TW201829440A - Novel indene-based transition metal compound, catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and [alpha]-olefin using the same - Google Patents

Abstract

Provided are a novel indene-based transition metal compound, a transition metal catalyst composition comprising the transition metal compound and having high catalytic activity for preparing an ethylene homopolymer or a copolymer of ethylene and at least one [alpha]-olefin, and a method for preparing an ethylene homopolymer or a copolymer of ethylene and [alpha]-olefin using the same.

Description

   Novel indene transition metal compound, catalyst composition containing the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the compound   

The invention relates to a novel indene-based transition metal compound and a transition metal catalyst composition containing the transition metal compound. The invention has high catalysis for preparing an ethylene homopolymer or a copolymer of ethylene and at least one α-olefin. Activity, and a method for preparing 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 composed of a main catalyst component of a titanium or vanadium compound and a co-catalyst component of an aluminum alkyl compound is generally used to prepare an ethylene homopolymer or an ethylene and Copolymers of alpha-olefins. The Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization. However, it has the disadvantage that the molecular weight distribution of the obtained polymer is generally wide due to the uneven catalytic activation point, and in particular, the composition distribution of the copolymer of ethylene and? -Olefin is not uniform.

Since the metallocene catalyst system composed of a metallocene compound of a Group 4 transition metal (such as titanium, zirconium, hafnium, etc.) in the periodic table and methylaluminoxane as a cocatalyst is a homogeneous phase with a single type of catalytic activation point The catalyst is characterized in that the metallocene catalyst system can prepare polyethylenes having a narrower molecular weight distribution and a uniform composition distribution than the existing Ziegler-Natta catalyst system. For example, European Patent Publication No. 320,762, No. 372,632 or Japanese Patent Publication No. S63-092621, No. H02-84405, or No. H03-2347 report that a metallocene can be activated by using a co-catalyst, methylalumoxane 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., to polymerize ethylene with high activity to prepare its molecular weight distribution (Mw / Mn) range Polyethylenes from 1.5 to 2.0. However, it is difficult to obtain high molecular weight polymers 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 reduced and the β-dehydrogenation reaction is dominant, so it is not suitable for preparing a weight average molecular weight (Mw) thereof. High molecular weight polymers of 100,000 or higher.

Meanwhile, as a catalyst capable of preparing a polymer having a high catalytic activity and a high molecular weight by a homopolymerization reaction of ethylene or a copolymerization reaction of ethylene with an α-olefin under solution polymerization conditions, it has been reported that the transition metal is cyclically linked The so-called geometrically restricted non-metallocene catalyst (so-called single activation point catalyst). European Patent Nos. 0416815 and 0420436 suggest examples in which the amido group is cyclically linked to a cyclopentadiene ligand. European Patent No. 0842939 discloses an example of a catalyst in which a phenol-based ligand as an electron donor compound is linked with a cyclopentadiene ligand in a ring. In geometrically-constrained catalysts, 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 advanced α-olefins, and the ability to prepare high molecular weight polymers, it is important to ensure that it has more competitive properties as a commercial catalyst Catalyst system.

[Related prior technical 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).

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 case 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 used as a center metal, which is passed through a rigid planar structure and contains Large and extensive non-localized indene chains; and the ability to easily introduce phenoxy substituted with fluorenyl or carbazole (with substituents to improve solubility and performance) in ethylene and It exhibits excellent catalytic activity in the polymerization of olefins. Based on this finding, the present inventors 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 performed at a high temperature, and completed the present invention.

One embodiment of the present invention aims to provide a transition metal compound used as a catalyst for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin, and a catalyst composition including the transition metal compound.

Another embodiment of the present invention is conceived to provide a method for economically preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using a catalyst composition containing a transition metal compound in consideration of a commercial aspect.

Another embodiment of the present invention is designed to provide a single activation point catalyst having a simple synthesis path to be synthesized very economically and having a high activity in the polymerization of olefins in consideration of commercial aspects, and to economically prepare the catalyst component using the catalyst component. Polymerization method of ethylene homopolymer or copolymer of ethylene and α-olefin having various physical properties.

In one general aspect, an indene-based transition metal compound 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 serves as a central metal, which is passed through an indene having a rigid planar structure and containing a large number and broadly unlocalized electrons or derivatives thereof. And a phenoxy group substituted with a fluorenyl group or a carbazole (wherein there are substituents for improving solubility and performance) can be easily introduced.

