| Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefins -> Monitor Keywords |
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  Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefinsUSPTO Application #: 20070004586Title: Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefins Abstract: The present invention relates to an arylphenoxy catalyst system producing an ethylene homopolymer or copolymers of ethylene and α-olefins, and a method of producing an ethylene homopolymer or copolymers of ethylene and α-olefins having a high molecular weight under a high temperature solution polymerization condition using the same. The catalyst system includes a group IV 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 group IV 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 α-olefins having various physical properties in commercial polymerization processes. (end of abstract) Agent: Darby & Darby P.C. - New York, NY, US Inventors: Tae Woo Woo, Myung Ahn Ok, Jong Sok Hahn, Mal Ou Lee, Sang Ook Kang, Sung Bo Ko, Tae Jin Kim, Sung Kwan Kim USPTO Applicaton #: 20070004586 - Class: 502117000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Plural Component System Comprising A - Group I To Iv Metal Hydride Or Organometallic Compound - And B - Group Iv To Viii Metal, Lanthanide Or Actinde Compound - (i.e., Alkali Metal, Ag, Au, Cu, Alkaline Earth Metal, Be, Mg, Zn, Cd, Hg, Sc, Y, Al, Ga, In, Tl, Ti, Zn, Hf, Ge, Sn Or Pb Hydride Or Organometallic Compound And Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, As, Sb, Bi, Cr, Mo, W, Po, Mn, Tc, Re, Iron Group, Platinum Group, Atomic Number 57 To 71 Inclusive Or Atomic Number 89 Or Higher Compound), Component A Metal Is Group Ia, Iia Or Iiia And Component B Metal Is Group Ivb To Viib Or Viii (i.e., Alkali Metal, Alkaline Earth Metal, Be, Mg, Al, Ga, In Or Tl And Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Iron Group Or Platinum Group) (e.g., Ziegler Catalyst, Etc.), Component B Metal Is Other Than Titanium Or Vanadium The Patent Description & Claims data below is from USPTO Patent Application 20070004586. Brief Patent Description - Full Patent Description - Patent Application Claims
INCORPORATION BY REFERENCE [0001] The present application claims priority under 35 U.S.C. .sctn.119 to Korean Patent Application No. 10-2005-0059354 filed on Jul. 1, 2005. The content of the application is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to an arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and .alpha.-olefins. More particularly, the present invention pertains to a group IV 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 .alpha.-olefins using the same. In the transition metal catalyst, a cyclopentadiene derivative and an arylphenoxide as fixed ligands are located around a group IV transition metal, arylphenoxide ligand is substituted with at least one aryl derivative and is located at ortho position thereof, and the ligands are not crosslinked to each other. [0004] In Formula 1, wherein M is the group IV transition metal of the periodic table; [0005] Cp is cyclopentadienyl group capable of forming an .eta..sup.5-bond along with the central metal, or derivatives thereof; [0006] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C.sub.1-C.sub.20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C.sub.6-C.sub.30 aryl group arbitrarily substituted with one or more halogen atoms, a C.sub.7-C.sub.30 arylalkyl group arbitrarily substituted with one or more halogen atoms, an alkoxy group which contains the C.sub.1-C.sub.20 alkyl group arbitrarily substituted with one or more halogen atoms, or a C.sub.3-C.sub.20 alkyl-substituted or C.sub.6-C.sub.20 aryl-substituted siloxy group, where the substituent groups may be arbitrarily bonded to form rings; [0007] X can be independently selected from a group including the halogen atom, the C.sub.1-C.sub.20 alkyl group which is not a Cp derivative, the C.sub.7-C.sub.30 arylalkyl group, an alkoxy group which contains the C.sub.1-C.sub.20 alkyl group, the C.sub.3-C.sub.20 alkyl-substituted siloxy group, and an amido group which has a C.sub.1-C.sub.20 hydrocarbon group; [0008] Y is the hydrogen atom, the halogen atom, the C.sub.1-C.sub.20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the silyl group which contains the C.sub.1-C.sub.20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, the C.sub.6-C.sub.30 aryl group arbitrarily substituted with one or more halogen atoms, the C.sub.7-C.sub.30 arylalkyl group