TWI646102B - Novel cyclopenta[b]thiophenyl transition metal compound, transition metal catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and a-olefin using the same - Google Patents

Abstract

Providing a novel transition metal compound based on cyclopenta[b]phenylthio group, a transition metal catalyst comprising the transition metal compound and having high catalytic activity for preparing an ethylene homopolymer or a copolymer of ethylene and at least one α -olefin A composition, and a method of using the same to prepare an ethylene homopolymer or a copolymer of ethylene and an α -olefin.

Description

Novel cyclopenta[B]phenylthio transition metal compound, transition metal catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the compound

The present invention relates to a novel transition metal compound based on cyclopenta[b]thiophenyl group, a transition metal catalyst composition comprising the transition metal compound, which is useful for preparing an ethylene homopolymer or A high catalytic activity of a copolymer of ethylene and at least one α -olefin, and a method of producing an ethylene homopolymer or a copolymer of ethylene and an α -olefin using the transition metal compound.

Generally, a so-called Ziegler-Natta catalyst system consisting of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkyl aluminum compound is generally used to prepare an ethylene homopolymer or ethylene. a copolymer of an α -olefin. The Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization. However, it is disadvantageous in that the polymer obtained generally has a broad molecular weight distribution due to the uneven catalytic activation point, and in particular, the composition distribution of the copolymer of ethylene and the α -olefin is not uniform.

Since the metallocene catalyst system consisting of a metallocene compound of a Group 4 transition metal (such as titanium, zirconium, hafnium, etc.) and a methylaluminoxane as a cocatalyst is a homogeneous phase having a single type catalytic activation point Catalyst characterized in that the metallocene catalyst system is capable of producing polyethylenes having a narrower molecular weight distribution and a uniform composition distribution than existing Ziegler-Natta catalyst systems. For example, European Patent Publication No. 320,762, No. 372,632, or Japanese Patent Laid-Open Publication No. S63-092621, No. H02-84405 or No. H03-2347 can be used to activate molybdenum by using a cocatalyst, methylaluminoxane. Metal compounds such as Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp ₂ ZrMeCl, Cp ₂ ZrMe ₂ , ethylene (IndH ₄ ) ₂ ZrCl _{2 ,} etc., thereby preparing a molecular weight distribution (Mw/Mn) range by polymerizing ethylene with high activity It is a polyethylene of 1.5 to 2.0. However, it is difficult to obtain a high molecular weight polymer in a catalyst system. In particular, it is known that when applied to a solution polymerization method carried out at a high temperature of 120 ° C or higher, the polymerization activity is rapidly lowered and the β-dehydrogenation reaction is dominant, and thus it is not suitable for preparation of a weight average molecular weight (Mw) therein. A high molecular weight polymer of 100,000 or higher.

Meanwhile, as a catalyst capable of preparing a polymer having high catalytic activity and high molecular weight by a homopolymerization reaction of ethylene or a copolymerization reaction of ethylene and an α -olefin under solution polymerization conditions, a transition chain of a transition metal has been reported. The so-called geometric configuration is limited to non-metallocene catalysts (so called single activation point catalysts). European Patent Nos. 0416815 and 0420436 propose examples in which a guanamine group is cyclically linked to a cyclopentadienyl ligand. European Patent No. 0842939 discloses an example of a catalyst in which a phenol-based ligand as an electron donor compound is cyclically bonded to a cyclopentadienyl ligand. In the geometry-constrained catalyst, the reactivity with high alpha -olefins is significantly improved due to the reduced steric hindrance effect of the catalyst itself, but there are still many difficulties in commercial use. Therefore, considering economic feasibility, including excellent high temperature activity, excellent reactivity with higher alpha olefins, and ability to produce high molecular weight polymers, it is important to ensure more competitive properties as a commercial catalyst. Catalyst system.

[Related prior art literature]

[Patent Literature]

Patent Document 1: European Patent Publication No. 320,762 (June 21, 1989).

Patent Document 2: European Patent Publication No. 372,632 (June 13, 1990).

Patent Document 3: Japanese Patent Laid-Open Publication No. S63-092621 (April 23, 1988).

Patent Document 4: Japanese Patent Laid-Open Publication No. H02-84405 (March 26, 1990).

Patent Document 5: Japanese Patent Laid-Open Publication No. H03-2347 (January 8, 1991).

Patent Document 6: European Patent No. 0416815 (March 13, 1991) day).

Patent Document 7: European Patent No. 0420436 (April 3, 1991).

Patent Document 8: European Patent No. 0842939 (May 20, 1998).

In order to overcome the problems of the related art, the inventors of the present invention conducted extensive research and found a transition metal compound having a structure in which a transition metal of Group 4 in the periodic table is a central metal, which has a rigid planar structure and contains a large number and extensive non-localized electron cyclopenta[ b ]thiol linkage; and can be easily introduced by fluorenyl or carbazole, which has substituents for improving solubility and properties. A phenoxy group in which the cyclopenta[ b ]phenylthio group and the phenoxy group are transmitted through a silyl chain exhibits excellent catalytic activity in the polymerization of ethylene and an olefin. Based on this finding, the inventors of the present invention have developed a catalyst capable of preparing a high-activity high molecular weight ethylene homopolymer or a copolymer of ethylene and an α -olefin in a solution polymerization process which is carried out at a high temperature, and completed the present invention.

An embodiment of the present invention is directed to a transition metal compound useful as a catalyst for preparing an ethylene homopolymer or a copolymer of ethylene and an α -olefin, and a catalyst composition comprising the transition metal compound.

Another embodiment of the present invention contemplates a commercial aspect intended to provide a process for economically preparing an ethylene homopolymer or a copolymer of ethylene and an alpha -olefin using a catalyst composition comprising a transition metal compound.

Still another embodiment of the present invention contemplates that the commercial aspect is intended to provide a single activation point catalyst having a simple synthesis route for very economical synthesis and high activity in olefin polymerization, and economical preparation using a catalyst component. A method of polymerizing an ethylene homopolymer having various physical properties or a copolymer of ethylene and an α -olefin.

In a general aspect, a novel transition metal compound based on cyclopenta[ b ]phenylthio group represented by the following Chemical Formula 1 is provided. More specifically, the transition metal compound may have a structure in which a transition metal of Group 4 in the periodic table is a central metal, which is transmitted through a cyclopentane having a rigid planar structure and containing a large amount and a wide range of non-localized electrons [ b ] a phenylthio group to be linked; and a phenoxy group which can be easily substituted with a mercapto group or a carbazole having a substituent for improving solubility and properties, wherein the cyclopenta[ b ]phenylthio group and the benzene group The oxy group is transmitted through a thiol linkage.

[Chemical Formula 1]

In Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; R ¹ to R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl a group, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ; R ⁵ and R ⁶ are each independently (C1-C20)alkyl, halo(C1-C20)alkyl, (C3- C20) cycloalkyl, (C6-C20) aryl, (C1-C20)alkyl (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) An aryl group, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁵ and R ⁶ permeable to a (C4-C7)alkylene chain to form a ring; R ⁷ Each of R ^{9 is} independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl, halogen, (C6-C20)aryl, (C3-C20)heteroaryl, -OR ^a1 , -SR ^A2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁷ to R ⁹ may be bonded to an adjacent substituent with or without an aromatic ring (C4-C7) to form a fused ring; R ^a1 to R ^a6 are each independently (C1-C20)alkyl or (C6-C20)aryl; Ar ¹ is a fluorenyl or N-carbazole, and the fluorenyl or carbazole of Ar ¹ may be further subjected to (C1- C20) alkyl substituent; X ¹ and X ² are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) (C6-C20) aryl (C1-C20) alkyl, ((C1-C20)alkyl (C6-C20) aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20)alkyl (C6-C20) aryloxy, (C1-C20) alkoxy (C6-C20) aryloxy, -OSiR ^a R ^b R ^c , -SR ^d , -NR ^e R ^f , -PR ^g R ^h or (C1-C20)alkylidene; R ^a to R ^d are each independently (C1-C20)alkyl, (C6-C20) aryl a group, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or (C3-C20) cycloalkyl; R ^e to R ^h are each independently (C1 -C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl, (C3-C20)cycloalkane a tris(C1-C20)alkylfluorenyl or a tris(C6-C20)arylfluorenyl group; the limitation is that when one of X ¹ and X ² is a (C1-C20) alkylene group, One is ignored; and the heteroaryl group includes at least one hetero atom selected from N, O and S.

In another general aspect, there is provided a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α -olefin, comprising a transition metal compound represented by Chemical Formula 1 and an aluminum compound selected from boron A cocatalyst of a compound or a mixture thereof.

In yet another general aspect, a method of making an ethylene homopolymer or a copolymer of ethylene and an alpha -olefin using the catalyst composition is provided.

The transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention may have a simple synthesis process so as to be easily produced in a high yield by an economical method, and further capable of providing high thermal stability of the catalyst, thereby enabling It maintains high catalytic activity at high temperatures, has good copolymerization reactivity with other olefins, and can produce high molecular weight polymers in high yield, and thus is commercially used higher than previously known metallocene and nonmetallocene single activation point catalysts. Therefore, the transition metal according to the present invention and the catalyst composition comprising the same can be effectively used for preparing an ethylene homopolymer having various physical properties or a copolymer of ethylene and an α -olefin.

1 shows the reaction rates of the catalysts of Example 1 (1), Example 2 (2), Example 3 (3), Example 4 (4), and Comparative Example 1 (C1) with ethylene until the respective catalysts were prepared for polymerization. (100 mg).

Hereinafter, the present invention will be described in more detail. Here, unless otherwise defined in the technical and scientific terms, they have the meaning understood by those of ordinary skill in the art to which the invention pertains. Known functions and components that may obscure the gist of the present invention are omitted in the following description.