In Chemical Formula 1, M is a transition metal of Group 4 in the periodic table; R ¹ to R ⁵ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl , -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ¹ to R ⁴ can pass through (C4-C7) alkylene with or without aromatic ring or ( C4-C7) alkenyl groups are linked to adjacent substituents to form a fused ring; R ⁶ and R ⁷ 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) heteroaryl , -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁶ and R ⁷ can be extended through (C4-C7) alkyl groups to form a ring; R ⁸ to R ¹⁰ are independent 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 ⁸ to R ¹⁰ may form a condensed ring through (C4-C7) alkenyl group with or without an aromatic ring and adjacent substituents; R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl; R ¹¹ and R ¹² are each independently , (C1-C20) alkyl or (C6-C20) aryl, or R ¹¹ and R ¹² may link with each other to form an aromatic ring; Ar ¹ is a fluorenyl group or carbazolyl N-, and Ar ¹ group or fluorenyl carbazole may be further (C1-C20) alkyl substituent; X ¹ and X ² are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (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, (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, tris (C1-C20) alkyl silicon Or tri (C6-C20) arylsilyl; it is limited in that when one of X ¹ and X ² is (C1-C50) alkylene, the other is ignored; and the heteroaryl includes at least One selected from N, O and S Hetero atom.

In another general aspect, a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin is provided, which includes a transition metal compound represented by Chemical Formula 1; and selected from an aluminum compound, Co-catalyst of boron compounds or mixtures thereof.

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

The transition metal compound or the catalyst composition containing the transition metal compound according to the present invention may have a simple synthetic process so that it can be easily prepared in a high yield by an economic method, and further, it can provide 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 yields, so it is commercially useful than previously known single activation point catalysts for metallocenes and non-metallocenes. Therefore, the transition metal and the catalyst composition containing the same according to the present invention can be effectively used to prepare an ethylene homopolymer or a copolymer of ethylene and an α-olefin having various physical properties.

Hereinafter, the present invention will be described in more detail. Unless otherwise defined, technical and scientific terms have the meanings understood by those having ordinary knowledge in the technical field to which the present invention belongs. In the following description, known functions and components that may obscure the subject matter of the present invention are omitted.

The transition metal compound according to an exemplary embodiment of the present invention is a transition metal compound based on an indenyl group represented by the following Chemical Formula 1, and may have a structure in which a transition metal of Group 4 in the periodic table is a center metal, which is borrowed from Substituted by an indene chain having a rigid planar structure and containing a large and wide range of unlocalized electrons or derivatives thereof; and the ability to easily introduce a fluorenyl or carbazole (with substituents for improving solubility and performance) The phenoxy group thus provides structural advantages that facilitate the efficient acquisition of high molecular weight ethylene polymers.

In Chemical Formula 1, M is a transition metal of Group 4 in the periodic table; R ¹ to R ⁵ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl , -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ¹ to R ⁴ can pass through (C4-C7) alkylene or (C4-C7) with or without aromatic ring ) Alkenyl groups are linked to adjacent substituents to form a fused ring; R ⁶ and R ⁷ 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) heteroaryl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁶ and R ⁷ can be extended through (C4-C7) alkyl groups to form a ring; R ⁸ to R ¹⁰ are each 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 ⁸ to R ¹⁰ may form a condensed ring through (C4-C7) alkenyl group with or without aromatic ring to form a fused ring; R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl; R ¹¹ and R ¹² are each independently hydrogen, (C1-C2 0) alkyl or (C6-C20) aryl, or R ¹¹ and R ¹² may be linked to each other to form an aromatic ring; Ar ¹ is a fluorenyl or N-carbazole, and the fluorenyl or carbazole of Ar ¹ may be further Substituted by (C1-C20) alkyl; X ¹ and X ² are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl (C1-C20) alkane ((C1-C20) alkyl (C6-C20) aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20) alkane (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; each of ^Ra to ^{Rd is} 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 ) Ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl, (C3-C20) cycloalkyl, tri (C1-C20) alkylsilyl or tri (C6-C20 ) Arylsilyl; its limitation is that when one of X ¹ and X ² is (C1-C50) alkylene, the other is ignored; and the heteroaryl includes at least one selected from N, O and Heteroatom of S.

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

The term "aryl" as used herein refers to an organic radical obtained by removing one hydrogen from an aromatic hydrocarbon, and includes suitably containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring. Single ring system or fused ring system, and even includes forms in which a plurality of aryl groups are connected 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. In addition, the aliphatic ring may include nitrogen, oxygen, sulfur, carbonyl, and the like in the ring. Specific examples of aryl radicals include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthryl, anthryl, triphenylene, fluorenyl, Chrysenyl, fused tetraphenyl, 9,10-dihydroanthryl and the like.

The term "heteroaryl" as used herein means an aryl group containing 1 to 4 heteroatoms selected from N, O, and S as an aromatic ring structure skeleton atom and carbon as the 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. In addition, the heteroaryl group in the present invention may include a form 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, benzoisoxazole, Thiophene, benzothiophene, furan, benzofuran, and the like, but the present invention is not limited thereto.

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

The term "halogen" or "halogen" as used herein refers to 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 refer to -O-alkyl and -O-aryl radicals, respectively, where alkyl and aryl are the same as defined above.

