Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
SUPPORTED MULTINUCLEAR METALLOCENE CATALYST FOR OLEFIN POLYMERIZATION AND METHOD FOR PREPARING THE SAME
Document Type and Number:
WIPO Patent Application WO/2004/076502
Kind Code:
A1
Abstract:
The present invention relates to a supported nultinuclear metallocene catalyst for olefin polymerization that comprises (A) a dinuclear metallocene catalyst, (B) a mononuclear metallocene catalyst, (C) an activator for activating the catalysts, and (D) a support. More particularly, the multinuclear metallocene catalyst has at least three active sites in the support and allows the control of molecular weight distribution of the polymer while varying the combination of catalysts in the reactor during olefin polymerization.

Inventors:
CHO HAN-SEOCK (KR)
YOON SEUNG-WOONG (KR)
CHOI KEE-HO (KR)
YOON BO-SANG (KR)
KIM SEONG-KYUN (KR)
HAN YONG-GYU (KR)
PARK SUNG-JIN (KR)
LEE JUN-SEONG (KR)
DO YOUNG-KYU (KR)
Application Number:
PCT/KR2003/001673
Publication Date:
September 10, 2004
Filing Date:
August 20, 2003
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
HONAM PETROCHEMICAL CORP (KR)
CHO HAN-SEOCK (KR)
YOON SEUNG-WOONG (KR)
CHOI KEE-HO (KR)
YOON BO-SANG (KR)
KIM SEONG-KYUN (KR)
HAN YONG-GYU (KR)
PARK SUNG-JIN (KR)
LEE JUN-SEONG (KR)
DO YOUNG-KYU (KR)
International Classes:
C08F4/64; C08F4/02; C08F4/642; C08F110/02; C08F4/659; C08F4/6592; C08F210/16; (IPC1-7): C08F10/00; C07F17/00; C08F4/02; C08F4/642
Domestic Patent References:
WO2002060964A12002-08-08
Attorney, Agent or Firm:
Kim, Nung-kyun (6Fl. Taekun Bldg., 822-5, Yoksam-don, Kangnam-ku Seoul 135-080, KR)
Download PDF:
Claims:
What is claimed is:
1. A supported multinuclear metallocene catalyst for olefin polymerization comprising: (A) a dinuclear metallocene catalyst, (B) a mononuclear metallocene catalyst, (C) an activator for activating the catalysts, and (D) a support.
2. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 1, wherein the dinuclear metallocene catalyst (A) is a transition metal compound represented by the following formula 1 and having at least two metals in the groups III to X of the periodic table as a central metal, the two metals being bound to a ligand having a cyclopentadienyl skeleton: Formula 1 wherein Ml and M2 are the same or different and include an element in the groups III to X of the periodic table; Cpl and Cp2 are the same or different and include a ligand having a cyclopentadienyl skeleton with or without a substituent, the cyclopentadienyl ligand being cyclopentadienyl, indenyl, or fluorenyl, the substituent of the cyclopentadienyl ligand being ClC20 alkyl, cycloalkyl, alkylsilyl or haloalkyl, C6C20 aryl, arylalkyl, arylsilyl or alkylaryl, ClC20 alkoxy or alkylsiloxy, CgCzo aryloxy, halogen, or amino group, the alkyl moiety being an alkyl chain or an alkyl branch, wherein if there are at least two substituents, the ligand forms a ring through a bonding between the substituents; Bl is a divalent hydrocarbyl radical as a bridging group between Cpl and Cp2 bounded to the central metal, the divalent hydrocarbyl radical being an arylene group represented by the following formula 2, Bl being an arylene group containing ClC20 alkylene, C3C20 cycloalkylene, alkylsilylene or haloalkylene, or C6C20 arylalkylene, arylsilylene or alkylarylene bound between C4C5o arylene or allylene groups: Formula 2 Ary (B Ary wherein Ary is an arylene group directly bonded to Cpl and Cp2 ; B1'is an arylene bridging group and including ClC20 alkylene, C3C20 cycloalkylene, alkylsilylene or haloalkylene, or C6C20 arylalkylene or arylsilylene; and q is an integer from 0 to 5; X and Y are the same or different and include Cpl or Cp2, ClC20 alkyl, cycloalkyl, alkylsilyl or haloalkyl, C6C20 aryl, arylalkyl, arylsilyl or alkylaryl, ClC20 alkoxy or alkylsiloxy, C6C20 aryloxy, halogen, amino, or tetrahydroborate, the alkyl moiety including a chain alkyl or a branch alkyl, the number of halogens bonded to the central metal being dependent upon the oxidation state of the central metal; a and b are an integer from 1 to 5 depending upon the oxidation state of the central metal; and p is an integer from 1,2 or 3, wherein for p = 1, the transition metal compound is a dinuclear transition metal compound with a Bl bridge ; and for p = 2, the transition metal compound is a trinuclear transition metal compound with one more Bl bridge to Cp2.
3. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 1, wherein the mononuclear metallocene catalyst (B) is a transition metal compound as a component coimpregnated with the component (A), the transition metal compound being represented by the following formula 3 and containing one metal in the groups III to X of the periodic table as a central metal, the central metal being bound to a ligand having a cyclopentadienyl skeleton: Formula 3 Cp*aMX'b'Y'c' wherein Cp* is a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl ligand being the same or different and including a pibonding ligand selected from cyclopentadienyl, indenyl, fluorenyl, or derivatives thereof, the ligand being a derivative containing a substituent including ClC2o alkyl, alkylsilyl, alkoxy or alkylsiloxy, wherein for a'of 2 or the greater, the transition metal compound containing silicon (Si) or ClClo alkylene bound between the Cp* ligands; M is a transition metal in the group IV, V or VI of the periodic table, including zirconium (Zr), titanium (Ti) or hafnium (Hf) ; X'and Y' are the same or different and include halogen, hydrogen, or alkyl ; a'is an integer of 1, 2 or 3; and b'and c'are an integer of 1,2 or 3, wherein a'+ b'+ c'is equal to the oxidation state of the transition metal M.
4. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 1, wherein the activator (C) is a compound represented by the following formula 4,5 or 6: Formula 4 wherein Rl is ClClo alkyl ; and n is an integer from 1 to 70, Formula 5 wherein R2, R3 and R4 are the same or different and include ClClo alkyl, alkoxy or halide, and at least one of R2, R3 and R4 is an alkyl group, Formula 6 [E] [F] wherein E is a cation bonded to the proton of a Lewis base, or an oxidative metal or nonmetal compound; and F is a compound of an element in the groups V to XV of the periodic table and an organic substance.
5. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 1, wherein the support (D) is a substance supporting the components (A), (B) and (C) and includes at least one selected from the group consisting of porous fine particles, inorganic substances such as inorganic oxides or inorganic chlorides, resinous substances such as polymers, or organic substances.
6. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein Ml and M2 include an element in the group IV of the periodic table, such as zirconium (Zr), titanium (Ti), or hafnium (Hf).
7. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein the ClC20 alkyl, cycloalkyl, alkylsilyl or haloalkyl group used as a substituent of the cyclopentadienyl ligand of Cpl and Cp2 includes methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, propylsilyl, dipropylsilyl, tripropylsilyl, butylsilyl, dibutylsilyl, tributylsilyl, or trifluoromethyl; the C6C20 aryl, arylalkyl, arylsilyl or alkylaryl group includes phenyl, biphenyl, terphenyl, naphtyl, fluorenyl, benzyl, phenylethyl, phenylpropyl, phenylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl, or tripropylphenyl ; the ClC20 alkoxy or alkylsiloxy group includes methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, methylsiloxy, dimethylsiloxy, trimethylsiloxy, ethylsiloxy, diethylsiloxy, or triethylsiloxy; the C6C20 aryloxy group includes phenoxy, naphtoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy, or tripropylphenoxy; the halogen group includes fluoro group, chloro group, bromo group, or iodo group; and the amino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, or dibenzylamino group.
8. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein the arylene group constituting Bl includes phenylene, biphenylene, terphenylene, naphtylene, binaphtylene, fluorenylene, anthracylene, pyridylene, bipyridylene, terpyridylene, quinolylene, pyridazylene, pyrimidylene, pyrazylene, or quinoxalylene.
9. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein theClC20 alkylene, C3C20 cycloalkylene, alkylsilylene or haloalkylene, or C6C20 arylalkylene or arylsilylene corresponding to Bl' include methylene, dimethylmethylene, diethyhnethylene, diphenylmethylene, ethylene, methylethylene, dimethylethylene, trimethylethylene, tetramethyl ethylene, tetraethylethylene, tetraphenylethylene, propylene, butylene, dimethylsilylene, diethylsilylene, diophenylsilylene, cyclohexylene, or tetrafluoroethylene.
10. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein at least either one of X and Y includes cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, diethylcyclopentadienyl, triethylcyclopentadienyl, n propylcyclopentadienyl, nbutylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, trimethylindenyl, ethylindenyl, diethylindenyl, triethylindenyl, phenoxy, naphtoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy, tripropylphenoxy, fluoro, chloro, bromo, or iodo group.
11. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein Cpl or Cp2 includes cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, diethylcyclopentadienyl, triethylcyclopentadienyl, npropylcyclopentadienyl, nbutylcyclopentadienyl, methylindenyl, dimethylndenyl, trimethylindenyl, ethylindenyl, diethylindenyl, or triethylindenyl.
12. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 2, wherein Bl includes phenylene, biphenylene,Ph <BR> <BR> <BR> <BR> <BR> CH2Ph,PhCH2CH2Ph,PhCH2CH2CH2Ph,PhCH2CH2CH2CH2Ph, terphenylene, anthracylene, or pyridylene.
13. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 4, wherein the compound represented by the formula 4 includes methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, or decylaluminoxane.
14. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 4, wherein the compound represented by the formula 5 includes trialkylaluminum such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or tridecylaluminum; dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum methoxide, or dibutylaluminum methoxide; dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, or dibutylaluminum chloride; alkylaluminum dialkoxide such as methylaluminum dimethoxide, ethylaluminum dimethoxide, or butylaluminum dimethoxide ; or alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, or butylaluminum dichloride.
15. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 4, wherein the compound represented by the formula 6 includes trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro phenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, tris (2,3, 5,6tetrafluorophenyl) borane, tris (2,3, 4,5tetraphenylphenyl) borane, or tris (3,4, 5 trifluorophenyl) borane.
16. The supported multinuclear metallocene catalyst for olefin polymerization as claimed in claim 5, wherein the support includes a porous substance having a surface area of 100 to 700 m2/g, a total porosity volume of 0.1 to 5.0 cc/g, an average particle size of 10 to 200 jjm, and an average porosity size of 50 to 500 A.
17. A synthesis method for a supported multinuclear metallocene catalyst, comprising: supporting (A) a dinuclear metallocene catalyst, (B) a mononuclear metallocene catalyst, and (C) an activator for activating the catalysts on (D) a support in the presence of a solvent at a temperature of80 to 150 °C.
18. The synthesis method as claimed in claim 17, wherein the solvent includes at least one selected from the group consisting of aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, undecane, or dodecane; aromatic hydrocarbons such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, or toluene; and halogenated aliphatic hydrocarbons such as dichloromethane, trichloromethane, dichloroethane, or trichloroethane.
19. The synthesis method as claimed in claim 17, wherein the molar ratio of transition metal in the catalyst (C) to transition metal in the catalysts (A) and (B), i. e., [moles of transition metal in (C) ] : [moles of transition metal in (A) + moles of transition metal in (B) ] is 1: 1 to 1000: 1.
20. An olefin polymerization method comprising: performing a slurry or gas phase polymerization reaction in the temperature range of50 to 200 °C at 1 to 1000 atom for 1 to 24 hours using the supported multinuclear metallocene catalyst according to claims 1 to 16.
Description:
SUPPORTED MULTINUCLEAR METALLOCENE CATALYST FOR OLEFIN POLYMERIZATION AND METHOD FOR PREPARING THE SAME Technical Field The present invention relates to a supported multinuclear metallocene catalyst for olefin polymerization that comprises (A) a dinuclear metallocene catalyst, (B) a mononuclear metallocene catalyst, (C) an activator for activating the catalysts, and (D) a support. More particularly, the multinuclear metallocene catalyst has at least three active sites in the support and allows the control of molecular weight distribution of the polymer with respect to the variation of catalyst combinations in olefin polymerization.