The transition metal compound according to an exemplary embodiment of the present invention is a transition metal compound based on cyclopenta[ b ]phenylthio represented by the following Chemical Formula 1, and may have a transition metal of Group 4 in the periodic table as a central metal Structure, which is linked by a cyclopenta[ b ]phenylthio group having a rigid planar structure and containing a large number and extensive non-localized electrons; and can be easily introduced into a sulfhydryl group or a carbazole (which is used for improvement) Solvent and performance substituents substituted phenoxy, wherein the cyclopenta[ b ]phenylthio group and the phenoxy group pass through a thiol linkage, thereby providing structural advantages that facilitate efficient high molecular weight ethylene polymers .

In Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; R ¹ to R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl a group, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ; R ⁵ and R ⁶ are each independently (C1-C20)alkyl, halo(C1-C20)alkyl, (C3- C20) cycloalkyl, (C6-C20) aryl, (C1-C20)alkyl (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) An aryl group, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁵ and R ⁶ are permeable to a (C4-C7) alkyl chain to form a ring; R ⁷ to R ⁹ Each independently is hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl, halogen, (C6-C20)aryl, (C3-C20)heteroaryl, -OR ^a1 , -SR ^a2 ,- NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁷ to R ⁹ may be bonded through a (C4-C7)-extended alkenyl group with or without an aromatic ring to form a fused ring; R ^a1 to R ^{a6 is} each independently (C1-C20)alkyl or (C6-C20)aryl; Ar ¹ is fluorenyl or N-carbazole, and the fluorenyl or carbazole of Ar ¹ may be further subjected to (C1-C20) alkane Substituent; X ¹ and X ² are each independently hydrogen, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C6 -C20) aryl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C20) aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20 An aryloxy group, (C1-C20)alkyl (C6-C20) aryloxy, (C1-C20) alkoxy (C6-C20) aryloxy, -OSiR ^a R ^b R ^c , -SR ^d , -NR ^e R ^f , -PR ^g R ^h or (C1-C20) alkylene; R ^a to R ^d are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20) Aryl (C1-C20)alkyl, (C1-C20)alkyl (C6-C20) aryl or (C3-C20)cycloalkyl; R ^e to R ^h are each independently (C1-C20)alkyl, ( C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl, (C3-C20) cycloalkyl, tri (C1-C20 An alkyl fluorenyl group or a tris(C6-C20) aryl fluorenyl group; the limitation is that when one of X ¹ and X ² is a (C1-C20) alkylene group, the other is ignored; The aryl group includes at least one hetero atom selected from N, O and S.

The term "alkyl" as used herein, refers to a monovalent straight or branched chain saturated hydrocarbon radical consisting solely of carbon atoms and hydrogen atoms. Examples of the alkyl radical include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group and the like, but the invention is not limited thereto .

The term "aryl" as used herein, refers to an organic radical obtained by the removal of one hydrogen from an aromatic hydrocarbon, and includes suitably 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring. A single ring system or a fused ring system, and even includes a form in which a plurality of aryl groups are linked by a single bond. The fused ring system may include an aliphatic ring such as a saturated ring or a partially saturated ring, and must contain at least one aromatic ring. Further, the aliphatic ring may include nitrogen, oxygen, sulfur, a carbonyl group or the like in the ring. Specific examples of the aryl radical include phenyl, naphthyl, biphenyl, anthracenyl, fluorenyl, phenanthryl, anthracenyl, triphenylene, fluorenyl, Chrysenyl, fused tetraphenyl, 9,10-dihydroindenyl, and the like.

The term "heteroaryl" as used herein means an aryl group which contains 1 to 4 hetero atoms selected from N, O and S as an aromatic ring structure skeleton atom and carbon as a remaining aromatic ring structure skeleton atom, It is a 5- or 6-membered monocyclic heteroaryl group and a polycyclic heteroaryl group condensed with at least one benzene ring, and may be partially saturated. Additionally, heteroaryl groups in the present invention may include those in which one or more heteroaryl groups are linked via a single bond. Examples of heteroaryl groups include pyrrole, quinoline, isoquinoline, pyridine, pyrimidine, oxazole, thiazole, thiadiazole, triazole, imidazole, benzimidazole, isoxazole, benzisoxazole, Thiophene, benzothiophene, furan, benzofuran, etc., but the invention is not limited thereto.

The term "cycloalkyl" as used herein, refers to a monovalent saturated carbocyclic radical consisting of one or more rings. Cycloalkyl free Examples of the group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, but the invention is not limited thereto.

The term "halo" or "halogen" as used herein means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

As an example, the term "haloalkyl" as used herein, refers to an alkyl group substituted with one or more halogens, and may include trifluoromethyl and the like.

The terms "alkoxy" and "aryloxy" as used herein mean -O-alkyl and -O-aryl, respectively, wherein alkyl and aryl are the same as defined above.

In an exemplary embodiment of the present invention, the cyclopenta[ b ]phenylthio group-based transition metal compound represented by Chemical Formula 1 may be a transition metal compound represented by the following Chemical Formula 2 or Chemical Formula 3.

In Chemical Formula 2 and Chemical Formula 3, M, R ¹ to R ⁴ , X ¹ and X ² are the same as defined in the above Chemical Formula 1; and R ⁵ and R ⁶ are each independently (C1-C20)alkyl, halogen ( C1-C20)alkyl or (C6-C20)aryl; R ⁸ and R ⁹ are each independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl or halo, R ⁸ and R ⁹ Permeable , , or Linked to form a fused ring; R ¹¹ and R ¹² are each independently (C1-C20)alkyl; and R ¹³ , R ¹⁴ and R ¹⁵ are each independently hydrogen or (C1-C20)alkyl.

In an exemplary embodiment of the present invention, the transition metal compound M may be a transition metal of Group 4 of the periodic table, preferably titanium (Ti), zirconium (Zr) or hafnium (Hf), and more preferably titanium.

In an exemplary embodiment of the invention, R ¹ to R ⁴ may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary Butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, benzene Base, pyridyl, methoxy, ethoxy, butoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenylamino, Dimethylphosphine, diethylphosphine or diphenylphosphine.

In an exemplary embodiment of the present invention, R ¹ may be (C1-C20)alkyl, preferably (C1-C10)alkyl, R ² may be hydrogen, and R ³ and R ⁴ may each independently be Hydrogen, (C1-C20)alkyl, preferably (C1-C10)alkyl, (C1-C20)alkoxy, preferably (C1-C10)alkoxy or di(C1-C20)alkyl Amino group, and preferably a di(C1-C10)alkylamino group.

In an exemplary embodiment of the present invention, R ¹ , R ³ and R ⁴ may each independently be a (C1-C10)alkyl group, and R ² may be hydrogen.

In an exemplary embodiment of the invention, R ¹ , R ³ and R ⁴ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl or tertiary butyl Base, and R ² may be hydrogen.

In an exemplary embodiment of the present invention, R ¹ may be (C1-C10)alkyl, R ² and R ³ may be hydrogen, and R ⁴ may be (C1-C10)alkyl, (C1-C10) alkane Oxy or di(C1-C10)alkylamino.

In an exemplary embodiment of the invention, R ¹ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl or tertiary butyl, R ² and R ³ may be hydrogen, and R ⁴ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, methoxy, ethoxy, Butoxy, dimethylamino, methylethylamino or diethylamino.

In an exemplary embodiment of the present invention, R ¹ may be (C1-C10)alkyl, R ² and R ⁴ may be hydrogen, and R ³ may be (C1-C10)alkyl, (C1-C10)alkane. Oxy or di(C1-C10)alkylamino.

In an exemplary embodiment of the invention, R ¹ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl or tertiary butyl, R ² and R ⁴ may be hydrogen, and R ³ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, methoxy, ethoxy, Butoxy, dimethylamino, methylethylamino or diethylamino.

In an exemplary embodiment of the invention, R ⁵ and R ⁶ may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl Base, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoro Base, trifluoromethyl, perfluoroethyl, perfluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, Trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, secondary butylphenyl, tertiary Butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, biphenyl, anthracenyl, tri Phenyl, naphthyl, anthracenyl, benzyl, naphthylmethyl, decylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methyl Ethylamino, diethylamino, diphenylamino, dimethylphosphine, two Diphenyl phosphine or phosphine groups, or R ⁵ and R ⁶ may be a through-butene or pentene (pentylene) link to form a ring.

In an exemplary embodiment of the present invention, R ⁵ and R ⁶ may each independently be a (C1-C20) alkyl group, preferably a (C1-C10) alkyl group, a halogen (C1-C20) alkyl group, preferably. It is a halogen (C1-C10) alkyl group or a (C6-C20) aryl group, and is preferably a (C6-C12) aryl group.

In an exemplary embodiment of the invention, R ⁵ and R ⁶ may each independently be a methyl group, an ethyl group or a phenyl group.

In an exemplary embodiment of the invention, R ⁷ to R ⁹ may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tri Butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, Fluoromethyl, trifluoromethyl, perfluoroethyl, perfluoropropyl, chloro, fluoro, bromo, phenyl, biphenyl, decyl, triphenyl, naphthyl, anthracenyl, benzyl, naphthalene Methyl, decylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenyl Amino, dimethylphosphine, diethylphosphine or diphenylphosphine, or R ⁸ and R ⁹ may be permeated , , or Chains to form a ring.

In an exemplary embodiment of the present invention, R ⁷ to R ⁹ may each independently be hydrogen, (C1-C20)alkyl, preferably (C1-C10)alkyl, halo(C1-C20)alkyl, Further, it is preferably a halogen (C1-C20) alkyl group or a halogen.

In an exemplary embodiment of the invention, R ⁷ to R ⁹ may each independently be hydrogen, methyl, ethyl, tert-butyl or fluoro.

In an exemplary embodiment of the present invention, R ⁷ may be hydrogen, and R ⁸ and R ⁹ may each independently be hydrogen, (C1-C20) alkyl, preferably (C1-C10) alkyl, halo ( C1-C20)alkyl, and preferably halo(C1-C10)alkyl or halogen, and R ⁸ and R ⁹ may be permeated , , or Chains to form a ring.

In an exemplary embodiment of the present invention, R ⁷ and R ⁹ may be hydrogen, R ⁸ may be (C1-C10)alkyl or halogen, or R ⁸ and R ⁹ may be permeated Chains to form a fused ring.