In an exemplary embodiment of the present invention, the transition metal compound represented by Chemical Formula 1 may be a transition metal compound represented by the following Chemical Formula 2, Chemical Formula 3, Chemical Formula 4, or Chemical Formula 5.

[Chemical Formula 2]

In Chemical Formulas 2 to 5, M, R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , X ¹ and X ² are the same as defined in the above Chemical Formula 1; R ¹ to R ⁵ are each independently hydrogen, (C1 -C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ; each of R ^a1 to R ^{a6 is} independent Is (C1-C20) alkyl or (C6-C20) aryl; R ¹¹ and R ¹² are each independently hydrogen, and R ¹¹ and R ¹² may be linked to each other to form a benzene ring; R ¹³ and R ¹⁴ are each independently (C1-C20) alkyl; and R ^15, R ¹⁶ and R ¹⁷ 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 in the periodic table, and is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

In an exemplary embodiment of the present invention, R ¹ to R ⁵ 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 Group, pyridyl, methoxy, ethoxy, butoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenylamino, Dimethylphosphine, diethylphosphine or diphenylphosphine, and the R ¹ to R ⁴ are permeable , , or Link to adjacent substituents to form a fused ring.

In an exemplary embodiment of the present invention, R ¹ to R ⁴ may be hydrogen, or R ³ and R ⁴ may be transparent , ,or Chain to form a fused ring, and R ⁵ may be (C1-C20) alkyl, and preferably (C1-C10) alkyl.

In an exemplary embodiment of the present invention, R ¹ to R ⁴ may be hydrogen, and R ⁵ may be a methyl group.

In an exemplary embodiment of the present invention, R ¹ to R ² may be hydrogen, and R ³ and R ⁴ may be transparent. Linked to form a fused ring, and R ⁵ may be methyl.

In an exemplary embodiment of the present invention, R ⁶ and R ⁷ may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, or tertiary butyl Base, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoromethyl 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, fluorenyl, triphenyl Phenyl, naphthyl, anthryl, benzyl, naphthylmethyl, anthrylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methyl Ethylamino, diethylamino, diphenylamino, dimethylphosphine, di Diphenyl phosphine or phosphine groups, or R ⁶ and R ⁷ may by butene or pentene (pentylene) link to form a ring.

In an exemplary embodiment of the present invention, R ⁶ and R ⁷ may be each independently a (C1-C20) alkyl group, preferably a (C1-C10) alkyl group, a halo (C1-C20) alkyl group, and more preferably Is a halogen (C1-C10) alkyl or (C6-C20) aryl, and is preferably a (C6-C12) aryl.

In an exemplary embodiment of the present invention, R ⁶ and R ⁷ may be each independently methyl, ethyl, or phenyl.

In an exemplary embodiment of the present invention, R ⁸ to R ¹⁰ may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tris Higher butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, Fluoromethyl, trifluoromethyl, perfluoroethyl, perfluoropropyl, chlorine, fluorine, bromine, phenyl, biphenyl, fluorenyl, triphenyl, naphthyl, anthryl, benzyl, naphthalene Methyl, anthrylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenyl Amine, dimethylphosphine, diethylphosphine or diphenylphosphine, or R ⁹ and R ¹⁰ are transparent , , or Link to form a fused ring.

In an exemplary embodiment of the present invention, R ⁸ to R ¹⁰ may each independently be hydrogen, (C1-C20) alkyl, preferably (C1-C10) alkyl, halo (C1-C20) alkyl, And preferably a halogen (C1-C20) alkyl or halogen, and R ⁹ and R ¹⁰ are transparent , , or Link to form a fused ring.

In an exemplary embodiment of the present invention, R ⁸ to R ¹⁰ may each independently be hydrogen, methyl, ethyl, tertiary butyl, or fluorine.

In an exemplary embodiment of the present invention, R ⁸ may be hydrogen, and R ⁹ and R ¹⁰ may each independently be hydrogen, (C1-C20) alkyl, preferably (C1-C10) alkyl, halogen ( C1-C20) alkyl, and preferably is a halogen (C1-C10) alkyl or halogen, and R ⁹ and R ¹⁰ may be permeable , , or Link to form a fused ring.

In an exemplary embodiment of the present invention, R ⁸ and R ¹⁰ may be hydrogen, R ⁹ may be (C1-C10) alkyl or halogen, or R ⁹ and R ¹⁰ may be transparent Link to form a fused ring.

In an exemplary embodiment of the present invention, R ⁸ and R ¹⁰ may be hydrogen, R ⁹ may be methyl, ethyl, tertiary butyl, or fluorine, and R ⁹ and R ¹⁰ may be transparent Link to form a fused ring.

In an exemplary embodiment of the present invention, R ¹¹ and R ¹² may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tris Higher butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, Phenyl, biphenyl, fluorenyl, triphenyl, naphthyl, or anthracenyl, or R ¹¹ and R ¹² may be linked to each other to form a benzene ring.

