group, and q is an integer of 2 to 10; R.sub.75 and R.sub.76 are the same as or different from each other and are each independently hydrogen, a C.sub.1-20 alkyl, a C.sub.3-20 cycloalkyl, a C.sub.1-10 alkoxy, a C.sub.2-20 alkoxyalkyl, a C.sub.6-20 aryl, a C.sub.6-10 aryloxy, a C.sub.2-20 alkenyl, a C.sub.7-40 alkylaryl, a C.sub.7-40 arylalkyl, a C.sub.8-40 arylalkenyl, or a C.sub.2-10 alkynyl; and Q.sub.1 and Q.sub.2 are the same as or different from each other and are each independently hydrogen, a halogen, a C.sub.1-20 alkyl, a C.sub.2-20 alkenyl, a C.sub.3-20 cycloalkyl, a C.sub.6-20 aryl, a C.sub.7-20 alkylaryl, or a C.sub.7-20 arylalkyl.

10. The method for preparing the polyethylene copolymer according to claim 9, wherein the first transition metal compound is contained in an amount of 1 to 80 parts by weight based on 100 parts by weight of the second transition metal compound.

11. The method for preparing the polyethylene copolymer according to claim 9, wherein in the step of polymerizing the ethylene monomer and the alpha olefin monomer, hydrogen is added in an amount of 0.005 wt % to 0.040 wt % relative to the ethylene monomer.

12. The method for preparing the polyethylene copolymer according to claim 9, wherein the support is silica, alumina, magnesia, or a mixture thereof.

13. The method for preparing the polyethylene copolymer according to claim 9, wherein the alpha olefin monomer includes one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicocene.

14. A pipe comprising the polyethylene copolymer of claim 1.

15. The method for preparing the polyethylene copolymer according to claim 9, wherein the second transition metal compound contains a compound represented by Chemical Formula 6 and a compound represented by Chemical Formula 7, and the compound represented by Chemical Formula 7 is contained in an amount of 10 to 80 parts by weight based on 100 parts by weight of the compound represented by Chemical Formula 6.

16. The method for preparing the polyethylene copolymer according to claim 9, wherein the support contains a hydroxyl group on its surface.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a view showing a molecular weight distribution curve (solid line) and an SCB distribution curve (dotted line) of the polyethylene copolymer of Example 1.

(2) FIG. 2 is a view showing a method of measuring the comonomer distribution index (CDI) of the polyethylene copolymer of Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) The present invention will be described in more detail by way of examples shown below. However, these examples are given to merely illustrate the invention, and are not intended to limit the scope of the invention thereto.

PREPARATION EXAMPLE

Preparation Examples of First Transition Metal Compound: Preparation Examples 1 to 3

Preparation Example 1

(4) ##STR00029##

(5) t-butyl-O—(CH.sub.2).sub.6—Cl was prepared using 6-chlorohexanol according to the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and reacted with NaCp to prepare t-butyl-O—(CH.sub.2).sub.6—C.sub.5H.sub.5 (yield: 60%, b.p. 80/0.1 mmHg).

(6) Further, t-butyl-O—(CH.sub.2).sub.6—C.sub.5H.sub.5 was dissolved in THF at −78° C., n-butyl lithium (n-BuLi) was slowly added thereto, the reaction temperature was raised to room temperature, and then was allowed to react for 8 hours. The solution was again reacted in which the already synthesized lithium salt solution 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 at room temperature for 6 hours.

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

(8) .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)

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

Preparation Example 2

(10) ##STR00030##

(11) (1) Preparation of Ligand Compound

(12) 10.8 g (100 mmol) of chlorohexanol was added to a dried 250 mL Schlenk flask, to which 10 g of a molecular sieve and 100 mL of MTBE (methyl tert-butyl ether) were added, and 20 g of sulfuric acid was added slowly over 30 minutes. The reaction mixture turned pink slowly over time. After 16 hours, it was poured into a saturated sodium bicarbonate solution with ice cooling. The mixture was extracted four times with 100 mL of ether, and the combined organic layer was dried over MgSO.sub.4 and filtered. The solvent was removed under vacuum reduced pressure. Thereby, 10 g (yield: 60%) of 1-(tertbutoxy)-6-chlorohexane in the form of a yellow liquid was obtained.

(13) .sup.1H NMR (500 MHz, CDCl.sub.3): 3.53 (2H, t), 3.33 (2H, t), 1.79 (2H, m), 1.54 (2H, m), 1.45 (2H, m), 1.38 (2H, m), 1.21 (9H, s)

(14) 4.5 g (25 mmol) of 1-(tert-butoxy)-6-chlorohexane synthesized above was added to a dried 250 mL Schlenk flask, and dissolved in 40 mL of THF. 20 mL of a sodium indenide THF solution was slowly added thereto and then stirred for one day. The reaction mixture was quenched by addition of 50 mL of water, and extracted with ether (50 mL×3), and then the combined organic layer was washed thoroughly with brine. The remaining moisture was dried over MgSO.sub.4 and filtered. The solvent was removed under vacuum reduced pressure. Thereby, a dark brown viscous product, 3-(6-tert-butoxy hexyl)-1H-indene, was obtained in a quantitative yield.