In an exemplary embodiment of the present invention, R ⁷ and R ⁹ may be hydrogen, R ⁸ may be methyl, ethyl, tert-butyl or fluorine, and R ⁸ and R ⁹ may be permeated Chains to form a fused ring.

In an exemplary embodiment of the present invention, R ¹¹ and R ¹² may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl , n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadecyl; R ¹³ , R ¹⁴ and R ¹⁵ may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, new Butyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadecyl.

In an exemplary embodiment of the present invention, preferably, R ¹¹ and R ¹² may be (C1-C20)alkyl, and R ¹³ , R ¹⁴ and R ¹⁵ may each independently be hydrogen or (C1-C10). alkyl.

In an exemplary embodiment of the invention, X ¹ and X ² may each independently be fluorine, chlorine, bromine, methyl, ethyl, isopropyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl. , cyclohexyl, phenyl, naphthyl, benzyl, methoxy, ethoxy, isopropoxy, tert-butoxy, phenoxy, 4-tributylphenoxy, trimethyl Mercaptooxy, tert-butyl dimethylformamoxy, dimethylamino, diphenylamino, dimethylphosphine, diethylphosphine, diphenylphosphine, ethylthio or isopropyl Sulfur based.

In an exemplary embodiment of the invention, X ¹ and X ² may be (C1-C20)alkyl, and preferably (C1-C10)alkyl or halogen.

In an exemplary embodiment of the invention, X ¹ and X ² may be methyl or chlorine.

In an exemplary embodiment of the present invention, R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ may each independently be a (C1-C20) alkyl group, preferably a (C1-C10) alkyl group; and R ¹³ may be hydrogen.

In an exemplary embodiment of the present invention, the transition metal compound may be selected from compounds having the following structure, but is not limited thereto:

Wherein M is titanium, zirconium or hafnium.

Meanwhile, in order to prepare an active catalyst component for preparing an ethylene-based polymer selected from the group consisting of an ethylene homopolymer and a copolymer of ethylene and an α -olefin, preferably a transition metal compound, by using the transition metal compound according to the present invention It can function with a cocatalyst selected from an aluminum compound, a boron compound or a mixture thereof, which acts as a relative ion having a weak binding force, that is, an anion, while extracting X ¹ and in the transition metal complex. The X ² ligand cationizes the central metal. Catalyst compositions comprising a transition metal compound and a cocatalyst are also within the scope of the invention.

In the catalyst composition according to an exemplary embodiment of the present invention, the aluminum compound which can be used as a co-catalyst may specifically be an aluminoxane compound represented by Chemical Formula 4 or Chemical Formula 5, and an organic compound represented by Chemical Formula 6. One or two or more of an aluminum compound or an organoaluminum oxide compound represented by Chemical Formula 7 or Chemical Formula 8: [Chemical Formula 4] (-Al(R ⁵¹ )-O-) _m

(R ⁵¹ ) ₂ Al-(-O(R ⁵¹ )-) _q -(R ⁵¹ ) ₂

[Chemical Formula 6] (R ⁵² ) _r Al(E) _3-r

[Chemical Formula 7] (R ⁵³ ) ₂ AlOR ⁵⁴

[Chemical Formula 8] R ⁵³ Al(OR ⁵⁴ ) ₂

In Chemical Formula 4 to Chemical Formula 8, R ⁵¹ is a (C1-C20) alkyl group, preferably a methyl group or an isobutyl group, and m and q are each an integer of 5 to 20; and each of R ⁵² and R ⁵³ is (C1- C20) alkyl; E is hydrogen or halogen; r is an integer from 1 to 3; and R ⁵⁴ is (C1-C20)alkyl or (C6-C20)aryl.

Specific examples of the aluminum compound may include methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane as the aluminoxane compound; examples of the organoaluminum compound may include trialkyl aluminum, including three Methyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum and trioctyl aluminum; dialkylaluminum chloride, including dimethyl aluminum chloride, diethyl Aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride and dihexyl aluminum chloride; alkylaluminum dichloride, including methyl aluminum dichloride, ethyl aluminum dichloride , propyl aluminum dichloride, isobutyl aluminum dichloride and hexyl aluminum dichloride; and hydrogenated dialkyl aluminum, including hydrogenated dimethyl aluminum, hydrogenated diethyl aluminum, hydrogenated dipropyl aluminum, hydrogenated two Isobutyl aluminum and hydrogenated dihexyl aluminum.

In an exemplary embodiment of the present invention, the aluminum compound may preferably be one or a mixture of two or more selected from the group consisting of an alkyl aluminoxane compound and a trialkyl aluminum. More preferably, the aluminum compound may be selected from the group consisting of methyl aluminoxane, modified methyl aluminoxane, tetraisobutyl aluminoxane, trimethyl aluminum, triethyl aluminum, trioctyl aluminum, and triisobutyl. One or a mixture of two or more of aluminum.

A boron compound which is a cocatalyst of the present invention can be used, and can be a boron compound selected from the following Chemical Formula 9 to Chemical Formula 11: [Chemical Formula 9] B(R ⁴¹ ) _{3 is} known from the U.S. Patent No. 5,198,401.

[Chemical Formula 10] [R ⁴² ] ⁺ [B(R ⁴¹ ) ₄ ] ^-

[(R ⁴³ ) _p ZH] ⁺ [B(R ⁴¹ ) ₄ ] ^-

In Chemical Formula 9 to Chemical Formula 11, B is a boron atom; R ⁴¹ is a phenyl group, and the phenyl group may further be 3 to 5 (C1-C20) alkyl groups selected from fluorine, unsubstituted or fluorine-substituted Substituted by a substituent of a (C1-C20) alkoxy group which is unsubstituted or substituted by fluorine; R ⁴² is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl group free a (C6-C20) aryl (C1-C20) alkyl radical such as a triphenylmethylium radical; Z is a nitrogen atom or a phosphorus atom; and R ⁴³ is a (C1-C50) alkane a radical or an anilinium radical substituted with two (C1-C10) alkyl groups together with a nitrogen atom; and p is an integer of 2 or 3.

Preferable examples of the boron-based co-catalyst may include quinone (pentafluorophenyl)borane, ginseng (2,3,5,6-tetrafluorophenyl)borane, and ginseng (2,3,4,5-tetrafluoro). Phenyl)borane, ginseng (3,4,5-trifluorophenyl)borane, ginseng (2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane, Bis(pentafluorophenyl)borate, bismuth (2,3,5,6-tetrafluorophenyl) borate, bismuth (2,3,4,5-tetrafluorophenyl) borate, hydrazine (3,4,5-tetrafluorophenyl)borate, bismuth(2,2,4-trifluorophenyl)borate, phenylbis(pentafluorophenyl)borate or hydrazine (3, 5-bistrifluoromethylphenyl)borate. Examples of specific compositions include ferrocenium tetrakis (pentafluorophenyl) boronate, quinone (pentafluorophenyl) borate 1,1'-dimethylferrocene (1,1'). -dimethylferrocenium tetrakis(pentafluorophenyl)borate), tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, Triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate, triethylammonium pentoxide (pentafluorophenyl)borate, lanthanum Fluorophenyl)tripropylammonium borate, tri(n-butyl)ammonium pentium (pentafluorophenyl)borate, tris(n-butyl)ammonium ruthenium (3,5-bistrifluoromethylphenyl)borate, hydrazine (pentafluorophenyl)boronic acid-N,N-dimethylanilinium, quinone (pentafluorophenyl)boronic acid-N,N-diethylanilinium, quinone (pentafluorophenyl)boronic acid-N,N- 2,4,6-pentamethylanilinium, cerium (3,5-bistrifluoromethylphenyl)boronic acid-N,N-dimethylanilinium, decyl (pentafluorophenyl)borate diisopropyl Ammonium bromide, ruthenium (pentafluorophenyl)borate dicyclohexyl Ammonium Benzate, triphenylsulfonium quinone (pentafluorophenyl)borate, tris(methylphenyl)phosphonium iridium (pentafluorophenyl)borate or tris(dimethylphenyl)phosphonium quinone (pentafluorophenyl)borate . Among them, more preferred is quinone (pentafluorophenyl)boronic acid-N,N-dimethylanilinium, quinone (pentafluorophenyl)borate triphenylmethyl ester or ginseng (pentafluorophenyl)borane. .

At the same time, the cocatalyst can be used as a scavenger for removing impurities as catalyst poisons in the reactants.

In an exemplary embodiment of the present invention, when an aluminum compound is used as a cocatalyst, the ratio between the transition metal compound of the present invention and the cocatalyst may have a preferred range, that is, transition metal (M): aluminum atom (Al) ) is 1:10 to 5,000.

In an exemplary embodiment of the present invention, when the aluminum compound and the boron compound are simultaneously used as a cocatalyst, the ratio between the transition metal compound of the present invention and the cocatalyst may have a preferred molar ratio range, that is, a transition metal ( M): boron atom (B): The aluminum atom (Al) is from 1:0.1 to 100:10 to 3,000, and more preferably from 1:0.5 to 5:100 to 3,000.

When the ratio between the transition metal compound of the present invention and the cocatalyst is outside the above range, since the amount of the cocatalyst is relatively small, the transition metal compound may not be fully activated, and thus the catalytic activity of the transition metal compound may be insufficient, or a total of If the amount of the catalyst exceeds the required amount, the preparation cost may be greatly increased. Within the above range, excellent catalytic activity for producing an ethylene homopolymer or a copolymer of ethylene and an α -olefin is shown, and the range of the ratio varies depending on the purity of the reaction.

As another aspect of the present invention, a method of preparing an ethylene polymer using a transition metal catalyst composition can be carried out by using a transition metal catalyst, a cocatalyst, and optionally an α -olefin comonomer in a suitable organic solvent. It is carried out in the presence of contact. Here, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or the respective components may be mixed and added to the reactor in advance, wherein there is no special mixing condition such as introduction order, temperature, concentration, and the like. limited.