In an exemplary embodiment of the present invention, R ¹³ and R ¹⁴ may be each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl R15, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadecyl; R ¹⁵ , R ¹⁶ and R ¹⁷ may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, neo Amyl, 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 ¹³ and R ¹⁴ may be (C1-C20) alkyl, and R ¹⁵ , R ¹⁶ and R ¹⁷ may each independently be hydrogen or (C1-C10) alkyl.

In an exemplary embodiment of the present 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, tertiary butoxy, phenoxy, 4-tert-butylphenoxy, trimethyl Silyloxy, tert-butyldimethylsilyloxy, dimethylamino, diphenylamino, dimethylphosphine, diethylphosphine, diphenylphosphine, ethylthio or isopropyl Sulfur.

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

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

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

Where M is titanium, zirconium or hafnium.

Meanwhile, in order to prepare an active catalyst component for the preparation of an ethylene-based polymer selected from an ethylene homopolymer and a copolymer of ethylene and an α-olefin by using the transition metal compound according to the present invention, preferably, the transition metal The compound can work with a co-catalyst selected from an aluminum compound, a boron compound, or a mixture thereof. The co-catalyst acts as a counter ion with a weak binding force, that is, an anion, and simultaneously extracts X ¹ in the transition metal complex. And X ² ligands cationize the central metal. A catalyst composition comprising a transition metal compound and a co-catalyst is also within the scope of the present invention.

In the catalyst composition according to an exemplary embodiment of the present invention, the aluminum compound that can be used as a co-catalyst may be specifically selected from an aluminoxane compound represented by Chemical Formula 6 or Chemical Formula 7, an organic compound represented by Chemical Formula 8 One or two or more of an aluminum compound or an organoaluminum oxide compound represented by Chemical Formula 9 or Chemical Formula 10: [Chemical Formula 6] (-Al (R ⁵¹ ) -O-) _m

[Chemical Formula 7] (R ⁵¹ ) ₂ Al-(-O (R ⁵¹ )-) _q- (R ⁵¹ ) ₂

[Chemical Formula 8] (R ⁵² ) _r Al (E) _3-r

[Chemical Formula 9] (R ⁵³ ) ₂ AlOR ⁵⁴

[Chemical Formula 10] R ⁵³ Al (OR ⁵⁴ ) ₂

In Chemical Formulas 6 to 10, R ⁵¹ is (C1-C20) alkyl, preferably methyl or isobutyl, and m and q are each an integer of 5 to 20; R ⁵² and R ⁵³ are each (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 methylalumoxane, modified methylalumoxane, and tetraisobutylalumoxane as the alumoxane compound; examples of the organoaluminum compound may include trialkylaluminum, including Methyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, and trioctyl aluminum; dialkylaluminum chloride, including dimethyl aluminum chloride, diethyl aluminum 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 dialkyl aluminum hydrides, including dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, Isobutyl aluminum and dihexyl aluminum hydride.

In an exemplary embodiment of the present invention, the aluminum compound may preferably be one or a mixture of two or more kinds selected from an alkylalumoxane compound and a trialkylaluminum. More preferably, the aluminum compound may be selected from the group consisting of methylalumoxane, modified methylalumoxane, tetraisobutylalumoxane, trimethylaluminum, triethylaluminum, trioctylaluminum, and triisobutyl One or a mixture of two or more of aluminum.

A boron compound which can be used as a co-catalyst of the present invention is known from U.S. Invention Patent No. 5,198,401, and may be a boron compound selected from the following Chemical Formula 11 to Chemical Formula 13: [Chemical Formula 11] B (R ⁴¹ ) ₃

[Chemical Formula 12] [R ⁴² ] ⁺ [B (R ⁴¹ ) ₄ ] ^-

[Chemical Formula 13] [(R ⁴³ ) _p ZH] ⁺ [B (R ⁴¹ ) ₄ ] ^-

In Chemical Formulas 11 to 13, B is a boron atom; R ⁴¹ is a phenyl group, and the phenyl group may be further substituted with 3 to 5 selected from fluorine, unsubstituted or fluorine-substituted (C1-C20) alkyl groups, and Unsubstituted or fluorine-substituted (C1-C20) alkoxy substituents; R ⁴² is (C5-C7) aromatic radical or (C1-C20) alkyl (C6-C20) aryl free Radical, (C6-C20) aryl (C1-C20) alkyl radical, such as triphenylmethylium radical; Z is nitrogen or phosphorus atom; and R ⁴³ is (C1-C50) alkane Radicals or anilinium radicals substituted with two (C1-C10) alkyl groups together with a nitrogen atom; and p is an integer of 2 or 3.