Background Art Since the development of the Ziegler-Natta catalyst as a polyolefin polymerization catalyst in the middle of the 1950's, polyethylene, isotactic polypropylene, EPDM (Ethylene Propylene Diene Copolymer), or the like with different properties have been polymerized. But the Ziegler-Natta catalyst hardly achieves the synthesis of polymers having a narrow molecular weight distribution (MWD) and a uniform compositional distribution due to its non-uniform active sites.

As a solution of this problem, the use of the metallocene catalyst developed since the early years of the 1980's provides polymers having a molecular weight distribution and a uniform compositional distribution, and polymers with different properties such as syndiotactic polypropylene, syndiotactic polystyrene, etc. that cannot be prepared with the Ziegler-Natta catalyst. The polymers synthesized by the metallocene catalyst have a narrow molecular weight distribution and a uniform compositional distribution, with higher strength, transparency and environmental resistance than the polymers synthesized

by the Ziegler-Natta catalyst. The fabrication of products such as films or sheets from those polymers prepared using the metallocene catalyst may reduce stickiness but deteriorates formability during a processing because of the narrow molecular weight distribution.

There are many approaches to the solution of the problem in regard to the narrow molecular weight distribution of the polymers synthesized using the metallocene catalyst.

One approach is blending polymers synthesized from the transition metal catalysts in different reactors. In this case, the molecular weight and the molecular weight distribution are readily controllable according to the blending ratio of the polymers, but a problem with the miscibility of the blended polymers is caused. Another approach is introducing polymerization parameters such as pressure or temperature in the continuous reactor to control the molecular weight distribution. This method requires expenses for regulation parameters for the polymerization reactor and additional equipment. And, a third approach is using the catalyst in one reactor to control the molecular weight distribution, which method is simple and low in cost relative to the above-mentioned two methods but requires the technique of the catalyst.

More specifically, U. S. Patent No. 4,703, 094 discloses a method of using a series reactor for the control of the molecular weight distribution that involves polymerization without hydrogen partial pressure in the one reactor, and using an excess of hydrogen to control the molecular weight distribution of the polymer in the other reactor.

Disadvantageously, this method requires an expense for additional equipment and an excessively large amount of fuel and has the difficulty in operation.

U. S. Patent No. 5,032, 562 discloses a method of preparing a polymerization catalyst by supporting two different transition metal catalysts on one support catalyst. This method is for supporting a Ti-based Ziegler-Natta catalyst for a relatively high molecular

weight and a Zr-based metallocene catalyst for a low molecular weight on one support to synthesize a bimodal distribution polymer. But, this method requires a complicated and troublesome process of supporting the metallocene catalyst and causes a deterioration of the polymer morphology due to the use of methyl aluminoxane (MAO) as a cocatalyst.

U. S. Patent No. 5,525, 678 discloses a method of using a catalyst system for olefin polymerization that comprises both a metallocene compound and a non-metallocene compound supported on a support to polymerize a polymer having a high molecular weight and a polymer having a low molecular weight at the same time. This method has a need for supporting the metallocene compound and the non-metallocene compound independently and pre-treating the support with various compounds to support the compounds.

In addition, U. S. Patent No. 5,914, 289 discloses a method of using metallocene catalysts supported on the individual supports to control the molecular weight and the molecular weight distribution of the polymer produced, which method requires an excessively large amount of the solvent and too much time in the synthesis of the supported catalyst, with a need for supporting the respective metallocene catalysts on the supports.

To solve these problems, many studies have been made on the catalysts that allow the control of molecular weight and molecular weight distribution in a slurry polymerization process or a gas phase polymerization process, and have a high catalytic activity for polymerization. As a result, the inventors of this invention have figured out that the molecular weight distribution can be controlled by preparing a novel supported multinuclear metallocene catalyst and varying the combination of catalysts, and finally contrived the present invention.

It is therefore an object of the present invention to provide a supported

multinuclear metallocene catalyst that allows the control of molecular weight and molecular weight distribution in a slurry polymerization process or a gas phase polymerization process.

It is another object of the present invention to provide a method for preparing an olefin polymer excellent in properties with different process parameters such as temperature, pressure, partial pressure of hydrogen, monomers for copolymerization, etc. in the presence of the supported multinuclear metallocene catalyst.

It is further another object of the present invention to provide a method for preparing the novel supported multinuclear metallocene catalyst for olefin polymerization.

Disclosure of Invention To achieve the objects of the present invention, there is provided a supported multinuclear metallocene catalyst for olefin polymerization that includes (A) a dinuclear metallocene catalyst, (B) a mononuclear metallocene catalyst, (C) an activator for activating the catalysts, and (D) a support.

Hereinafter, the present invention will be described in detail.

The supported multinuclear metallocene catalyst for olefin polymerization according to the present invention is largely comprised of two different metallocene catalysts and a cocatalyst (i. e. , activator) for activating the catalysts. Out of the two different transition metal catalysts, the one is a dinuclear metallocene catalyst used for producing a relatively high molecular weight and sensitive to the partial pressure of hydrogen among the parameters of polymerization. The other is a mononuclear metallocene catalyst used for producing a lower molecular weight and less sensitive to the partial pressure of hydrogen than the dinuclear metallocene catalyst.

The supported multinuclear metallocene catalyst for olefin polymerization according to the present invention is comprised of the components (A) to (D) as follows.

(A) The dinuclear metallocene catalyst is a transition metal compound having at least two metals in the groups III to X of the periodic table as a central metal. The two metals are bound to a ligand having a cyclopentadienyl skeleton.

(B) The mononuclear metallocene catalyst is a transition metal compound having one metal in the groups III to X of the periodic table as a central metal. The central metal is bound to a ligand having a cyclopentadienyl skeleton.

