Title of Invention	A METHOD OF PRODUCING AN ETHYLENE HOMOPOLYMER OR A COPOLYMER OF ETHYLENE AND ALPHA OLEFIN BY SOLUTION POLYMERIZATION
Abstract	Disclosed is an arylphenoxy catalyst system for producing an ethylene homopolymer or copolymers of ethylene and a-olefins, and a method of producing an ethylene homopolymer or copolymers of ethylene and a-olefins having a high molecular weight under a high temperature solution polymerization condition using the same. The catalyst system includes a 4 group arylphenoxy-based transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst. In the transition metal catalyst, a cyclopentadiene derivative and arylphenoxide as fixed ligands are located around the 4th group transition metal, arylphenoxide is substituted with at least one aryl derivative and is located at the ortho position thereof, and the ligands are not crosslinked to each other. The catalyst includes an environmentally-friendly raw material, synthesis of the catalyst is economical, and thermal stability of the catalyst is excellent. It is useful for producing an ethylene homopolymer or copolymers of ethylene and a-olefins having various physical properties in commercial polymerization processes.

Title of Invention

A METHOD OF PRODUCING AN ETHYLENE HOMOPOLYMER OR A COPOLYMER OF ETHYLENE AND ALPHA OLEFIN BY SOLUTION POLYMERIZATION

Abstract

Disclosed is an arylphenoxy catalyst system for producing an ethylene homopolymer or copolymers of ethylene and a-olefins, and a method of producing an ethylene homopolymer or copolymers of ethylene and a-olefins having a high molecular weight under a high temperature solution polymerization condition using the same. The catalyst system includes a 4 group arylphenoxy-based transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst. In the transition metal catalyst, a cyclopentadiene derivative and arylphenoxide as fixed ligands are located around the 4th group transition metal, arylphenoxide is substituted with at least one aryl derivative and is located at the ortho position thereof, and the ligands are not crosslinked to each other. The catalyst includes an environmentally-friendly raw material, synthesis of the catalyst is economical, and thermal stability of the catalyst is excellent. It is useful for producing an ethylene homopolymer or copolymers of ethylene and a-olefins having various physical properties in commercial polymerization processes.