(15) Mw=272.21 g/mol

(16) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.47 (1H, d), 7.38 (1H, d), 7.31 (1H, t), 7.21 (1H, t), 6.21 (1H, s), 3.36 (2H, m), 2.57 (2H, m), 1.73 (2H, m), 1.57 (2H, m), 1.44 (6H, m), 1.21 (9H, s)

(17) (2) Preparation of Transition Metal Compound

(18) The 3-(6-tert-butoxy hexyl)-1H-indene was dissolved in THF at −78° C., n-butyl lithium (n-BuLi) was slowly added thereto, the reaction temperature was raised to room temperature, and was then allowed to react for 8 hours. The solution was again reacted in which the already synthesized lithium salt solution 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 then further reacted at room temperature for 6 hours.

(19) All volatiles were vacuum dried, and a hexane solvent was added to the obtained oily liquid substance and the mixture was filtered out. The filtered solution was vacuum dried, and hexane was added thereto to induce a precipitate at a low temperature (−20° C.). The obtained precipitate was filtered off at a low temperature to obtain a [3-(6-tert-butoxy hexyl)-1H-indene].sub.2ZrCl.sub.2 compound in the form of a white solid (yield: 78%).

(20) .sup.1H NMR (300 MHz, CDCl.sub.3): 7.47 (2H, d), 7.38 (2H, d), 7.21 (2H, t), 6.95 (2H, m), 6.10 (1H, s), 5.87 (1H, s), 5.48 (1H, s), 5.36 (1H, s) 3.36 (4H, m), 2.95 (2H, m), 2.76 (2H, m), 1.47 (8H, m), 1.30 (4H, m), 1.05 (18H, s)

Preparation Example 3

(21) ##STR00031##

(22) (1) Preparation of Ligand Compound

(23) 10.8 g (100 mmol) of chlorohexanol was added to a dried 250 mL Schlenk flask, to which 10 g of a molecular sieve and 100 mL of MTBE (methyl tert-butyl ether) were added, and 20 g of sulfuric acid was added slowly over 30 minutes. The reaction mixture turned pink slowly over time. After 16 hours, it was poured into a saturated sodium bicarbonate solution with ice cooling. The mixture was extracted four times with 100 mL of ether, and the combined organic layer was dried over MgSO.sub.4 and filtered. The solvent was removed under vacuum reduced pressure. Thereby, 10 g (yield: 60%) of 1-(tertbutoxy)-6-chlorohexane in the form of a yellow liquid was obtained.

(24) .sup.1H NMR (500 MHz, CDCl.sub.3): 3.53 (2H, t), 3.33 (2H, t), 1.79 (2H, m), 1.54 (2H, m), 1.45 (2H, m), 1.38 (2H, m), 1.21 (9H, s)

(25) 4.5 g (25 mmol) of 1-(tert-butoxy)-6-chlorohexane synthesized above was added to a dried 250 mL Schlenk flask, and dissolved in 40 mL of THF. 20 mL of a sodium indenide THF solution was slowly added thereto and then stirred for one day. The reaction mixture was quenched by addition of 50 mL of water, and extracted with ether (50 mL×3), and then the combined organic layer was washed thoroughly with brine. The remaining moisture was dried over MgSO.sub.4 and filtered. The solvent was removed under vacuum reduced pressure. Thereby, a dark brown viscous product, 3-(6-tert-butoxy hexyl)-1H-indene, was obtained in a quantitative yield.

(26) Mw=272.21 g/mol

(27) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.47 (1H, d), 7.38 (1H, d), 7.31 (1H, t), 7.21 (1H, t), 6.21 (1H, s), 3.36 (2H, m), 2.57 (2H, m), 1.73 (2H, m), 1.57 (2H, m), 1.44 (6H, m), 1.21 (9H, s)

(28) (2) Preparation of Transition Metal Compounds

(29) 5.44 g (20 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene prepared above was added to a dried 250 mL Schlenk flask, and dissolved in 60 mL of ether. 13 mL of an n-BuLi 2.0 M hexane solution was added thereto, stirred for one day, and then a toluene solution of n-butyl cyclopentadiene ZrCl.sub.3 (concentration of 0.378 mmol/g) was slowly added at −78° C. When the reaction mixture was heated to room temperature, it turned into a white suspension with a yellow solid floating in a clear brown solution. After 12 hours, 100 mL of hexane was added to the reaction mixture to further precipitate. After that, the mixture was filtered under argon to obtain a yellow filtrate, which was dried. Thereby, it was confirmed that 3-(6-(tert-butoxy)hexyl)-1H-inden-1-yl)(3-butylcylcopenta-2,4-dien-1-yl) zirconium(IV) chloride was produced as the desired compound.

(30) Mw=554.75 g/mol

(31) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.62 (2H, m), 7.24 (2H, m), 6.65 (1H, s), 6.39 (1H, s), 6.02 (1H, s), 5.83 (1H, s), 5.75 (1H, s), 3.29 (2H, m), 2.99 (1H, m), 2.89 (1H, m), 2.53 (1H, m), 1.68 (2H, m), 1.39-1.64 (10H, m), 1.14 (9H, s), 0.93 (4H, m)

Preparation Example of Second Transition Metal Compound: Preparation Examples 4 to 7

Preparation Example 4

(32) ##STR00032##

(33) (1) Preparation of Ligand A

(34) 4.0 g (30 mmol) of 1-benzothiophene was dissolved in THF to prepare a 1-benzothiophene solution. Then, 14 mL (36 mmol, 2.5 M in hexane) of an n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution.