A preferred organic solvent which can be used in the production method may be a (C3-C20) hydrocarbon, and specific examples thereof may include butane, isobutane, pentane, hexane, heptane, octane, isooctane, decane, Decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and the like.

Specifically, in the preparation of the ethylene homopolymer, ethylene is used alone as a monomer, wherein the pressure of ethylene may suitably be from 1 atm to 1000 atm, and more preferably from 10 atm to 150 atm. Further, the polymerization reaction is carried out efficiently at a polymerization temperature of from 25 ° C to 200 ° C, preferably from 50 ° C to 180 ° C, more preferably from 100 ° C to 180 ° C, still more preferably from 130 ° C to 180 ° C.

Further, when preparing a copolymer of ethylene and an α -olefin, at least one selected from the group consisting of a C3-C18 α -olefin, a C5-C20 cyclic olefin, a styrene, and a styrene derivative may be used as a comonomer together with ethylene. . Preferred examples of the C3-C18 α -olefin may include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and 1 -undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and preferred examples of the C5-C20 cyclic olefin may include cyclopentene, cyclohexene, Norbornene and phenyl norbornene. Styrene and its derivatives may be selected from the group consisting of styrene, α -methylstyrene, p-methylstyrene, and 3-chloromethylstyrene. In the present invention, ethylene may be copolymerized with the above olefin, or two or more olefins, and more preferably 1-butene, 1-hexene, 1-octene or 1-decene may be copolymerized with ethylene. . In this case, the preferred pressure and polymerization temperature of ethylene may be the same as in the case of preparing an ethylene homopolymer, and the copolymer prepared by the method of the present invention usually has an ethylene content of 30% by weight or more, preferably. It is 60% by weight or more, and more preferably 60% by weight to 99% by weight.

As described above, when the catalyst of the present invention is used, it can be easily and economically produced by suitably using a C3-C18 α -olefin as a comonomer and ethylene, and has 0.850 g (g) / cubic centimeter (cc) to 0.960 g / cubic. Density of centimeters and polymer from elastomer to high density polyethylene (HDPE) with a melt flow index of 0.001 mm/min (dg/min) to 15 mm/min.

Further, when preparing an ethylene homopolymer or copolymer according to the present invention, hydrogen can be used as a molecular weight regulator to adjust the molecular weight. Its weight average molecular weight (Mw) is usually in the range of 5,000 g/m to 1,000,000 g/mole.

Since the catalyst composition proposed by the present invention is in a homogeneous state in the polymerization reactor, the catalyst composition can be preferably used in a solution polymerization method which is carried out at a temperature higher than the melting point of the corresponding polymer. However, as disclosed in U.S. Patent No. 4,752,597, the transition metal compound and cocatalyst can be supported on a porous metal oxide support for slurry polymerization or gas phase polymerization as a non-homogeneous catalyst composition. .

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the scope of the invention is not limited by the following examples.

Unless otherwise stated, all experiments for the synthesis of ligands and catalysts were carried out under nitrogen atmosphere using standard Schlenk or glove-box techniques. The organic solvent used in the reaction was refluxed on sodium metal and benzophenone to remove moisture, and then distilled immediately before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was carried out by using Brucker 500 MHz at room temperature.

Prior to use, cyclohexane as a polymerization solvent was passed through a tube filled with molecular sieves of 5 Å (Å) and activated alumina, and was bubbled with high-purity nitrogen gas to sufficiently remove moisture, oxygen, and other catalyst poisons. The polymerized polymer was analyzed by the measurement method described below.

1. Molecular weight and molecular weight distribution

The measurement was carried out at a rate of 1.0 mL/min at 135 ° C in the presence of 1,2,3-trichlorobenzene solvent by using Freeslate Rapid GPC, and the molecular weight was calibrated by using a PL polystyrene standard.

2. The content of α -olefin in the copolymer (% by mole)

At Bruker Avance 400 NMR spectrometer at 125MHz, ¹³ C-NMR mode, at 120 deg.] C, using 1,2,4-trichlorobenzene / C ₆ D ₆ (7/3 weight fraction) mixed solvent was measured α - the content of olefins. (See Randal, JCJMS-Rev. Macromol. Chem. Phys. 1980, C29, 201)

The ratio between ethylene and alpha -olefin in the copolymer was quantified using an infrared spectrometer.

3. Crystallinity of the polymer

The amorphous portion of the polymer (Amorphous Fraction; AF) was measured by analyzing the branched distribution of the polymer using PolymerChar A-CEF.

[Example 1 to Example 5] Preparation of Transition Metal Catalyst 1 to Transition Metal Catalyst 5 According to the Present Invention

Preparation of Compound B

Add 2,4,5-trimethyl-6H-cyclopenta[b]thiophene (30.08 mmol) to THF (112 mL), then slowly add n-BuLi in hexanes (2.5 M, 31.58 mmol) at -78 °C. . After the addition of n-BuLi was completed, the temperature was slowly raised to room temperature, and then the mixture was stirred for 2 hours. After the end of the stirring, the mixture was cooled to -78 ° C, and a solution of Compound A (33.09 mmol) in toluene (14 mL) was slowly added dropwise, and then the temperature of the reaction mixture was raised to room temperature. After stirring at room temperature for further 3 hours, the reaction mixture was added to distilled water (200 mL) to terminate the reaction. The organic layer with toluene (2 × 50mL) and extracted to remove water ₂ SO ₄ Na, and the solvent removed by vacuum distillation to obtain an oil in the form of a yellow residue. Then, the residue was purified by flash chromatography (distilled liquid: 1:10 volume of dichloromethane/hexane) using a column packed with silica gel 60 (40-63 μm) to obtain a compound as the title compound. B.

Compound B1 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = Me): 80% yield. ¹ H NMR (CDCl ₃ ): δ 7.81 (m, 1H), 7.80 (m, 1H) ), 7.77 (m, 1H), 7.60 (m, 1H), 7.47 (m, 1H), 7.33-7.40 (m, 3H), 7.11 (m, 1H), 6.66 (m, 1H), 5.76 (m, 1H), 5.24 (m, 1H), 5.07 (m, 1H), 4.06 (m, 2H), 3.92 (s, 1H), 2.50 (s, 3H), 2.40 (s, 3H), 2.07 (s, 3H) ), 1.93 (s, 3H), 1.54 (m, 6H), 0.18 (s, 6H).

Compound B2 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-Bu): 85% yield. 1H NMR (CDCl ₃ ): δ 7.77 (m, 1H), 7.74 (m, 1H), 7.65 (m, 1H), 7.58 (m, 1H), 7.30-7.38 (m, 4H), 7.10 (m, 1H), 6.65 (m, 1H), 5.71 (m, 1H), 5.22 (m) , 1H), 5.04 (m, 1H), 4.04 (m, 2H), 3.88 (s, 1H), 2.47 (s, 3H), 2.37 (s, 3H), 2.03 (s, 3H), 1.97 (t, J=6.5 Hz, 4H), 1.92 (s, 3H), 1.05 (m, 4H), 0.64 (m, 6H), 0.56-0.67 (m, 4H), 0.13 (s, 6H).

Compound B3 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = Me): 80% yield. ¹ H NMR (CDCl ₃ ): δ 7.81 (m, 1H), 7.79 (m, 1H) ), 7.77 (m, 1H), 7.59 (m, 1H), 7.47 (m, 1H), 7.37 (m, 2H), 7.20-7.25 (m, 1H), 6.96 (m, 1H), 6.65 (m, 1H), 5.74 (m, 1H), 5.24 (m, 1H), 5.09 (m, 1H), 4.06 (m, 2H), 3.88 (s, 1H), 2.49 (s, 3H), 2.06 (s, 3H) ), 1.94 (s, 3H), 1.53 (m, 6H), 0.21 (s, 3H), 0.14 (s, 3H).

Compound B4 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = n-Bu): 91% yield. ¹ H NMR (CDCl ₃ ): δ 7.79 (m, 1H), 7.76 (m) , 1H), 7.65 (m, 1H), 7.58 (m, 1H), 7.32-7.39 (m, 3H), 7.20 (m, 1H), 6.96 (m, 1H), 6.65 (m, 1H), 5.74 ( m, 1H), 5.26 (m, 1H), 5.09 (m, 1H), 4.07 (m, 2H), 3.89 (s, 1H), 2.49 (s, 3H), 2.06 (s, 3H), 2.01 (t) , J = 7.7 Hz, 4H), 1.94 (s, 3H), 1.09 (m, 4H), 0.67 (m, 6H), 0.62-0.67 (m, 4H), 0.20 (s, 3H), 0.13 (s, 3H).

Compound B5 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-tetradecyl): 64% yield. ¹ H NMR (CDCl ₃ ): δ 7.81 (m, 1H), 7.80 (m, 1H), 7.77 (m, 1H), 7.60 (m, 1H), 7.47 (m, 1H), 7.33-7.40 (m, 3H), 7.11 (m, 1H), 6.66 (m, 1H), 5.76 (m, 1H), 5.24 (m, 1H), 5.07 (m, 1H), 4.06 (m, 2H), 3.92 (s, 1H), 2.50 (s, 3H), 2.40 (s, 3H), 2.07 (s, 3H), 1.93 (s, 3H), 1.54 (m, 6H), 0.18 (s, 6H).

Preparation of Compound C

Toluene (70 mL) in which Compound B (10 mmol) and Et ₃ N (45 mmol) were dissolved was cooled to -78 ° C, and n-BuLi hexane solution (2.5 M, 22 mmol) was added thereto. After the addition of n-BuLi was completed, the reaction mixture was heated to room temperature and stirred at room temperature for 20 hours. After the reaction mixture was again cooled to -78 ° C, a solution of TiCl ₄ (15 mmol) in toluene (22 mL) was slowly added dropwise. After the addition of TiCl ₄ was completed, the reaction mixture was slowly heated to room temperature, and the reaction mixture was further stirred at 90 °C. The reaction was cooled to room temperature and the solvent was removed in vacuo under nitrogen. After removal of the solvent, warm methylcyclohexane was added and the resulting by-product was separated by a diatomaceous earth filter. The filtrate obtained from the filter was dried under vacuum, and a mixed solvent of methylcyclohexane and hexane was added to obtain the title compound C as a red-brown precipitate.