Preferred examples of the boron-based cocatalyst may include ginseng (pentafluorophenyl) borane, ginseng (2,3,5,6-tetrafluorophenyl) borane, ginseng (2,3,4,5-tetrafluoro) Phenyl) borane, ginseng (3,4,5-trifluorophenyl) borane, ginseng (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, (Pentafluorophenyl) borate, (2,3,5,6-tetrafluorophenyl) borate, (2,3,4,5-tetrafluorophenyl) borate, (3,4,5-tetrafluorophenyl) borates, (2,2,4-trifluorophenyl) borates, phenylbis (pentafluorophenyl) borates or (3,4,5-tetrafluorophenyl) borates 5-bistrifluoromethylphenyl) borate. Examples of specific compositions include ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium (pentafluorophenyl) borate 1,1'-dimethylferrocene (1,1 ' -dimethylferrocenium tetrakis (pentafluorophenyl) borate), tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (pentafluorophenyl) borate), (3,5-bistrifluoromethylphenyl) triphenylmethyl borate (triphenylmethyl tetrakis (3,5-bistrifluoromethylphenyl) borate), triethylammonium (pentafluorophenyl) borate, Fluorophenyl) tripropylammonium borate, tris (pentafluorophenyl) tris (n-butyl) ammonium borate, (3,5-bistrifluoromethylphenyl) tris (n-butyl) ammonium borate, (Pentafluorophenyl) boronic acid-N, N-dimethylaniline, (pentafluorophenyl) boronic acid-N, N-diethylaniline, (pentafluorophenyl) boronic acid-N, N- 2,4,6-pentamethylammonium ammonium, Iso (3,5-bistrifluoromethylphenyl) borate-N, N-dimethylaniline, Iso (pentafluorophenyl) borate diisopropyl Benzyl ammonium, di (pentafluorophenyl) borate dicyclohexyl aniline, tris (pentafluorophenyl) boric acid Phosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium, or tetrakis (pentafluorophenyl) borate, tris (dimethylphenyl) phosphonium. Among them, the best are penta (pentafluorophenyl) borate-N, N-dimethylaniline, triphenyl (pentafluorophenyl) borate, or gins (pentafluorophenyl) borane. .

At the same time, the co-catalyst can be used as a scavenger to remove impurities that are catalyst poisons in the reactants.

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

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

When the ratio between the transition metal compound and the co-catalyst of the present invention exceeds the above range, since the amount of the co-catalyst is relatively small, the transition metal compound may not be fully activated, so the catalytic activity of the transition metal compound may be insufficient, or the co-catalyst may be insufficient. If the amount of the catalyst exceeds the required amount, the production cost may increase significantly. Within the above range, excellent catalytic activity for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin is shown, and the range of this ratio varies depending on the purity of the reaction.

As another aspect of the present invention, a method for preparing an ethylene polymer using a transition metal catalyst composition can be obtained by using a transition metal catalyst, a co-catalyst, and ethylene or optionally an α-olefin comonomer in a suitable organic solvent. Contact in the presence of. Here, the transition metal catalyst and co-catalyst components may be separately introduced into the reactor, or the respective components may be mixed and added to the reactor in advance, wherein there are no particular restrictions on the mixing conditions such as the order of introduction, temperature, concentration, etc. limited.

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

Specifically, in preparing an ethylene homopolymer, ethylene is used alone as a monomer, wherein the pressure of ethylene may be appropriately from 1 atm to 1000 atm, and more preferably from 10 atm to 150 atm. In addition, the polymerization reaction system is effectively performed at a polymerization reaction temperature of 25 ° C to 200 ° C, preferably 50 ° C to 180 ° C, more preferably 100 ° C to 180 ° C, and still more preferably 110 ° C to 150 ° C.

In addition, when preparing a copolymer of ethylene and an α-olefin, at least one selected from a C3-C18 α-olefin, a C5-C20 cycloolefin, styrene, and a styrene derivative may be used as a comonomer 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, 1 -Undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene, and preferred examples of the C5-C20 cycloolefin may include cyclopentene, cyclohexene, Norbornene and phenyl norbornene. Styrene and its derivatives can be selected from styrene, alpha-methylstyrene, p-methylstyrene, and 3-chloromethylstyrene. In the present invention, ethylene may be copolymerized with the above-mentioned 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 those in the case of preparing an ethylene homopolymer, and the ethylene content of the copolymer prepared according to the method of the present invention usually contains 30% by weight or more, preferably It is 60% by weight or more, and more preferably 60% to 99% by weight.

As described above, when the catalyst of the present invention is used, a C3-C18 α-olefin as a comonomer and ethylene can be prepared simply and economically from 0.850 g (g) / cm 3 (cc) to 0.960 g / m 3 by using ethylene appropriately. Density in centimeters and polymers ranging from elastomers to high-density polyethylene (HDPE) with melt flow indexes from 0.001 mm / min (dg / min) to 15 mm / min.

In addition, 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 / mol to 1,000,000 g / mol.