Full Text	Description ARYLPHENOXY CATALYST SYSTEM FOR PRODUCING ETHYLENE HOMOPOLYMER OR COPOLYMERS OF ETHYLENE AND ALPHA-OLEFINS Techmical Field [1] The present invention relates to an arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and a-olefins. More particularly, the present invention pertains to a 4 group transition metal catalyst expressed by Formula 1, a catalyst system which includes the arylphenoxy-based transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst, and a method of producing an ethylene homopolymer or copolymers of ethylene and a-olefins using the same. In the transition metal catalyst, a cyclopentadiene derivative and an arylphenoxide as fixed ligands are located around a 4 group transition metal, arylphenoxide ligand is substituted with at least one aryl derivative and is located at ortho position thereof, and the ligands are not cross linked to each other. [2] [3] Formula 1 [4] [5] [6] In Formula 1, wherein M is the 4 group transition metal of the periodic table; [7] Cp is cyclopentadienyl group capable of forming an T] -bond along with the central metal, or derivatives thereof; [8] R1, R\ R\ R1, R1 R1, R1 and R1 of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily arylalkyl group arbitrarily substituted with one or more halogen atoms, an alkoxy group which contains the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, or a C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings; X is selected from or is two or more independently selected from a group consisting of the halogen atom, the C1-C20 alkyl group which is not a Cp derivative, the C7-C30 arylalkyl group, an alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which has a C1-C20 hydrocarbon group; Y is the hydrogen atom, the halogen atom, the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the alkoxy group which contains the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, the amido group or aphosphido group which contains the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group; and n is 1 or 2 depending on the oxidation state of transition metal. Background Art Conventionally, Ziegler-Natta catalyst system which comprises a main catalyst component of titanium or vanadium compounds and a cocataly st component of alkyl aluminum compounds has been used to produce an ethylene homopolymer or copolymers of ethylene and a-olefins. However, the Ziegler-Natta catalyst system is disadvantageous in that, even though it is highly active in the polymerization of ethylene, the molecular weight distribution of a resultant polymer is wide, and particularly, a compositional distribution is non-uniform in the copolymer of ethylene and a-olefin due to heterogeneous catalyst active sites. Recently, the metallocene catalyst system which comprises a metallocene compound of a 4 group transition metal in the periodic table, such as titanium, zirconium, or hafnium, and methylaluminoxane as a cocatalyst has been developed. Since the metallocene catalyst system is a homogeneous catalyst having one kind of 312632, md Japanese Patent Laid-Open Publication Nos. Sho.63-092621, Hei.02-84405, and Hei.03-2347 disclose metallocene compounds, such as Cp TiQ , Cp ZrCl, Cp ZiMeQ, Cp ZrMe , or (ethylene-bis tetrahydroindenyl)ZrCl, activated ii £i *i i, ii 2 with methylalmninoxane as a cocatalyst to polymerize elhylene at high catelytic activity, thereby making it possible to produce polyethylene having a molecular weight distribution (Mw/Mn) of 1.5 - 2.0. However, it is difficult to produce a polymer having a high molecular weight using the above catalyst system. Particularly, if it is applied to a solution polymerization process which is conducted at high temperatures of 140°C or higher, polymerization activity is rapidly reduced and a-hydrogen elimination reaction is dominant, thus it is unsuitable for producing a high molecular weight polymer having a weight average molecular weight (Mw) of 100,000 or more. Meanwhile, a constrained geometry non-metallocene catalyst (a so-called single-site catalyst) in which a transition metal is connected to a ligand system in a ring shape has been suggested as a catalyst which has high catalytic activity and is capable of producing a polymer having a high molecular weight in polymerization of only ethylene or in copolymerization of ethylene and a-olefin under a solution polymerization condition. EP Pat. Nos. 0416815 and 0420436 suggest a catalytic system in which a transition metal is connected to cyclopentadiene ligand and an amide group in a ring shape, and EP Pat. No. 0842939 discloses a catalyst in which a phenol-based ligand as an electron donor compound is connected with a cyclopentadiene ligand in a ring shape. However, since the cyclization of the ligands along with the transition metal compound is achieved at very low yield during synthesis of the constrained geometry catalyst, it is difficult to commercialize them. Meanwhile, an example of non-metallocene catalysts which is not a constrained geometry catalyst and is capable of being used under a high temperature solution condition are disclosed in US Pat. No. 6,329,478 and Korean Patent Laid-Open Publication No. 2001-0074722. The patents disclose a single-site catalyst using one or more phosphinimine compounds as a ligand, having high ethylene conversion during copolymerization of ethylene and a-olefins under the high temperature solution polymerization condition at 140°C or higher. However, a limited range of phosphine compounds may be used to produce the phosphinimine ligand, and, since these compounds are harmful to the environment and to humans, it might have some difficulties in using them to produce general-purpose olefin polymers. US Pat. No. 5,079,205 discloses a catalyst having a bis-phenoxide ligand, but it has too low catalytic acitivity to be commercially used. phenol ligand are limited to only simple alkyl substituents such as isopropyl group. On the other hand, /. Organomet Chenu 1999,591,148 (Rothwell, P. et al) discloses an arylphenoxy liganxi, but does not suggest the effects of aryl substituent at the ortho-position. Disclosure of Invention Technical Problem To accomplish the above problems occurring in the prior art, the present inventors have conducted extensive studies, resulting in the finding that a non-bridged type transition metal catalyst, in which cyclopentadiene derivatives and arylphenoxide substituted with at least one aryl derivative at the ortho-position thereof are used as fixed ligands, shows an excellent thermal stability. Based on the above finding, a catalyst, which is used to produce an ethylene homopolymer or copolymers of ethylene and a-olefins having a high molecular weight, at a high activity during a solution polymerization process at high temperatures of 80°C or higher, has been developed, thereby the present invention is accomplished. Accordingly, an object of the present invention is to provide a single-site catalyst and a high temperature solution polymerization method using the same. The single-site catalyst includes environmentally-friendly raw materials, synthesis of the catalyst is very economical and thermal stability of the catalyst is excellent. In the solution polymerization method, it is possible to easily and commercially produce an ethylene homopolymer or copolymers of ethylene and a-olefins having various physical properties using the catalyst. Technical Solution In order to accomplish the above object, an aspect of the present invention provides an arylphenoxy-based transition metal catalyst expressed by Formula 1, which includes a cyclopentadiene derivative and arylphenoxide as fixed ligands around a transition metal. Arylphenoxide is substituted with at least one aryl derivative and is located at the ortho position thereof, and the ligands are not crosslinked to each other. In Formula 1, wherein M is the 4 group transition metal of a periodic table; Cp is cyclopentadienyl group, capable of forming an T]1-bond along with the central metal, or a derivative thereof; R,R,R,R,R,R,R, and R of the arylphenoxide hgand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, a C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, an alkoxy group which has the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, or a C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings; X is selected from or two or more independently selected from a group consisting of the halogen atom, the C1-C20 alkyl group which is not a Cp derivative, the C7-C30 arylalkyl group, an alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which contains a C1-C20 hydrocarbon group; Y is the hydrogen atom, the halogen atom, the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the alkoxy group which has the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, the amido group or a phosphide group which has the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group; and n is 1 or 2 depending on the oxidation state of the transition metal. Another aspect of the present invention relates to a catalyst system which comprises the transition metal catalyst, and aluminum or a boron compound as a cocatalyst. Still another aspect of the present invention relates to a method of producing ethylene polymers using the transition metal catalyst. Advantageous Effects raw materials at high yield, and it has high catalytic activity in a high temperature solution polymerization condition due to its excellent thermal stability in the course of producing a polymer having a high molecular weight, thus it is more useful than a conventional non-metallocene single-site catalyst. Therefore, it is useful for producing an ethylene homopolymer or copolymers of ethylene and a-olefins haviag various physical properties. Brief Description of the Drawings The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. 1 illustrates a crystalline structure of a (dichloro)(cyclopentadienyl)(4-methyl-2,6-bis(2'-isopropylphenyl)phenoxy)titanium(I V) catalyst according to the present invention; and FIG. 2 illustrates a crystalline structure of a (dichloro)(pentamethylcyclopentadienyl)(2-phenylphenoxy)titanium(IV) catalyst according to the present invention. Best Mode for Carrying Out the Invention Hereinafter, a detailed description will be given of the present invention. M of the transition metal catalyst in Formula 1 is preferably titanium, zirconium, or hafnium. Furthermore, Cp is a cyclopentadiene anion capable of forming an ri -bond along with a central metal, or a derivative thereof. In detail, it is exemplified by cy-clopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcy-clopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butyhnethylcyclopentadienyl, trimethylsilylcy-clopentadienyl, indenyl, methylindenyl, dimethylindenyl, ethylindenyl, iso-propylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, and iso-propylfluorenyl. With respect to R\ R1 R1 R\ R1 R1 R\ and R1 of an arylphenoxide ligand, a halogen atom is exemplified by fluorine, chlorine, bromine, and iodine atoms; and a C1-C20 alkyl group is exemplified by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group, and preferably, methyl group, ethyl group, isopropyl group, tert-butyl group, and amyl group. The alkyl group may ar- group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, di-bromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, per-fluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, percbloropropyl group, perchlorobutyl group, per-chloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group, or perbromoeicosyl group. Among them, trifluoromethyl group is preferable. In R\ R , R1, R'1, R1, R1, R1, and R\ a C1-C20 alkyl-substituted silyl group is exemplified by meihylsilyl group, ethylsUyl group, phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tri-cyclohexylsilyl group, or triphenylsilyl group, and preferably trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group. A C6-C30 aryl group is exemplified by phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, biphenyl group, fluorenyl group, triphenyl group, naphthyl group, or anthracenyl group, and preferably, phenyl group, naphthyl group, biphenyl group, 2-isopropylphenyl group, 3,5-xylyl group, and 2,4,6-trimethylphenyl group. A C7-C30 arylalkyl group is exemplified by benzyl group, (2-methylphenyl)methyl group, (3-methylphenyl)methyl group. trhodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluo-ropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, per-chlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, per-bromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, peibromododecyl group, perbromopentadecyl group, or perbromoeicosyl group, aod preferably, trifluoromethyl group. Furthermore, in Y, a C1-C20 alkyl-substituted silyl group is exemphfied by methylsilyl group, ethylsilyl group, phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, trhsopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyldimethylsilyl group, txi-n-pentylsilyl group, tri-n-hexylsilyl group, tri-cyclohexylsilyl group, or triphenylsilyl group, and preferably trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group. A C6-C30 aryl group is exemphfied by phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimeihylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trijnethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, biphenyl group, fluorenyl group, triphenyl group, naphthyl group, or anthracenyl group, and preferably, phenyl group, naphthyl group, biphenyl group, 2-isopropylphenyl group, 3,5-xylyl group, and 2,4,6-trimethylphenyl group. A C7-C30 arylalkyl group is exemphfied by benzyl group, (2-methylphenyl)methyl group, (3-methylphenyl)methyl group. (3,4,5-trhnethylphenyl)ine1hyl group, (2,4,6-trimethylphenyl)methyl group, (2,3,4,5-te1xaniethylphenyl)inethyl group, (2,3,4,6-tetrainethylphenyl)methyl group, (2,3,5,6-tetramethylphenyl)inethyl group, (pentainethylphenyl)methyl group, (ethylphenyl)methyl group, (n-propylphenyl)methyl group, (isopropylphenyl)inethyl group, (n-butylphenyl)methyl group, (sec-butylphehyl)inethyl group, (tert-butylphenyl)methyl group, (h-pentylphenyl)methyl group, (neopentylphenyl)methyl group, (h-hexylphenyl)methyl group, (n-octylphenyl)inethyl group, (n-decylphenyl)methyl group, (n-dodecylphenyl)methyl group, (n-tetradecylphenyl)inethyl group, naphthylmethyl group, or anthracenylmethyl group, and preferably, benzyl group. A C1-C20 alkoxy group is exemphfied by methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadecoxy group, or n-eicosoxy group, and preferably, methoxy group, ethoxy group, isopropoxy group, and tert-butoxy group. A C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group is exemphfied by trimethylsiloxy group, triethylsiloxy group, tri-n-propylsiloxy group, trhsopropylsiloxy group, tri-n-butylsiloxy group, tri-sec-butylsiloxy group, tri-tert-butylsiloxy group, tri-isobutylsiloxy group, tert-butyldimethylsiloxy group, tri-n-pentylsiloxy group, tri-n-hexylsiloxy group, tricyclohexylsiloxy group, or triphenylsiloxy group, and preferably, trimethylsiloxy group, tert-butyldimethylsiloxy group, and triphenylsiloxy group. The above-mentioned substituent groups may be substituted with one or more halogen atoms. As well, with respect to Y, an amido group or a phosphido group having a CI-020 hydrocarbon group is exemphfied by dimethylamino group, di-ethylamino group, di-n-propylamino group, dhsopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, dhsobutylamino group, tert-butyhsopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, dibenzylamide group, methylethylamide group, methylphenylamide group, benzylhexylamide group, bistrimethylsilylamino group, or bis-tert-butyldimethylsilylamino group, or phosphido group which is substituted with the same alkyl. Among them, dimethylamino group, diethylamino group, and diphenylamide group are preferable. A C1-C20 mercapto group is exemphfied by methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, 1-butyl mercaptan, or isopentyl mercaptan, and preferably, ethyl mercaptan and isopropyl mercaptan. which is expressed by Formula 2 and substituted with one or two halogen atoms, and a substituted or unsubstituted arylboronic acid, which is as shown in Fonnula 3, are reacted with an organic phosphine hgand using a palladium metal compound as a catalyst in an organic solvent at preferably -20 to 120°C to produce an aryl-substituted anisole compound, and reacted with a tribromoboron compound in an organic solvent at a temperature preferably ranging from -78 to 50°C to produce an aryl-substituted phenoxide hgand. The hgand thus produced is reacted with sodium hydride, alkyl hthium, or alkyl magnesium hahde compound in an organic solvent at a temperature preferably ranging from -78 to 120°C so as to be converted into anions, and then subjected to a hgand exchange reaction along with the 4 transition metal compound which is expressed by Formula 4 and has one cyclopentadiene derivative at -20 to 120°C in an equivalent ratio. The resulting product is purified to produce an arylphenoxide-based transition metal catalyst component. Formula 2 In the above Formula 2or3, R,R,R,R,R,R,R, and R are independently a hydrogen atom, a halogen atom, a C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, alkyl-substituted siloxy group or C6-C20 aryl-snbstituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings; Q is the halogen atom; and Y is the hydrogen atom, the halogen atom, the C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halog1i atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the C1-C20 alkylalkoxy group arbitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-substituted siloxy group or C6-C20 aryl-substituted siloxy group, the amido group or a phosphido group which has the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group. Formula 4 CpM(X) Dl In Formula 4, Cp is cyclopentadienyl capable of forming an T] -bond along with a central metal, or a derivative thereof, M is a 4 group transition metal in a periodic table, X is a halogen atom, a C1-C20 alkyl group which is not a Cp derivative, a C7-C30 arylalkyl group, a C1-C20 alkylalkoxy group, a C3-C20 alkyl-substituted siloxy group, or an amido group having a C1-C20 hydrocarbon group, and m is 2 or 3 depending on the oxidation value of the transition metal. Meanwhile, in order to use the transition metal catalyst of Formula 1 as an active catalyst component which is used to produce an ethylene homopolymer or copolymer of ethylene and an a-olefin comonomers, an X hgand is extracted from a transition metal complex to convert the central metal into cations, and aluminoxane compounds or boron compounds which are capable of acting as opposite ions having weak bonding strength, that is, anions, are used along with a cocatalyst. As well known in the art, aluminoxane, which is expressed by the following Formula 5 or 6, is frequentiy used as the aluminoxane compound used in the present invention. Formula 5 (-Al(R')-O-) m or an isobutyl group, and m and p are integers ranging from 5 to 20. In order to use the transition metal catalyst of the present invention as an active catalyst, the mixing ratio of the two components is set so that the molar ratio of the central metal to aluminum is preferably 1:20 to 1:10,000, and more preferably, 1:50 to 1:5,000. Furthermore, a boron compound which is capable of being used as a cocatalyst of the present invention may be selected from compounds of the following Formulae 7 to 9 as disclosed in US Patent No. 5,198,401. In the above Formulae, B is a boron atom; R is an unsubstituted phenyl group, or a phenyl group which is substituted with 3 to 5 substituent groups selected from the group consisting of a C1-C4 aDcyl group which is substituted or unsubstituted with a fluorine atom and a C1-C4 alkoxy group which is substituted or unsubstituted with the fluorine atom; R11 is a C5-C7 cychc aromatic cation or an alkyl-substituted aromatic cation, for example, triphenylmethyl cation; Z is a nitrogen atom or a phosphorus atom; R11 is a C1-C4 alkyl radical or an anihnium radical which is substituted with two C1-C4 alkyl groups along with a nitrogen atom; and q is an integer of 2 or 3. Examples of the boron-based cocatalyst taclude tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate, tetra]ds(2,3,5,6-tetrafluorophenyl)borate, tetralds(2,3,4,5-tetrafluorophenyl)borate, tetra]ds(3,4,5-tetrafluorophenyl)borate, tetrakis(2,2,4-trifluorophenyl)borate, phenylbis(pentafIuorophenyl)borate, andtetrakis(3,5-bistrifluoromethylphenyl)borate. Furthermore, a combiaation of the above-mentioned examples is exemphfied by ferrocenium tetra]ds(pentafluorophenyl)borate, l,l'-dimethylferrocenium In a catalyst system using the boron-based cocatalyst, the molar ratio of the central metal to the boron atom is preferably 1:0.01 -1:100, and more preferably, 1:0.5 -1:5. Meanwhile, a mixture of the boron compound and the organic aluminum compound or a mixture of the boron compound and the aluminoxane compound may be used, if necessary. In connection with this, the aluminum compound is used to remove polar compounds acting as a catalytic poison from a reaction solvent, and may act as an alkylating agent if X of the catalyst components is halogen. The organic aluminum compound is expressed by the foDowing Formula 10. Formula 10 (R')A1(E) r 3-r In the above Formula, R is a C1-C8 alkyl group, E is a hydrogen atom or a halogen atom, and r is an integer ranging from 1 to 3. The organic aluminum compound is exemplified by trialkkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dialkylaluminum chloride including dimethylalumiaum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride; alkylaluminum dichloride including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum preferable, and triethylaluininum and trhsobutylaluininuin are more preferable. In connection wifb this, the molar ratio of the central metal: the boron atom: the aluminunxatonhs preferably 1: 0.1 - 100 :10 - 1000, and more preferably, 1: 0.5 - 5 : 25 - 500. According to another aspect of the present invention, in a method of producing ethylene polymers using the transition metal catalyst system, the transition metal catalyst, the cocatalyst, and ethylene or a vinyl-based comonomer come into contact with each other in the presence of a predetermined organic solvent At this stage, the transition metal catalyst and the cocatalyst are separately loaded into a reactor, or loaded into the reactor after they are previously mixed with each other. There are no hmits to miring conditions, such as the order of addition, temperature, or concentration. The organic solvent useful in the method is C3-C20 hydrocarbons, and is exemphfied by butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene. In detail, when the ethylene homopolymer, that is, high density polyethylene (HDPE), is produced, ethylene is used alone as a monomer, and pressure of ethylene useful to the present invention is 1 -1000 atm, and preferably, 10-150 atm. Furthermore, a polymerization temperature is 80 - 300°C, and preferably, 120 - 250111. Additionally, when the copolymers of ethylene and a-olefins are produced, C3-C18 a-olefins are used as comonomers along with ethylene, and are selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene. More preferably, 1-butene, 1-hexene, 1-octene, or 1-decene is copolymerized with ethylene. In connection with this, the pressure of ethylene and the polymerization temperature are preferably the same as in the method of producing high density polyethylene. The ethylene copolymers produced according to the present invention include 60 wt% or more ethylene, and preferably, 75 wt% ethylene. As described above, hnear low density polyethylene (LLDPE) which is produced using C4-C10 a-olefin as the comonomer has a density of 0.910 - 0.940 g/cc, and, in connection with this, it is possible to produce very or ultra low density polyethylene (VLDPE or ULDPE) having a density of 0.910 g/cc or less. As well, in the course of producing the ethylene homopolymer or copolymers according to the present invention, hydrogen may be used as a molecular weight controlhng agent to control a molecular weight, and the ethylene homopolymer or copolymers typically has weight average molecular weight (Mw) of 80,000 -500,000. which is conducted at a temperature of a melting point or higher of the polymer to be produced. However, as disclosed in US Patent No. 4,752,597, the transition metal catalyst and the cocatalyst may be supported by a porous metal oxide supporter so as to be used in a slurry polymerization process or a gaseous polymerization process as a heterogeneous catalyst system. Mode for the Invention A better understanding of the present invention may be obtained through the following examples which are set forth to illustrate, but are not to be construed as the hmit of the present invention. Syntheses of all hgands and cataysts were conducted using standard Schlenk or globe box technology in a nitrogen atmosphere if not specifically described otherwise. The organic solvents used in the reactions were refluxed in the presence of sodium metal and benzophenone to remove moisture, and distilled immediately before they were used. 'H-NMR analyses of the produced hgands and catalysts were carried out at normal temperature using Varian Oxford 300 MHz. n-heptane as a polymerization solvent was passed through a column in which a molecular sieve 5A and activated alumina were packed, and bubbhng was conducted using highly pure nitrogen to sufficiently remove moisture, oxygen, and other catalytic poison materials before it was used. The resulting polymers were analyzed using the following methods. L Melt index (MI) Measurement was conducted based on ASTM D 2839. 2. Density Measurement was conducted using a density gradient colurm based on ASTM D 1505. 