(C) The activator for activating the catalysts is an oligomer or bulky compound that is reactive to an aluminoxane compound, an organoaluminum compound or a transition metal compound to make the transition metal compound cationic and activated.

(D) The support is for supporting the components (A), (B) and (C).

Hereinafter, the constituent components (A) to (D) of the supported multinuclear metallocene catalyst for olefin polymerization according to the present invention will be described in further detail.

(A) Dinuclear Metallocene Catalyst In the supported multinuclear metallocene catalyst for olefin polymerization according to the present invention, the component (A) has a structure of the following formula 1.

Formula 1 In the formula, Ml and M2 are the same or different and include an element in the groups III to X of the periodic table, preferably an element in the group IV of the periodic table, more preferably zirconium (Zr), titanium (Ti), or hafnium (Hf). Cpl and Cp2 are the same or different and include a ligand having a cyclopentadienyl skeleton with or without

a substituent.

The cyclopentadienyl ligand includes cyclopentadienyl, indenyl, or fluorenyl. The substituent of the cyclopentadienyl ligand includes Cl-C20 alkyl, cycloalkyl, alkylsilyl or haloalkyl, C6-C20 aryl, arylalkyl, arylsilyl or alkylaryl, Cl-C20 alkoxy or alkylsiloxy, C6- C20 aryloxy, halogen, or amino group. The alkyl moiety can be an alkyl chain or an alkyl branch. If there are at least two substituents, the ligand forms a ring through a bonding between the substituents.

More specifically, the Cl-C20 alkyl, cycloalkyl, alkylsilyl or haloalkyl group includes methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, propylsilyl, dipropylsilyl, tripropylsilyl, butylsilyl, dibutylsilyl, tributylsilyl, or trifluoromethyl. The C6-C2o aryl, arylalkyl, arylsilyl or alkylaryl group includes phenyl, biphenyl, terphenyl, naphtyl, fluorenyl, benzyl, phenylethyl, phenylpropyl, phenylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl, or tripropylphenyl.

The Cl-C20 alkoxy or alkylsiloxy group includes methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, methylsiloxy, dimethylsiloxy, trimethylsiloxy, ethylsiloxy, diethylsiloxy, or triethylsiloxy. The C6-C20 aryloxy group includes phenoxy, naphtoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy, or tripropylphenoxy. The halogen group includes fluoro group, chloro group, bromo group, or iodo group. The amino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, or dibenzylamino group.

Preferably, the cyclopentadienyl ligand includes cyclopentadienyl,

methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, diethylcyclopentadienyl, triethylcyclopentadienyl, n-propylcyclopentadienyl, n-butylcyclopentadienyl, methylindenyl, dimethylindenyl, trimethylindenyl, ethylindenyl, diethylindenyl, or triethylindenyl.

In the formula 1, Bl is a divalent hydrocarbyl radical as a bridging group between Cpl and Cp2 bounded to the central metal. Bl is an arylene group containing Cl-C20 alkylene, C3-C20 cycloalkylene, alkylsilylene or haloalkylene, or C6-C20 arylalkylene, arylsilylene or alkylarylene bound between C5-C40 arylene or allylene groups, and represented by the following formula 2.

Formula 2 Ary- (B') qAry In the formula 2, Ary is an arylene group directly bonded to Cpl and Cp2 ; B1'is an arylene-bridging group and including Cl-C20 alkylene, C3-C20 cycloalkylene, alkylsilylene or haloalkylene, or C6-C20 arylalkylene or arylsilylene; and q is an integer from 0 to 5.

The arylene group includes phenylene, biphenylene, terphenylene, naphtylene, binaphtylene, fluorenylene, anthracylene, pyridylene, bipyridylene, terpyridylene, quinolylene, pyridazylene, pyrimidylene, pyrazylene, or quinoxalylene. The specific examples of B 1'include methylene, dimethylmethylene, diethylmethylene, diphenylmethylene, ethylene, methylethylene, dimethylethylene, trimethylethylene, tetramethyl ethylene, tetraethylethylene, tetraphenylethylene, propylene, butylene, dimethylsilylene, diethylsilylene, diophenylsilylene, cyclohexylene, or tetrafluoroethylene.

Preferably, Bl includes phenylene, biphenylene,-Ph-CH2-Ph-,-Ph-CH2CH2-Ph-,- Ph-CH2CH2CH2-Ph-,-Ph-CH2CH2CH2CH2-Ph-, terphenylene, anthracylene, or pyridylene.

In the formula 1, X and Y are the same or different and include Cpl or Cp2, Cl-C2o alkyl, cycloalkyl, alkylsilyl or haloalkyl, C6-C20 aryl, arylalkyl, arylsilyl or alkylaryl, Cl- C2o alkoxy or alkylsiloxy, C6-C20 aryloxy, halogen, amino, or tetrahydroborate. The alkyl moiety can be a chain alkyl or a branch alkyl. Preferably, X and Y include Cpl or Cp2, C6- 20 aryloxy, or halogen. More preferably, at least either one of X and Y includes cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, diethylcyclopentadienyl, triethylcyclopentadienyl, n- propylcyclopentadienyl, n-butylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, trimethylindenyl, ethylindenyl, diethylindenyl, triethylindenyl, phenoxy, naphtoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy, tripropylphenoxy, fluoro, chloro, bromo, or iodo group. Here, the number of halogens bonded to the central metal is dependent upon the oxidation state of the central metal. a and b are an integer from 1 to 5 depending upon the oxidation state of the central metal. p is an integer from 1, 2 or 3. For p = 1, the transition metal compound is a dinuclear transition metal compound with a Bl bridge. For p = 2, the transition metal compound is a trinuclear transition metal compound with one more Bl bridge to Cp2.

Preferably, p is 1.

(B) Mononuclear Metallocene Catalyst In the supported multinuclear metallocene catalyst for olefin polymerization according to the present invention, the component (B) coimpregnated with the dinuclear metallocene catalyst (A) is a mononuclear metallocene catalyst represented by the following formula 3.

Formula 3

Cp*a-MX MX'b-Y'..

In the formula 3, Cp* is a ligand having a cyclopentadienyl skeleton. The Cp* ligands are the same or different and include a pi-bonding ligand selected from cyclopentadienyl, indenyl, fluorenyl, or derivatives thereof. The Cp* ligand is a derivative containing a substituent including Cl-C20 alkyl, alkylsilyl, alkoxy or alkylsiloxy. For a'of 2 or the greater, the transition metal compound contains silicon (Si) or Cl-Coo alkylene bound between the Cp* ligands. M is a transition metal in the group IV, V or VI of the periodic table, including zirconium (Zr), titanium (Ti) or hafnium (Hf). X'and Y'are the same or different and include halogen, hydrogen, or alkyl. a'is an integer of 1,2 or 3. b' and c'are an integer of 1,2 or 3, where a'+ b'+ c'is equal to the oxidation state of the transition metal M.

The preferred mononuclear metallocene catalyst as used in the present invention is as follows.

The specific examples of the mononuclear metallocene catalyst include bis cyclopentadienyl zirconium dichloride, bis cyclopentadienyl zirconium dibromide, bis cyclopentadienyl methyl zirconium monochloride, bis cyclopentadienyl ethyl zirconium monochloride, bis cyclopentadienyl dimethyl zirconium, bis cyclopentadienyl titanium dichloride, bis cyclopentadienyl titanium dibromide, bis cyclopentadienyl methyl titanium monochloride, bis cyclopentadienyl ethyl titanium monochloride, bis cyclopentadienyl dimethyl titanium, bis cyclopentadienyl hafnium dichloride, bis cyclopentadienyl hafnium dibromide, bis cyclopentadienyl methyl hafnium monochloride, bis cyclopentadienylethyl hafnium monochloride, bis cyclopentadienyl dimethyl hafnium, bis indenyl zirconium dichloride, bis indenyl zirconium dibromide, bis indenyl dimethyl zirconium, bis indenyl diphenyl zirconium, or bis indenyl methyl zirconium monochloride. The more preferable

catalyst is a metallocene catalyst containing zirconium (Zr) as a central metal.

(C ! Activator In the supported multinuclear metallocene catalyst for olefin polymerization according to the present invention, the component (C) is an activator for activating the catalysts and represented by the following formula 4,5 or 6.

Formula 4

where Rl is Cl-Clo alkyl ; and n is an integer from 1 to 70.

Formula 5 where R2, R3 and R4 are the same or different and include C1-C10 alkyl, alkoxy or halide, and at least one of R2, R3 and iEt4 is an alkyl group.

Formula 6 [E][F] where E is a cation bonded to the proton of a Lewis base, or an oxidative metal or nonmetal compound; and F is a compound of an element in the groups V to XV of the periodic table and an organic substance.

In the formula 6, without E, F is a compound exhibiting the property of a Lewis acid.

The compound of the formula 4 is of a chain, cyclic or network structure and specifically includes methylaluminoxane, ethylaluminoxane, butylaluminoxane,

hexylaluminoxane, octylaluminoxane, or decylaluminoxane.

