Method of preparing supported metallocene catalyst

Abstract

A method of preparing a supported metallocene catalyst capable of more effectively preparing a polyolefin which may be preferably used for blow molding, etc., because its molecular weight distribution is such that polymer elasticity is increased to improve swell, is provided.

Claims

1. A method of preparing a supported metallocene catalyst, comprising: preparing a molecular weight modifier composition by mixing a cyclopentadienyl metal compound of the following Chemical Formula 1 and an organic aluminum compound of the following Chemical Formula 2 and stirring a resulting mixture at room temperature for 50 hours to 108 hours; and supporting one or more metallocene compounds represented by any one of the following Chemical Formulae 3 to 6 and the molecular weight modifier composition on a support, wherein the molecular weight modifier composition is supported in an amount of about 1 mol % to 85 mol %, based on the total weight of the metallocene compound:
(R.sup.1Cp.sup.1)(R.sup.2-Cp.sup.2)M.sup.4X.sub.2Chemical Formula 1 in Chemical Formula 1, Cp.sup.1 and Cp.sup.2 are each independently a ligand comprising a cyclopentadienyl group, an indenyl group, or a fluorenyl group; R.sup.1 and R.sup.2 are substituents of Cp.sup.1 and Cp.sup.2, and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms, a heteroalkylaryl group having 6 to 20 carbon atoms, a heteroarylalkyl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms; M.sup.4 is a Group 4 transition metal element; and X is a halogen,
R.sup.3R.sup.4R.sup.5AlChemical Formula 2 in Chemical Formula 2, R.sup.3, R.sup.4, and R.sup.5 are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R.sup.3, R.sup.4, and R.sup.5 is an alkyl group having 4 to 20 carbon atoms,
(Cp.sup.5R.sup.a).sub.n(Cp.sup.6R.sup.b)M.sup.1Z.sup.1.sub.3-nChemical Formula 3 in Chemical Formula 3, M.sup.1 is a Group 4 transition metal; Cp.sup.5 and Cp.sup.6 are the same as or different from each other, and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals-which are optionally substituted with a hydrocarbon having 1 to 20 carbon atoms; R.sup.a and R.sup.b are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl; Z.sup.1 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy; and n is 1 or 0,
(Cp.sup.7R.sup.c).sub.mB.sup.1(Cp.sup.8R.sup.d)M.sup.2Z.sup.2.sub.3-mChemical Formula 4 in Chemical Formula 4, M.sup.2 is a Group 4 transition metal; Cp.sup.7 and Cp.sup.8 are the same as or different from each other, and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms; R.sup.c and R.sup.d are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl; Z.sup.2 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy; B.sup.1 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp.sup.3R.sup.c ring and a Cp.sup.4R.sup.d ring or crosslink one Cp.sup.4R.sup.d ring to M.sup.2, or a combination thereof; and m is 1 or 0,
(Cp.sup.9R.sup.e)B.sup.2(J)M.sup.3Z.sup.3.sub.2Chemical Formula 5 in Chemical Formula 5, M.sup.3 is a Group 4 transition metal; Cp.sup.9 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms; R.sup.e is hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl; Z.sup.3 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy; B.sup.2 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp.sup.5R.sup.e ring to J, or a combination thereof; J is any one selected from the group consisting of NR.sup.f, O, PR.sup.f and S; and R.sup.f is a C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl, ##STR00035## in Chemical Formula 6, A is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group; D is O, S, N(R), or Si(R)(R), in which R and R are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group; L is a C1 to C10 straight or branched alkylene group; B is carbon, silicon, or germanium; Q is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group; M is a Group 4 transition metal; X.sup.1 and X.sup.2 are the same as or different from each other, and are each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group; C.sup.1 and C.sup.2 are the same as or different from each other, and are each independently represented by any one of the following Chemical Formula 7a, Chemical Formula 7b, and Chemical Formula 7c, excluding that both C.sup.1 and C.sup.2 are Chemical Formula 7c, ##STR00036## in Chemical Formulae 7a, 7b, and 7c, R.sub.1 to R.sub.17 and R.sub.1 to R.sub.9 are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and two or more neighboring groups of R.sub.10 to R.sub.17 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

2. The method of preparing the supported metallocene catalyst of claim 1, wherein the supporting is performed by mixing the support, the metallocene catalyst, and the molecular weight modifier composition, and stirring a resulting mixture at a temperature of 30 C. to 100 C. for 1 hour to 12 hours.