3. Analysis of a melting point (T ) Measurement was conducted using Dupont DSC2910 in a nitrogen atmosphere at a rate of 10°C/min under a 211111 heating condition. 4. Molecular weight and molecular weight distribution Measurement was conducted using PL210 GPC which was equipped with PL Mixed-BX2+preCol in a 1,2,3-trichlorobenzene solvent at 135X and a rate of 1.0 mlV min, and the molecular weight was revised using a PL polystyrene standard material. 5. a-olefin content of copolymer (wt%) Measurement was conducted using a Bruker DRX500 nuclear magnetic resonance Macromol Chenu Phys, 1980, C29,201). PREPARA.TION EXAMPLE 1 Synthesis of 4-methyl-2,6-bisr2'-isopropvlpheDyl)phenol A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibroTno-4-methylanisole (400 mg, 1.43 inmol), 2-isopropylphenylboronic acid (720 mg, 4.39 mmol), palladium acetate (14 mg, 0,062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were then removed to produce 670 mg of grey 4-methyl-2,6-bis(2'-isopropylphenyl)anisole sohd. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) was dropped thereon at -78°C, and a reaction was carried out while the temperature was slowly mcreased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 0.47 g of white 4-methyl-2,6-bis(2'-isopropylphenyl)phenol sohd. Yield: 95 %, 'H-NMR (CDCy6= 1.12-1.19 (m, 12H), 2.34 (s, 3H), 2.93 (m, 2H), 4.51 (s, IH), 6.95 (s, 2H), 7.24 (d, 4H), 7.42 (t, 4H) ppm Synthesis of ('dichloro)fpentamethylcvclopentadienvl)4-methvl-216-bisf2'-isopropvlph&nvl)phenox y)titanium(IV) 4-methyl-2,6-bis(2'-isopropylphenyl)phenol (344 mg, 1 mmol) and sodium hydride (72 mg, 3 mmol) were dissolved in 10 mL of toluene, and then refluxed for 4 hours. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (289 mg, 1 mmol) was dissolved in 5 mL of toluene was slowly added thereto, and reflux was conducted for 24 hours. conducted at reduced pressure to produce 352 mg of red sohd component Yield: 67 %, 'H-NMR (C Dp5= 0.95-1.26 (m, 12H), 1.62 (s, 15H), 1.88 (s, 3H), 3.17 (m, 2H), 6.94-7.29 (m, lOH) ppm EXAMPLE 1 300 mL of n-heptane was added into a stainless steel reactor which was purged with nitrogen after sufficient drying and had a volume of 500 mL, and 0.5 mL of trhsobuty-laluminum (Aldrich) (200 vcM n-heptane solution) was added thereto. The temperature of the reactor was then increased to 140°C, and, subsequently, 0.2 mL of (dichIoro)(pentamethylcyclopentadienyl)(4-methyl-2,6-bis(2'-isopropylphenyl)phenox y)titanium(IV) (5 mM toluene solution), produced according to preparation example 1, and 0.3 mL of triphenylmethyhnium tetrakis(pentafluorophenyl)borate (99 %, Boulder Scientific) (5 mM toluene solution) were sequentially added thereto. Ethylene was then injected into the reactor until the pressure in the reactor was 30 atm, and was continuously fed for polymerization. 10 min after the reaction started, 10 mL of ethanol (including 10 vol% hydrochloric acid aqueous solution) were added to finish the polymerization, agitation was conducted for 4 hours along with 1500 mL of additional ethanol, and products were filtered and separated. The resulting product was dried in a vacuum oven at 60°C for 8 hours to produce 7.3 g of polymer. The polymer had a melting point of 132.1°C and a melt index of 0.001 g/10 min or less, and a weight average molecular weight of 393,000 and a molecular weight distribution of 3.36, which were determined through gel chromatography analysis. EXAMPLE 2 15 mL of 1-octene were injected into a reactor which was the same as in example 1, and polymerization was then conducted through the same procedure as in example 1 except that 0.3 mL of (dichloro)(pentamethylcyclopentadienyl)(4-metfayl-2,6-bis(211isopropylphenyl)phenox y)titanium(IV) (5 mM toluene solution) and 0.45 mL of triphenylmethyhnium tetra]ds(pentafluorophenyl)borate (Boulder Scientific) (5 mM toluene solution) were added after 0.75 mL of trhsobutylaluminum (Aldrich) (200 mM n-heptane solution) were added. 4.0 g of dried polymer was obtained. The weight average molecular weight was 175,000 and a molecular weight distribution was 5.91, which were PREPARATION EXAMPLE 2 Synthesis of 4-methvl'2-(2'-isapropvlphenyl>phenQl A mixed solution of 1 IDL of water and 4 mL of dimethoxyethane was added into a flask into which 2-bromo-4-methylanisole (600 mg, 2.98 mmol), 2-isopropylphenylboronic acid (734 mg, 4.47 mmol), palladium acetate (16 mg, 0.074 mmol), triphenylphosphine (72 mg, 0.27 mmol), and potassium phosphate (1.12 g, 5.28 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues with diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were removed to produce 850 mg of grey 4-methyl-2-(2'-isopropylphenyl)anisole sohd. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 inL of boron tribromide (1 M methylene chloride solution) was dropped thereonto at -781C, and a reaction was carried out while the temperature slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 633 mg of white 4-methyl-2,6-(2'-isopropylphenyl)phenol sohd. Yield: 93 %, 'H-NMR (CDQ )6= 1.10-1.21(q, 6H), 2.33 (s, 3H), 2.91 (m, IH), 4.63 (s, IH), 6.87-7.51 (m, 7H) ppm Synthesis of (dicbloro>fpentamethvlcvclopentadienvl¥4-methvl-2-f2'-isopropvlDhenvl')phenoxv>tita niumflV) 4-methyl-2-(2'-isopTopylphenyl)phenol (1 g, 4.41 mmol) and sodium hydride (318 mg, 13.25 mmol) were dissolved in 10 mL of toluene, and then refluxed for 4 hours. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (1.15 g, 4.0 mmol) was dissolved in 5 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction was finished, volatile materials were removed, washing Yield: 67 %, 'H-NMR (Cp1b1 0.96-1.07 (m, 6H), 1.76 (s, 15H), 1.89 (s, 3H), 2.99 (m, IH), 6.85-7.37 (m, 7H) ppm EXAMPLES Polymerization was conducted through the same procedxire as in example 2 except that 0.2 mL of (dichloro)(pentamethylcyclopentadienyl)(4-met hyl-2-(2'-isopropylphenyl)phenoxy)titanium(IV) (5 mM toluene solution) produced according to preparation example 2 were used. The product was dried to produce 5.5 g of polymer. The polymer had a melting point of 132.11 and a melt index of 0.06 g/10 min, and a weight average molecular weight of 188,000 and a molecular weight distribution of 4.30 which were determined through gel chromatography analysis. PREPARATION EXAMPLE 3 Synthesis of 4-methvl-2.6-dipbenvlphenol A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), phenylboronic acid (535 mg, 4.39 mmol), palladium acetate (14 mg, 0.062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of di-ethylether were added thereto to separate an organic layer and extract residues usmg diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were removed to produce 420 mg of grey 4-methyl-2,6-diphenylanisole sohd. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was carried out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 333 mg of white 4-methyl-2,6-diphenylphenol sohd. Synthesis of (dicbloroVpentametfavlcvclopeDtadienvlV4-metfayl-2.6-diphenvlpheDOXv>tit1 4-inethyl-2,6-diphehylphenol (400 mg, 1.53 imnol) and sodium hydride (110 mg, 4.60 mmol) were dissolved in 10 niL of toluene, and then refluxed for 4 hours. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentaniethylcyclopentadienyl)titaniuin(rV) (376 mg, 1.30 imnol) was dissolved in 5 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction finished, volatile materials were removed, washing was conducted using purified hexane, recrystalhzation was conducted using a mixed solution of toluene/hexane at -35X, filtration was conducted, and drying was conducted at reduced pressure to produce 308 mg of red sohd component. Yield: 46 %, 'H-NMR (C1D1&= 1.87 (s1H), 1.67 (s, 15H), 6.97-7.18 (m, 12H) ppm EXAMPLE 4 Polymerization was conducted through the same procedure as in example 2 except that 0.2 mL of (dichloro)(pentamethylcyclopentadienyl)(4-methyl~2,6-diphenylphenoxy)titanium(rV) (5 mM toluene solution) produced according to preparation example 3 were used. The product was dried to produce 5.8 g of polymer. The polymer had a melting point of 131-4°C and a melt index of 0.011 g/10 min, and a weight average molecular weight of 349,000 and a molecular weight distribution of 2.74, which were determined through gel chromatography analysis. PREPARATION EXAMPLE 4 Svnthesis of rdichloro¥pentametfavlcvclopentadienvl¥2-pbenvlphenoxy')titaniumrrV> After 0.86 g of 2-phenylphenol (5.07 mmol) (Aldrich, 99 %) were dissolved in 40 mL of toluene, 2.4 mL of butyl hthhmi (2.5 M hexane solution) were slowly dropped thereonto at 0°C. After the reaction was conducted at normal temperature for 12 hours, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (1.32 g, 4.56 mmol) was dissolved in 10 mL of toluene was slowly dropped thereonto at O1'C. After agitation was conducted at normal temperature for 12 hours, filtration was conducted, Yield: 85 %; 'H-NMR (C D18= 1,68 (s, 15H), 6.82-7.26 (m, 9H) ppm EXAMPLES Polymerization was conducted through the same procedure as in example 2 except that 0.2 mL of (dicUoro)(pentamethylcyclopentadienyl)(2-phenylphenoxy)titaaium(IV) (5 mM toluene solution) produced according to preparation example 4 were used TTie product was dried to produce 10.5 g of polymer. The polymer had a melting point of 130.3°C and a melt index of 0.001 g/10 min or less, and a weight average molecular weight of 303,000 and a molecular weight distribution of 3.4, which were determined through gel chromatography analysis. EXAlvIPLE6 Polymerization was conducted through the same procedure as in example 2 except that 03 mL of (dichloro)(pentamethylcyclopentadienyl)(2-phenylphenoxy)titanium(TV) (5 mM toluene solution) produced according to preparation example 4 were used. 7.8 g of dried polymer were obtained. The weight average molecular weight was 139,000 and the molecular weight distribution was 2.5, as determined through gel chromatography analysis. The melt index was 0.2 g/10 min, the melting point was 118.7'1C, the density was 0.9197, and the content of 1-octene was 4.5 wt%. PREPARATION EXAMPLE 5 Svntfaesis of 2-isopTopyl-6-phenylphenol A mixed solution of 8 mL of water and 32 mL of dimethoxyethane was added into a flask into which 2-bromo-64sopTopylanisole (L98 g, 8.64 mmol), phenylboronic acid (2.10 g, 17.28 mmol), palladium acetate (96 mg, 0.43 mmol), triphenylphosphine (0.225 g, 0.86 mmol), and potassium phosphate (11 g, 51.84 mmol) were already added, and then refluxed at normal temperature for 12 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (15 mL) and 30 mL of di-ethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and solution) were dropped thereonto at -78°C, and the reaction was carried out for 12 hours while the temperature was slowly increased to norma] temperature. After the reaction, a mixed solution of water (15 luL) and diethylether (30 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (15 inL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 1.72 g of white 2-isopropyl-6-phenylphenol sohd. Yield: 94 %. 'H-NMR (CDCl )6= 1.307 (d, 6H), 3.45 (m, IH), 5.09 (s, IH), 6.95-7.43 (m, 8H) ppm Synthesis of fdichlQrQVpentamethvlcvclopenta(Kenvl>f2-isopropvl-6-phenvlphenoxv1titaniumnrV1 2-isopropyl-6-phenylphenol (700 mg, 3.28 mmol) and sodium hydride (236 mg, 9.84 mmol) were dissolved in 10 mL of toluene, and then refluxed for 4 hours. Subsequently, coohng to nonnal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (930 mg, 3.21 mmol) was dissolved in 5 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction was finished, volatile materials were removed, washing was conducted using purified hexane, recrystalhzation was conducted using a mixed solution of toluene/hexane at -35°C, filtration was conducted, and drying was conducted at reduced pressure to produce 1.0 g of red sohd component Yield: 64 %, 'H-NMR (C1Dp5= 1.324 (d, 6H), 1,63 (s, 15H), 3.53 (m, IH), 7.05-7.66 (m, 8H) ppm EXAMPLE 7 Polymerization was conducted through the same procedure as in example 2 except that 0.2 mL of (dichloro)(pentamethylcyclopentadienyl)(2--isopropyl-611phenylphenoxy)titanium(IV) (5 mM toluene solution) produced according to preparation example 5 were used. The product was dried to produce 5.5 g of polymer. The polymer had a melting point of 132.6°C and a melt index of 0.002 g/10 min, and a weight average molecular weight of 390,000 and a molecular weight distribution of 4.08, as determined through gel chromatography analysis. PREPARATION EXAI1LE 6 Synthesis of 4-iD&tfavl-2.6-bisf3',5'--dhnethvlphenyl1 phenol A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), 3,5-diniethylphenylboronic acid (658 mg, 4.39 mmol), palladium acetate (14 mg, 0.062 mmol), thphenylphosphine (60 mg, 0,23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coolmg to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were removed to produce 453 mg of white 4-methyl-2,6-bis(3\5'-dimethylphenyl)anisole sohd (yield 96 %). The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was carried out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 0.41 g of white 4-methyl-2,6-bis(3',5'-dimethylphenyl)phenol sohd. Yield: 92 %, 'H-NMR (CDCy6= L55 (s, 3H), 2.37 (s, 12H), 5.35 (s, IH), 7.05 (s, 2H), 7.15 (s, 4H), 7.27 (4, 2H) ppm PREPARATION EXAMPLE 7 Synthesis of 4-metfayl-2,6-bisfbiphenvl)phenol A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), biphenylboronic acid (870 mg, 4.39 mmol), palladixun acetate (14 mg, 0.062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was earned out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 raL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 540 mg of white 4-methyl-2,6-bis(biphenyI)phenol sohd. [193] Yield: 92 %, 'H-NMR (CDap6= 2.39 (s, 3H), 5.34 (s, IH), 7.16-7.72 (m, 20H) ppm [194] [195] Synthesis Qf rdichloro¥pentamethvlcyclopentadienvlV4-metbvl-2.6-bisrbiph&nvl1phenoxy1titanium OYl [196] 4-methyl-2,6-bis(biphenyl)phenol (206 mg, 0.5 mmol) and sodium hydride (36 mg, 1.5 mmol) were dissolved in 10 mL of toluene, and then refluxed for 1 hour. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(rV) (130 mg, 0.45 mmol) was dissolved in 10 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction was finished, volatile materials were removed, washing was conducted using purified hexane, recrystalhzation was conducted using a mixed solution of toluene/hexane at -35°C, filtration was conducted, and drying was conducted at reduced pressure to produce 0.12 g of yellow sohd component. [197] Yield: 42 %, 'H-NMR (CDCy8= 1.60 (s, 15H), 2.48 (s, 3H), 7.08-8.15 (m, 20H) ppm [198] [199] PREPARATION EXAMPLE 8 [200] [201] Svntfaesis of 4-metfavl-2.6-bisf l'-naphtbvl>phenol [202] A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (700 mg, 2.63 mmol), 1-naphthylboronic acid (1.39 g, 8.07 mmol), palladium acetate (25 mg, 0.12 mmol), triphenylphosphine (94 mg, 0.35 mmol), and potassium phosphate (1.9 g, 8.9 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of 4-Tnethyl-2,6-bis(r-naphthyl)anisole sohd (yield 89 %). The anisole thus produced was dissolved in 10 mL of methylene chloride without separate purification, 5 mL of boron tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was carried out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 xnL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 805 mg of white 4-methyl-2,6-bis(r-naphthyl)phenol sohd. [203] Yield: 85 %, 'H-NMR(CDa )6= 2.41(s,3H), 4.71(s,lH), 7.21-7.92 (m,16H) ppm [204] [205] COMPARATIVE PREPARATION EXAMPLE 1 [206] [207] Synthgsis of fdiQMorQ)fpgPtamgthyigyd9pgPtadifinyl) f2,1-tert-t)1ty?pbgDQ?y)tit1um(IV) [208] After 600 mg of 2,6-di-tert-butylphenol (2.91 mmol) (Aldrich, 99 %) were dissolved in 30 n1L of diethylether, 1.28 mL of butyl hthium (2.5 M hexane solution) were slowly dropped thereonto at 1131°C. After 1 hour, agitation was conducted at normal temperature for 6 hours. The resulting mixture was dissolved m diethylether, and a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (752 mg, 2.60 mmol) was dissolved in 10 mL of diethylether was slowly dropped thereonto at -30°C. After 1 hour, agitation was conducted at normal temperature for 6 hours. The solvent was removed from the resulting product, and the solvent-free product was dissolved in 10 mL of toluene and then recrystalhzed to produce 829 mg of red sohd component. [209] Yield: 69 %; IH-NMR (CDCl )8= 1.37 (s, 18H), 2.10 (s, 15H), 6.50-7.20 (m, 3H) ppm [210] [211] COMPARATIVE EXAMPLE 1 [212] [213] Polymerization was conducted through the same procedure as in example 1 except that 0.2 mL of (dichloro)(pentamethylcyclopentadienyl)(2,6-di-tert-butylphenoxy)titanium(IV)(5 mM toluene solution) produced according to comparative preparation example 1 were through gel chromatography analysis. [214] [215] COMPARATIVE EXAMPLE 2 [216] [217] PolyrQehzation was conducted through the same procedure as in example 2 except that 0.2 mL of (trimethyl)(pentamethylcyclopentadienyl)titamuTn(IV) (97 %, Strem) (5 inM toluene solution), 0,24 mL of trhsobutylaluminum (200 mM n-heptane solution) (Aldrich), and 0.25 mL of triphenyhnethyhnium tetralds(pentafluorophenyl)borate (99 %, Boulder Scientific) (5 mM toluene solution) were used. The product was dried to produce 3.0 g of polymer. The polymer had a melting point of 132.0°C and a melt index of 0.16 g/10 min, and a weight average molecular weight of 150,000 and a molecular weight distribution of 5.47, which were determined through gel chromatography analysis. [218] [219] COMPARATIVE EXAMPLE 3 [220] [221] Polymerization was conducted through the same procedure as in example 3 except that 0.4 mL of (trimethyl)(pentamethylcyclopentadienyl)titanium(IV) (97 %, Strem) (5 mM toluene solution), 1.0 mL of trhsobutylal\ammum (200 mM n-heptane solution) (Aldrich), and 0.6 mL of triphenyhnethyhnium tetrakis(pentafluorophenyl)borate (99 %, Boulder Scientific) (5 mM toluene solution) were used. 1.1 g of dried polymer were produced. [222] [223] COMPARATIVE EXAMPLE 4 [224] [225] Polymerization was conducted through the same procedure as in example 1 except that 0.2 mL of rac-dimethylsilylbis(2-methyhndenyl)2irconium dichloride (Boulder Scientific) (5 mM toluene solution) were used as a catalyst component. The product was dried to produce 25.0 g of polymer. The polymer had a melting point of 132.5°C and a melt index of 4.4 g/10 min, and a weight average molecular weight of 59,000 and a molecular weight distribution of 8.9, which were determined through gel chromatography analysis. [226] [227] COMPARATIVE EXAMPLE 5 [228] Claims [1] An arylphenoxy-based transition metal catalyst expressed by Formula 1, which includes a cyclopentadiene derivative and arylphenoxide as fixed ligands around a transition metal, the arylphenoxide being substituted with at least one aryl derivative and being located at an ortho position thereof, and the ligands not being crosslinked to each other: Formula 1 wherein M is a 4' group transition metal of a periodic table; Cp is a cyclopentadienyl anion capable of forming an r\| -bond along with the central metal, or a derivative thereof; R' R1 R1, R1, R1 R1, R1, and R1 of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, a C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, a C1-C20 alkylalkoxy group arbitrarily substituted with one or more halogen atoms, or a C3-C20 alkyl-substituted siloxy group or C6-C20 aryl-substituted siloxy group, optionally with the proviso that substituent groups may be arbitrarily bonded to form rings; X is selected from or is two or more independently selected from a group consisting of the halogen atom, the C1'C20 alkyl group which is not the Cp derivative, the C7-C30 arylalkyl group, an alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which has a C1-C20 hydrocarbon group; with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the CI-020 alkylalkoxy group ar bitrarily substituted with one or more halogen atoms, the C3-C20 alkyl- substituted siloxy group or C6-C20 aryl-substituted siloxy group, the amido group or a phosphido group which has the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group; and n is 1 or 2 depending on an oxidation value of the transition metal. [2] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein M is selected from a group consisting of titanium, zirconium, and hafnium. [3] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein Cp is the cyclopentadiene anion capable of forming the r\| -bond along with the central metal or the derivative thereof, and is selected from a group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetram- ethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylmethylcyclopentadienyl, trimethylsilylcy- clopentadienyl, indenyl, methylindenyl, dimethylindenyl, ethylindenyl, iso- propylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, and isopropylfluorenyl. [4] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein R' R1 R1, R', R1 R1 R' and R' of the arylphenoxide ligand are independently selected from a group consisting of the hydrogen atom, the halogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a phenyl group, a naphthyl group, a biphenyl group, a 2-isopropylphenyl group, a 3,5-xylyl group, a 2,4,6-tTimethylphenyl group, a benzyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a triphenylsiloxy group, a trifluoromethyl group, and a pentafluorophenyl group. [5] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein X of the arylphenoxide ligand is one or more selected from a group consisting of the halogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, a benzyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a dimethylamino group, and a diethylamino group. group, a tert-butyl group, an amyl group, a trime&ylsilyl group, a tert- butyldimethylsilyl group, a tripheuylsilyl group, a phenyl group, a naphfhyl group, a biphenyl group, a 2-isopropylphenyl group, a 3,5-xylyl group, a 2,4,6-trimetiiylphenyl group, a benzyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a trimethylsiloxy group, a dimethylsiloxy group, a triphenylsiloxy group, a trifluoromethyl group, a pentafluorophenyl group, a dimethylamino group, a diethylamino group, an ethylmercaptan group, an isopropylmercaptan group, and a nitro group. [7] An arylphenoxy catalyst system for producing an ethylene homopolymer or a copolymer of ethylene and a-olefin, comprising: a transition metal catalyst which includes a cyclopentadiene derivative and arylphenoxide as fixed ligands around a transition metal, the arylphenoxide being substituted with at least one aryl derivative and being located at an ortho position thereof, and the ligands not being crosslihked to each other; and an aluminoxane or boron compound cocatalyst, wherein the transition metal catalyst being expressed by Formula 1: Formula 1 wherein M is a 4 group transition metal of a periodic table; Cp is a cyclopentadienyl anion capable of forming an r\|1-bond along with the central metal, or a derivative thereof; R,R,R,R,R,R,R, and R of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, a C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, a C1-C20 alkylalkoxy group arbitrarily substituted with groups may be arbitrarily bonded to form rings; X is selected from or is two or more independently selected from a group consisting of the halogen atom, the C1-C20 alkyl group which is not the Cp derivative, the C7-C30 arylalkyl group, the alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which has a C1-C20 hydrocarbon group; Y is the hydrogen atom, the halogen atom, the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the C1-C20 alkylalkoxy group ar bitrarily substituted with one or more halogen atoms, the C3-C20 alkyl- substituted siloxy group or C6-C20 aryl-substituted siloxy group, the amido group or a phosphido group which has the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group; and n is 1 or 2 depending on an oxidation value of the transition metal. [8] The arylphenoxy catalyst system as set forth in claim 7, whereia the aluminoxane cocatalyst is expressed by Formula 5 or 6, and a molar ratio of a central metal to aluminum is 1: 50 - 1: 5000: Formula 5 (-A1(RV0-) ID Formula 6 (R'A1-(-0(RV) -(R'9) wherein R is a C1-C4 alkyl group, and m and p are each an integer ranging from 5 to 20. [9] The arylphenoxy catalyst system as set forth in claim 7, whereia the boron compound cocatalyst is selected from a group consisting of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylmethylinium tetrakis(pentafluorophenyl)borate, and tris(pentafluoro)borane. [10] The arylphenoxy catalyst system as set forth in claim 7, wherein the boron compound cocatalyst is additionally mixed with aluminoxane or organic alkyl aluminum so that a molar ratio of the central metal: a boron atom : an aluminum atom is 1 : 0.5-5 : 25-500. [11] The arylphenoxy catalyst system as set forth in claim 10, wherein the aluminoxane is selected from a group consisting of compounds expressed by Formula 5 (-Al(R')-O-) Formula 6 (R1) A1-(-0(RV) -(R' 1 1 wherein R is a C1-C20 alkyl group, and preferably a methyl group or aa isobutyl group, and in and p are each an integer ranging from 5 to 20, Formula 10 (R')A1(E) wherein R is a C1-C8 alkyl group, E is a hydrogen atom or a halogen atom, and r is an integer ranging from 1 to 3. [12] The arylphenoxy catalyst system as set forth in claim 11, wherein the organic alkyl aluminum is triethylaluminum or triisobutylaluminum. [13] A method of producing an ethylene homopolymer or a copolymer of ethylene and a-olefin using the arylphenoxy-based transition metal catalyst according to claim 1, wherein pressure in a reaction system of ethylene monomers is 10 -150 atm and a polymerization temperature is 120 - 250°C. [14] A method of producing a copolymer of ethylene and a-olefin using the arylphenoxy catalyst system according to claim 7, wherein a comonomer which is used to conduct polymerization along with ethylene is one or more selected from a group consisting of 1-butene, 1-hexene, 1-octene, and 1-decene, and an ethylene content of the copolymer is 60 wt% or more.