The specific examples of the compound of the formula 5 include trialkylaluminum such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or tridecylaluminum; dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum methoxide, or dibutylaluminum methoxide; dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, or dibutylaluminum chloride; alkylaluminum dialkoxide such as methylaluminum dimethoxide, ethylaluminum dimethoxide, or butylaluminum dimethoxide; or alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, or butylaluminum dichloride.

The specific examples of the compound of the formula 6 include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro phenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, tris (2,3, 5,6-tetrafluorophenyl) borane, tris (2,3, 4,5-tetraphenylphenyl) borane, or tris (3,4, 5- trifluorophenyl) borane.

The component (C) is not specifically limited to the compound represented by the formula 4,5 or 6, and may used alone or in combination in the polymerization reaction.

(D ! Support In the supported multinuclear metallocene catalyst for olefin polymerization

according to the present invention, the component (D) as a support for supporting the components (A) to (C) can be porous fine particles, inorganic substances such as inorganic oxides or inorganic chlorides, resinous substances such as polymers, or organic substances.

The preferred substance for the support is porous inorganic oxides, which contain substances obtained from the oxides of a metal in the groups II, III, IV, V, XIII or XIV of the periodic table. The more preferred substance for the support is silica (Si02), alumina (A1203), silica-alumina (Si02-A1203), or a mixture of them.

The preferred support is a porous silica having a surface area of 100 to 700 m2/g, a total porosity volume of 0.1 to 5.0 cc/g, an average particle size of 10 to 200 um, and an average porosity size of 50 to 500 A. The more preferred support is a porous silica having a surface area of 200 to 500 m2/g, a total porosity volume of 1.0 to 3.0 cc/g, an average particle size of 20 to 80 jj. m, and an average porosity size of 80 to 400 A.

The supported multinuclear metallocene catalyst for olefin polymerization according to the present invention is prepared from the components (A) to (C) supported on the support of the component (D). Next, the synthesis method of the supported multinuclear metallocene catalyst will be described as follows.

The synthesis method of the supported multinuclear metallocene catalyst includes: (1) a method of adding the activator of the component (C) on the support (D), and supporting the mixture of the components (A) and (B); (2) a method of adding the activator of the component (C) on the support (D), and sequentially supporting the components (A) and (B); (3) a method of adding the activator of the component (C) on the support (D), and sequentially supporting the components (B) and (A); (4) a method of supporting the mixture of the components (A) and (B) on the support (D), and adding the component (C) for activation;

(5) a method of sequentially supporting the components (A) and (B) on the support (D), and adding the component (C) for activation; (6) a method of sequentially supporting the components (B) and (A) on the support (D), and adding the component (C) for activation; (7) a method of supporting the mixture of the components (C) and (A) on the support (D), and supporting the component (B); (8) a method of supporting the mixture of the components (C) and (B) on the support (D), and supporting the component (A); or (9) a method of supporting the mixture of the components (A), (B) and (C) on the support (D).

More specifically, the synthesis method of the supported multinuclear metallocene catalyst includes: (1) a method of adding the activator of the component (C) dissolved in a solvent at-80 to 100 °C on the support (D), sequentially or simultaneously supporting the compounds of the components (A) and (B) dissolved in the solvent, and then removing the solvent at 0 to 100 °C to prepare a supported multinuclear metallocene catalyst in a fine powder form; (2) a method of sequentially or simultaneously supporting the compounds of the components (A) and (B) dissolved in a solvent at-80 to 100 °C on the support (D), adding the activator of the component (C) dissolved in the solvent, and then removing the solvent at 0 to 100 °C to prepare a supported multinuclear metallocene catalyst in a fine powder form; (3) a method of adding a compound of the component (A) or (B) activated with the component (C) at-80 to 100 °C on the support (D), supporting the component (B) or (A) dissolved in the solvent, and then removing the solvent at 0 to 100 °C to prepare a

supported multinuclear metallocene catalyst in a fine powder form; or (4) a method of supporting the compound of both the components (A) and (B) activated with the component (C) at-80 to 100 °C on the support (D), and then removing the solvent at 0 to 100 °C to prepare a supported multinuclear metallocene catalyst in a fine powder form.

The synthesis method of the supported multinuclear metallocene catalyst according to the present invention is not specifically limited to the above-stated methods, and a method of supporting the components with the catalysts activated is preferred.

In the supporting step of the synthesis method, the molar ratio of transition metal in the catalyst (C) to transition metal in the catalysts (A) and (B), i. e. , [moles of transition metal in (C) ] : [moles of transition metal in (A) + moles of transition metal in (B) ] is 1: 1 to 1000: 1, preferably 1: 1 to 200: 1, more preferably 1: 1 to 100: 1. The molar ratio of transition metal in the component (A) to transition metal in the component (B), i. e., [moles of transition metal in (A) ] : [moles of transition metal in (B) ] is 100: 1 to 1: 200, preferably 40: 1 to 1: 80, more preferably 20 : 1 to 1: 40.

In supporting the supported multinuclear metallocene catalyst for olefin polymerization according to the present invention, the temperature is in the range of-80 to 150 °C, preferably 0 to 80 °C.

The specific examples of the solvent used in supporting the supported multinuclear metallocene catalyst for olefin polymerization according to the present invention include aliphatic hydrocarbon solvents (e. g., pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc. ) ; aromatic hydrocarbon solvents (e. g. , benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, etc. ) ; or halogenated aliphatic hydrocarbon solvents (e. g. , dichloromethane, trichloromethane, dichloroethane, trichloroethane, etc. ). These solvents can be used alone or in combination.

The olefin polymerization using the supported multinuclear metallocene catalyst according to the present invention is performed in the nitrogen (N2) or argon (Ar) atmosphere while preventing the influx of exterior air. To eliminate moisture in the reactor, the temperature of the reactor is raised to 100 °C and then slowly cooled down to the room temperature. The solvent for polymerization is added in the nitrogen or argon atmosphere with an exterior air barrier, and the supported multinuclear metallocene catalyst for olefin polymerization is then added.

Subsequently, the nitrogen or argon atmosphere in the reactor is replaced with the monomer atmosphere for polymerization, and the polymerization reaction is initiated when the temperature reaches the polymerization temperature.

In adding the supported multinuclear metallocene catalyst according to the present invention, the polymerization time is 1 to 24 hours, preferably 2 to 8 hours, with the pressure of 1 to 1000 atm, preferably 1 to 20 atm.

For olefin polymerization using the supported multinuclear metallocene catalyst according to the present invention, the polymerization is performed in a slurry phase or a gas phase. In the slurry polymerization, the solvent or the olefin itself can be used as a medium, and the olefins for the polymerization can be used alone or in combination of at least two of them. The specific examples of the solvent for polymerization includes aliphatic hydrocarbons (e. g. , butane, pentane, hexane, heptane, octane, decane, dodecane, etc. ), cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2-dichloroethane, or chlorobenzene. These solvents can be used alone or in combination at a predetermined mixing ratio.

The specific examples of the olefin used for polymerization using the

polymerization catalyst include C2-C20 Olefins (e. g. , ethylene, propylene, 1-butene, 1- pentene, 1-hexene, etc. ) ; C4-C20 diolefins (e. g. , 1,3-butadiene, 1,4-pentadiene, 2-Methyl- 1,3-butadiene, etc. ) ; C3-C2 cycloolefins or cyclodiolefins (e. g., cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, methyl-2-norbonene, etc. ) ; or substituted styrenes containing a Cl-Clo alkyl, Cl-Clo alkoxy, halogen, amine, silyl, or halogenated alkyl group bonded to a styrene or a phenyl ring of styrene.

In the polymerization using the supported catalyst of the present invention, the supported catalyst can be directly added to the reactor, or added to the reactor after prepolymerization. The prepolymerization as used herein refers to a method of polymerizing a predetermined amount of olefin in the supported catalyst prior to the main polymerization. The prepolymerization can prevent a sudden fracture of the support in the early stage of the polymerization, and avoid the leaching effect of the supported catalyst from the solvent, thereby enhancing the morphology and bulk density of the polymer product. The olefin and the solvent for prepolymerization are as defined above, and preferably the same as used for the main polymerization. In the prepolymerization according to the present invention, the temperature is, if not specifically limited to,-100 to 100 °C, preferably-78 to 50 °C, and the pressure is the ambient pressure. In the main polymerization according to the present invention, the temperature is, if not specifically limited to, -50 to 200 °C, preferably 20 to 150 °C, and the polymerization is performed in a batch, semicontinous or continuous way with a pressure of 1.0 to 3,000 atm, preferably 2 to 100 atm.

Brief Description of the Drawings FIG. 1 shows the X-ray molecular structure of the synthesis example 1; and FIG. 2 shows the X-ray molecular structure of the synthesis example 2.

Best Mode for Carrying out the Invention Hereinafter, the present invention will be described in detail by way of the following examples, which are not intended to limit the scope of the present invention.