(35) Subsequently, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at −80° C., and the obtained solution was stirred at room temperature for about 10 hours.

(36) Then, 10% HCl was poured into the solution to quench the reaction, and the organic layer was separated with dichloromethane to obtain (2E)-1-(1-benzothiene-2-yl)-2-methyl-2-buten-1-one as a beige solid.

(37) ##STR00033##

(38) .sup.1H NMR (CDCl.sub.3): 7.85-7.82 (m, 2H), 7.75 (m, 1H), 7.44-7.34 (m, 2H), 6.68 (m, 1H), 1.99 (m, 3H), 1.92 (m, 3H)

(39) While vigorously stirring a solution in which 5.0 g (22 mmol) of the (2E)-1-(1-benzothiene-2-yl)-2-methyl-2-buten-1-one prepared above was dissolved in 5 mL of chlorobenzene, 34 mL of sulfuric acid was slowly added to the solution. Then, the solution was stirred at room temperature for about 1 hour. Subsequently, ice water was poured into the solution, and the organic layer was separated with an ether solvent to obtain 4.5 g (yield: 91%) of 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopenta[d] thiophen-3-one as a yellow solid.

(40) ##STR00034##

(41) .sup.1H NMR (CDCl.sub.3): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 (m, 1H), 2.63 (m, 1H), 1.59 (d, 3H), 1.39 (d, 3H)

(42) To a solution in which 2.0 g (9.2 mmol) of 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopenta[d]thiophen-3-one was dissolved in a mixed solvent of 20 mL of THF and 10 mL of methanol, 570 mg (15 mmol) of NaBH.sub.4 was added at 0° C. Then, the solution was stirred at room temperature for about 2 hours. After that, HCl was added to the solution to adjust the pH to 1, and the organic layer was separated with an ether solvent to obtain an alcohol intermediate.

(43) The alcohol intermediate was dissolved in toluene to prepare a solution. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution and refluxed for about 10 minutes. The resulting reaction mixture was separated by column chromatography to obtain 1.8 g (9.0 mmol, yield: 98%) of orange-brownish liquid 1,2-dimethyl-3H-benzo[b]cyclopenta[d] thiophene (ligand A).

(44) ##STR00035##

(45) .sup.1H NMR (CDCl.sub.3): 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s, 1H), 3.35 (q, 1H), 2.14 (s, 3H), 1.14 (d, 3H)

(46) (2) Preparation of Ligand B

(47) 13 mL (120 mmol) of t-butylamine and 20 mL of an ether solvent were added to a 250 mL Schlenk flask, and 16 g (60 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane and 40 mL of an ether solvent were added to a different 250 mL Schlenk flask, to prepare a t-butylamine solution and a (6-tert-butoxyhexyl)dichloro(methyl)silane solution, respectively. Then, the t-butylamine solution was cooled to −78° C., and then a (6-tert-butoxyhexyl)dichloro(methyl)silane solution was slowly added to the cooled solution, which was stirred at room temperature for about 2 hours. The resulting white suspension was filtered to obtain an ivory liquid 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilanamine (ligand B).

(48) ##STR00036##

(49) .sup.1H NMR (CDCl.sub.3): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0.40 (s, 3H)

(50) (3) Crosslinking of Ligands A and B

(51) To a 250 mL Schlenk flask, 1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (ligand A) was added and 30 mL of THF was added to prepare a ligand A solution. The ligand A solution was cooled to −78° C., and then 3.6 mL (9.1 mmol, 2.5 M in hexane) of an n-BuLi solution was added to the ligand A solution, which was stirred at room temperature overnight to obtain a purple-brown solution. The solvent of the purple-brown solution was replaced with toluene, and in this solution, a solution in which 39 mg (0.43 mmol) of CuCN was dispersed in 2 mL of THF was injected to prepare a solution A.

(52) Meanwhile, 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilanamine (ligand B) and toluene were injected in a 250 mL Schlenk flask to prepare a solution B, which was then cooled to −78° C. Then, the solution A previously prepared was slowly added to the cooled solution B, and the mixture of solutions A and B was stirred at room temperature overnight. The resulting solid was removed by filtration to obtain 4.2 g of a brownish viscous liquid 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1-methylsilanamine (crosslinked product of ligands A and B) (>99% yield).

(53) ##STR00037##

(54) In order to confirm the structure of the crosslinked product of ligands A and B, the crosslinked product was lithiated at room temperature, and then H-NMR spectra were obtained using a sample dissolved in small amounts of pyridine-D5 and CDCl.sub.3.

(55) .sup.1H NMR (pyridine-D5 and CDCl.sub.3): 7.81 (d, 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t, 2H), 3.15 (s, 6H), 2.23-1.73 (m, 10H), 2.15 (s, 9H), 1.91 (s, 9H), 1.68 (s, 3H)

(56) (4) Preparation of Transition Metal Compounds

(57) 4.2 g (8.6 mmol) of 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1-methylsilane amine (crosslinked product of ligands A and B) was added to a 250 mL Schlenk flask, and 14 mL of toluene and 1.7 mL of n-hexane were injected into the flask to dissolve the crosslinked product. After cooling the solution to −78° C., 7.3 mL (18 mmol, 2.5 M in hexane) of an n-BuLi solution was injected into the cooled solution. Then, the solution was stirred at room temperature for about 12 hours. Subsequently, 5.3 ml (38 mmol) of trimethylamine was added to the solution, and this solution was stirred at about 40° C. for about 3 hours to prepare a solution C.