Full Text

Description
ARYLPHENOXY CATALYST SYSTEM FOR PRODUCING
ETHYLENE HOMOPOLYMER OR COPOLYMERS OF
ETHYLENE AND ALPHA-OLEFINS
Techmical Field
[1] The present invention relates to an arylphenoxy catalyst system for producing
ethylene homopolymer or copolymers of ethylene and a-olefins. More particularly, the present invention pertains to a 4 group transition metal catalyst expressed by Formula 1, a catalyst system which includes the arylphenoxy-based transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst, and a method of producing an ethylene homopolymer or copolymers of ethylene and a-olefins using the same. In the transition metal catalyst, a cyclopentadiene derivative and an arylphenoxide as fixed ligands are located around a 4 group transition metal, arylphenoxide ligand is substituted with at least one aryl derivative and is located at ortho position thereof, and the ligands are not cross linked to each other.
[2]
[3] Formula 1
[4]

[5]
[6] In Formula 1, wherein M is the 4 group transition metal of the periodic table;
[7] Cp is cyclopentadienyl group capable of forming an T] -bond along with the central
metal, or derivatives thereof;
[8] R1, R\ R\ R1, R1 R1, R1 and R1 of the arylphenoxide ligand are independently a
hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily

arylalkyl group arbitrarily substituted with one or more halogen atoms, an alkoxy group which contains the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, or a C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings;
X is selected from or is two or more independently selected from a group consisting of the halogen atom, the C1-C20 alkyl group which is not a Cp derivative, the C7-C30 arylalkyl group, an alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which has a C1-C20 hydrocarbon group;
Y is the hydrogen atom, the halogen atom, the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the alkoxy group which contains the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, the amido group or aphosphido group which contains the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group; and
n is 1 or 2 depending on the oxidation state of transition metal.
Background Art
Conventionally, Ziegler-Natta catalyst system which comprises a main catalyst component of titanium or vanadium compounds and a cocataly st component of alkyl aluminum compounds has been used to produce an ethylene homopolymer or copolymers of ethylene and a-olefins. However, the Ziegler-Natta catalyst system is disadvantageous in that, even though it is highly active in the polymerization of ethylene, the molecular weight distribution of a resultant polymer is wide, and particularly, a compositional distribution is non-uniform in the copolymer of ethylene and a-olefin due to heterogeneous catalyst active sites.
Recently, the metallocene catalyst system which comprises a metallocene compound of a 4 group transition metal in the periodic table, such as titanium, zirconium, or hafnium, and methylaluminoxane as a cocatalyst has been developed. Since the metallocene catalyst system is a homogeneous catalyst having one kind of