3. The method of preparing the supported metallocene catalyst of claim 1, wherein R.sup.1 and R.sup.2 in Chemical Formula 1 are each independently selected from the group consisting of hydrogen, methyl, ethyl, butyl, and t-butoxy hexyl.

4. The method of preparing the supported metallocene catalyst of claim 1, wherein R.sup.3, R.sup.4, and R.sup.5 in Chemical Formula 2 are each independently an isobutyl group.

5. The method of preparing the supported metallocene catalyst of claim 1, wherein M.sup.4 in Chemical Formula 1 is selected from the group consisting of titanium, zirconium, and hafnium.

6. The method of preparing the supported metallocene catalyst of claim 1, wherein the molecular weight modifier composition comprises a compound represented by the following Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, or Chemical Formula 11: ##STR00037##

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

8. The method of preparing the supported metallocene catalyst of claim 1, wherein the support is one on which a first aluminum-containing cocatalyst of the following Chemical Formula 12 is supported:
-[-Al(R.sup.18)O-].sub.n-Chemical Formula 12 in Chemical Formula 12, each R.sup.18 is independently a halogen, or a halogen-substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms, and n is an integer of 2 or more.

9. The method of preparing the supported metallocene catalyst of claim 8, wherein the molecular weight modifier composition is supported immediately after supporting the metallocene compound onto the first cocatalyst-supported support.

10. The method of preparing the supported metallocene catalyst of claim 1, wherein a second borate-based cocatalyst of the following Chemical Formula 13 is further supported:
T.sup.+[BQ.sub.4].sup.Chemical Formula 13 in Chemical Formula 13, T.sup.+ is a positive monovalent (+1) polyatomic ion, B is boron having an oxidation state of +3, each Q is independently selected from the group consisting of a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, in which Q has 20 or fewer carbon atoms, provided that only one or fewer of Q is a halide group.

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

12. The method of preparing the polyolefin of claim 11, wherein the polymerizing of olefinic monomers is performed by slurry polymerization of olefinic monomers in the presence of a supported metallocene catalyst which is obtained by supporting a metallocene compound on a support, together with a molecular weight modifier composition comprising a reaction product of a cyclopentadienyl metal compound and an organic aluminum compound.

13. The method of preparing the polyolefin of claim 11, wherein the olefinic monomer comprises one or more monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undencene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a graph showing molecular weight distributions of polymers which were polymerized by using supported metallocene catalysts prepared in Examples 10 to 12 and Comparative Example 4 (brown: Polymerization Example 10, red: Polymerization Example 11, purple: Polymerization Example 12, blue: Comparative Polymerization Example 4);

(2) FIG. 2 is a graph showing molecular weight distributions of polymers which were polymerized by using supported metallocene catalysts prepared in Comparative Example 3 and Example 8 (red: Polymerization Example 8, green: Comparative Polymerization Example 3); and

(3) FIG. 3 is a graph showing molecular weight distributions of polymers which were polymerized by using supported metallocene catalysts prepared in Comparative Example 2 and Example 5 (red: Polymerization Example 5, blue: Comparative Polymerization Example 2).

DETAILED DESCRIPTION OF THE EMBODIMENTS

(4) Hereinafter, preferred examples are provided for better understanding. However, the following examples are for illustrative purposes only, and the scope of the present invention is not intended to be limited by the following examples.

EXAMPLES

Preparation Example of Metallocene Catalyst Precursor

Synthesis Example 1 Synthesis of [t-Bu-O(CH2)6C5H4]2ZrMe2

(5) ##STR00028##

(6) t-butyl-O(CH.sub.2).sub.6Cl was prepared using 6-chlorohexanol according to a method described in the document (Tetrahedron Lett. 2951 (1988)), and reacted with NaC.sub.5H.sub.5 to obtain t-butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5(yield: 60%, b.p. 80 C./0.1 mmHg). 2.0 g (9.0 mmol) of t-butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 was dissolved in THF at 78 C., and 1.0 equivalent weight of normal butyl lithium (n-BuLi) was slowly added thereto. The temperature was raised to room temperature, and reaction was allowed for 8 h. This reaction solution was slowly added to a suspension solution of Zr(CH.sub.3).sub.2(THF).sub.2 (1.70 g, 4.50 mmol)/THF (30 mL) at 78 C., and then further reacted at room temperature for 6 h to obtain a final reaction solution.