Among the materials used in the experiments, tetrahydrofuran (THF), toluene, n- hexane, and so forth were purified with a sodium-potassium alloy, dietyl ether was purified on a sodium-benzophenone ketyl, and methylene chloride (CH2C12) was purified on calcium hydride (CaH2). Deuterated chloroform (CDC13) used for analysis of organometallic compounds was dried on an activated molecular sieve 4A.

Some materials, including 4,4'-dibromobiphenyl, 2,3, 4,5-tetramethyl-cyclopent-2- enone, n-butyllithium (2. 5M solution in n-Hexane), para-toluenesulfonic acid monohydrate (p-TsOH H2O), cyclopentadienylzirconium trichloride (CpZrCl3), 1,4- dibromobenzene, 4-bromobenzylbromide, etc. were used without further purification. 3,4- dimethyl-2-cyclopentenone was synthesized by a known method.

For the identification of the products synthesized in the individual steps, the mainly used methods were 1H NMR and 13C NMR with a Bruker Avance 400 spectrometer at the room temperature, an element analysis with EA 1110-FISION (CE Instruments), and an X-ray molecular structure analysis with an Enrarf-Nonius CAD4TSB diffractometer. The measurements were computed on a Silicon Graphics Indigo2XZ Workstation and analyzed.

Synthesis Example 1: Synthesis of 4, 4'-biphenylene bis (2,3, 4,5- tetramethylcyclopentadienyl) di (cyclopentadienylzirconium dichloride) ([4,4'-

(C5Me4) 2 (C6H4) 2] [CpZrCl2] 2) Synthesis Example 1-1: Synthesis of 4, 4'-bis (2, 3, 4, 5-tetra methylcyclopentadienyl biphenylene (4,4'-(C5Me4H)2(C6H4)2) 9.36g (30 mmol) of 4,4'-dibromobiphenyl was treated with 40 m of diethylether into slurry, and 24 m of n-butyllithium (2 equivalent weights) was added at-30 °C.

The temperature was raised to 0 °C. The reaction solution became clear with an increase in the temperature and subsequently formed a precipitate (4,4'-biphenyl dilithium salt).

After stirring for more 30 minutes at the same temperature, the solution was heated to the room temperature and further stirred for more 2 hours until the precipitation stopped.

The precipitate was allowed to settle, and the supernatant was separated from the precipitate. 30 m of tetrahydrofuran was then added to the resultant precipitate. The reaction solution was cooled down again to-78 °C, and slowly treated with a solution of 2,3, 4, 5-tetramethylcyclopentane-2-enone (8.29 g) in tetrahydrofuran (20 mQ). The resultant solution was heated to the room temperature, stirred overnight, and treated with 30 m of a saturated ammonium chloride (NH4C1) solution to terminate the reaction.

After separating the organic phase from the aqueous phase, the residual product was extracted from the aqueous phase with 50 m of diethylether. The diethylether phase was combined with the previously separated organic phase. The combined organic phases were removed of water by adding anhydrous MgS04. The solid was filtered out and the filtrate was dried under vacuum to obtain an oily colorless product.

The product is dissolved in 30 mg of methylene chloride at the room temperature without any further purification, and treated with a catalytic amount of p-toluene

sulfonate (p-TsOH, 0.1 g) in the solid state to form an ivory solid. After stirring for more 30 minutes, the methylene chloride was removed in vacuuo until it remained to moisten the solid. The solid was further precipitated and treated with 30 m of n- hexane so as to dissolve out the unreacted materials. The ivory yellow solid thus obtained was filtered out with a glass filter, washed with ethanol (30 mQ), diethylether (30 mQ) and n-pentane (30 m#) in sequence, and dried under vacuum to yield 7.50 g (63 % yeield) of 4,4'-bis (2,3, 4, 5-tetra methylcyclopentadienyl) biphenylene.

1H NMR (400.13 MHz, CDC13) : d 7.61 (d, 4H), 7.30 (d, 4H), 3.22 (q, 2H), 2.08 (s, 6H), 1.94 (s, 6H), 1.87 (s, 6H), 0.99 (s, 6H).

I3C {lH} NMR (100.62 MHz, CDC13): d 142.3, 140.9, 137.8, 137.5, 135.8, 135.2, 128.7, 126.5, 50.0, 14.9, 12.9, 12.0, 11.1.

Synthesis Example 1-2: Synthesis of 4, 4'-biphenylene bis (2, 3, 4, 5- tetramethylcyclopentadienyl) di (cyclopentadienylzirconium dichloride) (L4, 4'- (C5Me4)2(C6H4)2][CpZr(Cl2]2) 0.59 g of the 4, 4'-bis (2, 3, 4,5-tetra methylcyclopentadienyl) biphenylene prepared in the Synthesis Example 1-1 was dissolved in 20 m. of tetrahydrofixran, and treated with 1.2 mi of n-butyllithium (2 equivalent weights) at 0 °C. The reaction solution was heated to the room temperature and stirred overnight to form a brown solid in the green-purple solution.

The reaction solution was cooled down to-78 °C, and treated with 2 equivalent weights (0.79 g, 3.0 mmol) of cyclopentadienylzirconium trichloride (CpZrCl3) slurry in tetrahydrofuran (10 m#).

Subsequently, the reaction solution was heated to the room temperature and

further stirred for one hour under reflux. The resultant yellow solution was dried under vacuum and dissolved in 30 mQ of methylene chloride. The methylene chloride solution was filtered through a celite layer to obtain a green-yellow solution, and removed of methylene chloride. The resultant solid was washed with 10 m-C ofn-hcxane/diethylether (v/v = 2/1) twice and dried under vacuum to yield 1.02 g (80 % yield) of ivory yellow 4,4'- biphenylene bis (2,3, 4,5-tetramethylcyclopentadienyl) di (cyclopentadienylzirconium dichloride).

The synthesis mechanism is presented in the Reaction Scheme 1, and the X-ray molecular structure of the product is illustrated in FIG. 1.

IH NMR (400.13 MHz, CDC13) : d 7.69 (d, 4H), 7.25 (d, 4H), 6.17 (s, 10H), 2.27 (s, 12H), 2. 07 (s, 12H).

I3C {1H} NMR (100.62 MHz, CDC13) : d 138.9, 133.3, 130.3, 126. 8, 126.6, 126.2, 123.7, 116.7, 14.0, 12.3.

Anal. Calcd for C40H42Cl4Zr2 : C, 56.72 ; H, 5.00. Found: C, 56.96 ; H, 5.89.

[Reaction Scheme 1] 0 2 7 2 Br \/Br Et20 Li Li 1. THF in 2. p-TsOH/MC Aryl2 1. , r/x, 12 ZrCb 44'-IsMeaH) sHa) 4'- sHa)

Synthesis Example 2: 1, 2-bis [4-1 (2, 3,4, 5-tetramethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride} phenyl] ethane) ( (1, 2- [4- {(C5Me4) CpZrCl2} C6H4] 2 (CH2CH2)) Synthesis Example 2-1: Synthesis of 1, 2-di- (4-bromophenyl) ethane (1, 2- BrC6H4)2 (CH2CH2)) 1, 4-dibromobenzene (20.0 mmol, 4.72 g) was dissolved in 30m of diethylether and cooled down to 0 °C. To this solution, 1.1 equivalent weight of n-butyllithium (21 m mol, 8.4 m#) was added dropwise via a syringe. The resultant solution was stirred at 0 °C for 20 minutes and cooled down to-78 °C to form a white precipitate. The precipitate was allowed to settle and the supernatant was removed. At-78 0 °C, the precipitate was dissolved in 30 m-C ofTHF. In another flask, 4-bromobenzylbromide (20.0 mmol, 4.99 g) was dissolved in 20 m of THF, and the solution was slowly added dropwise to the above precipitate solution via a cannular. The mixed solution was then slowly heated to the room temperature and stirred for 6 hours or more to form an ivory yellowish brown solution and complete the reaction. To the resultant solution, an appropriate amount of an aqueous saturated ammonium chloride solution was added. The organic phase was extracted with 50 m. (x 3) of diethylether, dried over anhydrous magnesium sulfate and filtered. The filtrate was removed of the solvent on a rotary evaporator and isolated to yield 2. 89 g (85 % yield) of a white solid.

1H NMR (400.13 MHz, CDC13) : 7. 36 (d, 4H), 6.96 (d, 4H), 2.82 (s, 4H) Synthesis Example 2-2: Synthesis of 1, 2-di- [4- (2, 3, 4, 5- tetramethylcyclopentadienyl) phenyl] ethane (1, 2-[4-(C5Me4H)C6H4]2 (CH2CH2)) 1, 2-di- (4-bromophenyl) ethane (10 mmol, 3.40 g) prepared in the Synthesis

Example 2-1 was dissolved in 50mQ of diethylether, and cooled down to 0 °C. To this solution, 2.1 equivalent weight of n-butyllithium (21 mmol, 8.4 mg) was added dropwise via a syringe. The resultant solution was stirred at 0 °C for 1 hour, slowly heated to the room temperature, and further stirred for 2 hours to form a white precipitate. The precipitate was allowed to settle and the supernatant was removed. At-78 0 °C, the precipitate was dissolved in 30 m of THF. In another flask, 2,3, 4,5- tetramethylcyclopenta-2-enone (20.0 mmol, 2.76 g) was dissolved in 20 mg of THF, and the solution was slowly added dropwise to the above precipitate solution via a cannular.