312632, md Japanese Patent Laid-Open Publication Nos. Sho.63-092621, Hei.02-84405, and Hei.03-2347 disclose metallocene compounds, such as Cp TiQ , Cp ZrCl, Cp ZiMeQ, Cp ZrMe , or (ethylene-bis tetrahydroindenyl)ZrCl, activated
ii £i *i i, ii 2
with methylalmninoxane as a cocatalyst to polymerize elhylene at high catelytic activity, thereby making it possible to produce polyethylene having a molecular weight distribution (Mw/Mn) of 1.5 - 2.0. However, it is difficult to produce a polymer having a high molecular weight using the above catalyst system. Particularly, if it is applied to a solution polymerization process which is conducted at high temperatures of 140°C or higher, polymerization activity is rapidly reduced and a-hydrogen elimination reaction is dominant, thus it is unsuitable for producing a high molecular weight polymer having a weight average molecular weight (Mw) of 100,000 or more.
Meanwhile, a constrained geometry non-metallocene catalyst (a so-called single-site catalyst) in which a transition metal is connected to a ligand system in a ring shape has been suggested as a catalyst which has high catalytic activity and is capable of producing a polymer having a high molecular weight in polymerization of only ethylene or in copolymerization of ethylene and a-olefin under a solution polymerization condition. EP Pat. Nos. 0416815 and 0420436 suggest a catalytic system in which a transition metal is connected to cyclopentadiene ligand and an amide group in a ring shape, and EP Pat. No. 0842939 discloses a catalyst in which a phenol-based ligand as an electron donor compound is connected with a cyclopentadiene ligand in a ring shape. However, since the cyclization of the ligands along with the transition metal compound is achieved at very low yield during synthesis of the constrained geometry catalyst, it is difficult to commercialize them.
Meanwhile, an example of non-metallocene catalysts which is not a constrained geometry catalyst and is capable of being used under a high temperature solution condition are disclosed in US Pat. No. 6,329,478 and Korean Patent Laid-Open Publication No. 2001-0074722. The patents disclose a single-site catalyst using one or more phosphinimine compounds as a ligand, having high ethylene conversion during copolymerization of ethylene and a-olefins under the high temperature solution polymerization condition at 140°C or higher. However, a limited range of phosphine compounds may be used to produce the phosphinimine ligand, and, since these compounds are harmful to the environment and to humans, it might have some difficulties in using them to produce general-purpose olefin polymers. US Pat. No. 5,079,205 discloses a catalyst having a bis-phenoxide ligand, but it has too low catalytic acitivity to be commercially used.

phenol ligand are limited to only simple alkyl substituents such as isopropyl group. On the other hand, /. Organomet Chenu 1999,591,148 (Rothwell, P. et al) discloses an arylphenoxy liganxi, but does not suggest the effects of aryl substituent at the ortho-position.
Disclosure of Invention
Technical Problem
To accomplish the above problems occurring in the prior art, the present inventors have conducted extensive studies, resulting in the finding that a non-bridged type transition metal catalyst, in which cyclopentadiene derivatives and arylphenoxide substituted with at least one aryl derivative at the ortho-position thereof are used as fixed ligands, shows an excellent thermal stability. Based on the above finding, a catalyst, which is used to produce an ethylene homopolymer or copolymers of ethylene and a-olefins having a high molecular weight, at a high activity during a solution polymerization process at high temperatures of 80°C or higher, has been developed, thereby the present invention is accomplished.
Accordingly, an object of the present invention is to provide a single-site catalyst and a high temperature solution polymerization method using the same. The single-site catalyst includes environmentally-friendly raw materials, synthesis of the catalyst is very economical and thermal stability of the catalyst is excellent. In the solution polymerization method, it is possible to easily and commercially produce an ethylene homopolymer or copolymers of ethylene and a-olefins having various physical properties using the catalyst. Technical Solution
In order to accomplish the above object, an aspect of the present invention provides an arylphenoxy-based transition metal catalyst expressed by Formula 1, which includes a cyclopentadiene derivative and arylphenoxide as fixed ligands around a transition metal. Arylphenoxide is substituted with at least one aryl derivative and is located at the ortho position thereof, and the ligands are not crosslinked to each other.

In Formula 1, wherein M is the 4 group transition metal of a periodic table; Cp is cyclopentadienyl group, capable of forming an T]1-bond along with the central metal, or a derivative thereof;

R,R,R,R,R,R,R, and R of the arylphenoxide hgand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, a C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, an alkoxy group which has the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, or a C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings;
X is selected from or two or more independently selected from a group consisting of the halogen atom, the C1-C20 alkyl group which is not a Cp derivative, the C7-C30 arylalkyl group, an alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which contains a C1-C20 hydrocarbon group;
Y is the hydrogen atom, the halogen atom, the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the alkoxy group which has the C1-C20 alkyl group arbitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group, the amido group or a phosphide group which has the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group; and
n is 1 or 2 depending on the oxidation state of the transition metal.
Another aspect of the present invention relates to a catalyst system which comprises the transition metal catalyst, and aluminum or a boron compound as a cocatalyst.
Still another aspect of the present invention relates to a method of producing ethylene polymers using the transition metal catalyst.
Advantageous Effects

raw materials at high yield, and it has high catalytic activity in a high temperature solution polymerization condition due to its excellent thermal stability in the course of producing a polymer having a high molecular weight, thus it is more useful than a conventional non-metallocene single-site catalyst. Therefore, it is useful for producing an ethylene homopolymer or copolymers of ethylene and a-olefins haviag various physical properties.
Brief Description of the Drawings
The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 illustrates a crystalline structure of a (dichloro)(cyclopentadienyl)(4-methyl-2,6-bis(2'-isopropylphenyl)phenoxy)titanium(I V) catalyst according to the present invention; and
FIG. 2 illustrates a crystalline structure of a (dichloro)(pentamethylcyclopentadienyl)(2-phenylphenoxy)titanium(IV) catalyst according to the present invention.
Best Mode for Carrying Out the Invention
Hereinafter, a detailed description will be given of the present invention.
M of the transition metal catalyst in Formula 1 is preferably titanium, zirconium, or hafnium. Furthermore, Cp is a cyclopentadiene anion capable of forming an ri -bond along with a central metal, or a derivative thereof. In detail, it is exemplified by cy-clopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcy-clopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butyhnethylcyclopentadienyl, trimethylsilylcy-clopentadienyl, indenyl, methylindenyl, dimethylindenyl, ethylindenyl, iso-propylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, and iso-propylfluorenyl.
With respect to R\ R1 R1 R\ R1 R1 R\ and R1 of an arylphenoxide ligand, a halogen atom is exemplified by fluorine, chlorine, bromine, and iodine atoms; and a C1-C20 alkyl group is exemplified by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group, and preferably, methyl group, ethyl group, isopropyl group, tert-butyl group, and amyl group. The alkyl group may ar-

group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, di-bromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, per-fluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, percbloropropyl group, perchlorobutyl group, per-chloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group, or perbromoeicosyl group. Among them, trifluoromethyl group is preferable. In R\ R , R1, R'1, R1, R1, R1, and R\ a C1-C20 alkyl-substituted silyl group is exemplified by meihylsilyl group, ethylsUyl group, phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tri-cyclohexylsilyl group, or triphenylsilyl group, and preferably trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group. A C6-C30 aryl group is exemplified by phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, biphenyl group, fluorenyl group, triphenyl group, naphthyl group, or anthracenyl group, and preferably, phenyl group, naphthyl group, biphenyl group, 2-isopropylphenyl group, 3,5-xylyl group, and 2,4,6-trimethylphenyl group. A C7-C30 arylalkyl group is exemplified by benzyl group, (2-methylphenyl)methyl group, (3-methylphenyl)methyl group.

trhodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluo-ropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, per-chlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, per-bromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, peibromododecyl group, perbromopentadecyl group, or perbromoeicosyl group, aod preferably, trifluoromethyl group. Furthermore, in Y, a C1-C20 alkyl-substituted silyl group is exemphfied by methylsilyl group, ethylsilyl group, phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, trhsopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyldimethylsilyl group, txi-n-pentylsilyl group, tri-n-hexylsilyl group, tri-cyclohexylsilyl group, or triphenylsilyl group, and preferably trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group. A C6-C30 aryl group is exemphfied by phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimeihylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trijnethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, biphenyl group, fluorenyl group, triphenyl group, naphthyl group, or anthracenyl group, and preferably, phenyl group, naphthyl group, biphenyl group, 2-isopropylphenyl group, 3,5-xylyl group, and 2,4,6-trimethylphenyl group. A C7-C30 arylalkyl group is exemphfied by benzyl group, (2-methylphenyl)methyl group, (3-methylphenyl)methyl group.

(3,4,5-trhnethylphenyl)ine1hyl group, (2,4,6-trimethylphenyl)methyl group, (2,3,4,5-te1xaniethylphenyl)inethyl group, (2,3,4,6-tetrainethylphenyl)methyl group, (2,3,5,6-tetramethylphenyl)inethyl group, (pentainethylphenyl)methyl group, (ethylphenyl)methyl group, (n-propylphenyl)methyl group, (isopropylphenyl)inethyl group, (n-butylphenyl)methyl group, (sec-butylphehyl)inethyl group, (tert-butylphenyl)methyl group, (h-pentylphenyl)methyl group, (neopentylphenyl)methyl group, (h-hexylphenyl)methyl group, (n-octylphenyl)inethyl group, (n-decylphenyl)methyl group, (n-dodecylphenyl)methyl group, (n-tetradecylphenyl)inethyl group, naphthylmethyl group, or anthracenylmethyl group, and preferably, benzyl group. A C1-C20 alkoxy group is exemphfied by methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadecoxy group, or n-eicosoxy group, and preferably, methoxy group, ethoxy group, isopropoxy group, and tert-butoxy group. A C3-C20 alkyl-substituted or C6-C20 aryl-substituted siloxy group is exemphfied by trimethylsiloxy group, triethylsiloxy group, tri-n-propylsiloxy group, trhsopropylsiloxy group, tri-n-butylsiloxy group, tri-sec-butylsiloxy group, tri-tert-butylsiloxy group, tri-isobutylsiloxy group, tert-butyldimethylsiloxy group, tri-n-pentylsiloxy group, tri-n-hexylsiloxy group, tricyclohexylsiloxy group, or triphenylsiloxy group, and preferably, trimethylsiloxy group, tert-butyldimethylsiloxy group, and triphenylsiloxy group. The above-mentioned substituent groups may be substituted with one or more halogen atoms. As well, with respect to Y, an amido group or a phosphido group having a CI-020 hydrocarbon group is exemphfied by dimethylamino group, di-ethylamino group, di-n-propylamino group, dhsopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, dhsobutylamino group, tert-butyhsopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, dibenzylamide group, methylethylamide group, methylphenylamide group, benzylhexylamide group, bistrimethylsilylamino group, or bis-tert-butyldimethylsilylamino group, or phosphido group which is substituted with the same alkyl. Among them, dimethylamino group, diethylamino group, and diphenylamide group are preferable. A C1-C20 mercapto group is exemphfied by methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, 1-butyl mercaptan, or isopentyl mercaptan, and preferably, ethyl mercaptan and isopropyl mercaptan.

which is expressed by Formula 2 and substituted with one or two halogen atoms, and a substituted or unsubstituted arylboronic acid, which is as shown in Fonnula 3, are reacted with an organic phosphine hgand using a palladium metal compound as a catalyst in an organic solvent at preferably -20 to 120°C to produce an aryl-substituted anisole compound, and reacted with a tribromoboron compound in an organic solvent at a temperature preferably ranging from -78 to 50°C to produce an aryl-substituted phenoxide hgand. The hgand thus produced is reacted with sodium hydride, alkyl hthium, or alkyl magnesium hahde compound in an organic solvent at a temperature preferably ranging from -78 to 120°C so as to be converted into anions, and then subjected to a hgand exchange reaction along with the 4 transition metal compound which is expressed by Formula 4 and has one cyclopentadiene derivative at -20 to 120°C in an equivalent ratio. The resulting product is purified to produce an arylphenoxide-based transition metal catalyst component. Formula 2