(58) Meanwhile, 2.3 g (8.6 mmol) of TiCl.sub.4(THF).sub.2 and 10 mL of toluene were added to a separately prepared 250 mL Schlenk flask to prepare a solution D in which TiCl.sub.4(THF).sub.2 was dispersed in toluene. The previously prepared solution C was added slowly to the above solution D at −78° C., and the mixture of solutions C and D was stirred at room temperature for about 12 hours. After that, the solution was depressurized to remove the solvent, and the resulting solute was dissolved in toluene. The solids that did not dissolve in toluene were removed by filtration. The solvent was removed from the filtered solution to obtain 4.2 g (yield: 83%) of the transition metal compound in the form of a brown solid.

(59) .sup.1H NMR (CDCl.sub.3): 8.01 (d, 1H), 7.73 (d, 1H), 7.45-7.40 (m, 2H), 3.33 (t, 2H), 2.71 (s, 3H), 2.33 (d, 3H), 1.38 (s, 9H), 1.18 (s, 9H), 1.80-0.79 (m, 10H), 0.79 (d, 3H)

Preparation Example 5

(60) ##STR00038##

(61) 50 g of Mg (s) was added to a 10 L reactor at room temperature, and then 300 mL of THF was added thereto. About 0.5 g of I.sub.2 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-buthoxyhexyl chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. It was observed that, as 6-t-buthoxyhexyl chloride was added, the temperature of the reactor increased by about 4 to 5° C. While 6-t-buthoxyhexyl chloride was continuously added, 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 to obtain an organic layer, and 6-t-buthoxyhexane was confirmed by 1H-NMR. It could be seen from the 6-t-buthoxyhexane that a Grignard reaction progressed well. Thereby, 6-t-buthoxyhexyl magnesium chloride was synthesized.

(62) 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-buthoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. After the feeding of the 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 salt was produced. 4 L of hexane was added, and the salt was removed through a Labdori to obtain a filtered solution. The obtained filtered solution was added to a reactor, and then hexane was removed at 70° C. to obtain a light yellow liquid. It was confirmed through 1H-NMR that the obtained liquid was desired methyl(6-t-buthoxy hexyl)dichlorosilane.

(63) .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)

(64) 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to a reactor, and then the reactor was cooled 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 the n-BuLi was added, the solution was stirred for 12 hours while slowly raising the temperature of the reactor to room temperature. After reaction for 12 hours, an equivalent of methyl(6-t-buthoxy hexyl)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 a 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 was methyl(6-t-buthoxyhexyl)(tetramethylCpH)t-butylaminosilane).

(65) To the dilithium salt of the ligand at −78° C. synthesized from n-BuLi and the ligand methyl(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 (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 as desired ([methyl(6-t-buthoxyhexyl)silyl(η5-tetramethylCp)(t-butylamido)]TiCl.sub.2.

(66) .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)

Preparation Example 6

(67) ##STR00039##

(68) (1) Preparation of Ligand Compound

(69) 102.54 g (376.69 mmol) of 3-tether indene was added to a dried 1 L Schlenk flask, and 450 ml of THF was injected under argon. The solution was cooled to −30° C., and 173.3 ml (119.56 g, d=0.690 g/ml) of a 2.5 M n-BuLi hexane solution was added dropwise thereto. The reaction mixture was slowly warmed to room temperature and then stirred until the next day. The lithiated 3-tether indene solution was cooled to −78° C., and then 24.3 g (188.3 mmol) of dimethyldichlorosilicone was prepared and added dropwise to the Schlenk flask. After the injection, the mixture was slowly heated to room temperature, stirred for a day, and then quenched by adding 200 ml of water in the flask. The organic layer was separated and dried over MgSO.sub.4. As a result, 115 g (191.4 mmol, 101.6%) of a yellow oil was obtained.

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

(71) (2) Preparation of Transition Metal Compounds

(72) 191.35 mmol of the ligand compound synthesized above was added to a 2 L Schlenk flask dried in an oven. 4 equivalents of MTBE (67.5 g, d=0.7404 g/ml) and 696 g of toluene (d=0.87 g/ml) were dissolved in a solvent, and 2.1 equivalents of an n-BuLi solution (160.7 ml) was added and lithiated until the next day. 72.187 g (191.35 mmol) of ZrCl.sub.4(THF).sub.2 was taken in a glove box and placed in in a 2 L Schlenk flask to prepare a suspension containing toluene. Both flasks were cooled to −78° C., and the ligand anion was slowly added to the Zr suspension. After completion of the injection, the reaction mixture was slowly warmed to room temperature. The mixture was stirred for one day, and then the slurry was filtered under argon and filtered. Both the filtered solid and the filtrate were evaporated under vacuum pressure. From 115 g (191.35 mmol) of the ligand, 150.0 g (198 mmol, >99%) of the catalyst precursor was obtained in the filtrate and stored in the toluene solution (1.9446 g/mmol).