The mixed solution was then slowly heated to the room temperature and stirred for 6 hours or more to form an ivory yellow solution. To the resultant solution, an appropriate amount of an aqueous saturated ammonium chloride solution was added. The organic phase was extracted with 50 mg (x 3) of diethylether, dried over anhydrous magnesium sulfate and filtered. The filtrate was removed of the solvent on a rotary evaporator to remain a yellow sticky oil. This oil was dissolved in 50 mg of dichlorometane, treated with a catalytic amount of p-toluene sulfonate hydrate (0.1 g), and stirred at the room temperature for 2 hours to form a yellow solid. After removal of the solvent on a rotary evaporator until the solid was moistened, the solid was washed with 30 mg of hexane and filtered. The filtered yellow solid was washed with 30 m. C (x 3) of anhydrous ethanol and 30 mQ (x 2) of pentane, and dried under vacuum to yield 2.83 g (67 % yield) of a yellow solid.

'H NMR (400.13 MHz, CDC13): 7. 18 (m, 8H), 3.17 (q, 2H), 2.93 (m, 4H), 2.02 (s, 6H), 1. 91 (s, 6H), 1.85 (s, 6H), 0.95 (d, 6H).

13C {lH} NMR (100.62 MHz, CDC13) : 142.7, 140.4, 139.0, 136.7, 135.0, 134.8,

128.4, 128.1, 50.1, 37.6, 14.9, 12.7, 11.9, 11.1.

Synthesis Example 2-3: Synthesis of 1, 2-bis [4-{(2345- <BR> <BR> <BR> <BR> <BR> tetramethylcyclopentadienyl (cyclopentadienyl) zircomum dichloridc phenyl] ethane ((1,2-[4-{(C5Me4)CpZrCl2}C6H4]2 (CH2CH2)) 1, 2-di- [4- (2, 3,4, 5-tetramethylcyclopentadienyl) phenyl] ethane (1.0 mmol, 0.42 g) prepared in the Synthesis Example 2-2 was dissolved in 30mQ of THF, and cooled down to-78 °C. To this solution, 2.5 equivalent weight of n-butyllithium (2.5 mmol, 1.0 m. C) was added dropwise via a syringe. The resultant solution was slowly heated to the room temperature and stirred for 4 hours to form a yellow precipitate. In another flask, cyclopentadienylzirconium trichloride (2.0 mmol, 0.52 g) was dissolved in 20 mE of THF, and the solution was slowly added dropwise to the above precipitate solution via a cannular at-78 0 °C. The mixed solution was then slowly heated to the room temperature and stirred for 24 hours or more to form a clear yellow solution. This solution was removed of the solvent under vacuum, and the resultant solid was dissolved in toluene and removed of the residual LiCl through a celite filtration. The resultant solution was removed of the solvent under vacuum, treated with an appropriate amount of pentane, and cooled down to form 0.64 g (73 % yield) of a yellow solid.

The synthesis mechanism is presented in the Reaction Scheme 2, and the X-ray molecular structure of the synthesized 1, 2-bis [4-1 (2, 3,4, 5- tetramethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride} phenyl] ethane is illustrated in FIG. 3.

'H NMR (400.13 MHz, CDC13) : 7.20 (d, 4H), 7.05 (d, 4H), 6.13 (s, 10H), 2.99 (s, 4H), 2.22 (s, 12H), 2.05 (s, 12H).

13C {lH} NMR (100.62 MHz, CDC13): 140.6, 131.7, 129.7, 128.5, 126.5, 126.1, 124.2, 116.7, 37.3, 13.9, 12.3 Anal. Calcd for C42H46Cl4Zr2 : C, 57.65 ; H, 5.30. Found: C, 57.96 ; H, 5.81.

[Reaction Scheme 2]

Synthesis Example 3: Synthesis of 1, 2-Bis [4-{(3, 4-dimethyl cyclopentadienyl) (cyclopentadienyl) zirconium dieMoride} phenyI] ethane ( (1, 2- [4- {(C5Me2H2)CpZrCl2}C6H4]2 (CH2CH2)) Synthesis Example 3-1 : Synthesis of 1, 2-bis- [4- (3, 4- dimethylcyclopentadienyl)phenyl] ethane (1, 2-[4-(C5Me2H3)C6H4]2 (CH2CH2)) 1, 2-di- (4-bromophenyl) ethane (10 mmol, 3.40 g) prepared in the Synthesis Example 2-1 was dissolved in 50m# of diethylether, and cooled down to 0 °C. To this solution, 2.1 equivalent weight of n-butyllithium (21 mmol, 8.4 mE) was added dropwise via a syringe. The resultant solution was stirred at 0 °C for 1 hour, slowly heated to the room temperature, and further stirred for 2 hours to form a white precipitate. The

precipitate was allowed to settle and the supernatant was removed. At-78 0 °C, the precipitate was dissolved in 30 m of THF. In another flask, 3,4-dimethyl-2- cyclopentenone (20.0 mmol, 2.18 g) was mixed with 20 mE of THF, and the solution was slowly added dropwise to the above precipitate solution via a canular. The mixed solution was then slowly heated to the room temperature and stirred for 6 hours or more to form an ivory yellow solution. To the resultant solution, an appropriate amount of an aqueous saturated ammonium chloride solution was added to complete the reaction. The organic phase was extracted with 50 mt (x 3) of diethylether, dried over anhydrous magnesium sulfate and filtered. The filtrate was removed of the solvent on a rotary evaporator to remain a yellow sticky oil. This oil was dissolved in 50 m of dichlorometane, treated with a catalytic amount of p-toluene sulfonate hydrate (0.1 g), and stirred at the room temperature for 2 hours to form an light brown solid. After removal of the solvent on a rotary evaporator until the solid was moistened, the solid was washed with 30 mg of hexane and filtered. The filtered solid was washed with 30 mQ (x 3) of anhydrous ethanol and 30 mE (x 2) of pentane, and dried under vacuum to yield 2.31 g (63 % yield) of an ivory solid.

'H NMR (400.13 MHz, CDC13) : 7.35 (d, 4H), 7.09 (d, 4H), 6.60 (s, 2H), 3.24 (s, 4H), 2.86 (s, 4H), 1.96 (s, 6H), 1.87 (s, 6H).

13C {lH} NMR (100.62 MHz, CDC13) : 142.4, 139.7, 135.5, 135.4, 134.2, 131.0, 128.6, 124.5, 45.3, 37.6, 13.4, 12.6.

Synthesis Example 3-2 : 1, 2-bis [4-f (3. 4- dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride}phenyl] ethane (1, 2- fol (C5Me2H2)CpZrCl2}C6H4]2(CH2CH2))

1, 2-bis- [4- (3, 4-dimethylcyclopentadienyl) phenyl] ethane (1.00 mmol, 0.37 g) prepared in the Synthesis Example 3-1 was dissolved in 30mQ of diethylether, and cooled down to-78 °C. To this solution, 2.5 equivalent weight of n-butyllithium (2.5 mmol, 1.0 mQ) was added dropwise via a syringe. The resultant solution was slowly heated to the room temperature and stirred for 4 hours to form an ivory precipitate solution. In another flask, cyclopentadienylzirconium trichloride (2.0 mmol, 0.52 g) was dissolved in 20 m of THF, and the solution was slowly added dropwise to the above precipitate solution via a cannular at-78 °C. The mixed solution was then slowly heated to the room temperature and stirred for 24 hours or more to form an ivory yellow solution. This solution was completely removed of the solvent under vacuum, and the resultant solid was dissolved in toluene and removed of the residual LiCl through a celite filtration. The resultant solution was properly removed of the solvent under vacuum, treated with an appropriate amount of pentane, and cooled down to form 0.57 g (70 % yield) of a yellow solid.

The synthesis mechanism is presented in the Reaction Scheme 3.

'H NMR (400.13 MHz, CDC13): 7.35 (d, 4H), 7.12 (d, 4H), 6.50 (s, 4H), 6.11 (s, 10H), 2.97 (s, 4H), 2.14 (s, 12H).

13C {lH} NMR (100.62 MHz, CDC13) : 140.8, 131.4, 129.4, 128.2, 125.1, 124.5, 116.5, 114.0, 37. 3,13. 8.

Anal. Calcd for C38H38Cl4Zr2 : C, 55.74 ; H, 4.68. Found: C, 56.98 ; H, 5.18.

[Reaction Scheme 3]

The above-described synthesis reactions were performed in the inert (e. g., nitrogen or argon) atmosphere using Standard Schlenk and Glove Box techniques. The mononuclear metallocene catalyst other than the dinuclear metallocene catalysts prepared in the Synthesis Examples was purchased and used without further purification.