In the above Formula 2or3, R,R,R,R,R,R,R, and R are independently a hydrogen atom, a halogen atom, a C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms,

alkyl-substituted siloxy group or C6-C20 aryl-snbstituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings; Q is the halogen atom; and Y is the hydrogen atom, the halogen atom, the C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C1-C20 hnear or nonhnear alkyl group arbitrarily substituted with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted with one or more halog1i atoms, the C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the C1-C20 alkylalkoxy group arbitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-substituted siloxy group or C6-C20 aryl-substituted siloxy group, the amido group or a phosphido group which has the C1-C20 hydrocarbon group, or a C1-C20 alkyl-substituted mercapto or nitro group.
Formula 4 CpM(X)
Dl
In Formula 4, Cp is cyclopentadienyl capable of forming an T] -bond along with a central metal, or a derivative thereof, M is a 4 group transition metal in a periodic table, X is a halogen atom, a C1-C20 alkyl group which is not a Cp derivative, a C7-C30 arylalkyl group, a C1-C20 alkylalkoxy group, a C3-C20 alkyl-substituted siloxy group, or an amido group having a C1-C20 hydrocarbon group, and m is 2 or 3 depending on the oxidation value of the transition metal.
Meanwhile, in order to use the transition metal catalyst of Formula 1 as an active catalyst component which is used to produce an ethylene homopolymer or copolymer of ethylene and an a-olefin comonomers, an X hgand is extracted from a transition metal complex to convert the central metal into cations, and aluminoxane compounds or boron compounds which are capable of acting as opposite ions having weak bonding strength, that is, anions, are used along with a cocatalyst.
As well known in the art, aluminoxane, which is expressed by the following Formula 5 or 6, is frequentiy used as the aluminoxane compound used in the present invention.
Formula 5 (-Al(R')-O-)
m

or an isobutyl group, and m and p are integers ranging from 5 to 20.
In order to use the transition metal catalyst of the present invention as an active catalyst, the mixing ratio of the two components is set so that the molar ratio of the central metal to aluminum is preferably 1:20 to 1:10,000, and more preferably, 1:50 to 1:5,000.
Furthermore, a boron compound which is capable of being used as a cocatalyst of the present invention may be selected from compounds of the following Formulae 7 to 9 as disclosed in US Patent No. 5,198,401.

In the above Formulae, B is a boron atom; R is an unsubstituted phenyl group, or a phenyl group which is substituted with 3 to 5 substituent groups selected from the group consisting of a C1-C4 aDcyl group which is substituted or unsubstituted with a fluorine atom and a C1-C4 alkoxy group which is substituted or unsubstituted with the fluorine atom; R11 is a C5-C7 cychc aromatic cation or an alkyl-substituted aromatic cation, for example, triphenylmethyl cation; Z is a nitrogen atom or a phosphorus atom; R11 is a C1-C4 alkyl radical or an anihnium radical which is substituted with two C1-C4 alkyl groups along with a nitrogen atom; and q is an integer of 2 or 3.
Examples of the boron-based cocatalyst taclude tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate, tetra]ds(2,3,5,6-tetrafluorophenyl)borate, tetralds(2,3,4,5-tetrafluorophenyl)borate, tetra]ds(3,4,5-tetrafluorophenyl)borate, tetrakis(2,2,4-trifluorophenyl)borate, phenylbis(pentafIuorophenyl)borate, andtetrakis(3,5-bistrifluoromethylphenyl)borate. Furthermore, a combiaation of the above-mentioned examples is exemphfied by ferrocenium tetra]ds(pentafluorophenyl)borate, l,l'-dimethylferrocenium

In a catalyst system using the boron-based cocatalyst, the molar ratio of the central metal to the boron atom is preferably 1:0.01 -1:100, and more preferably, 1:0.5 -1:5.
Meanwhile, a mixture of the boron compound and the organic aluminum compound or a mixture of the boron compound and the aluminoxane compound may be used, if necessary. In connection with this, the aluminum compound is used to remove polar compounds acting as a catalytic poison from a reaction solvent, and may act as an alkylating agent if X of the catalyst components is halogen.
The organic aluminum compound is expressed by the foDowing Formula 10.
Formula 10
(R')A1(E)
r 3-r
In the above Formula, R is a C1-C8 alkyl group, E is a hydrogen atom or a halogen atom, and r is an integer ranging from 1 to 3.
The organic aluminum compound is exemplified by trialkkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dialkylaluminum chloride including dimethylalumiaum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride; alkylaluminum dichloride including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum

preferable, and triethylaluininum and trhsobutylaluininuin are more preferable.
In connection wifb this, the molar ratio of the central metal: the boron atom: the aluminunxatonhs preferably 1: 0.1 - 100 :10 - 1000, and more preferably, 1: 0.5 - 5 : 25 - 500.
According to another aspect of the present invention, in a method of producing ethylene polymers using the transition metal catalyst system, the transition metal catalyst, the cocatalyst, and ethylene or a vinyl-based comonomer come into contact with each other in the presence of a predetermined organic solvent At this stage, the transition metal catalyst and the cocatalyst are separately loaded into a reactor, or loaded into the reactor after they are previously mixed with each other. There are no hmits to miring conditions, such as the order of addition, temperature, or concentration.
The organic solvent useful in the method is C3-C20 hydrocarbons, and is exemphfied by butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene.
In detail, when the ethylene homopolymer, that is, high density polyethylene (HDPE), is produced, ethylene is used alone as a monomer, and pressure of ethylene useful to the present invention is 1 -1000 atm, and preferably, 10-150 atm. Furthermore, a polymerization temperature is 80 - 300°C, and preferably, 120 - 250111. Additionally, when the copolymers of ethylene and a-olefins are produced, C3-C18 a-olefins are used as comonomers along with ethylene, and are selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene. More preferably, 1-butene, 1-hexene, 1-octene, or 1-decene is copolymerized with ethylene. In connection with this, the pressure of ethylene and the polymerization temperature are preferably the same as in the method of producing high density polyethylene. The ethylene copolymers produced according to the present invention include 60 wt% or more ethylene, and preferably, 75 wt% ethylene. As described above, hnear low density polyethylene (LLDPE) which is produced using C4-C10 a-olefin as the comonomer has a density of 0.910 - 0.940 g/cc, and, in connection with this, it is possible to produce very or ultra low density polyethylene (VLDPE or ULDPE) having a density of 0.910 g/cc or less. As well, in the course of producing the ethylene homopolymer or copolymers according to the present invention, hydrogen may be used as a molecular weight controlhng agent to control a molecular weight, and the ethylene homopolymer or copolymers typically has weight average molecular weight (Mw) of 80,000 -500,000.

which is conducted at a temperature of a melting point or higher of the polymer to be produced. However, as disclosed in US Patent No. 4,752,597, the transition metal catalyst and the cocatalyst may be supported by a porous metal oxide supporter so as to be used in a slurry polymerization process or a gaseous polymerization process as a heterogeneous catalyst system.
Mode for the Invention
A better understanding of the present invention may be obtained through the following examples which are set forth to illustrate, but are not to be construed as the hmit of the present invention.
Syntheses of all hgands and cataysts were conducted using standard Schlenk or globe box technology in a nitrogen atmosphere if not specifically described otherwise. The organic solvents used in the reactions were refluxed in the presence of sodium metal and benzophenone to remove moisture, and distilled immediately before they were used. 'H-NMR analyses of the produced hgands and catalysts were carried out at normal temperature using Varian Oxford 300 MHz.
n-heptane as a polymerization solvent was passed through a column in which a molecular sieve 5A and activated alumina were packed, and bubbhng was conducted using highly pure nitrogen to sufficiently remove moisture, oxygen, and other catalytic poison materials before it was used. The resulting polymers were analyzed using the following methods.
L Melt index (MI)
Measurement was conducted based on ASTM D 2839.
2. Density
Measurement was conducted using a density gradient colurm based on ASTM D 1505.
3. Analysis of a melting point (T )
Measurement was conducted using Dupont DSC2910 in a nitrogen atmosphere at a rate of 10°C/min under a 211111 heating condition.
4. Molecular weight and molecular weight distribution
Measurement was conducted using PL210 GPC which was equipped with PL Mixed-BX2+preCol in a 1,2,3-trichlorobenzene solvent at 135X and a rate of 1.0 mlV min, and the molecular weight was revised using a PL polystyrene standard material.
5. a-olefin content of copolymer (wt%)
Measurement was conducted using a Bruker DRX500 nuclear magnetic resonance

Macromol Chenu Phys, 1980, C29,201). PREPARA.TION EXAMPLE 1
Synthesis of 4-methyl-2,6-bisr2'-isopropvlpheDyl)phenol
A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibroTno-4-methylanisole (400 mg, 1.43 inmol), 2-isopropylphenylboronic acid (720 mg, 4.39 mmol), palladium acetate (14 mg, 0,062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were then removed to produce 670 mg of grey 4-methyl-2,6-bis(2'-isopropylphenyl)anisole sohd. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) was dropped thereon at -78°C, and a reaction was carried out while the temperature was slowly mcreased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 0.47 g of white 4-methyl-2,6-bis(2'-isopropylphenyl)phenol sohd.
Yield: 95 %, 'H-NMR (CDCy6= 1.12-1.19 (m, 12H), 2.34 (s, 3H), 2.93 (m, 2H), 4.51 (s, IH), 6.95 (s, 2H), 7.24 (d, 4H), 7.42 (t, 4H) ppm
Synthesis of
('dichloro)fpentamethylcvclopentadienvl)4-methvl-216-bisf2'-isopropvlph&nvl)phenox y)titanium(IV)
4-methyl-2,6-bis(2'-isopropylphenyl)phenol (344 mg, 1 mmol) and sodium hydride (72 mg, 3 mmol) were dissolved in 10 mL of toluene, and then refluxed for 4 hours. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (289 mg, 1 mmol) was dissolved in 5 mL of toluene was slowly added thereto, and reflux was conducted for 24 hours.

conducted at reduced pressure to produce 352 mg of red sohd component
Yield: 67 %, 'H-NMR (C Dp5= 0.95-1.26 (m, 12H), 1.62 (s, 15H), 1.88 (s, 3H), 3.17 (m, 2H), 6.94-7.29 (m, lOH) ppm
EXAMPLE 1
300 mL of n-heptane was added into a stainless steel reactor which was purged with nitrogen after sufficient drying and had a volume of 500 mL, and 0.5 mL of trhsobuty-laluminum (Aldrich) (200 vcM n-heptane solution) was added thereto. The temperature of the reactor was then increased to 140°C, and, subsequently, 0.2 mL of (dichIoro)(pentamethylcyclopentadienyl)(4-methyl-2,6-bis(2'-isopropylphenyl)phenox y)titanium(IV) (5 mM toluene solution), produced according to preparation example 1, and 0.3 mL of triphenylmethyhnium tetrakis(pentafluorophenyl)borate (99 %, Boulder Scientific) (5 mM toluene solution) were sequentially added thereto. Ethylene was then injected into the reactor until the pressure in the reactor was 30 atm, and was continuously fed for polymerization. 10 min after the reaction started, 10 mL of ethanol (including 10 vol% hydrochloric acid aqueous solution) were added to finish the polymerization, agitation was conducted for 4 hours along with 1500 mL of additional ethanol, and products were filtered and separated. The resulting product was dried in a vacuum oven at 60°C for 8 hours to produce 7.3 g of polymer. The polymer had a melting point of 132.1°C and a melt index of 0.001 g/10 min or less, and a weight average molecular weight of 393,000 and a molecular weight distribution of 3.36, which were determined through gel chromatography analysis.
EXAMPLE 2
15 mL of 1-octene were injected into a reactor which was the same as in example 1, and polymerization was then conducted through the same procedure as in example 1 except that 0.3 mL of
(dichloro)(pentamethylcyclopentadienyl)(4-metfayl-2,6-bis(211isopropylphenyl)phenox y)titanium(IV) (5 mM toluene solution) and 0.45 mL of triphenylmethyhnium tetra]ds(pentafluorophenyl)borate (Boulder Scientific) (5 mM toluene solution) were added after 0.75 mL of trhsobutylaluminum (Aldrich) (200 mM n-heptane solution) were added. 4.0 g of dried polymer was obtained. The weight average molecular weight was 175,000 and a molecular weight distribution was 5.91, which were

PREPARATION EXAMPLE 2
Synthesis of 4-methvl'2-(2'-isapropvlphenyl>phenQl
A mixed solution of 1 IDL of water and 4 mL of dimethoxyethane was added into a flask into which 2-bromo-4-methylanisole (600 mg, 2.98 mmol), 2-isopropylphenylboronic acid (734 mg, 4.47 mmol), palladium acetate (16 mg, 0.074 mmol), triphenylphosphine (72 mg, 0.27 mmol), and potassium phosphate (1.12 g, 5.28 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues with diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were removed to produce 850 mg of grey 4-methyl-2-(2'-isopropylphenyl)anisole sohd. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 inL of boron tribromide (1 M methylene chloride solution) was dropped thereonto at -781C, and a reaction was carried out while the temperature slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 633 mg of white 4-methyl-2,6-(2'-isopropylphenyl)phenol sohd.
Yield: 93 %, 'H-NMR (CDQ )6= 1.10-1.21(q, 6H), 2.33 (s, 3H), 2.91 (m, IH), 4.63 (s, IH), 6.87-7.51 (m, 7H) ppm
Synthesis of
(dicbloro>fpentamethvlcvclopentadienvl¥4-methvl-2-f2'-isopropvlDhenvl')phenoxv>tita niumflV)
4-methyl-2-(2'-isopTopylphenyl)phenol (1 g, 4.41 mmol) and sodium hydride (318 mg, 13.25 mmol) were dissolved in 10 mL of toluene, and then refluxed for 4 hours. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (1.15 g, 4.0 mmol) was dissolved in 5 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction was finished, volatile materials were removed, washing