Compound C1 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = Me): 42% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.72-7.75 (m, 3H), 7.45 (m, 2H), 7.37 (m, 2H), 7.32 (m, 2H), 6.90 (m, 1H), 2.59 (s, 3H), 2.54 (s, 3H), 2.47 (s, 3H), 2.17 ( s, 3H), 1.51 (s, 3H), 1.49 (s, 3H), 0.71 (s, 3H), 0.67 (s, 3H).

Compound C2 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-Bu): 64% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.70 (m, 2H), 7.59 (m, 1H), 7.45 (m, 1H), 7.26-7.35 (m, 5H), 6.91 (m, 1H), 2.58 (s, 3H), 2.54 (s, 3H), 2.46 (s, 3H), 2.15 (s, 3H), 1.92-2.08 (m, 4H), 0.98-1.11 (m, 4H), 0.70 (s, 3H), 0.66 (s, 3H), 0.63 (t, J = 7.4 Hz, 6H) , 0.48-0.54 (m, 4H).

Compound C3 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = Me): 69% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.70-7.75 (m, 3H), 7.41 -7.44(m,2H), 7.30-7.33(m,2H), 7.22-7.27(m,2H), 6.90(m,1H), 2.58(s,3H),2.54(s,3H),2.16(s , 3H), 1.49 (s, 3H), 1.48 (s, 3H), 0.70 (s, 3H), 0.68 (s, 3H).

Compound C4 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = n-Bu): 54% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.71 (m, 2H), 7.58 (m, 1H), 7.45 (m, 1H), 7.30-7.36 (m, 3H), 7.23 (m, 2H), 6.91 (m, 1H), 2.58 (s, 3H), 2.55 (s, 3H), 2.46 (s, 3H), 2.16 (s, 3H), 1.92-2.07 (m, 4H), 0.98-1.11 (m, 4H), 0.70 (s, 3H), 0.68 (s, 3H), 0.63 (t, J = 7.3 Hz, 6H), 0.44-0.61 (m, 4H).

Compound C5 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-tetradecyl): 14% yield. ¹ H NMR (CDCl ₃ ): δ 7.66 (m, 2H), 7.52 (m, 1H), 7.40 (m, 1H), 7.25-7.31 (m, 5H), 6.85 (m, 1H), 2.55 (s, 3H), 2.53 (s, 3H), 2.14 (s, 3H), 1.92-2.05 (m, 4H), 1.01-1.28 (m, 51H), 0.87 (m, 9H), 0.55-0.71 (m, 4H).

Preparation of Compound 1 to Compound 5

Compound C (10 mmol) was dissolved in diethyl ether (100 mL), and a solution of MeMgBr (2.9 M in diethyl ether, 22 mmol) was slowly added at -30 °C. The reaction mixture was slowly warmed to room temperature and stirred for 22 hours, then the solvent was evaporated in vacuo under nitrogen. Warm hexane was added and the mixture was filtered through a diatomaceous earth filter to obtain a filtrate. Then, the solvent was removed under vacuum under a nitrogen atmosphere. The obtained solid was dissolved in hexane (70 mL), EtOAc (EtOAc)

Example 1. Transition metal catalyst compound 1 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = Me), 64% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.01 (m, 1H), 7.83 (m, 1H), 7.78 (m, 1H), 7.71 (m, 1H), 7.49 (m, 1H), 7.31-7.38 (m, 3H), 7.25 (m, 1H), 6.87 (m) , 1H), 2.57 (s, 3H), 2.42 (s, 3H), 2.36 (s, 3H), 1.66 (s, 3H), 1.61 (s, 3H), 1.56 (m, 3H), 0.59 (s, 3H), 0.48 (s, 3H), 0.28 (s, 3H), 0.05 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 162.73, 154.44, 153.77, 148.4, 142.01, 139.62, 139.06, 138.10, 136.15, 135.48, 134.64, 133.24, 131.72, 129.15, 128.87, 127.47, 127.36, 124.47, 123.02, 120.31, 119.80, 118.11, 116.59, 99.79, 57.96, 55.34, 47.35, 27.63, 20.97, 16.84, 13.11, 12.75, -0.69 , -1.69.

Example 2. Transition metal catalyst compound 2 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-Bu), 40% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.80 ( m, 1H), 7.78 (m, 1H), 7.73 (m, 1H), 7.71 (m, 1H), 7.37 (m, 1H), 7.33 (m, 1H), 7.30 (m, 1H), 7.27 (m) , 1H), 7.20 (m, 1H), 6.86 (m, 1H), 2.55 (s, 3H), 2.38 (s, 3H), 2.33 (s, 3H), 2.00-2.08 (m, 4H), 1.62 ( s, 3H), 1.01-1.06 (m, 4H), 0.71-0.77 (m, 1H), 0.62 (t, J = 7.25 Hz, 6H), 0.56 (s, 3H), 0.50-0.58 (m, 3H) , 0.44 (s, 3H), 0.24 (s, 3H), 0.00 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 162.75, 151.41, 150.88, 148.24, 141.87, 141.66, 140.12, 139.04, 136.21, 135.65,134.52,133.47,131.61,129.14,129.11,128.78,127.20,127.10,124.39,123.33,119.92,119.40,118.24,116.69,99.53,57.99,55.61,55.46,40.93,40.66,26.67,26.51,23.54,23.50, 20.95, 16.85, 14.13, 14.09, 13.21, 12.76, -0.68, -1.71.

Example 3. Transition metal catalyst compound 3 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = Me), 43% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.99 (m, 1H), 7.82 (m, 1H), 7.77 (m, 1H), 7.68 (m, 1H), 7.47 (m, 1H), 7.32-7.37 (m, 3H), 7.21 (m, 1H), 6.86 (m) , 1H), 2.55 (s, 3H), 2.34 (s, 3H), 1.64 (s, 3H), 1.58 (s, 3H), 1.54 (m, 3H), 0.57 (s, 3H), 0.47 (s, 3H), 0.26 (s, 3H), 0.06 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 160.79,159.31,156.92,154.47,153.88,148.59,142.10,139.40,138.65,137.83,136.34,135.68 , 130.95, 129.05, 127.65, 127.38, 124.39, 123.04, 120.41, 119.93, 119.48, 119.27, 118.56, 118.33, 116.65, 99.31, 58.79, 56.07, 47.38, 27.56, 16.82, 13.11, 12.74, -1.07, -1.92.

Example 4. Transition metal catalyst compound 4 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = n-Bu), 71% yield. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.89- 7.82 (m, 2H), 7.74 (m, 2H), 7.31-7.39 (m, 3H), 7.18 (m, 1H), 7.10 (m, 1H), 6.87 (m, 1H), 2.55 (s, 3H) , 2.35 (s, 3H), 2.02-2.08 (m, 4H), 1.64 (s, 3H), 1.03-1.08 (m, 4H), 0.72-0.79 (m, 1H), 0.63 (t, J = 7.43 Hz) , 6H), 0.57 (s, 3H), 0.51 - 0.59 (m, 3H), 0.47 (s, 3H), 0.27 (s, 3H), 0.05 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 160.81,159.25,156.86,151.43,151.05,148.45,141.99,141.43,140.67,137.82,136.39,135.84,129.07,127.40,127.14,124.23,123.36,120.04,119.51,119.37,119.17,118.80,118.56,118.48,116.75 , 99.07, 58.88, 56.24, 55.63, 40.87, 40.61, 26.62, 26.46, 23.50, 23.46, 14.10, 14.06, 13.19, 12.74, -1.06, -1.94.

Example 5. Transition metal catalyst compound 5 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-tetradecyl), 92% yield, ¹ H NMR (CD ₂ Cl ₂ ): δ 7.73-7.80 (m, 4H), 7.28-7.38 (m, 4H), 7.18 (m, 1H), 6.86 (m, 1H), 2.56 (s, 3H), 2.40 (s, 3H), 2.34 (s, 3H), 2.02-2.10 (m, 4H), 1.61 (s, 3H), 1.09-1.38 (m, 34H), 0.97-1.09 (m, 17H), 0.88-0.92 (m, 9H), 0.58-0.84 ( m, 4H), 0.24 (s, 3H), 0.02 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 163.22, 154.42, 150.93, 148.19, 142.03, 141.44, 140.05, 139.04, 136.26, 136.05, 135.23 , 133.39, 131.28, 129.17, 127.15, 127.08, 126.49, 124.30, 123.32, 119.92, 119.34, 118.10, 116.62, 98.45, 57.81, 55.65, 55.59, 41.05, 40.81, 32.39, 30.47, 30.12, 30.02, 29.81, 24.44, 24.28 , 23.15, 21.01, 16.83, 14.35, 13.23, 12.82, 7.72, 7.50, 4.74, 4.33.

[Example 6] Preparation of Transition Metal Catalyst 6 According to the Present Invention

Preparation of Compound D6

P-cresol (30.0 g, 277 mmol, 1 eq.) was dissolved in MeCN (3000 mL). p-Toluenesulfonic acid monohydrate (p-TSA) (52.8 g, 277 mmol, 1 equivalent) was added to the reaction solution and stirred for 15 minutes, and N-iodosuccinimide (N-iodosuccinimide; NIS was slowly added thereto. (62.0 g, 277 mmol, 1 equivalent) for 30 minutes or more, and the reaction solution was stirred for 12 hours. After stirring for 12 hours, the same volume of distilled water was added. The product thus formed was extracted with diethyl ether (200 mL×2), and the organic material thus recovered was treated with aqueous Na ₂ SO ₃ and distilled water and dried over anhydrous Na ₂ SO ₄ to remove solvent. The obtained compound (2-iodo-4-methylphenol; 56.5 g, yield 87%) was used for the next reaction without further purification.