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

Preparation Example 7

(74) ##STR00040##

(75) (1) Preparation of Ligand Compound

(76) 2.63 g (12 mmol) of 5-methyl-5,10-dihydroindeno[1,2-b]indole was added to a 250 mL flask and dissolved in 50 mL of THF. 6 mL of a 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred at room temperature overnight. In another 250 mL flask, 1.62 g (6 mmol) of (6-(tert-butoxy)hexyl)dichloro(methyl)silane was dissolved in 100 mL of hexane, and a lithiated solution of 5-methyl-5,10-dihydroindeno[1,2-b]indole was slowly added dropwise under a dry ice/acetone bath, and stirred at room temperature overnight. After reaction, the mixture was extracted with ether/water, and then the residual water in the organic layer was removed with MgSO.sub.4 and vacuum dried to obtain 3.82 g (6 mmol) of the ligand compound, and this was confirmed by 1H-NMR.

(77) .sup.1H NMR (500 MHz, CDCl3): −0.33 (3H, m), 0.86˜1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 (3H, d), 4.17 (1H, d), 4.25 (1H, d), 6.95˜7.92 (16H, m)

(78) (2) Preparation of Transition Metal Compound

(79) 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 above was dissolved in 100 mL of toluene and 5 mL of MTBE, and then 5.6 mL (14 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred at room temperature overnight. 2.26 g (6 mmol) of ZrCl.sub.4(THF).sub.2 was added to another flask, and 100 ml of toluene was added to prepare a slurry. The toluene slurry of ZrCl.sub.4(THF).sub.2 was transferred to a litiated ligand in a dry ice/acetone bath. It was stirred overnight at room temperature and changed to violet color. The reaction solution was filtered to remove LiCl. The obtained filtrate was vacuum dried, and hexane was added thereto and sonicated. The slurry was filtered to obtain 3.40 g (yield: 71.1 mol %) of a dark violet transition metal compound as a filtered solid.

(80) .sup.1H NMR (500 MHz, CDCl3): 1.74 (3H, d), 0.85˜2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H, m), 6.48˜8.10 (16H, m)

EXAMPLE

Example 1

(81) (1) Preparation of Cocatalyst-Supported Support

(82) In a 300 mL glass reactor, 100 mL of toluene was added and 10 g of silica (SP2410 available from Grace Davison) was added thereto. The mixture was stirred while raising the temperature of the reactor to about 40° C. After sufficiently dispersing the silica, 60 mL of a methylaluminoxane (MAO) solution (10 wt % in toluene) (Albemarle) was added to the reactor. After raising the temperature of the reactor to about 60° C., it was stirred at about 200 rpm for about 12 hours. After that, the temperature of the reactor was lowered to about 40° C., and stirring was stopped. After sitting for about 10 minutes, the reaction solution was decanted. To the resulting reaction, 100 ml of toluene was added, and the mixture was stirred for about 10 minutes, and stirring was stopped. After sitting for 10 minutes, toluene was decanted. As a result, a cocatalyst-supported support (MAO/SiO.sub.2) was obtained.

(83) (2) Preparation of Supported Catalyst

(84) 50 mL of toluene was added to a reactor containing a cocatalyst-supported support (MAO/SiO.sub.2), and 0.8 g of the transition metal compound prepared in Preparation Example 1 and 10 ml of toluene were added to a reactor and stirred at 200 rpm for 60 minutes. 10.0 g of the transition metal compound prepared in Preparation Example 4 and 10 ml of toluene were added to the reactor and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(85) (3) Preparation of Polyethylene Copolymer

(86) While adding 34 kg/h of hexane, 10 kg/h of ethylene, 1.06 g/h of hydrogen, 600 to 720 ml/h of 1-butene, and 35 g/h of Teal to a 200 L two-stage continuous high-pressure reactor, 7 to 10 g/h of the hybrid supported catalyst prepared above was mixed with a hexane solution and added thereto.

(87) The mixture was stirred under a pressure of 8.0 bar with a three-stage agitator and a circulation pump so as to mix the polymerized product. The temperature of the reactor was maintained at 80° C. through a cooling jacket and an outer cooler, and the reactor level was maintained at 75% and transferred to a latter stage reactor with a pressure difference. In a slurry after the completion of reaction, hexane was primarily removed using a centrifugal separator and dried with a dryer via a hot N.sub.2 purge. Thereby, about 9 kg/h of a polyethylene copolymer was obtained.

Example 2

(88) (1) Preparation of Cocatalyst-Supported Support

(89) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(90) (2) Preparation of Supported Catalyst

(91) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 1.5 g of the transition metal compound prepared in Preparation Example 2 and 10 ml of toluene were added to a reactor, and stirred at 200 rpm for 60 minutes. 6.0 g of the transition metal compound prepared in Preparation Example 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(92) (3) Preparation of Polyethylene Copolymer

(93) The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the hybrid supported catalyst prepared in (2) of Example 2 and 3.50 g/h of hydrogen were used.

Example 3

(94) (1) Preparation of Cocatalyst-Supported Support

(95) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(96) (2) Preparation of Supported Catalyst

(97) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 1.5 g of the transition metal compound prepared in Preparation Example 2 and 10 ml of toluene were added to a reactor, and stirred at 200 rpm for 60 minutes. 5.0 g of the transition metal compound prepared in Preparation Example 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(98) (3) Preparation of Polyethylene Copolymer

(99) The polyethylene copolymer was prepared in the same manner as in (3) of Example 2, except that the hybrid supported catalyst prepared in (2) of Example 2 and 3.45 g/h of hydrogen were used.