Example 1 To a 100m# glass reactor, 11. 8, ol of 4,4'-biphenylene bis (2,3, 4,5- tetramethylcyclopentadienyl) di (cyclopentadienylzirconium dichloride) ([4,4'- (C5Me4) 2 (C6H4) 2] [CpZrCl2] 2) prepared in the Synthesis Example 1 and 102 mol of bis- indenylzirconium dichloride (Ind2ZrCl2) were added. Then, 5.4 cc of toluene and 4.6 cc (7.70 mmol) of methylaluminoxane (MMAO, Witco AL 5100/1OT) were added to the catalyst-containing glass reactor at the room temperature, and the mixture was stirred for 30 minutes. To another 100mg glass reactor, l. Og of silica (Grace Davison Co. , XP02412) and then 5.0 cc of toluene were added. The catalyst solution was added dropwise to the silica-containing glass reactor via a syringe with stirring, and then stirred at the room

temperature for 4 hours. Subsequently, a nitrogen purging was performed at 50 °C until the production of a free flowing powder, thereby obtaining a supported multinuclear metallocene catalyst, which was an ivory yellow powder.

100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. The polymerization reaction was performed with an ethylene polymerization pressure of 6.0 atm, a polymerization temperature of 70 °C and a hydrogen partial pressure of 0.05 atm in the presence of a solvent (hexane, 700 mQ). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 0. 82 Kg-PE/g-Cat. , a bulk density of 0.22, a polymer melting point of 136. 7 °C, a molecular weight (Mw) of 373,100, and a molecular weight distribution (MWD) of 8.56.

Example 2 To a 100mu glass reactor, 12. 6 Mol of 4, 4'-biphenylene bis (2,3, 4,5- tetramethylcyclopentadienyl) di (cyclopentadienylzirconium dichloride) ([4,4'- (C5Me4) 2 (C6H4) 2] [CpZrCl2] 2) prepared in the Synthesis Example 1 and 162. 7, cmol of bis- indenylzirconium dichloride (Ind2ZrCl2) were added. Then, 3.0 cc (14.10 mmol) of methylaluminoxane (MMAO, Witco AL 5100/30T) were added to the catalyst-containing glass reactor at the room temperature, and the mixture was stirred for 30 minutes. To another 100mQ glass reactor, l. Og of silica (Grace Davison Co., XP02412) and then 2.0 cc of toluene were added. The catalyst solution was added dropwise to the silica-containing vitreous bottle via a syringe with stirring, and then stirred at the room temperature for 4 hours. Subsequently, a nitrogen purging was performed at 50 °C until the production of a

free flowing powder, thereby obtaining a supported multinuclear metallocene catalyst, which was an ivory yellow powder.

100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. The polymerization reaction was performed with an ethylene polymerization pressure of 6.0 atm, a polymerization temperature of 70 °C and a hydrogen partial pressure of 0.05 atm in the presence of a solvent (hexane, 700 mQ). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.7 Kg-PE/g-Cat. , a bulk density of 0.27, a polymer melting point of 138. 5 °C, a molecular weight (Mw) of 345,000, and a molecular weight distribution (MWD) of 6.13.

Example 3 The catalyst was prepared in the same manner as described in the Example 2. The polymerization reaction was carried out, without a hydrogen partial pressure, with a polymerization time of 2 hours, an ethylene polymerization pressure of 6.0 atm, and a polymerization temperature of 70 °C in the presence of a solvent (hexane, 700 mQ). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.0 Kg-PE/g-Cat. , a bulk density of 0.28, a polymer melting point of 138. 9 °C, a molecular weight (Mw) of 404,000, and a molecular weight distribution (MWD) of 4.23.

Example 4 To a 100mg glass reactor, 25/mol of 1, 2-Bis [4- { (3, 4-dimethyl

cyclopentadienyl) (cyclopentadienyl) zirconium dichloride} phenyl] ethane ( (1, 2- [4- {(C5Me2H2) CpZrCk} C6H4] 2 (CH2CH2)) prepared in the Synthesis Example 3 and 200 tri mol of bis-indenylzirconium dichloride (Ind2ZrCla) were added. Then, 3.2 cc (15. 0 mmol) of methylaluminoxane (MMAO, Witco AL 5100/30T) were added to the catalyst- containing glass reactor at the room temperature, and the mixture was stirred for 60 minutes. To another lOOmQ glass reactor, l. Og of silica (Grace Davison Co., XP02412) was added. The catalyst solution was added dropwise to the silica-containing glass reactor via a syringe with stirring, and then stirred at the room temperature for 4 hours.

Subsequently, a nitrogen purging was performed at 50 °C until the production of a free flowing powder, thereby obtaining a supported multinuclear metallocene catalyst, which was a thick yellow powder.

100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. Before the ethylene polymerization, a prepolymerization was performed in a looms glass reactor. For the prepolymerization, ethylene was flown into the bottle at 10 cc/min with an MFC (Mass Flow Controller) at the room temperature over 40 minutes. The prepolymerized catalyst particle was transferred to the main reactor to perform a main polymerization. The polymerization reaction was carried out with an ethylene polymerization pressure of 6.0 atm, a polymerization temperature of 70 °C and a hydrogen partial pressure of 0.06 atm in the presence of a solvent (hexane, 700 m). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.6 Kg-PE/g-Cat. , a bulk density of 0.35, a polymer melting point of 137. 0 °C, a molecular weight (Mw) of 305,000, and a molecular weight

distribution (MWD) of 6.40.

Example 5 The catalyst was prepared in the same manner as described in the Example 4. The polymerization reaction was carried out with a polymerization time of 2 hours in the same conditions as described in the Example 4, excepting that 4.5 g of 1-butene was injected for copolymerization with 1-butene and that the hydrogen partial pressure was 0.03 atm.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 2.1 Kg-PE/g-Cat. , a bulk density of 0.33, a polymer melting point of 128. 1 °C, a molecular weight (Mw) of 258,000, and a molecular weight distribution (MWD) of 3.96.

Example 6 The catalyst was prepared in the same manner as described in the Example 4. The polymerization reaction was carried out with a polymerization time of 2 hours in the same conditions as described in the Example 4, excepting that 4.5 g of 1-butene was injected for copolymerization with 1-butene and that the hydrogen partial pressure was 0.10 atm.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.4 Kg-PE/g-Cat. , a bulk density of 0.37, a polymer melting point of 126. 8 °C, a molecular weight (Mw) of 212,000, and a molecular weight distribution (MWD) of 5.00.

Example 7 The catalyst was prepared in the same manner as described in the Example 4. The polymerization reaction was carried out with a polymerization time of 2 hours in the same conditions as described in the Example 4, excepting that 3.0 g of 1-butene was injected for

copolymerization with 1-butene and that the polymerization was performed without hydrogen.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.8 Kg-PE/g-Cat. , a bulk density of 0.36, a polymer melting point of 128. 1 °C, a molecular weight (Mw) of 255,000, and a molecular weight distribution (MWD) of 3.69.

Example 8 The catalyst was prepared in the same manner as described in the Example 4. The polymerization reaction was carried out with a polymerization time of 2 hours in the same conditions as described in the Example 4, excepting that 4.5 g of 1-butene was injected for copolymerization with 1-butene and that polymerization was performed without hydrogen.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 2.7 Kg-PE/g-Cat. , a bulk density of 0.34, a polymer melting point of 127. 8 °C, a molecular weight (Mw) of 228,000, and a molecular weight distribution (MWD) of 3.56.

Example 9 The catalyst was prepared in the same manner as described in the Example 4. The polymerization reaction was carried out with a polymerization time of 2 hours in the same conditions as described in the Example 4, excepting that 7.5 g of 1-butene was injected for copolymerization with 1-butene and that polymerization was performed without hydrogen.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.7 Kg-PE/g-Cat. , a bulk density of 0.34, a polymer melting point of 124. 3 °C, a molecular weight (Mw) of 186,000, and a molecular weight

distribution (MWD) of 3.43.

Example 10 To a 100mu glass reactor, 50, aol of 1, 2-Bis [4- { (3, 4-dimethyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride} phenyl] ethane ( (1, 2- [4- {(CsMe2H2) CpZrCk} C6H4] 2 (CH2CH2)) prepared in the Synthesis Example 3 and 200, u mol of bis-indenylzirconium dichloride (Ind2ZrCl2) were added. Then, 3.2 cc (15. 0 mmol) of methylaluminoxane (MMAO, Witco AL 5100/30T) were added to the catalyst- containing glass reactor at the room temperature, and the mixture was stirred for 60 minutes. To another 100mut glass reactor, l. Og of silica (Grace Davison Co. , XP02412) was added. The catalyst solution was added dropwise to the silica-containing glass reactor via a syringe with stirring at 0 °C, and a nitrogen purging was performed at 25 °C until the production of a free flowing powder, thereby obtaining a supported multinuclear metallocene catalyst, which was a thick yellow powder.

100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. Before the ethylene polymerization, a prepolymerization was performed in a 100mi glass reactor. For the prepolymerization, ethylene was flown into the bottle at 10 cc/min with an MFC (Mass Flow Controller) at the room temperature over 40 minutes. The prepolymerized catalyst particle was transferred to the main reactor to perform a main polymerization.