2-iodo-4-methylphenol (56.5 g, 240 mmol, 1 eq.) was dissolved in dry THF (250 mL). N,N-Diisopropylethylamine (DIPEA) (62.7 mL, 360 mmol, 1.5 eq.) and chloromethyl methyl ether (MOMCl) (27.5 mL, 360 mmol, 1.5 eq. The reaction solution was stirred at 60 ° C for 12 hours and then added to distilled water (500 mL) to terminate the reaction. The reaction solution was extracted with hexane (200 mL × 2), and the obtained organic layer was treated with distilled water and anhydrous Na ₂ SO ₄ and dried to give a crude product. The crude product was purified by flash chromatography (EtOAc: EtOAc) .

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.60 (s, 1H), 7.05-7.08 (m, 1H), 6.94 (d, J = 8.3Hz, 1H), 5.19 (s, 2H), 3.50 (s, 3H), 2.25 (s, 3H).

Preparation of Compound E6

2,7-di-tertiary butyl-9H-carbazole (24.8 g, 89.0 mmol, 1 eq.), compound D6 (29.6 g, 107 mmol, 1.2 eq.), CuI (3.4 g, 18.0 mmol, 0.2 eq.) , K ₃ PO ₄ (57.0 g, 267 mmol, 3 equivalents) and N,N'-dimethyl-1,2-ethanediamine (2.35 g, 26.7 mmol, 0.3 eq.) were dissolved in anhydrous toluene (180 mL). Stir at 120 ° C for 12 hours. Then, distilled water (500 mL) was added to terminate the reaction. The organic layer was extracted with toluene (100 mL×3), successively treated with distilled water and anhydrous Na ₂ SO ₄ and dried to obtain a crude product. The crude product was purified by EtOAc EtOAc (EtOAc)

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 8.05 (d, J = 8.2Hz, 2H), 7.29-7.41 (m, 7H), 4.98 (s, 2H), 3.24 (s, 3H), 2.45 (s, 3H), 1.42 (s, 18H).

Preparation of Compound F6

The n-BuLi (58.0 mL, 145 mmol, 2 eq.) was slowly added to a solution of EtOAc (EtOAc, EtOAc. 1,2-Dibromotetrafluoroethane (74.8 g, 288 mmol, 4 equivalents) was slowly added to the reaction solution at 0 ° C, stirred for 12 hours, and then added to distilled water (500 mL) to terminate the reaction. The organic layer was recovered and treated with anhydrous Na ₂ SO ₄ and dried to give the product (9-{3-bromo-5-methyl-2-(methoxymethoxy)phenyl}-2,7- -Tribasin-9H-carbazole; 32.1 g, yield 88%) and was used in the next step without further purification.

Add 9-{3-bromo-5-methyl-2-(methoxymethoxy)phenyl}-2,7-di-tert-butyl-9H-indazole (32.1 g, 75.0 mmol) To a mixed solution of methanol (220 mL) and THF (220 mL) and hydrochloric acid (12M, 2.5 mL), the mixture was stirred at 60 ° C for 12 hours, and then distilled water (1000 mL) was added to terminate the reaction. The mixture was treated with diethyl ether (200 mL×2) to give an organic layer, and the organic layer was treated with anhydrous Na ₂ SO ₄ and dried to give a crude product. The crude product was purified by flash chromatography eluting EtOAc EtOAc (EtOAc:EtOAc Yield).

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 8.00 (dd, J 1 = 8.3Hz, J 2 = 0.5Hz, 2H), 7.51 (dd, J 1 = 2.1Hz, J 2 = 0.6Hz, 1H), 7.35 (dd, J ₁ = 8.2 Hz, J ₂ = 1.7 Hz, 2H), 7.15 (dd, J ₁ = 2.1 Hz, J ₂ = 0.7 Hz, 1H), 7.08 (d, J = 1.2 Hz, 2H), 5.42 (s, 1H), 2.37 (s, 3H), 1.36 (s, 18H).

Preparation of Compound G6

K ₂ CO ₃ (30 mmol) and allyl bromide (30 mmol) were added to dry acetone (200 mL) and phenol (20 mmol) and then refluxed for 16 hr. The acetone was removed via vacuum, and distilled water was added, followed by extraction with dichloromethane (50 mL×3). The organic layer was treated with anhydrous Na ₂ SO ₄ and dried, and the obtained residue was purified by flash chromatography (distilled liquid: hexane) using a column packed with silica gel 60 (40-63 μm) to obtain a title. Compound G6 (99% yield).

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 8.00 (d, J = 8.2Hz, 2H), 7.57 (d, J = 1.9Hz, 2H), 7.35 (dd, J 1 = 8.2Hz, J 2 = 1.6Hz , 2H), 7.25 (s, 1H), 7.20 (d, J = 1.3 Hz, 2H), 5.40-5.50 (m, 1H), 4.76-4.84 (m, 2H), 3.85 (d, J = 6.0 Hz, 2H), 2.41 (s, 3H), 1.40 (s, 18H).

Preparation of Compound H6

n-BuLi (2.5 M in hexane, 91 mmol) was slowly added to a solution of compound G6 (70 mmol) in toluene (200 mL) and then warmed to -20 °C. The reaction solution was again cooled to -78 ° C, dichlorodiethyl decane (210 mmol) was quickly added, the temperature was warmed to room temperature, and the mixture was stirred for 5 hr. The inorganic salt was removed by filtration through diatomaceous earth. After the solvent was removed, the excess of dichloromethane was evaporated in vacuo to afford title compound H6 (yield: 99%).

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.99 (d, J = 8.0Hz, 2H), 7.61 (s, 1H), 7.40 (s, 1H), 7.34 (d, J = 8.2Hz, 2H), 7.28 (s, 2H), 5.29-5.39 (m, 1H), 4.80 (d, J = 10.5 Hz, 1H), 4.65 (d, J = 17.2 Hz, 1H), 3.59 (d, J = 5.7 Hz, 2H) , 2.44 (s, 3H), 1.38 (s, 18H), 1.03-1.31 (m, 10H).

Preparation of Compound I6

n-BuLi (2.5 M in hexane, 31.6 mmol) was slowly added dropwise to 2,4,5-trimethyl-6H-cyclopenta[b]thiophene (30.1 mmol) in THF (112 mL). ) in the solution. The reaction mixture was warmed to room temperature and further stirred for 2 hours. After the stirring was completed, the mixture was cooled to -78 ° C, and a solution of compound H6 (33.1 mmol) in toluene (14 mL) was added through a syringe. The reaction mixture solution was heated to room temperature, further stirred for 3 hours, and then added to distilled water (200 mL) to terminate the reaction. The organic layer was extracted with toluene (2×50 mL), water was removed with Na ₂ SO ₄ and solvent was evaporated from vacuo to afford crude. Then, the crude product was purified by flash chromatography (distilled liquid: hexane/dichloromethane, 10/1, volume) using a column packed with silica gel 60 (40-63 μm) to obtain the title compound I6 (65). %Yield).

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.99 (d, J = 8.2Hz, 2H), 7.31-7.35 (m, 4H), 7.23-7.27 (m, 2H), 6.83 (s, 1H), 5.30- 5.40 (m, 1H), 4.67-4.78 (m, 2H), 3.86 (s, 1H), 3.55-3.68 (m, 2H), 2.48 (s, 3H), 2.40 (s, 3H), 2.04 (s, 3H), 1.97 (s, 3H), 1.36 (s, 18H), 0.72-1.06 (m, 10H)

Preparation of Compound J6

The Et ₃ N (45mmol) and the compound I6 (10mmol) was cooled in toluene (70 mL) to the -78 ℃, was slowly added n-BuLi (2.5M, in hexanes, 22mmol). The reaction mixture was warmed to room temperature and stirred for 20 hours, cooled again to -78 deg.] C, and then TiCl ₄ (15mmol) in toluene (22mL) was slowly added dropwise via syringe. After the addition of TiCl ₄ was completed, the reaction mixture was heated to room temperature and stirred at 90 ° C for 16 hours. The mixture was cooled to room temperature and then the solvent was removed via vacuum. After removing the solvent, hot methylcyclohexane was added to remove the insoluble inorganic salt through a diatomaceous earth filter. The solvent of the filtrate was concentrated in vacuo and then recrystallized from a solvent mixture of methyl cyclohexane and hexane to afford the title compound J6 (61% yield).

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.90 (d, J = 8.2Hz, 2H), 7.41 (d, J = 5.0Hz, 2H), 7.21-7.25 (m, 2H), 7.07 (s, 1H) , 7.01 (s, 1H), 6.64 (s, 1H), 2.51 (s, 3H), 2.37 (s, 3H), 2.33 (s, 3H), 2.07 (s, 3H), 1.33 (s, 9H), 1.31 (s, 9H), 1.08-1.28 (m, 10H).

Preparation of compound 6

Compound J6 (10 mmol) was dissolved in diethyl ether (100 mL), and a solution of MeMgBr (2.9 M in diethyl ether, 22 mmol) was slowly added at -30 °C. The reaction mixture was slowly warmed to room temperature and stirred for 22 hours then the solvent was removed in vacuo. Hot hexane was added to the reaction and the insoluble inorganic salt was removed through a diatomaceous earth filter. The filtrate was dried under vacuum, dissolved in hexane (70 mL), and then passed through a diatomaceous earth filter to remove insoluble inorganic salt. The resulting filtrate was stored at -30 °C for 12 hours to afford compound 6 (54% yield) as a yellow solid.

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.98 (d, J = 8.2Hz, 1H), 7.94 (d, J = 8.2Hz, 1H), 7.39 (m, 1H), 7.14-7.32 (m, 4H) , 6.95 (m, 1H), 6.65 (m, 1H), 2.45 (s, 3H), 2.42 (m, 3H), 2.07 (s, 3H), 1.42 (s, 3H), 1.29 (s, 9H), 1.28(s,9H), 0.87-1.18(m,10H), -0.50(s,3H), -0.62(s,3H). ¹³ C{ ¹ H}NMR (101MHz, CDCl ₃ ): δ 161.9,148.2 , 147.9, 147.0, 142.5, 142.4, 140.8, 135.2, 135.1, 134.8, 131.5, 131.0, 126.6, 124.0, 120.9, 120.5, 118.9, 118.8, 116.8, 116.6, 116.2, 115.8, 106.7, 105.4, 97.8, 76.7, 76.4 , 58.5, 55.6, 34.7, 34.7, 31.5, 31.4, 31.3, 22.3, 20.6, 16.2, 13.8, 12.4, 12.1, 7.3, 7.2, 4.2, 4.0.