Yield: 67 %, 'H-NMR (Cp1b1 0.96-1.07 (m, 6H), 1.76 (s, 15H), 1.89 (s, 3H), 2.99 (m, IH), 6.85-7.37 (m, 7H) ppm
EXAMPLES
Polymerization was conducted through the same procedxire as in example 2 except that 0.2 mL of (dichloro)(pentamethylcyclopentadienyl)(4-met hyl-2-(2'-isopropylphenyl)phenoxy)titanium(IV) (5 mM toluene solution) produced according to preparation example 2 were used. The product was dried to produce 5.5 g of polymer. The polymer had a melting point of 132.11 and a melt index of 0.06 g/10 min, and a weight average molecular weight of 188,000 and a molecular weight distribution of 4.30 which were determined through gel chromatography analysis.
PREPARATION EXAMPLE 3
Synthesis of 4-methvl-2.6-dipbenvlphenol
A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), phenylboronic acid (535 mg, 4.39 mmol), palladium acetate (14 mg, 0.062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of di-ethylether were added thereto to separate an organic layer and extract residues usmg diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were removed to produce 420 mg of grey
4-methyl-2,6-diphenylanisole sohd. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was carried out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 333 mg of white 4-methyl-2,6-diphenylphenol sohd.

Synthesis of (dicbloroVpentametfavlcvclopeDtadienvlV4-metfayl-2.6-diphenvlpheDOXv>tit1
4-inethyl-2,6-diphehylphenol (400 mg, 1.53 imnol) and sodium hydride (110 mg, 4.60 mmol) were dissolved in 10 niL of toluene, and then refluxed for 4 hours. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentaniethylcyclopentadienyl)titaniuin(rV) (376 mg, 1.30 imnol) was dissolved in 5 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction finished, volatile materials were removed, washing was conducted using purified hexane, recrystalhzation was conducted using a mixed solution of toluene/hexane at -35X, filtration was conducted, and drying was conducted at reduced pressure to produce 308 mg of red sohd component.
Yield: 46 %, 'H-NMR (C1D1&= 1.87 (s1H), 1.67 (s, 15H), 6.97-7.18 (m, 12H) ppm
EXAMPLE 4
Polymerization was conducted through the same procedure as in example 2 except that 0.2 mL of
(dichloro)(pentamethylcyclopentadienyl)(4-methyl~2,6-diphenylphenoxy)titanium(rV) (5 mM toluene solution) produced according to preparation example 3 were used. The product was dried to produce 5.8 g of polymer. The polymer had a melting point of 131-4°C and a melt index of 0.011 g/10 min, and a weight average molecular weight of 349,000 and a molecular weight distribution of 2.74, which were determined through gel chromatography analysis.
PREPARATION EXAMPLE 4
Svnthesis of rdichloro¥pentametfavlcvclopentadienvl¥2-pbenvlphenoxy')titaniumrrV>
After 0.86 g of 2-phenylphenol (5.07 mmol) (Aldrich, 99 %) were dissolved in 40 mL of toluene, 2.4 mL of butyl hthhmi (2.5 M hexane solution) were slowly dropped thereonto at 0°C. After the reaction was conducted at normal temperature for 12 hours, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (1.32 g, 4.56 mmol) was dissolved in 10 mL of toluene was slowly dropped thereonto at O1'C. After agitation was conducted at normal temperature for 12 hours, filtration was conducted,

Yield: 85 %; 'H-NMR (C D18= 1,68 (s, 15H), 6.82-7.26 (m, 9H) ppm EXAMPLES
Polymerization was conducted through the same procedure as in example 2 except
that 0.2 mL of
(dicUoro)(pentamethylcyclopentadienyl)(2-phenylphenoxy)titaaium(IV) (5 mM toluene solution) produced according to preparation example 4 were used TTie product was dried to produce 10.5 g of polymer. The polymer had a melting point of 130.3°C and a melt index of 0.001 g/10 min or less, and a weight average molecular weight of 303,000 and a molecular weight distribution of 3.4, which were determined through gel chromatography analysis.
EXAlvIPLE6
Polymerization was conducted through the same procedure as in example 2 except that 03 mL of
(dichloro)(pentamethylcyclopentadienyl)(2-phenylphenoxy)titanium(TV) (5 mM toluene solution) produced according to preparation example 4 were used. 7.8 g of dried polymer were obtained. The weight average molecular weight was 139,000 and the molecular weight distribution was 2.5, as determined through gel chromatography analysis. The melt index was 0.2 g/10 min, the melting point was 118.7'1C, the density was 0.9197, and the content of 1-octene was 4.5 wt%.
PREPARATION EXAMPLE 5
Svntfaesis of 2-isopTopyl-6-phenylphenol
A mixed solution of 8 mL of water and 32 mL of dimethoxyethane was added into a flask into which 2-bromo-64sopTopylanisole (L98 g, 8.64 mmol), phenylboronic acid (2.10 g, 17.28 mmol), palladium acetate (96 mg, 0.43 mmol), triphenylphosphine (0.225 g, 0.86 mmol), and potassium phosphate (11 g, 51.84 mmol) were already added, and then refluxed at normal temperature for 12 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (15 mL) and 30 mL of di-ethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and

solution) were dropped thereonto at -78°C, and the reaction was carried out for 12 hours while the temperature was slowly increased to norma] temperature. After the reaction, a mixed solution of water (15 luL) and diethylether (30 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (15 inL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 1.72 g of white 2-isopropyl-6-phenylphenol sohd.
Yield: 94 %. 'H-NMR (CDCl )6= 1.307 (d, 6H), 3.45 (m, IH), 5.09 (s, IH), 6.95-7.43 (m, 8H) ppm
Synthesis of fdichlQrQVpentamethvlcvclopenta(Kenvl>f2-isopropvl-6-phenvlphenoxv1titaniumnrV1
2-isopropyl-6-phenylphenol (700 mg, 3.28 mmol) and sodium hydride (236 mg, 9.84 mmol) were dissolved in 10 mL of toluene, and then refluxed for 4 hours. Subsequently, coohng to nonnal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (930 mg, 3.21 mmol) was dissolved in 5 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction was finished, volatile materials were removed, washing was conducted using purified hexane, recrystalhzation was conducted using a mixed solution of toluene/hexane at -35°C, filtration was conducted, and drying was conducted at reduced pressure to produce 1.0 g of red sohd component
Yield: 64 %, 'H-NMR (C1Dp5= 1.324 (d, 6H), 1,63 (s, 15H), 3.53 (m, IH), 7.05-7.66 (m, 8H) ppm
EXAMPLE 7
Polymerization was conducted through the same procedure as in example 2 except that 0.2 mL of
(dichloro)(pentamethylcyclopentadienyl)(2--isopropyl-611phenylphenoxy)titanium(IV) (5 mM toluene solution) produced according to preparation example 5 were used. The product was dried to produce 5.5 g of polymer. The polymer had a melting point of 132.6°C and a melt index of 0.002 g/10 min, and a weight average molecular weight of 390,000 and a molecular weight distribution of 4.08, as determined through gel chromatography analysis.
PREPARATION EXAI1LE 6

Synthesis of 4-iD&tfavl-2.6-bisf3',5'--dhnethvlphenyl1 phenol
A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), 3,5-diniethylphenylboronic acid (658 mg, 4.39 mmol), palladium acetate (14 mg, 0.062 mmol), thphenylphosphine (60 mg, 0,23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coolmg to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were removed to produce 453 mg of white 4-methyl-2,6-bis(3\5'-dimethylphenyl)anisole sohd (yield 96 %). The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was carried out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 0.41 g of white 4-methyl-2,6-bis(3',5'-dimethylphenyl)phenol sohd.
Yield: 92 %, 'H-NMR (CDCy6= L55 (s, 3H), 2.37 (s, 12H), 5.35 (s, IH), 7.05 (s, 2H), 7.15 (s, 4H), 7.27 (4, 2H) ppm
PREPARATION EXAMPLE 7
Synthesis of 4-metfayl-2,6-bisfbiphenvl)phenol
A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), biphenylboronic acid (870 mg, 4.39 mmol), palladixun acetate (14 mg, 0.062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and

tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was earned out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 mL) and diethylether (10 raL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 540 mg of white 4-methyl-2,6-bis(biphenyI)phenol sohd.
[193] Yield: 92 %, 'H-NMR (CDap6= 2.39 (s, 3H), 5.34 (s, IH), 7.16-7.72 (m, 20H)
ppm
[194]
[195] Synthesis Qf
rdichloro¥pentamethvlcyclopentadienvlV4-metbvl-2.6-bisrbiph&nvl1phenoxy1titanium
OYl
[196] 4-methyl-2,6-bis(biphenyl)phenol (206 mg, 0.5 mmol) and sodium hydride (36 mg,
1.5 mmol) were dissolved in 10 mL of toluene, and then refluxed for 1 hour. Subsequently, coohng to normal temperature was conducted, a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(rV) (130 mg, 0.45 mmol) was dissolved in 10 mL of toluene was slowly dropped thereonto, and reflux was conducted for 24 hours. After the reaction was finished, volatile materials were removed, washing was conducted using purified hexane, recrystalhzation was conducted using a mixed solution of toluene/hexane at -35°C, filtration was conducted, and drying was conducted at reduced pressure to produce 0.12 g of yellow sohd component.
[197] Yield: 42 %, 'H-NMR (CDCy8= 1.60 (s, 15H), 2.48 (s, 3H), 7.08-8.15 (m, 20H)
ppm
[198]
[199] PREPARATION EXAMPLE 8
[200]
[201] Svntfaesis of 4-metfavl-2.6-bisf l'-naphtbvl>phenol
[202] A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a
flask into which 2,6-dibromo-4-methylanisole (700 mg, 2.63 mmol), 1-naphthylboronic acid (1.39 g, 8.07 mmol), palladium acetate (25 mg, 0.12 mmol), triphenylphosphine (94 mg, 0.35 mmol), and potassium phosphate (1.9 g, 8.9 mmol) were already added, and then refluxed at normal temperature for 6 hours. After coohng to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of

4-Tnethyl-2,6-bis(r-naphthyl)anisole sohd (yield 89 %). The anisole thus produced was dissolved in 10 mL of methylene chloride without separate purification, 5 mL of boron tribromide (1 M methylene chloride solution) were dropped thereonto at -78°C, and the reaction was carried out while the temperature was slowly increased to normal temperature. After the reaction, a mixed solution of water (5 xnL) and diethylether (10 mL) was added to separate an organic layer and extract an aqueous solution layer using diethylether (5 mL X 3), and the separated organic layer was dried. Residues from which volatile components were removed at reduced pressure were purified using a sihca gel chromatography tube in a mixed solvent of hexane and methylene chloride to produce 805 mg of white 4-methyl-2,6-bis(r-naphthyl)phenol sohd.
[203] Yield: 85 %, 'H-NMR(CDa )6= 2.41(s,3H), 4.71(s,lH), 7.21-7.92 (m,16H) ppm
[204]
[205] COMPARATIVE PREPARATION EXAMPLE 1
[206]
[207] Synthgsis of fdiQMorQ)fpgPtamgthyigyd9pgPtadifinyl) f2,1-tert-t)1ty?pbgDQ?y)tit1um(IV)
[208] After 600 mg of 2,6-di-tert-butylphenol (2.91 mmol) (Aldrich, 99 %) were
dissolved in 30 n1L of diethylether, 1.28 mL of butyl hthium (2.5 M hexane solution) were slowly dropped thereonto at 1131°C. After 1 hour, agitation was conducted at normal temperature for 6 hours. The resulting mixture was dissolved m diethylether, and a solution in which (trichloro)(pentamethylcyclopentadienyl)titanium(IV) (752 mg, 2.60 mmol) was dissolved in 10 mL of diethylether was slowly dropped thereonto at -30°C. After 1 hour, agitation was conducted at normal temperature for 6 hours. The solvent was removed from the resulting product, and the solvent-free product was dissolved in 10 mL of toluene and then recrystalhzed to produce 829 mg of red sohd component.
[209] Yield: 69 %; IH-NMR (CDCl )8= 1.37 (s, 18H), 2.10 (s, 15H), 6.50-7.20 (m, 3H)
ppm
[210]
[211] COMPARATIVE EXAMPLE 1
[212]
[213] Polymerization was conducted through the same procedure as in example 1 except
that 0.2 mL of
(dichloro)(pentamethylcyclopentadienyl)(2,6-di-tert-butylphenoxy)titanium(IV)(5 mM toluene solution) produced according to comparative preparation example 1 were