Example 4

(100) (1) Preparation of Cocatalyst-Supported Support

(101) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(102) (2) Preparation of Supported Catalyst

(103) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 2.1 g of the transition metal compound prepared in Preparation Example 3 and 10 ml of toluene were added to a reactor, and stirred at 200 rpm for 60 minutes. 6.7 g of the transition metal compound prepared in Preparation Example 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(104) (3) Preparation of Polyethylene Copolymer

(105) The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the hybrid supported catalyst prepared in (2) of Example 4 and 1.50 g/h of hydrogen were used.

Example 5

(106) (1) Preparation of Cocatalyst-Supported Support

(107) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(108) (2) Preparation of Supported Catalyst

(109) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 2.1 g of the transition metal compound prepared in Preparation Example 1 and 10 ml of toluene were added to a reactor and stirred at 200 rpm for 60 minutes. 1.8 g of the transition metal compound prepared in Preparation Example 6 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Here, 3.4 g of the transition metal compound prepared in Preparation Example 7 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(110) (3) Preparation of Polyethylene Copolymer

(111) The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the hybrid supported catalyst prepared in (2) of Example 5 and 0.8 g/h of hydrogen were used.

COMPARATIVE EXAMPLE

Comparative Example 1

(112) An ethylene-1-hexene copolymer [XP9000 product available from Daelim Industrial] was used.

Comparative Example 2

(113) An ethylene-1-octene copolymer [DX800 available from SK Global Chemical] was used.

Comparative Example 3

(114) (1) Preparation of Cocatalyst-Supported Support

(115) In a 300 mL glass reactor, 100 mL of toluene was added and 10 g of silica (SP2410 available from Grace Davison) was added. The mixture was stirred while raising the temperature of the reactor to about 40° C. After sufficiently dispersing the silica, 60 mL of a methylaluminoxane (MAO) solution (10 wt % in toluene) (Albemarle) was added to the reactor. After raising the temperature of the reactor to about 60° C., it was stirred at about 200 rpm for about 12 hours. After that, the temperature of the reactor was lowered to about 40° C., and stirring was stopped. After sitting for about 10 minutes, the reaction solution was decanted. To the resulting reaction, 100 ml of toluene was added, and the mixture was stirred for about 10 minutes, and stirring was stopped. After sitting for 10 minutes, toluene was decanted. As a result, a cocatalyst-supported support (MAO/SiO.sub.2) was obtained.

(116) (2) Preparation of Supported Catalyst

(117) 50 mL of toluene was added to a reactor containing a cocatalyst-supported support (MAO/SiO.sub.2), and 2.1 g of the transition metal compound of the following Chemical Formula A and 10 ml of toluene were added to a reactor and stirred at 200 rpm for 60 minutes. 6.7 g of the transition metal compound prepared in Preparation Example 5 and 10 ml of toluene were added to the reactor and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(118) ##STR00041##

(119) (3) Preparation of Polyethylene Copolymer

(120) While adding 34 kg/h of hexane, 10 kg/h of ethylene, 1.50 g/h of hydrogen, 600 to 720 ml/h of 1-butene and 35 g/h of Teal to a 200 L two-stage continuous high-pressure reactor, 7 to 10 g/h of the hybrid supported catalyst prepared above was mixed with a hexane solution and added thereto.

(121) The mixture was stirred under a pressure of 8.0 bar with a three-stage agitator and a circulation pump so as to mix the polymerized product. The temperature of the reactor was maintained at 80° C. through a cooling jacket and an outer cooler, and the reactor level was maintained at 75% and transferred to a rear stage reactor with a pressure difference. In a slurry after the completion of reaction, hexane was primarily removed using a centrifugal separator and dried with a dryer via a hot N.sub.2 purge.

(122) Thereby, about 9 kg/h of a polyethylene copolymer was obtained.

REFERENCE EXAMPLE

Reference Example 1

(123) (1) Preparation of Cocatalyst-Supported Support

(124) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(125) (2) Preparation of Supported Catalyst

(126) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 0.8 g of the transition metal compound prepared in Preparation Example 1 and 10 ml of toluene were added to a reactor, and stirred at 200 rpm for 60 minutes. 10 g of the transition metal compound prepared in Preparation Example 4 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(127) (3) Preparation of Polyethylene Copolymer

(128) The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the hybrid supported catalyst prepared in (2) of Reference Example 1 and 1.50 g/h of hydrogen were used.

Reference Example 2

(129) (1) Preparation of Cocatalyst-Supported Support

(130) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(131) (2) Preparation of Supported Catalyst

(132) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 0.8 g of the transition metal compound prepared in Preparation Example 1 and 10 ml of toluene were added to a reactor, and stirred at 200 rpm for 60 minutes. 10 g of the transition metal compound prepared in Preparation Example 4 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(133) (3) Preparation of Polyethylene Copolymer

(134) The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the hybrid supported catalyst prepared in (2) of Reference Example 2 and 1.40 g/h of hydrogen were used.

Reference Example 3

(135) (1) Preparation of Cocatalyst-Supported Support

(136) The cocatalyst-supported support (MAO/SiO.sub.2) was prepared in the same manner as in (1) of Example 1.