(7) The reaction solution was dried under vacuum to remove all volatile materials, and then hexane was added to a remaining oily liquid, followed by filtration using a Schlenk glass filter. A filtrate solution was dried under vacuum to remove hexane, and then hexane was added thereto to induce precipitation at a low temperature (20 C.). A resulting precipitate was filtered at a low temperature to obtain a [t-Bu-O(CH.sub.2).sub.6C.sub.5H.sub.4].sub.2ZrCl.sub.2 compound as a white solid with a yield of 92%. .sup.1H NMR and .sup.13C NMR data of [t-Bu-O(CH.sub.2).sub.6C.sub.5H.sub.4].sub.2ZrCl.sub.2 thus obtained are as follows.

(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-J=6.6 Hz, 2H), 2.62 (t, J=8 Hz, 2H), 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

Synthesis Example 2 Synthesis of 2(t-Bu-O(CH2)6)(CH3)Si(C5(CH3)4)(tBu-N)TiCl2)

(10) ##STR00029##

(11) 50 g of Mg(s) was added to a 10 L reactor at room temperature, and then 300 mL of THF was added thereto.

(12) About 0.5 g of I.sub.2 was added, and the reactor temperature was maintained at 50 C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor by using a feeding pump at a speed of 5 mL/min. According to the addition of 6-t-butoxyhexyl chloride, it was observed that the reactor temperature was increased by about 4 C. to 5 C. While 6-t-butoxyhexyl chloride was continuously added, agitation was performed for 12 h.

(13) A black reaction solution was obtained after reaction for 12 h. After 2 mL of the formed black solution was sampled, water was added thereto to obtain an organic layer. 6-t-butoxyhexane was confirmed by .sup.1H-NMR. 6-t-butoxyhexane indicates that a Grignard reaction occurred well. Accordingly, 6-t-butoxyhexyl magnesium chloride was synthesized.

(14) 500 g of MeSiCl.sub.3 and 1 L of THF were added to a reactor, and the reactor temperature was cooled to 20 C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor by using the feeding pump at a speed of 5 mL/min.

(15) After injection of the Grignard reagent was finished, the reactor temperature was slowly raised to room temperature and agitation was performed for 12 h.

(16) After reaction for 12 h, it was confirmed that a white MgCl.sub.2 salt was generated. 4 L of hexane was added and the salt was removed through a labdori to obtain a filter solution.

(17) After the filter solution was added to the reactor, hexane was removed at 70 C. to obtain a light yellow liquid.

(18) The obtained liquid was identified as a desired methyl(6-t-butoxyhexyl)dichlorosilane compound by .sup.1H-NMR.

(19) .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)

(20) 1.2 mol of tetramethylcyclopentadiene (150 g) and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to 20 C. 480 mL of n-BuLi was added to the reactor by using the feeding pump at a speed of 5 mL/min. After n-BuLi was added, the reactor temperature was slowly raised to room temperature and agitation was performed for 12 h. After reaction for 12 h, an equivalent amount of methyl(6-t-butoxy hexyl)dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. The reactor temperature was slowly raised to room temperature and agitation was performed for 12 h. After reaction for 12 hrs, THF was removed, and 4 L of hexane was added and salts were removed through a labdori to obtain a filter solution. After the filter solution was added to the reactor, hexane was removed at 70 C. to obtain a yellow liquid. The obtained yellow liquid was identified as a desired methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane compound by .sup.1H-NMR.

(21) TiCl.sub.3(THF).sub.3 (10 mmol) was rapidly added to n-BuLi and a dilithium salt of the ligand at 78 C., which was synthesized from a ligand dimethyl(tetramethylCpH)t-butylaminosilane in a THF solution. This reaction solution was agitated for 12 h while the temperature was slowly increased from 78 C. to room temperature.