through gel chromatography analysis. [214]
[215] COMPARATIVE EXAMPLE 2
[216]
[217] PolyrQehzation was conducted through the same procedure as in example 2 except
that 0.2 mL of (trimethyl)(pentamethylcyclopentadienyl)titamuTn(IV) (97 %, Strem) (5 inM toluene solution), 0,24 mL of trhsobutylaluminum (200 mM n-heptane solution) (Aldrich), and 0.25 mL of triphenyhnethyhnium tetralds(pentafluorophenyl)borate (99 %, Boulder Scientific) (5 mM toluene solution) were used. The product was dried to produce 3.0 g of polymer. The polymer had a melting point of 132.0°C and a melt index of 0.16 g/10 min, and a weight average molecular weight of 150,000 and a molecular weight distribution of 5.47, which were determined through gel chromatography analysis. [218]
[219] COMPARATIVE EXAMPLE 3
[220]
[221] Polymerization was conducted through the same procedure as in example 3 except
that 0.4 mL of (trimethyl)(pentamethylcyclopentadienyl)titanium(IV) (97 %, Strem) (5 mM toluene solution), 1.0 mL of trhsobutylal\ammum (200 mM n-heptane solution) (Aldrich), and 0.6 mL of triphenyhnethyhnium tetrakis(pentafluorophenyl)borate (99 %, Boulder Scientific) (5 mM toluene solution) were used. 1.1 g of dried polymer were produced. [222]
[223] COMPARATIVE EXAMPLE 4
[224]
[225] Polymerization was conducted through the same procedure as in example 1 except
that 0.2 mL of rac-dimethylsilylbis(2-methyhndenyl)2irconium dichloride (Boulder Scientific) (5 mM toluene solution) were used as a catalyst component. The product was dried to produce 25.0 g of polymer. The polymer had a melting point of 132.5°C and a melt index of 4.4 g/10 min, and a weight average molecular weight of 59,000 and a molecular weight distribution of 8.9, which were determined through gel chromatography analysis. [226]
[227] COMPARATIVE EXAMPLE 5
[228]

Claims
[1] An arylphenoxy-based transition metal catalyst expressed by Formula 1, which
includes a cyclopentadiene derivative and arylphenoxide as fixed ligands around a transition metal, the arylphenoxide being substituted with at least one aryl derivative and being located at an ortho position thereof, and the ligands not being crosslinked to each other: Formula 1

wherein M is a 4' group transition metal of a periodic table; Cp is a cyclopentadienyl anion capable of forming an r| -bond along with the central metal, or a derivative thereof;
R' R1 R1, R1, R1 R1, R1, and R1 of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, a C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, a C1-C20 alkylalkoxy group arbitrarily substituted with one or more halogen atoms, or a C3-C20 alkyl-substituted siloxy group or C6-C20 aryl-substituted siloxy group, optionally with the proviso that substituent groups may be arbitrarily bonded to form rings;
X is selected from or is two or more independently selected from a group consisting of the halogen atom, the C1'C20 alkyl group which is not the Cp derivative, the C7-C30 arylalkyl group, an alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which has a C1-C20 hydrocarbon group;

with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted
with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily
substituted with one or more halogen atoms, the CI-020 alkylalkoxy group ar
bitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-
substituted siloxy group or C6-C20 aryl-substituted siloxy group, the amido
group or a phosphido group which has the C1-C20 hydrocarbon group, or a
C1-C20 alkyl-substituted mercapto or nitro group; and
n is 1 or 2 depending on an oxidation value of the transition metal.
[2] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein
M is selected from a group consisting of titanium, zirconium, and hafnium.
[3] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein
Cp is the cyclopentadiene anion capable of forming the r| -bond along with the
central metal or the derivative thereof, and is selected from a group consisting of
cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetram-
ethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-
butylcyclopentadienyl, tert-butylmethylcyclopentadienyl, trimethylsilylcy-
clopentadienyl, indenyl, methylindenyl, dimethylindenyl, ethylindenyl, iso-
propylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, and
isopropylfluorenyl.
[4] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein
R' R1 R1, R', R1 R1 R' and R' of the arylphenoxide ligand are independently
selected from a group consisting of the hydrogen atom, the halogen atom, a
methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl
group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl
group, a phenyl group, a naphthyl group, a biphenyl group, a 2-isopropylphenyl
group, a 3,5-xylyl group, a 2,4,6-tTimethylphenyl group, a benzyl group, a
methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a
trimethylsiloxy group, a tert-butyldimethylsiloxy group, a triphenylsiloxy group,
a trifluoromethyl group, and a pentafluorophenyl group.
[5] The arylphenoxy-based transition metal catalyst as set forth in claim 1, wherein
X of the arylphenoxide ligand is one or more selected from a group consisting of the halogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, a benzyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a dimethylamino group, and a diethylamino group.

group, a tert-butyl group, an amyl group, a trime&ylsilyl group, a tert-
butyldimethylsilyl group, a tripheuylsilyl group, a phenyl group, a naphfhyl
group, a biphenyl group, a 2-isopropylphenyl group, a 3,5-xylyl group, a
2,4,6-trimetiiylphenyl group, a benzyl group, a methoxy group, an ethoxy group,
an isopropoxy group, a tert-butoxy group, a trimethylsiloxy group, a
dimethylsiloxy group, a triphenylsiloxy group, a trifluoromethyl group, a
pentafluorophenyl group, a dimethylamino group, a diethylamino group, an
ethylmercaptan group, an isopropylmercaptan group, and a nitro group.
[7] An arylphenoxy catalyst system for producing an ethylene homopolymer or a
copolymer of ethylene and a-olefin, comprising:
a transition metal catalyst which includes a cyclopentadiene derivative and arylphenoxide as fixed ligands around a transition metal, the arylphenoxide being substituted with at least one aryl derivative and being located at an ortho position thereof, and the ligands not being crosslihked to each other; and an aluminoxane or boron compound cocatalyst, wherein the transition metal catalyst being expressed by Formula 1: Formula 1

wherein M is a 4 group transition metal of a periodic table; Cp is a cyclopentadienyl anion capable of forming an r|1-bond along with the central metal, or a derivative thereof;
R,R,R,R,R,R,R, and R of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C6-C30 aryl group arbitrarily substituted with one or more halogen atoms, a C7-C30 arylalkyl group arbitrarily substituted with one or more halogen atoms, a C1-C20 alkylalkoxy group arbitrarily substituted with

groups may be arbitrarily bonded to form rings;
X is selected from or is two or more independently selected from a group consisting of the halogen atom, the C1-C20 alkyl group which is not the Cp derivative, the C7-C30 arylalkyl group, the alkoxy group which contains the C1-C20 alkyl group, the C3-C20 alkyl-substituted siloxy group, and an amido group which has a C1-C20 hydrocarbon group;
Y is the hydrogen atom, the halogen atom, the C1-C20 linear or nonlinear alkyl
group arbitrarily substituted with one or more halogen atoms, the silyl group
which contains the C1-C20 linear or nonlinear alkyl group arbitrarily substituted
with one or more halogen atoms, the C6-C30 aryl group arbitrarily substituted
with one or more halogen atoms, the C7-C30 arylalkyl group arbitrarily
substituted with one or more halogen atoms, the C1-C20 alkylalkoxy group ar
bitrarily substituted with one or more halogen atoms, the C3-C20 alkyl-
substituted siloxy group or C6-C20 aryl-substituted siloxy group, the amido
group or a phosphido group which has the C1-C20 hydrocarbon group, or a
C1-C20 alkyl-substituted mercapto or nitro group; and
n is 1 or 2 depending on an oxidation value of the transition metal.
[8] The arylphenoxy catalyst system as set forth in claim 7, whereia the aluminoxane
cocatalyst is expressed by Formula 5 or 6, and a molar ratio of a central metal to aluminum is 1: 50 - 1: 5000: Formula 5 (-A1(RV0-)
ID
Formula 6
(R'A1-(-0(RV) -(R'9)
wherein R is a C1-C4 alkyl group, and m and p are each an integer ranging from
5 to 20.
[9] The arylphenoxy catalyst system as set forth in claim 7, whereia the boron
compound cocatalyst is selected from a group consisting of
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylmethylinium
tetrakis(pentafluorophenyl)borate, and tris(pentafluoro)borane.
[10] The arylphenoxy catalyst system as set forth in claim 7, wherein the boron
compound cocatalyst is additionally mixed with aluminoxane or organic alkyl
aluminum so that a molar ratio of the central metal: a boron atom : an aluminum
atom is 1 : 0.5-5 : 25-500.
[11] The arylphenoxy catalyst system as set forth in claim 10, wherein the
aluminoxane is selected from a group consisting of compounds expressed by

Formula 5
(-Al(R')-O-)
Formula 6
(R1) A1-(-0(RV) -(R'
1 1
wherein R is a C1-C20 alkyl group, and preferably a methyl group or aa
isobutyl group, and in and p are each an integer ranging from 5 to 20,
Formula 10
(R')A1(E)
wherein R is a C1-C8 alkyl group, E is a hydrogen atom or a halogen atom, and
r is an integer ranging from 1 to 3.
[12] The arylphenoxy catalyst system as set forth in claim 11, wherein the organic
alkyl aluminum is triethylaluminum or triisobutylaluminum.
[13] A method of producing an ethylene homopolymer or a copolymer of ethylene
and a-olefin using the arylphenoxy-based transition metal catalyst according to
claim 1, wherein pressure in a reaction system of ethylene monomers is 10 -150
atm and a polymerization temperature is 120 - 250°C.
[14] A method of producing a copolymer of ethylene and a-olefin using the
arylphenoxy catalyst system according to claim 7, wherein a comonomer which
is used to conduct polymerization along with ethylene is one or more selected
from a group consisting of 1-butene, 1-hexene, 1-octene, and 1-decene, and an
ethylene content of the copolymer is 60 wt% or more.

Documents:

6071-CHENP-2007 CORRESPONDENCE OTHERS 16-09-2011.pdf

6071-CHENP-2007 ENGLISH TRANSLATION 16-09-2011.pdf

6071-CHENP-2007 FORM-13 16-09-2011.pdf

6071-CHENP-2007 OTHER DOCUMENT 16-09-2011.pdf

6071-CHENP-2007 AMENDED CLAIMS 28-11-2014.pdf

6071-CHENP-2007 AMENDED PAGES OF SPECIFICATION 22-12-2014.pdf

6071-CHENP-2007 CORRESPONDENCE OTHERS 04-03-2014.pdf

6071-CHENP-2007 ENGLISH TRANSLATION 28-11-2014.pdf

6071-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 28-11-2014.pdf

6071-CHENP-2007 FORM-1 22-12-2014.pdf

6071-CHENP-2007 FORM-1 28-11-2014.pdf

6071-CHENP-2007 POWER OF ATTORNEY 28-11-2014.pdf

6071-chenp-2007 correspondance others.pdf

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6071-chenp-2007-abstract.pdf

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6071-chenp-2007-description(complete).pdf

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Patent Number

264344

Indian Patent Application Number

6071/CHENP/2007

PG Journal Number

52/2014

Publication Date

26-Dec-2014

Grant Date

23-Dec-2014

Date of Filing

31-Dec-2007

Name of Patentee

SK INNOVATION CO., LTD

Applicant Address

99 SEORIN-DONGJONGRO-GU, SEOUL 110-110

Inventors:

#	Inventor's Name	Inventor's Address
1	WOO, TAE, WOO	108-404, SEJONG APT JEONMIN-DONG YUSEONG-GU DAEJEON 305-728
2	KIM, TAE, JIN	102-502, HANGANG APT 29 DANGSAN-DONG 4-GA YEONGDEUNGPO-GU SEOUL 150-044
3	OK, MYUNG, AHN	308-603, EXPO APT JEONMIN-DONG, YUSEONG-GU DAEJEON 305-761
4	HAHN, JONG, SOK	211-1702, EXPO APT JEONMIN-DONG, YUSEONG-GU DAEJEON 305-761
5	LEE, MAL, OU	2-1306, SUJEONG TOWN APT DUNSAN-DONG, SEO-GU DAEJEON 302-775
6	KANG, SANG, OOK	112-801, SEOCHO RAEMIAN APT SEOCHO 4-DONG SEOCHO-GU, SEOUL 137-775
7	KO, SUNG, BO	501-701, EXPO APT JEONMIN-DONG, YUSEONG-GU DAEJEON 305-762
8	KIM, SUNG, KWAN	449-10, OKSAN-RI SANCHEONG-EUP SANCHEONG-GUN GYEONGSANG-NAM-DO 666-805

PCT International Classification Number

C08F 4/64

PCT International Application Number

PCT/KR05/03441

PCT International Filing date

2005-10-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10-2005-0059354	2005-07-01	Republic of Korea