(137) (2) Preparation of Supported Catalyst

(138) 50 mL of toluene was added to a reactor containing the cocatalyst-supported support (MAO/SiO.sub.2), and 1.5 g of the transition metal compound prepared in Preparation Example 2 and 10 ml of toluene were added to a reactor, and stirred at 200 rpm for 60 minutes. 6.0 g of the transition metal compound prepared in Preparation Example 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. After stirring was stopped, the reaction solution was allowed to stand for 10 minutes and decanted. 100 ml of hexane was added to the reactor, and the resulting mixture was placed in a 200 ml Schlenk flask and the hexane solution was decanted. After that, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a hybrid supported catalyst.

(139) (3) Preparation of Polyethylene Copolymer

(140) The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the hybrid supported catalyst prepared in (2) of Reference Example 3 and 3.2 g/h of hydrogen were used.

Test Example

(141) The physical properties of the polyethylene copolymers obtained according to the examples, comparative examples and reference examples were evaluated by the following method, and the results are shown in Table 1 below.

(142) (1) Density (unit: g/cm.sup.3): Measured according to the ASTM D1505 standard.

(143) (2) Melt index (MI, unit: g/10 min): The weight of the molten polyethylene copolymer passing through a 2.1 mm orifice at 190° C. for 10 minutes under the condition of applying a force of 2.16 kg or 21.6 kg in the vertical direction with respect to gravity was measured according to the ASTM D1238 standard.

(144) (3) Average value of SCB (Short Chain Branch: branch of 2 to 7 carbon atoms per 1000 carbon atoms) unit: number/1000 C) content

(145) The molecular weight (M) was determined using gel permeation chromatography (GPC).

(146) Specifically, the logarithm of the molecular weight (log M) is represented by the x-axis.

(147) A molecular weight distribution curve was obtained using gel permeation chromatography (GPC), wherein the molecular weight (M), specifically the log value (log M) of the molecular weight, is represented by the x-axis, and the polymer chain content (dwt/d log M) relative to the molecular weight value is represented by the y-axis. This is indicated by the continuous solid line in FIG. 1.

(148) Subsequently, an FT-IR device connected to a GPC device was used for an SCB distribution curve wherein the molecular weight (M) obtained by gel permeation chromatography, specifically the log value (log M) of the molecular weight, is represented by the x-axis, and the side chain branch content of 2 to 7 carbon atoms per 1000 carbon atoms relative to the molecular weight value obtained by FT-IR is represented by the y-axis.

(149) The average value of the side chain branch content of 2 to 7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains contained in the polyethylene copolymer has was calculated using the SCB distribution curve.

(150) The average value was obtained by dividing the total of the side chain branch content of 2 to 7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains contained in the polyethylene copolymer has by the number of the polymer chains contained in the polyethylene copolymer.

(151) At this time, measuring instruments and measurement conditions of the gel permeation chromatography are as follows.

(152) <Measuring Instrument> Polymer Laboratories PLgel MIX-B 300 mm Column, Waters PL-GPC220

(153) <Measurement Condition>

(154) The evaluation temperature was 160° C., 1,2,4-trichlorobenzene was used as a solvent, the flow rate was 1 mL/min, samples were prepared at a concentration of 10 mg/10 mL and then fed in an amount of 200 μL, and the values of Mw, Mn, and PDI can be determined using a calibration curve formed using a polystyrene standard. The molecular weight of the polystyrene standards used was 9 types of 2000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000.

(155) Further, the FT-IR measuring instruments and measurement conditions are as follows.

(156) <Measuring Instrument> PerkinElmer Spectrum 100

(157) <Measurement Condition>

(158) Wavenumber: 2700 cm.sup.−1 to 3000 cm.sup.−1

(159) Number of scans: 16

(160) Resolution: 8 cm.sup.−1

(161) Detector: DTGS

(162) (4) SCG index (unit: g/10 min): defined as a value (p/q) obtained by dividing the melt index measured by ASTM 1238 (load of 21.6 kg, 190° C.) by the following CDI(q).

(163) (5) Comonomer Distribution Index (CDI): Referring to FIG. 2, a molecular weight distribution curve (shown by a continuous solid line in FIG. 2) was obtained using gel permeation chromatography (GPC,) wherein the molecular weight (M), specifically the log value (log M) of the molecular weight, is represented by the x-axis, and the polymer chain content (dwt/d log M) relative to the molecular weight value is represented by the y-axis. The SCB (short chain branch) content (c) of the polymer chain which is a molecular weight value m satisfying the following Equation 2, and the SCB (short chain branch) content (d) of the polymer chain which is a molecular weight value n satisfying the following Equation 3, were measured using an FT-IR device connected to a GPC device. The contents of GPC and FT-IR are the same as those described in “(3) Average value of the short chain branch (SCB) (branch of 2 to 7 carbon atoms per 1000 carbon atoms) unit: number/1000 C) content”.
∫.sub.a.sup.mf(x)dx=0.8∫.sub.a.sup.bf(x)dx  [Equation 2]
∫.sub.a.sup.nf(x)dx=0.2∫.sub.a.sup.bf(x)dx  [Equation 3]

(164) In Equations 2 and 3, a is the minimum value of molecular weight which is represented by the x-axis in the molecular weight distribution curve by GPC, b is the maximum value of the molecular weight which is represented by the x-axis in the molecular weight distribution curve by GPC, f(x) is a function formula of the molecular weight distribution curve obtained using gel permeation chromatography (GPC) wherein the molecular weight (M), specifically the log value (log M) of the molecular weight, is represented by the x-axis, and the polymer chain content (dwt/d log M) relative to the molecular weight value is represented by the y-axis.