(22) After agitation for 12 h, an equivalent amount of PbCl.sub.2 (10 mmol) was added to the reaction solution at room temperature, followed by agitation for 12 h. After agitation for 12 h, a dark black solution with a blue tinge was obtained. After THF was removed from the generated reaction solution, hexane was added to filter a product. After hexane was removed from a filter solution, the solution was identified as a desired [methyl(6-t-butoxyhexyl)silyl(5-tetramethylCp)(t-butylamido)]TiCl.sub.2 compound by .sup.1H-NMR.

(23) .sup.1H-NMR (CDCl.sub.3): =3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6G), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (3, 3H)

Synthesis Example 3

(24) ##STR00030##

(25) 3-1 Preparation of Ligand Compound

(26) 2 g of fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and then 5.5 mL of a 2.5 M, n-BuLi hexane solution was added dropwise thereto in a dry ice/acetone bath, followed by agitation at room temperature overnight. 3.6 g of (6-(tert-butoxy)hexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane, and a fluorene-Li slurry was transferred in a dry ice/acetone bath for 30 min, followed by agitation 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 hexane solution was added dropwise thereto in a dry ice/acetone bath, followed by agitation at room temperature overnight. NMR sampling of a reaction solution of fluorene and (6-(tert-butoxy)hexyl)dichloro(methyl)silane was performed to confirm completion of the reaction, and then a 5,8-dimethyl-5,10-dihydroindeno [1,2-b]-indole-Li solution was transferred in a dry ice/acetone bath. The mixture was agitated at room temperature overnight. After reaction, extraction was performed using ether/water, and remaining water of an organic layer was dried over MgSO.sub.4 to obtain a ligand compound (Mw 597.90, 12 mmol). Production of two isomers was confirmed by .sup.1H-NMR.

(27) .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)

(28) 3-2 Preparation of Metallocene Compound

(29) 7.2 g (12 mmol) of the ligand compound prepared in 3-1 was dissolved in 50 mL of diethylether, and 11.5 mL of a 2.5 M, n-BuLi hexane solution was added dropwise thereto in a dry ice/acetone bath, followed by agitation at room temperature overnight. The solution was dried under vacuum to obtain a brown sticky oil, which was dissolved in toluene to obtain a slurry. ZrCl.sub.4(THF).sub.2 was prepared, and 50 mL of toluene was added thereto to prepare a slurry. 50 mL of the toluene slurry of ZrCl.sub.4(THF).sub.2 was transferred in a dry ice/acetone bath, followed by agitation at room temperature overnight. The solution changed to a violet color. This reaction solution was filtered to remove LiCl. Toluene was removed from a filtrate by drying under vacuum, and then hexane was added thereto, followed by sonication for 1 h. A slurry was filtered, and a filtered solid was 6 g of a dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol %). Two isomers were observed in .sup.1H-NMR.

(30) .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)

Preparation Example of Molecular Weight Modifier

Synthesis Example 4: Preparation of Molecular Weight Modifier

(31) ##STR00031##

(32) 1.08 g (3 mmol) of bis(2-butylcyclopenta-2,4-dien-1-yl)titanium(IV) chloride was placed in a 250 mL round bottom flask, and 50 mL of hexane was added thereto, followed by agitation. 6 mL (6 mmol) of triisobutyl aluminum (1 M in hexane) was added thereto, followed by agitation at room temperature for 3 days. The solvent was removed under vacuum to obtain a blue liquid mixture. Since this mixture was under reduction of titanium, it was not oxidized or color-changed. The blue mixture was used as is without purification, as below.

(33) .sup.1H NMR (CDCl.sub.3, 500 MHz): 6.1-6.6 (br m, 8H), 2.2 (m, 4H), 1.0-1.8 (br m, 16H), 0.4 (br s, 24H)

Synthesis Example 5: Preparation of Molecular Weight Modifier

(34) ##STR00032##

(35) 0.91 g (3 mmol) of bis(2-ethylcyclopenta-2,4-dien-1-yl)titanium(IV) chloride was placed in a 250 mL round bottom flask, and 50 mL of hexane was added thereto, followed by agitation. 6 mL (6 mmol) of triisobutyl aluminum (1 M in hexane) was added thereto, followed by agitation at room temperature for 3 days. The solvent was removed under vacuum to obtain a blue liquid mixture. Since this mixture was under reduction of titanium, it was not oxidized or color-changed. The blue mixture was used as is without purification, as below.