[Comparative Example 1] Preparation of Comparative Catalyst 1

Comparative Catalyst 1 was prepared using the methods of Examples 1 to 5 above.

¹ H NMR (CDCl ₃ ): δ 0.06 (s, 3H), 0.23 (s, 3H), 0.59 (s, 3H, Si-Me), 0.63 (s, 3H, Si-Me), 1.35 (s, 9H) , Ar-tBu), 2.12 (s, 3H, Cp'-Me), 2.38 (s, 3H, Ar-Me), 2.56 (s, 3H, Cp'-Me), 2.56 (s, 3H, thiophene-Me) ), 6.87 (d, J = 1.3 Hz, ¹ H, thiophene-H), 7.18 (d, J = 2.1 Hz, 1H, Ar-H), 7.20 (d, J = 2.1 Hz, 1H, Ar-H) .

[Comparative Example 2] Preparation of Comparative Catalyst 2

Comparative Catalyst 2 was prepared using the methods of Examples 1 to 5 above.

¹ H NMR (CDCl ₃ ): δ 8.01 (m, 1H), 7.82 (m, 1H), 7.76 (m, 1H), 7.72 (m, 1H), 7.51 (m, 1H), 7.31-7.39 (m, 3H), 7.23 (m, 1H), 6.25 (t, 2H), 5.99 (t, 2H), 1.77 (s, 3H), 1.45 (m, 3H), 1.39 (m, 3H), 0.78 (s, 3H) ), 0.57 (s, 3H), 0.55 (m, 3H).

[Comparative Example 3] Preparation of Comparative Catalyst 3

Preparation of compound a

1-Bromo-2,6-diisopropylbenzene (37.1 g, 154 mmol, 1.5 eq.) was dissolved in anhydrous THF (150 mL), and n-BuLi (68.0 mL, 170 mmol, 1.65) was slowly added dropwise at -78 °C. equivalent). The mixture was stirred for 1 hour, and ZnCl ₂ (25.3 g, 185 mmol, 1.8 eq.) was quickly added thereto, and the mixture was stirred for 1 hour and heated to room temperature, and further stirred for 1 hour. The reaction solution was transferred to a pressure vessel, and then Pd(dba) ₂ (0.83 g, 1.00 mmol, 0.01 equivalent), RuPhos [S. Buchwald, J. Am. Chem. Soc., 2004, 126 ( 40), 13028-13032] (1.92 g, 4.00 mmol, 0.04 eq.) and 2-bromo-1-(methoxymethoxy)-4-methylbenzene (23.7 g, 103 mmol, 1 eq.). The reaction solution was diluted with THF (50 mL) and NMP (100 mL). The reaction solution was stirred at 100 ° C for 12 hours, and distilled water (150 mL) was added to terminate the reaction. The resulting solution was extracted twice with diethyl ether (200 mL). The obtained organic material was treated with distilled water, dried over anhydrous Na ₂ SO ₄ and then solvent was evaporated from vacuo. The obtained product was solidified with ethanol, and the obtained solid was separated to give 2',6'-diisopropyl-2-methoxymethoxy-5-methylbiphenyl (23.1 g, 72% yield). It is a white crystalline solid. The obtained white solid (23.1 g, 74.0 mmol) was dissolved in a mixture of methanol (220 mL) and THF (220 mL). Then, HCl (aq) (12 M, 2.2 mL) was added thereto, and the mixture was stirred at 60 ° C for 12 hours, and distilled water (1000 mL) was added to terminate the reaction. After completion of the reaction, the product (200mL × 2) and extracted with diethyl ether, treated with distilled water, dried over anhydrous Na ₂ SO _4, the solvent was removed, to obtain compound a, as a white solid (19.3g, 97%).

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.39 (t, J = 7.8Hz, 1H), 7.27 (d, J = 7.7Hz, 1H), 7.08 (d, J = 8.3Hz, 1H), 6.88 (d , J = 8.3 Hz, 1H), 6.82 (s, 1H), 4.45 (s, 1H), 2.62 (m, 2H), 2.30 (s, 3H), 1.10 (d, J = 6.9 Hz, 6H), 1.07 (d, J = 6.8 Hz, 6H).

Preparation of compound b

Compound b (95% yield) was prepared in the same manner as Compound 6F of Example 6.

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.41 (t, J = 7.8Hz, 1H), 7.35 (s, 1H), 7.27 (d, J = 7.8Hz, 2H), 6.82 (s, 1H), 5.06 (s, 1H), 2.52-2.60 (m, 2H), 2.31 (s, 3H), 1.15 (d, J = 6.9 Hz, 6H), 1.09 (d, J = 6.9 Hz, 6H).

Preparation of Compound C

Compound c (79% yield) was prepared in the same manner as Compound G6 of Example 6.

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.40 (s, 1H), 7.35 (t, J = 7.7Hz, 1H), 7.20 (d, J = 7.7Hz, 2H), 6.86 (s, 1H), 5.57 -5.67 (m, 1H), 4.97-5.05 (m, 2H), 4.06 (d, J = 5.4 Hz, 2H), 2.53-2.63 (m, 2H), 2.32 (s, 3H), 1.18 (d , J) =6.9 Hz, 6H), 1.05 (d, J = 6.8 Hz, 6H).

Preparation of compound d

Compound d (79% yield) was prepared in the same manner as Compound H6 of Example 6.

_{^{1 H NMR (400MHz, CDCl 3}} ): δ 7.47-7.48 (m, 1H), 7.33-7.37 (m, 1H), 7.21 (s, 1H), 7.19 (s, 1H), 6.96-6.97 (m, 1H ), 5.51-5.61 (m, 1H), 4.93-5.00 (m, 2H), 3.88 (dt, J1 = 5.6 Hz, J2 = 1.4 Hz, 2H), 2.67 (m, 2H), 2.35 (s, 3H) , 1.16 (d, J = 6.9 Hz, 6H), 0.98-1.10 (m, 16H).

Preparation of compound e

Compound e (77% yield) was prepared in the same manners as Compound I6 of Example 6.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.37 (t, J = 7.7 Hz, 1H), 7.22 - 7.26 (m, 2H), 7.13 (d, J = 2.2 Hz, 1H), 6.98 (d, J = 2.2 Hz, 1H), 6.64 (s, 1H), 5.59-5.68 (m, 1H), 4.99-5.06 (m, 2H), 3.98 (d, J = 5.32 Hz, 2H), 3.89 (s, 1H), 2.77-2.91 (m, 2H), 2.50 (s, 3H), 2.36 (s, 3H), 2.04 (s, 3H), 1.90 (s, 3H), 1.21 (d, J = 6.7 Hz, 3H), 1.19 (d, J = 6.7 Hz, 3H), 1.14 (d, J = 6.8 Hz, 3H), 1.08 (d, J = 6.8 Hz, 3H), 0.68-0.93 (m, 10H).

Preparation of compound f

Compound f (17% yield) was prepared in the same manner as Compound J6 of Example 6.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.26 (s, 1H), 7.24 - 7.26 (m, 1H), 7.09-7.12 (m, 1H), 6.99 (s, 1H), 6.78 (s, 1H), 2.51 (s, 3H), 2.45 (s, 3H), 2.41 (s, 3H), 2.41-2.45 (m, 2H), 2.12 (s, 3H), 1.0-1.24 (m, 22H).

Comparative preparation of catalyst 3

Comparative catalyst 3 was prepared in the same manner as compound 6 of Example 6. (91% yield).

_{^{1 H NMR (400MHz, CD 2}} Cl 2): δ 7.29-7.36 (m, 1H), 7.23-7.28 (m, 1H), 7.16-7.23 (m, 2H), 6.98 (m, 1H), 6.82 (m , 1H), 2.79 (m, 1H), 2.55 (m, 1H), 2.52 (m, 3H), 2.37 (s, 3H), 2.29 (m, 3H), 1.63 (s, 3H), 1.22 (d, J = 6.9 Hz, 3H), 1.10 - 1.20 (m, 2H), 1.02-1.10 (m, 9H), 0.85-1.02 (m, 8H), -0.02 (s, 3H), -0.22 (s, 3H) ¹³ C{ ¹ H} NMR (101 MHz, CDCl ₃ ): δ 186.8, 171.4, 171.1, 170.5, 165.2, 160.3, 158.9, 158.5, 158.0, 156.9, 153.9, 151.0, 150.7, 149.0, 145.6, 145.5, 140.8, 139.6, 121.3, 80.3, 77.7, 77.5, 77.3, 76.7, 76.5, 54.2, 53.9, 48.5, 48.1, 46.8, 46.7, 44.2, 40.0, 36.1, 35.9, 30.9, 30.7, 28.2, 27.9.

[Example 7 to Example 21 and Comparative Example 4 to Comparative Example 8] Copolymerization of ethylene and 1-hexene

The ethylene/1-hexene copolymerization process is carried out as follows.

The polymerization is carried out in a temperature-controlled continuous polymerization reactor equipped with a mechanical stirrer. TiBA/BHT as a scavenger (triisobutylaluminum/2,6-di-tert-butyl-4-methylphenol with a molar ratio of 1:1, nAl=30 μmol, 120 μL, 0.25 M toluene solution) ), 1-hexene (200 μL, 270 μL or 300 μL) and toluene were added to the reactor to make a total volume of 5 mL. The temperature of the reactor was adjusted to the polymerization temperature (130 ° C or 150 ° C), and then the stirring rate was set to 800 rpm. Depending on the polymerization temperature, ethylene will be Add at 200 psi or 220 psi at 150 °C and 175 psi or 180 psi at 130 °C to keep the ethylene constant. The polymerization catalyst was used in an amount of 10 nmole or 15 nmole, and the amount of the cocatalyst was fixed to 5 equivalents with respect to the polymerization catalyst. The polymerization catalyst was introduced into the reactor, and then polymerization was started by adding 5 equivalents of a co-catalyst triphenylmethyl pentoxide (pentafluorophenyl)borate (TTB). The polymerization is carried out for 1 minute to 5 minutes, or the polymerization is terminated when the polymer to be prepared does not exceed 100 mg to 200 mg.