Since the catalyst composition proposed in the present invention is in a homogeneous state in a polymerization reactor, the catalyst composition can be preferably used in a solution polymerization reaction method 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, transition metal compounds and co-catalysts can be supported on porous metal oxide supports for use in slurry polymerization or gas phase polymerization processes as heterogeneous catalyst compositions .

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

Unless otherwise stated, all experiments for synthesizing ligands and catalysts were performed under a 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 ligands and catalyst was performed by using a Brucker 500 MHz at room temperature.

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

Molecular weight and molecular weight distribution

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

2. α-olefin content in copolymer (mole%)

Measured in a Bruker Avance 400 nuclear magnetic resonance spectrometer at 125 MHz, ¹³ C-NMR mode, and 120 ° C using a 1, 2, 4-trichlorobenzene / C ₆ D ₆ (weight fraction 7/3) mixed solvent -Olefin content. (See Randal, JCJMS-Rev. Macromol. Chem. Phys. 1980, C29, 201)

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

3. Crystallinity of polymers

Amorphous Fraction (AF) of the polymer was measured by analyzing the branching distribution of the polymer using PolymerChar A-CEF.

[Examples 1 to 4] Preparation of transition metal catalysts 1 to 4 according to the present invention

Preparation of compound B

Pyrrolidin-2-methyl-1H-indene (30.08 mmol) was added to THF (112 mL), and then a solution of n-BuLi in hexane (2.5M, 31.58 mmol) was slowly added at -78 ° C. After the addition of n-BuLi was completed, the temperature was slowly raised to room temperature, and the mixture was stirred for 2 hours. After the stirring was completed, the mixture was cooled to -78 ° C, and (2- (allyloxy) -5-substituted-3- (9,9-disubstituted-9H-fluoren-7-yl) benzene was slowly added dropwise. Solution) of chlorodimethylsilane (Compound A, 33.09 mmol) in toluene (14 mL), and then the temperature of the reaction mixture was raised to room temperature. After further stirring at room temperature for 3 hours, the reaction mixture was added to distilled water (200 mL) to stop the reaction. The organic layer was extracted with toluene (2 × 50 mL), water was removed with Na ₂ SO ₄ , and the solvent was removed by vacuum distillation to obtain an oily yellow residue. Then, using a column packed with silica gel 60 (40-63 μm), the residue was purified by flash chromatography (diluent: 1:10 volume of dichloromethane / hexane) to obtain Compound B as the title compound. .

Compound B1 (R ⁹ = Me, R ¹³ = R ¹⁴ = Me): 1- {1-[[2- (allyloxy) -3- (9,9-dimethyl-9H-fluorene-2- Group) -5-methylphenyl] (dimethyl) silyl] -2-methyl-1H-inden-3-yl} pyrrolidine. Quantitative yield. ¹ H NMR (CDCl ₃ ): δ 7.80 (m, 1H), 7.77 (m, 2H), 7.58 (m, 1H), 7.46 (m, 1H), 7.44 (m, 1H), 7.32-7.37 (m, 3H), 7.18 (m, 1H), 7.04 (m, 2H), 7.00 (m, 1H), 5.77 (m, 1H), 5.27 (m, 1H), 5.08 (m, 1H), 4.06 (m, 2H ), 3.92 (s, 1H), 3.44 (m, 2H), 3.29 (m, 2H), 2.37 (s, 3H), 2.00 (s, 3H), 1.93-1.99 (m, 4H), 1.53 (m, 6H), 0.14 (s, 3H), 0.12 (s, 3H).

Compound B2 (R ⁹ = Me, R ¹³ = R ¹⁴ = n-Bu): 1- {1-[[2- (allyloxy) -3- (9,9-dibutyl-9H-fluorene- 2-yl) -5-methylphenyl] (dimethyl) silyl] -2-methyl-1H-inden-3-yl} pyrrolidine. Quantitative yield. ¹ H NMR (CDCl ₃ ): δ 7.77 (m, 1H), 7.75 (m, 1H), 7.63 (m, 1H), 7.57 (m, 1H), 7.44 (m, 1H), 7.36 (m, 2H) , 7.33 (m, 1H), 7.30 (m, 1H), 7.18 (m, 1H), 7.04 (m, 2H), 7.00 (m, 1H), 5.76 (m, 1H), 5.30 (m, 1H), 5.10 (m, 1H), 4.09 (m, 2H), 3.92 (s, 1H), 3.44 (m, 2H), 3.30 (m, 2H), 2.38 (s, 3H), 2.00 (s, 3H), 1.93 -2.02 (m, 8H), 1.08 (m, 4H), 0.67 (m, 6H), 0.57-0.66 (m, 4H), 0.13 (s, 3H), 0.11 (s, 3H).