(36) .sup.1H NMR (CDCl.sub.3, 500 MHz): 6.2-6.6 (br m, 8H), 1.0-1.8 (br m, 7H), 0.8 (br s, 24H)

Synthesis Example 6: Preparation of Molecular Weight Modifier

(37) ##STR00033##

(38) 1.68 g (3 mmol) of bis(2-(6-t-butoxy-hexyl)cyclopenta-2,4-dien-1-yl)titanium(IV) chloride was placed in a 250 mL round bottom flask, and 50 mL of hexane was added thereto, followed by agitation. 6 mL (6 mmol) of triisobutyl aluminum (1 M in hexane) was added thereto, followed by agitation at room temperature for 3 days. The solvent was removed under vacuum to obtain a blue liquid mixture. Since this mixture was under reduction of titanium, it was not oxidized or color-changed. The blue mixture was used as is without purification, as below.

(39) .sup.1H NMR (CDCl.sub.3, 500 MHz): 6.31 (br m, 8H), 3.5 (m, 4H), 1.1-1.9 (br m, 28H), 0.9 (br s, 18H), 0.3 (br s, 18H)

Synthesis Example 7: Preparation of Molecular Weight Modifier

(40) ##STR00034##

(41) 0.83 g of bis(cyclopentadienyl)-titanium dichloride and 50 mL of hexane were serially placed in a 250 mL round bottom flask, followed by agitation. 6 mL of triisobutyl aluminum (1 M in hexane) was added thereto, followed by agitation at room temperature for 3 days. The solvent was removed under vacuum to obtain a green mixture. Since this mixture was under reduction of titanium, it was not oxidized or color-changed. The green mixture was used as is without purification, as below.

(42) .sup.1H NMR (CDCl.sub.3, 500 MHz): 6.3-6.6 (br m, 10H), 1.2-1.8 (br m, 4H), 0.8 (br s, 18H)

Preparation Example of Supported Metallocene Catalyst

Example 1: Preparation of Supported Metallocene Catalyst

(43) First, silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was dehydrated under vacuum at 400 C. for 15 h.

(44) 49.7 mL of 10 wt % methylaluminoxane(MAO)/toluene solution was added to a glass reactor, and 9.1 g of silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was added thereto at 40 C., followed by agitation while raising the reactor temperature to 80 C. Thereafter, the temperature was maintained at 80 C., and 550 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 1 was dissolved in 20 mL of toluene and immediately added to the reactor, together with 53 mg (10 mol % of the precursor) of the molecular weight modifier prepared in Synthesis Example 4. After agitation for 2 h, 948 mg (0.12 mmol/g SiO.sub.2) of anilinium borate (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) previously dissolved in 20 mL of toluene was added in a solution state, followed by agitation at 40 C. for 2 h. After reaction was completed, agitation was stopped and a toluene layer was separated and removed. Remaining toluene was removed under reduced pressure at 40 C. to prepare a supported metallocene catalyst.

Examples 2 and 3: Preparation of Supported Metallocene Catalyst

(45) Supported metallocene catalysts were prepared in the same manner as in Example 1, except that the molecular weight modifier was added in an amount of 160 mg (30 mol %) and 270 mg (50 mol %) as shown in the following Table 1.

Example 4: Preparation of Supported Metallocene Catalyst

(46) A supported metallocene catalyst was prepared in the same manner as in Example 1, except that 465 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 2 was used as shown in the following Table 1.

Examples 5 and 6: Preparation of Supported Metallocene Catalyst

(47) Supported metallocene catalysts were prepared in the same manner as in Example 4, except that the molecular weight modifier was added in an amount of 160 mg (30 mol %) and 270 mg (50 mol %) as shown in the following Table 1.

Example 7: Preparation of Supported Metallocene Catalyst

(48) A supported metallocene catalyst was prepared in the same manner as in Example 1, except that 690 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 3 was used as shown in the following Table 1.

Examples 8 and 9: Preparation of Supported Metallocene Catalyst

(49) Supported metallocene catalysts were prepared in the same manner as in Example 7, except that the molecular weight modifier was added in an amount of 160 mg (30 mol %) and 270 mg (50 mol %) as shown in the following Table 1.

Example 10: Preparation of Supported Metallocene Catalyst

(50) First, silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was dehydrated under vacuum at 400 C. for 15 h.