After the polymerization was completed, the reactor temperature was cooled to room temperature, and ethylene in the reactor was slowly removed via evacuation. The prepared polymer was then dried by vacuum.

The polymerization conditions of the examples and comparative examples and the physical properties of the obtained polymer are shown in Table 1 below.

As shown in Table 1, it is understood that when ethylene and 1-hexene were copolymerized using the catalysts of Examples 1 to 5 of the present invention, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were used therein. In the case of a catalyst, the obtained copolymer of the present invention has more copolymerization characteristics. It is particularly understood that the activity of the examples at a polymerization temperature of 130 ° C is higher than that of the comparative examples. It is understood that the catalytic activity of Example 20 using the catalyst of Example 5 was slightly lower than that of Comparative Example 4, but the content of 1-hexene of the comonomer in the copolymer was very high, so Example 20 was compared with Comparative Example 4 had more excellent copolymerization characteristics. Further, the example at a polymerization temperature of 150 ° C exhibited a higher activity of about 2 to 45 times as compared with Comparative Example 1, and exhibited a higher activity of about 10 to 213 times compared with Comparative Example 2, and a phase. It exhibited a higher activity of about 1.7 to 33 times than Comparative Example 3.

Further, in view of the polymerization characteristics with respect to the comonomer, i.e., 1-hexene, it is understood that when the catalysts of Comparative Examples 1 to 3 are used, as compared with the case where the catalysts of Examples 1 to 5 are used, The content of 1-hexene in the copolymer was much lower, and therefore, Comparative Examples 1 to 3 had very poor copolymerization characteristics as compared with Examples 1 to 5. On the other hand, when the catalyst of Comparative Example 2 was used, the content of 1-hexene in the copolymer was similar to the case in which the catalysts of Examples 1 to 5 were used, but the polymerization activity was poor.

That is, it can be understood that when the catalyst of the present invention is used as a polymerization catalyst, a copolymer having a high comonomer content can be prepared while maintaining high polymerization activity at a high polymerization temperature of 150 °C.

Meanwhile, 1-hexene ([1-C6]=450 μL), polymerization temperature (T=150 ° C), ethylene pressure (pE=220 psi), and catalyst usage amount (15 nmol) were used in the same manner as in the above examples. The polymerization is carried out, and the polymerization is terminated when the polymer to be prepared does not exceed 100 mg. The copolymerization characteristics of the catalysts of Examples 1 to 4 of the present invention were confirmed by the reactivity of each catalyst to ethylene until 100 mg of the copolymer was prepared. The results are shown in Figure 1, where the higher the slope, the better the activity. As can be seen from Fig. 1, in the order of the polymerization catalysts of Example 4, Example 3, Example 2, Example 1 and Comparative Example 1, as shown in Table 1 above, the polymerization activity of the polymerization catalyst was improved. That is, it was confirmed that when the polymerization catalysts of Example 4, Example 3 and Example 2 were used, it was necessary to add ethylene for about 70 seconds to prepare 100 mg of the copolymer. However, when the catalysts of Example 1 and Comparative Example 1 were used, it was necessary to add ethylene for about 300 seconds. However, when the catalysts of Example 1 and Comparative Example 1 were used, although it was expected to have the same activation level, the reactivity to ethylene at the start of the reaction was good, which was confirmed by consumption of ethylene up to about 150 seconds. That is, it can be confirmed that when the catalysts of Example 1, Example 2, Example 3, and Example 4 of the present invention are used in the ethylene/1-hexene copolymerization reaction, the activity is higher, and the reactivity of the comonomer is further It is higher than the case where the catalyst of Comparative Example 1 is used.

While the invention has been described in detail hereinabove, it is understood that the invention may be Therefore, further modifications in the examples of the invention will not depart from the techniques of the invention.

Claims (13)

A transition metal compound represented by the following Chemical Formula 1: In Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; R ¹ to R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl a group, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ; R ⁵ and R ⁶ are each independently (C1-C20)alkyl, halo(C1-C20)alkyl, (C3- C20) cycloalkyl, (C6-C20) aryl, (C1-C20)alkyl (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) An aryl group, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁵ and R ⁶ are permeable to a (C4-C7) alkyl chain to form a ring; R ⁷ to R ⁹ Each independently is hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl, halogen, (C6-C20)aryl, (C3-C20)heteroaryl, -OR ^a1 , -SR ^a2 ,- NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁷ to R ⁹ may be bonded through a (C4-C7)-extended alkenyl group with or without an aromatic ring to form a fused ring; R ^a1 to R ^{a6 is} each independently (C1-C20)alkyl or (C6-C20)aryl; Ar ¹ is fluorenyl or N-carbazole, and the fluorenyl or carbazole of Ar ¹ may be further subjected to (C1-C20) alkane Substituent; X ¹ and X ² are each independently hydrogen, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C 6-C20) aryl (C1-C20) alkyl, ((C1-C20)alkyl(C6-C20)aryl)(C1-C20)alkyl, (C1-C20)alkoxy, (C6- C20) aryloxy, (C1-C20)alkyl (C6-C20) aryloxy, (C1-C20) alkoxy (C6-C20) aryloxy, -OSiR ^a R ^b R ^c , -SR ^d , -NR ^e R ^f , -PR ^g R ^h or (C1-C20) alkylene; R ^a to R ^d are each independently (C1-C20) alkyl, (C6-C20) aryl, (C6-C20 An aryl (C1-C20) alkyl group, a (C1-C20) alkyl (C6-C20) aryl group or a (C3-C20) cycloalkyl group; and R ^e to R ^h are each independently a (C1-C20) alkyl group, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl, (C3-C20) cycloalkyl, tri (C1- C20) an alkyl fluorenyl group or a tri(C6-C20) aryl fluorenyl group; the limitation is that when one of X ¹ and X ² is a (C1-C20) alkylene group, the other is ignored; The heteroaryl group includes at least one hetero atom selected from N, O and S. The transition metal compound according to claim 1, wherein the transition metal compound is represented by the following Chemical Formula 2 or Chemical Formula 3: In Chemical Formula 2 or Chemical Formula 3, M, R ¹ to R ⁴ , X ¹ and X ² are the same as defined in Chemical Formula 1 of Claim 1; R ⁵ and R ⁶ are each independently (C1-C20) alkyl a halogen (C1-C20) alkyl group or a (C6-C20) aryl group; R ⁸ and R ⁹ are each independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl or halogen, and R ⁸ And R ⁹ can pass through , , or Linked to form a fused ring; R ¹¹ and R ¹² are each independently (C1-C20)alkyl; and R ¹³ , R ¹⁴ and R ¹⁵ are each independently hydrogen or (C1-C20)alkyl. The transition metal compound according to claim 2, wherein the transition metal compound is selected from the group consisting of: Wherein M is titanium, zirconium or hafnium. A transition metal catalyst composition for use in the preparation of an ethylene homopolymer or a copolymer of ethylene and an α -olefin, the transition metal catalyst composition comprising: the transition metal compound according to any one of claims 1 to 3; And a cocatalyst selected from the group consisting of aluminum compounds, boron compounds, or mixtures thereof. The transition metal catalyst composition according to claim 4, wherein the aluminum compound used as the cocatalyst is one or a mixture of two or more selected from the group consisting of aluminoxane and organoaluminum, and includes a methyl group selected from the group consisting of aluminoxane and organoaluminum. Aluminoxane, modified methyl aluminoxane, tetraisobutyl aluminoxane, trimethyl aluminum, One of triethyl aluminum, trioctyl aluminum, and triisobutyl aluminum or a mixture thereof. The transition metal catalyst composition according to claim 4 or 5, wherein the aluminum compound used as the cocatalyst has a transition metal (M) of 1:10 to 5,000 and an aluminum atom (Al) (M:Al). Ear ratio. The transition metal catalyst composition according to claim 4, wherein the boron compound used as the cocatalyst comprises a group selected from the group consisting of ruthenium (pentafluorophenyl) borate-N,N-dimethylanilinium, ruthenium (pentafluorobenzene) One of or a mixture of triphenylmethyl borate and quinone (pentafluorophenyl)borane. The transition metal catalyst composition according to claim 4 or 7, wherein a molar ratio of the transition metal compound to the cocatalyst, that is, a transition metal (M): a boron atom (B): a mole of an aluminum atom (Al) The ratio ranges from 1:0.1 to 100:10 to 3,000. The transition metal catalyst composition according to claim 5, wherein a molar ratio of the transition metal compound to the cocatalyst, that is, a transition metal (M): a boron atom (B): an aluminum atom (Al) molar ratio The range is 1:0.5 to 5:100 to 3,000. A process for producing an ethylene homopolymer or a copolymer of ethylene and an α -olefin using the transition metal catalyst composition of claim 4. The method of claim 10, wherein the α -olefin copolymerized with ethylene is selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- Heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, ring At least one of pentene, cyclohexene, norbornene, phenyl norbornene, styrene, α -methylstyrene, p-methylstyrene, and 3-chloromethylstyrene, and the ethylene and The copolymer of the α -olefin has an ethylene content of from 30% by weight to 99% by weight. The method according to claim 11, wherein the pressure in the reactor for ethylene homopolymerization or copolymerization of the ethylene monomer and the α -olefin is from 1 atm to 1000 atm, and the polymerization temperature is from 25 ° C to 200 ° C. The method according to claim 12, wherein the pressure in the reactor for ethylene homopolymerization or copolymerization of the ethylene monomer and the α -olefin is from 10 atm to 150 atm, and the polymerization temperature is from 50 ° C to 180 ° C.