arbitrarily substituted with one or more halogen atoms, the alkoxy group which contains the C.sub.1-C.sub.20 alkyl group arbitrarily substituted with one or more halogen atoms, the C.sub.3-C.sub.20 alkyl-substituted or C.sub.6-C.sub.20 aryl-substituted siloxy group, the amido group or a phosphido group which contains the C.sub.1-C.sub.20 hydrocarbon group, or a C.sub.1-C.sub.20 alkyl-substituted mercapto or nitro group; and [0009] n is 1 or 2 depending on the oxidation state of the transition metal. [0010] 2. Description of the Related Art [0011] Conventionally, Ziegler-Natta catalyst system which includes a main catalyst component of titanium or vanadium compounds and a cocatalyst component of alkyl aluminum compounds has been used to produce an ethylene homopolymer or copolymers of ethylene and .alpha.-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 .alpha.-olefin due to heterogeneous catalyst active sites. [0012] Recently, the metallocene catalyst system which comprises a metallocene compound of a group IV 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 catalytic active site, it can be used to produce polyethylene having a narrow molecular weight distribution and a uniform compositional distribution in comparison with the conventional Ziegler-Natta catalyst system. For example, EP Pat. Nos. 320762 and 372632, and Japanese Patent Laid-Open Publication Nos. Sho. 63-092621, Hei. 02-84405, and Hei. 03-2347 disclose metallocene compounds, such as Cp.sub.2TiCl.sub.2, Cp.sub.2ZrCl.sub.2, Cp.sub.2ZrMeCl, Cp.sub.2ZrMe.sub.2, or (ethylene-bis tetrahydroindenyl)ZrCl.sub.2, activated with methylaluminoxane as a cocatalyst to polymerize ethylene at high catalytic 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.degree. C. or higher, polymerization activity is rapidly reduced and a .beta.-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. [0013] 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 .alpha.-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. [0014] 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 U.S. 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 .alpha.-olefins under the high temperature solution polymerization condition at 140.degree. 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. U.S. Pat. No. 5,079,205 discloses a catalyst having a bis-phenoxide ligand, but it has too low catalytic acitivity to be commercially used. [0015] In addition to the above-mentioned examples, Nomura et al., Organometallics 1998, 17, 2152 discloses the synthesis of a non-metallocene catalyst with a phenol-based ligand and polymerization using the same, in which the substituents on the phenol ligand are limited to only simple alkyl substituents such as isopropyl group. On the other hand, Rothwell, P. et al., J. Organomet. Chem. 1999, 591, 148 discloses an arylphenoxy ligand, but does not suggest the effects of aryl substituent at the ortho-position. SUMMARY OF THE INVENTION [0016] To overcome 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 .alpha.-olefins having a high molecular weight, at a high activity during a solution polymerization process at high temperatures of 80.degree. C. or higher, has been developed, thereby the present invention is accomplished. [0017] 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 .alpha.-olefins having various physical properties using the catalyst. [0018] 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. [0019] In Formula 1, wherein M is the group IV transition metal of a periodic table; [0020] Cp is cyclopentadienyl group, capable of forming an .eta..sup.5-bond along with the central metal, or a derivative thereof; [0021] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 of the arylphenoxide ligand are independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a silyl group which contains the C.sub.1-C.sub.20 linear or nonlinear alkyl group arbitrarily substituted with one or more halogen atoms, a C.sub.6-C.sub.30 aryl group arbitrarily substituted with one or more halogen atoms, a C.sub.7-C.sub.30 arylalkyl group arbitrarily substituted with one or more halogen atoms, an alkoxy group which has the C.sub.1-C.sub.20 alkyl group arbitrarily substituted with one or more halogen atoms, or a C.sub.3-C.sub.20 alkyl-substituted or C.sub.6-C.sub.20 aryl-substituted siloxy group, optionally with the proviso that the substituent groups may be arbitrarily bonded to form rings; Continue reading... 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