(51) 49.7 mL of 10 wt % methylaluminoxane(MAO)/toluene solution was added to a glass reactor, and 9.1 g of silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was added thereto at 40 C., followed by agitation while raising the reactor temperature to 80 C. Thereafter, the temperature was maintained at 80 C., and 520 mg (0.075 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 3 was dissolved in 20 mL of toluene and immediately added to the reactor, together with 53 mg (10 mol % of the precursor) of the molecular weight modifier prepared in Synthesis Example 4. After agitation for 2 h, 550 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 1 was reacted at 40 C. for 2 h, and then 948 mg (0.12 mmol/g SiO.sub.2) of anilinium borate (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) previously dissolved in 20 mL of toluene was added in a solution state, followed by agitation at 40 C. for 2 h. After reaction was completed, agitation was stopped and a toluene layer was separated and removed. Remaining toluene was removed under reduced pressure at 40 C. to prepare a supported metallocene catalyst.

Examples 11 and 12: Preparation of Supported Metallocene Catalyst

(52) Supported metallocene catalysts were prepared in the same manner as in Example 10, except that the molecular weight modifier was added in an amount of 160 mg (30 mol %) and 270 mg (50 mol %) as shown in the following Table 1.

Comparative Example 1: Preparation of Supported Metallocene Catalyst

(53) First, silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was dehydrated under vacuum at 400 C. for 15 h. 49.7 mL of a 10 wt % methylaluminoxane(MAO)/toluene solution was added to a glass reactor, and 9.1 g of silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was added thereto at 40 C., followed by agitation while raising the reactor temperature to 80 C. Thereafter, the temperature was maintained at 80 C., and 550 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 1 was dissolved in 20 mL of toluene, and immediately added to the reactor. After agitation for 2 h, 948 mg (0.12 mmol/g SiO.sub.2) of anilinium borate (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) previously dissolved in 20 mL of toluene was added in a solution state, followed by agitation at 40 C. for 2 h. After reaction was completed, agitation was stopped and a toluene layer was separated and removed. Remaining toluene was removed under reduced pressure at 40 C. to prepare a supported metallocene catalyst.

Comparative Examples 2 to 3: Preparation of Supported Metallocene Catalyst

(54) Supported metallocene catalysts were prepared in the same manner as in Comparative Example 1, except that 465 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 2 and 690 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 3 were used, respectively, as shown in the following Table 1.

Comparative Example 4: Preparation of Supported Metallocene Catalyst

(55) First, silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was dehydrated under vacuum at 400 C. for 15 h.

(56) 49.7 mL of 10 wt % methylaluminoxane(MAO)/toluene solution was added to a glass reactor, and 9.1 g of silica (SYLOPOL 948 manufactured by Grace Davison, Co., Ltd.) was added thereto at 40 C., followed by agitation while raising the reactor temperature to 80 C. Thereafter, the temperature was maintained at 80 C., and 520 mg (0.075 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 3 was dissolved in 20 mL of toluene, and added to the reactor, followed by agitation for 2 h. 550 mg (0.1 mmol/g SiO.sub.2) of the catalyst precursor prepared in Synthesis Example 1 was reacted at 40 C. for 2 h. Then, 948 mg (0.12 mmol/g SiO.sub.2) of anilinium borate (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) previously dissolved in 20 mL of toluene was added in a solution state, followed by agitation at 40 C. for 2 h. After reaction was completed, agitation was stopped and a toluene layer was separated and removed. Remaining toluene was removed under reduced pressure at 40 C. to prepare a supported metallocene catalyst.

Polymerization ExamplePolymerization Example 1

(57) 400 mL of hexane was added to an argon-filled closed system using a Parr reactor. Then, 1 g of trimethylaluminum was added to dry the inside of the reactor, and the hexane was discarded. The reactor was filled with 400 mL of hexane, and then 0.5 g of triisobutylaluminum was added thereto. 10 mg of the supported catalyst prepared in Example 1 was weighed in an argon-filled glove box, and added to the reactor. Then, argon was vented, and then polymerization was performed under ethylene pressure of 30 bar at 78 C. for 1 h.

Polymerization ExamplePolymerization Examples 2 to 12

(58) Slurry polymerization was performed in the same manner as in Polymerization ExamplePolymerization Example 1, except that each of the supported catalysts prepared in Examples 2 to 12 was used, as shown in the following Table 1.