Compound B3 (R ⁹ = F, R ¹³ = R ¹⁴ = Me): 1- {1-[[2- (allyloxy) -3- (9,9-dimethyl-9H-fluorene-2- Group) -5-fluorophenyl] (dimethyl) silyl] -2-methyl-1H-inden-3-yl} pyrrolidine. Quantitative yield. ¹ H NMR (CDCl ₃ ): δ 7.81 (m, 1H), 7.77-7.79 (m, 2H), 7.58 (m, 1H), 7.48 (m, 1H), 7.46 (m, 1H), 7.37 (m, 2H), 7.19-7.23 (m, 2H), 7.01-7.05 (m, 2H), 6.93 (m, 1H), 5.77 (m, 1H), 5.29 (m, 1H), 5.11 (m, 1H), 4.07 (m, 2H), 3.90 (s, 1H), 3.46 (m, 2H), 3.29 (m, 2H), 2.02 (s, 3H), 1.93-1.99 (m, 4H), 1.54 (s, 6H), 0.15 (s, 6H).

Compound B4 (R ⁹ = F, R ¹³ = R ¹⁴ = n-Bu): 1- {1-[[2- (allyloxy) -3- (9,9-dibutyl-9H-fluorene- 2-yl) -5-fluorophenyl] (dimethyl) silyl] -2-methyl-1H-inden-3-yl} pyrrolidine. Quantitative yield. ¹ H NMR (CDCl ₃ ): δ 7.78 (m, 1H), 7.75 (m, 1H), 7.62 (m, 1H), 7.57 (m, 1H), 7.44 (m, 1H), 7.33-7.38 (m, 3H), 7.18 (m, 2H), 7.03 (m, 2H), 6.93 (m, 1H), 5.75 (m, 1H), 5.30 (m, 1H), 5.11 (m, 1H), 4.08 (m, 2H) ), 3.89 (s, 1H), 3.44 (m, 2H), 3.30 (m, 2H), 2.00 (s, 3H), 1.91-2.02 (m, 8H), 1.08 (m, 4H), 0.67 (m, 6H), 0.57-0.70 (m, 4H), 0.13 (s, 3H), 0.12 (s, 3H).

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 a hexane solution (2.5M, 22 mmol) of n-BuLi was added thereto. After the addition of n-BuLi was completed, the reaction mixture was warmed to room temperature and stirred at room temperature for 20 hours. After the reaction mixture was cooled to -78 ° C again, 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 warmed to room temperature, and the reaction mixture was further stirred at 90 ° C. The temperature of the reaction was cooled to room temperature, and the solvent was removed under vacuum under a nitrogen atmosphere. After removing the solvent, warm methylcyclohexane was added, and the obtained by-product was separated through a celite 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 solid at -30 ° C as a dark green or green precipitate.

Compound C1 (R ⁹ = Me, R ¹³ = R ¹⁴ = Me): dimethylsilene (2-methyl-1- (N-pyrrolidinyl) inden-3-yl) (2- (9,9 -Dimethyl-9H-fluoren-2-yl) -4-methylphenoxy) titanium dichloride. 28% yield, dark green solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.27 (m, 1H), 7.70-7.73 (m, 3H), 7.64 (m, 1H), 7.53 (m, 1H), 7.29-7.42 (m, 7H), 4.21 (m, 2H), 4.14 (m, 2H), 2.48 (s, 3H), 2.47 (s, 3H), 1.94-2.03 (m, 4H), 1.46 (s, 3H), 1.45 (s, 3H) , 0.72 (s, 3H), 0.71 (s, 3H).

Compound C2 (R ⁹ = Me, R ¹³ = R ¹⁴ = n-Bu): dimethylsilene (2-methyl-1- (N-pyrrolidinyl) inden-3-yl) (2- (9 , 9-dibutyl-9H-fluoren-2-yl) -4-methylphenoxy) titanium dichloride. 33% yield, green solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.29 (m, 1H), 7.70 (m, 2H), 7.64 (m, 2H), 7.57 (m, 1H), 7.37-7.40 (m, 3H), 7.27- 7.34 (m, 4H), 4.21 (m, 2H), 4.17 (m, 2H), 2.49 (s, 3H), 2.48 (s, 3H), 1.91-2.10 (m, 8H), 0.99-1.09 (m, 4H), 0.73 (s, 3H), 0.72 (s, 3H), 0.61-0.65 (m, 6H), 0.44-0.58 (m, 4H).

Compound C3 (R ⁹ = F, R ¹³ = R ¹⁴ = Me): dimethylsilene (2-methyl-1- (N-pyrrolidinyl) inden-3-yl) (2- (9,9 -Dimethyl-9H-fluoren-2-yl) -4-fluorophenoxy) titanium dichloride. 28% yield, dark green solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.28 (m, 1H), 7.70-7.75 (m, 3H), 7.63 (m, 1H), 7.53 (m, 1H), 7.28-7.44 (m, 7H), 4.21 (m, 2H), 4.15 (m, 2H), 2.49 (s, 3H), 1.95-2.04 (m, 4H), 1.46 (s, 3H), 1.45 (s, 3H), 0.75 (s, 3H) , 0.73 (s, 3H).