(165) Then, the value (c/d) obtained by dividing the SCB (short chain branch) content (c) of a polymer chain which is a molecular weight m satisfying Equation 2 by the SCB (short chain branch) content (d) of a polymer chain which is a molecular weight n satisfying Equation 3 was defined as the Comonomer Distribution Index (CDI) and calculated.

(166) (6) S.H. Modulus (unit: MPa): measured according to the ISO 18488 standard.

(167) (7) Stress crack resistance (Full Notch Creep Test (FNCT), unit: hour (h)): Measured according to the ISO 16770 standard under the conditions of 80° C., 4 MPa, and an IGEPAL CA-630 10% solution.

(168) TABLE-US-00001 TABLE 1 Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Transition Preparation Preparation Preparation Preparation Preparation — metal compound Example 1/ Example 2/ Example 2/ Example 3/ Example 1/ Preparation Preparation Preparation Preparation Preparation Example 4 Example 5 Example 5 Example 5 Example 6/ Preparation Example 7 Comonomer 1-butene 1-butene 1-butene 1-butene 1-butene 1-hexene Addition 1.06 3.50 3.45 1.50 0.80 amount of hydrogen (g/h) Density 0.9383 0.9370 0.9355 0.9397 0.9365 0.9346 MI(2.16 Kg) 0.226 0.502 0.591 0.174 0.036 0.600 MI(21.6 Kg) 15.965 17.076 24.458 9.644 9.574 13.200 Average value 7.2 8.7 10.1 7.3 7.2 6.5 of SCB content [number/1000 C] CDI 1.80 2.20 2.56 1.91 1.23 1.05 SCG index 8.9 7.8 9.6 5.0 7.8 12.6 SCG index/(carbon 4.45 3.9 4.8 2.5 3.9 5.14 number of comonomer).sup.1/2 S.H. Modulus 0.92 0.92 0.90 0.97 0.97 0.76 (80° C.) FNCT(4 MPa) more 1963 more more more 20 than 2527 than 2915 than 3118 than 8615 Comparative Comparative Reference Reference Reference Example 2 Example 3 Example 1 Example 2 Example 3 Transition — Formula Preparation Preparation Preparation metal compound A/Preparation Example 1/ Example 1/ Example 2/ Example 5 Preparation Preparation Preparation Example 4 Example 4 Example 5 Comonomer 1-octene 1-butene 1-butene 1-butene 1-butene Addition 1.50 1.50 1.40 3.20 amount of hydrogen (g/h) Density 0.9337 0.9341 0.9365 0.9362 0.9375 MI(2.16 Kg) 0.640 0.653 0.604 0.439 0.765 MI(21.6 Kg) 20.500 22.0 42.060 21.824 32.791 Average value 6.8 6.7 8.5 8.4 9.5 of SCB content [number/1000 C] CDI 0.94 0.87 1.85 1.56 2.17 SCG index 21.8 17.6 22.7 14.0 15.1 SCG index/(carbon 7.71 6.57 11.35 7 7.55 number of comonomer).sup.1/2 S.H. Modulus 0.76 0.77 0.77 0.84 0.82 (80° C.) FNCT(4 MPa) 425 350 71 155 130

(169) As shown in Table 1, the polyethylene copolymers obtained in Examples 1 to 5 can satisfy the conditions that an SCG index is 5 to 9.6, CDI is 1.23 to 2.56, S.H. Modulus (measured at 80° C.) is 0.90 MPa to 0.97 MPa, the stress crack resistance (FNCT, measured at 4 MPa) is 1963 h or more, a melt index (measured at 190° C. under a load of 2.16 kg according to ASTM D 1238) is 0.036 g/10 min to 0.591 g/10 min, a melt index (measured at 190° C. under a load of 21.6 kg according to ASTM D 1238) is 9.574 g/10 min to 24.458 g/10 min, and the average value of the SCB content is 7.2/1000 C to 10.1/1000 C.

(170) In addition, in the polyethylene copolymers obtained in Examples 1 to 5, the SCG index values are shown as 4.45 times, 3.9 times, 4.8 times, 2.5 times, and 3.9 times, respectively, as compared with the square root of the carbon number of the alpha olefin used as the comonomer, confirming that they satisfy 5 times or less compared to the square root value of the carbon number.

(171) On the other hand, in the polyethylene copolymers obtained in Comparative Examples 1 to 3, SCG index values were shown as 5.14 times, 7.71 times, and 6.57 times, compared to the square root value of the carbon number of the alpha olefin used as the comonomer, which exceeds 5 times the square root value of the carbon number.

(172) In addition, in the polyethylene copolymers obtained in Comparative Examples 1 to 3, the SCG index was shown to be 12.6 to 21.8, which is higher than that of the examples, S.H. modulus (measured at 80° C.) was shown to be 0.76 MPa to 0.77 MPa which is lower than that of the examples, and the stress crack resistance (FNCT, measured at 4 MPa) was shown to be 20 h to 425 h which is lower than that of the examples, thus confirming that the physical properties are deteriorated as compared with the examples.