Comparative Polymerization ExamplePolymerization Examples 1 to 4

(59) Slurry polymerization was performed in the same manner as in Polymerization ExamplePolymerization Example 1, except that each of the supported catalysts prepared in Comparative Examples 1 to 4 was used, as shown in the following Table 1.

Comparative Polymerization ExamplePolymerization Examples 5 to 8

(60) Slurry polymerization was performed in the same manner as in Polymerization ExamplePolymerization Example 1, except that each of the supported catalysts prepared in Comparative Examples 1 to 4 was used, and 1.5 mg (0.6 mmol/g SiO.sub.2) of the molecular weight modifier prepared in Synthesis Example 4 was further added to the reactor, as shown in the following Table 1.

Experimental Example

Experimental Example for Evaluation of Physical Properties of Polymers

(61) Properties of the polyethylenes prepared in Polymerization ExamplePolymerization Examples 1 to 12 and Comparative Polymerization ExamplePolymerization Examples 1 to 4 were measured by the following methods, and the results are shown in the following Table 1.

(62) a) Molecular weight (Mw): Molecular weight was determined as a weight average molecular weight by using gel permeation chromatography (GPC).

(63) b) Molecular weight distribution (PDI): Molecular weight distribution was determined as a value obtained by dividing the weight average molecular weight by the number average molecular weight by using gel permeation chromatography (GPC).

(64) c) Catalytic activity (Activity): 0.5 g of TMA was dried in a reactor, and about 100 mg of the supported catalyst was added to 400 mL of hexane, together with alkyl aluminum and the molecular weight modifier (MWE). Polymerization was performed at 80 C. under ethylene pressure of 9 bar for 1 h to obtain a polymer. The polymer was filtered and dried overnight, and then weighed to calculate the catalytic activity per unit time (h).

(65) TABLE-US-00001 TABLE 1 Feed amount of MWE Activity Polymerization Catalyst (mol %) (gPE/gCat/h) Mw PDI Polymerization Supported Support/ 10* 10.4 128,000 2.2 Example 1 catalyst catalyst slurry precursor polymerization 1/soluble MWE Polymerization Supported Support/ 30* 10.1 252,000 2.5 Example 2 catalyst catalyst slurry precursor polymerization 1/soluble MWE Polymerization Supported Support/ 50* 9.8 281,000 2.4 Example 3 catalyst catalyst slurry precursor polymerization 1/soluble MWE Polymerization Supported Support/ 10* 2.6 594,000 2.4 Example 4 catalyst catalyst slurry precursor polymerization 2/soluble MWE Polymerization Supported Support/ 30* 2.3 660,000 2.3 Example 5 catalyst catalyst slurry precursor polymerization 2/soluble MWE Polymerization Supported Support/ 50* 1.8 780,000 2.3 Example 6 catalyst catalyst slurry precursor polymerization 2/soluble MWE Polymerization Supported Support/ 10* 2.3 791,000 3.4 Example 7 catalyst catalyst slurry precursor polymerization 3/soluble MWE Polymerization Supported Support/ 30* 2.0 972,000 3.1 Example 8 catalyst catalyst slurry precursor polymerization 3/soluble MWE Polymerization Supported Support/ 50* 1.5 1,020,900 3.1 Example 9 catalyst catalyst slurry precursor polymerization 3/soluble MWE Polymerization Supported Support/ 10* 11.6 273,000 3.4 Example 10 catalyst catalyst slurry precursor polymerization 1(0.1) + 3(0.075)/ soluble MWE Polymerization Supported Support/ 30* 11.3 318,000 3.9 Example 11 catalyst catalyst slurry precursor polymerization 1(0.1) + 3(0.075)/ soluble MWE Polymerization Supported Support/ 50* 11.5 298,000 3.3 Example 12 catalyst catalyst slurry precursor polymerization 1(0.1) + 3(0.075)/ soluble MWE Comparative Supported Support/ 10.1 103,100 2.1 Polymerization catalyst catalyst Example 1 slurry precursor polymerization 1 Comparative Supported Support/ 2.8 553,000 2.5 Polymerization catalyst catalyst Example 2 slurry precursor polymerization 2 Comparative Supported Support/ 2.3 693,000 3.6 Polymerization catalyst catalyst Example 3 slurry precursor polymerization 3 Comparative Supported Support/ 11.1 263,000 3.6 Polymerization catalyst catalyst Example 4 slurry precursor polymerization 1(0.1) + 3(0.075) Comparative Supported Support/ 600** 6.3 228,000 2.2 Polymerization catalyst catalyst Example 5 slurry precursor polymerization 1 Comparative Supported Support/ 600** 1.3 710,000 2.3 Polymerization catalyst catalyst Example 6 slurry precursor polymerization 2 Comparative Supported Support/ 600** 1.0 730,000 3.4 Polymerization catalyst catalyst Example 7 slurry precursor polymerization 3 Comparative Supported Support/ 600** 7.3 293,000 3.2 Polymerization catalyst catalyst Example 8 slurry precursor polymerization 1(0.1) + 3(0.075 *Polymerization Examples 1 to 12: the molecular weight modifier supported on the support was used. **Comparative Polymerization Examples 5 to 8: soluble MWE as the molecular weight modifier was injected in an amount of 6 equivalent weights with respect to the precursor during the polymerization process