The polymerization reaction was carried out with an ethylene polymerization pressure of 6.0 atm, and a polymerization temperature of 70 °C in the presence of a solvent (hexane, 700 mE). Here, 1.5 mmol of triisobutylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 4.7 Kg-PE/g-Cat. , a bulk density of 0.32, a polymer melting point of 135. 1 °C, a molecular weight (Mw) of 536,000, and a molecular weight distribution (MWD) of 2.70.

Example 11 The catalyst was prepared in the same manner as described in the Example 10.

The polymerization reaction was carried out in the same conditions as described in the Example 10, excepting that the ethylene polymerization pressure was 7.0 atm with the hydrogen partial pressure of 0. 30.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 9. 6 Kg-PE/g-Cat. , a bulk density of 0.31, a polymer melting point of 135. 8 °C, a molecular weight (Mw) of 517,000, and a molecular weight distribution (MWD) of 8. 66.

Example 16 The catalyst was prepared in the same manner as described in the Example 10.

The polymerization reaction was carried out in the same conditions as described in the Example 10, excepting that the ethylene polymerization pressure was 7.0 atm with the hydrogen partial pressure of 0. 50.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 10. 5 Kg-PE/g-Cat., a bulk density of 0. 27, a polymer melting point of 135. 6 °C, a molecular weight (Mw) of 477,000, and a molecular weight distribution (MWD) of 10. 8.

Example 13

The catalyst was prepared in the same manner as described in the Example 10.

The polymerization reaction was carried out in the same conditions as described in the Example 10, excepting that the ethylene polymerization pressure was 7.0 atm with the hydrogen partial pressure of 0. 50 and that 3.0 g of 1-butene was added.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 5.3 Kg-PE/g-Cat. , a bulk density of 0.27, a polymer melting point of 127. 9 °C, a molecular weight (Mw) of 271,000, and a molecular weight distribution (MWD) of 6.71.

Comparative Example 1 l. Og of silica (Grace Davison Co., XP02412) and then 5.0 cc of toluene were added to a 100mQ glass reactor. 102, ol of bis-indenylzirconium dichloride (Ind2ZrCl2) was added to another lOOm-C glass reactor. Then, 4.6 cc (7.70 mmol) of methylaluminoxane (MMAO, Witco AL 5100/1OT) and 5.4 cc of toluene were added to this glass reactor at the room temperature, and the mixture was stirred for 30 minutes. This catalyst solution was slowly added to the silica-containing glass reactor via a syringe pump. Subsequently, a nitrogen purging was performed at 50 °C until the production of a free flowing powder, thereby obtaining a supported multinuclear metallocene catalyst, which was a thick yellow solid powder.

100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. The polymerization reaction was performed with an ethylene polymerization pressure of 6.0 atm and a hydrogen partial pressure of 0.05 atm in the presence of a solvent (hexane, 700 m4). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 0.91 Kg-PE/g-Cat. , a bulk density of 0.23, a polymer melting point of 136. 6 °C, a molecular weight (Mw) of 402,100, and a molecular weight distribution (MWD) of 2.85.

Comparative Example 2 After addition of silica (Grace Davison Co., XP02412) (2.0 g) to a 100mu glass reactor, 4.8 cc (80.0 mmol) of methylaluminoxane (MMAO, Witco AL 5100/10T) was slowly injected to the vitreous bottle via a syringe pump at 0 °C. The mixture was reacted at 0 °C, 30 °C and 60 °C each for 60 minutes, and further reacted at 80 °C for 240 minutes.

After removal of the unreacted methylaluminoxane, a solution of 4, 4'-biphenylene bis (2,3, 4,5-tetramethylcyclopentadienyl) di [cyclopentadienylzirconium dichloride] ( [4, 4'- (C5Me4) 2 (C6H4) 2] [CpZrCl2] 2) (162. 7 mol) in toluene (50 cc) was added to this silica slurry. After 3 hours of reaction at 50 °C, the resultant solution was removed of the unreacted catalyst filtrate and dried under vacuum at 80 °C to prepare a supported catalyst.

Subsequently, 100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. The polymerization reaction was performed with an ethylene polymerization pressure of 6.0 atm in the presence of a solvent (hexane, 700 m). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 0.21 Kg-PE/g-Cat. , a bulk density of 0.24, a polymer melting point of 136. 1 °C, a molecular weight (Mw) of 326,100, and a molecular weight distribution (MWD) of 3.09.

Comparative Example 3

l. Og of silica (Grace Davison Co., XP02412) was added to a 100mg glass reactor.

25/-Mol of bis-cyclopentadienylzirconium dichloride (Cp2ZrCl2) and 200 mol of bis- indenylzirconium dichloride (Ind2ZrCl2) were added to another 100mQ glass reactor. Then, 3.2 cc (15. 0 mmol) of methylaluminoxane (MMAO, Witco AL 5100/30T) and 5. 4 cc of toluene were added to this vitreous bottle glass reactor at the room temperature, and the mixture was stirred for 30 minutes. This catalyst solution was slowly added to the silica- containing vitreous bottle via a syringe pump. Subsequently, a nitrogen purging was performed at 50 °C until the production of a free flowing powder, thereby obtaining a supported multinuclear metallocene catalyst, which was a thick yellow solid powder.

100 mg of the supported catalyst was used to perform an ethylene polymerization in a 2L reactor for 2 hours. Before the ethylene polymerization, a prepolymerization was performed in a lOOmC glass reactor. For the prepolymerization, ethylene was flown into the bottle at 10 cc/min with an MFC (Mass Flow Controller) at the room temperature over 40 minutes. The prepolymerized catalyst particle was transferred to the main reactor to perform a main polymerization. The polymerization reaction was then carried out with an ethylene polymerization pressure of 6.0 atm and a hydrogen partial pressure of 0.05 atm in the presence of a solvent (hexane, 700 mQ). Here, 1 mmol of triethylaluminum was used as a moisture scavenger.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.3 Kg-PE/g-Cat., a bulk density of 0.32, a polymer melting point of 136. 8 °C, a molecular weight (Mw) of 349,300, and a molecular weight distribution (MWD) of 2.76.

Comparative Example 4

The catalyst was prepared in the same manner as described in the Example 3. The polymerization reaction was carried out with a polymerization time of 2 hours in the same conditions as described in the Example 3, excepting that 4.5 g of 1-butene was injected for copolymerization with 1-butene and that the hydrogen partial pressure was 0.03 atm.

As a result of the polymerization, a fine polyethylene powder was obtained with a polymerization activity of 1.2 Kg-PE/g-Cat. , a bulk density of 0.30, a polymer melting point of 129. 7 °C, a molecular weight (Mw) of 289, 700, and a molecular weight distribution (MWD) of 2.88.

The properties of the polymers prepared in the Examples and the Comparative Examples are presented in Table 1.

[Table 1] Butene Ethylene. Activity Bulk Melting Molecular Molecular Content Pressure Partial (kg-PE/g- Density Point Weight Weight Pressure Distribution (g) (atm) Cat.) (g/cc) (°C (Mw) (atm) (Mw/Mn) A 1 - 6.0 0.05 0.82 0.22 136.7 373,100 8.56 A 2-6. 0 0. 05 1. 7 0. 27 138. 5 345, 000 6. 13 A 3-6. 0-1. 0 0. 28 138.9 404, 000 4. 23 A 4-6. 0 0. 06 1. 6 0. 35. 137.0 305, 000 6. 40 A 5 4. 5 6. 0 0. 03 2. 1 0. 33 128.1 258, 000 3. 96 A 6 4. 5 6. 0 0. 10 1. 4 0. 37 126. 8 212, 000 5. 00 A 7 3.0 6.0 - 1.8 0. 36 128.1 255, 000 3. 69 A 8 4.5 6.0 - 2.7 0. 34 127.8 228, 000 3. 56 A 9 7.5 6.0 - 1.7 0. 34 124.3 186, 000 3. 43 A10-6. 0-4. 7 0. 32 135.1 536, 000 2. 70 All 7. 0 0. 30 9. 6 0. 31 135. 8 517, 000 8. 66 A 12-7. 0 0. 50 10.5 0.27 135.6 477, 000 10. 8 A 13 3. 0 7. 0 0. 50 5. 3 0. 27 127. 9 271,000 6. 71 B 1 - 6.0 0.05 0.91 0. 23 136.6 402,100 2. 85 B 2 6. 0-0. 21 0.24 136.1 326, 000 3. 09 B 3 6. 0 0. 06 1. 3 0. 32 136. 8 349, 300 2. 76 B4 4. 5 6. 0 0. 03 1. 2 0. 30 129. 7 289, 700 2. 88 Note) A 1-13: Examples 1-13 B 1-4: Comparative Examples 1-4 Industrial Applicability As described the above, the supported multinuclear metallocene catalyst for olefin polymerization of the present invention allows the control of molecular weight and molecular weight distribution in a slurry polymerization process or a gas phase polymerization process, and have a high catalytic activity for polymerization.