(66) Further, a graph showing molecular weight distributions of the polymers which were polymerized by using the supported metallocene catalysts prepared according to Examples 10 to 12 and Comparative Example 4 is shown in FIG. 1 (brown: Polymerization Example 10, red: Polymerization Example 11, purple: Polymerization Example 12, blue: Comparative Polymerization Example 4). A graph showing molecular weight distributions of the polymers which were polymerized by using the supported metallocene catalysts prepared according to Comparative Example 3 and Example 8 is shown in FIG. 2 (red: Polymerization Example 8, green: Comparative Polymerization Example 3). A graph showing molecular weight distributions of the polymers which were polymerized by using supported metallocene catalysts prepared in Comparative Example 2 and Example 5 is shown in FIG. 3 (red: Polymerization Example 5, blue: Comparative Polymerization Example 2). Here, the x axis represents dlogwf/dlogM and the y axis represents logM, and the vertical axis represents the intensity axis of the polymer and the horizontal axis represents the molecular weight axis of the polymer.

(67) According to the graphs of the molecular weight distributions of the polymers, the present invention shows a little fluctuation in activity, compared to the prior technology. Also, it shows that the range of variation of the molecular weight depends on the amount of the modifier, indicating that the technology of the present invention enables fine control upon preparation of supported catalysts. Particularly, according to FIG. 2, when the existing molecular weight modifier was added during polymerization, the activity was greatly reduced and the molecular weight was not greatly increased. In contrast, when the catalyst was supported, increases of the molecular weight and activity were maintained to some degree. Further, as the molecular weight modifier varies, the peak of a molecular weight distribution graph moved toward the area of a high molecular weight polymer, and the shape of a molecular weight distribution graph is changed from a bimodal molecular weight distribution to a narrow unimodal molecular weight distribution. The shape of a narrow unimodal molecular weight distribution indicates that polymers having good physical properties were prepared, because the molecular weight distribution changes such that polymer elasticity being considered important in blow molding is increased to improve swell.

(68) As shown in Table 1, the present invention may provide an effect of increasing a molecular weight of a polymer without a reduction in its activity or copolymerization property during olefin polymerization. Particularly, when an excessive amount of a molecular weight modifier is used, unreacted modifiers may enter a reactor again during a recovery process to cause a disruption of a polymerization, in some cases. In this case, an undesired polymerization process may occur to destabilize the process, and therefore injection of the molecular weight modifier into the reactor is not a commercially suitable method.

(69) Moreover, as in Comparative Polymerization Examples 5 to 8, use of the molecular weight modifier during the polymerization process is not desirable in terms of reaction efficiency. In actual plants for mass-production, raw materials are reacted through recycling, and unreacted molecular weight modifiers unintentionally act on other reaction processes, resulting in undesired polymerization processes. That is, since the molecular weight modifier injected during the polymerization may cause instability in the entire polymerization process, it may cause instability in the actual large-scale system, even though the molecular weight control effect may be obtained at an experimental level. To solve these problems, in the present invention, the molecular weight modifier was used in a catalytic amount relative to the precursor, and thus the present invention is advantageous in that there are few side effects caused by the molecular weight modifier when actually applied to plants.