Compound C4 (R ⁹ = F, R ¹³ = R ¹⁴ = n-Bu): dimethylsilene (2-methyl-1- (N-pyrrolidinyl) inden-3-yl) (2- (9 , 9-dibutyl-9H-fluoren-2-yl) -4-fluorophenoxy) titanium dichloride. 48% yield, green solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.29 (m, 1H), 7.70 (m, 2H), 7.64 (m, 2H), 7.57 (m, 1H), 7.40 (m, 1H), 7.27-7.36 ( m, 6H), 4.15-4.24 (m, 4H), 2.49 (s, 3H), 1.91-2.08 (m, 8H), 0.99-1.09 (m, 4H), 0.75 (s, 3H), 0.73 (s, 3H), 0.60-0.64 (m, 6H), 0.42-0.58 (m, 4H).

Preparation of compound 1 to compound 4

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, stirred for 22 hours, and then the solvent was removed in vacuo under a nitrogen atmosphere. Warm hexane was added, and the mixture was filtered through a celite filter to obtain a filtrate. Then, the solvent was removed under a nitrogen atmosphere and under vacuum. The obtained solid was dissolved in hexane (70 ml), treated again with a celite filter, and the obtained filtrate was cooled to -30 ° C to obtain the title compound 1 to compound 4 as a red solid.

Example 1 Transition metal catalyst compound 1 (R ⁹ = Me, R ¹³ = R ¹⁴ = Me), 47% yield, red solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.02 (m, 1H), 7.96 (m, 1H), 7.76 (m, 2H), 7.62 (m, 1H), 7.45 (m, 1H), 7.25-7.35 ( m, 4H), 7.23 (m, 1H), 7.13 (m, 1H), 6.93 (m, 1H), 3.84 (m, 2H), 3.62 (m, 2H), 2.42 (s, 3H), 2.07 (s , 3H), 1.94-2.06 (m, 4H), 1.54 (s, 6H), 0.62 (s, 3H), 0.59 (s, 3H), 0.54 (s, 3H), -0.34 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 162.62,154.42,153.67,140.11,139.57,139.04,137.99,134.30,132.93,131.93,131.61,131.08,129.99,129.05,128.52,127.39,127.30,126.79,126.72,125.57, 124.52, 124.38, 123.96, 122.97, 120.25, 119.74, 96.04, 57.25, 55.63, 52.33, 47.30, 27.57, 26.26, 20.96, 15.39, 0.82, 0.34.

Example 2 Transition metal catalyst compound 2 (R ⁹ = Me, R ¹³ = R ¹⁴ = n-Bu), 87% yield, red solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.05 (m, 1H), 7.88 (m, 1H), 7.81 (m, 1H), 7.77 (m, 1H), 7.72 (m, 1H), 7.30-7.43 ( m, 6H), 7.18 (m, 1H), 6.98 (m, 1H), 3.87 (m, 2H), 3.64 (m, 2H), 2.47 (s, 3H), 2.12 (s, 3H), 1.96-2.11 (m, 8H), 1.07-1.14 (m, 4H), 0.72-0.82 (m, 2H), 0.69 (m, 6H), 0.68 (s, 3H), 0.65-0.71 (m, 2H), 0.65 (s , 3H), 0.61 (s, 3H), -0.26 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 162.72, 151.43, 150.81, 141.69, 140.16, 140.10, 139.08, 134.26, 133.27, 131.57, 131.06,130.26,129.12,128.85,127.24,127.15,126.92,125.75,124.59,124.55,124.40,124.08,123.32,119.96,119.44,95.71,57.60,55.89,55.62,52.39,40.85,26.60,26.36,23.57.21. 15.48, 14.18, 1.00, 0.40.

Example 3 Transition metal catalyst compound 3 (R ⁹ = F, R ¹³ = R ¹⁴ = Me), 67% yield, red solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.03 (m, 1H), 7.98 (m, 1H), 7.79 (m, 1H), 7.76 (m, 1H), 7.63 (m, 1H), 7.45 (m, 1H), 7.33 (m, 2H), 7.19-7.24 (m, 2H), 7.12-7.17 (m, 2H), 6.95 (m, 1H), 3.85 (m, 2H), 3.62 (m, 2H), 2.08 (s, 3H), 1.94-2.04 (m, 4H), 1.54 (s, 6H), 0.64 (s, 3H), 0.61 (s, 3H), 0.57 (s, 3H),-0.30 (s, 3H) ¹³ C NMR (CD ₂ Cl ₂ ): δ 160.67,159.34,156.94,154.46,153.82,140.38,139.39,138.58,137.85,133.25,133.20,130.45,130.38,130.16,128.98,127.61,127.36,126.67,126.42, 125.75, 124.78, 124.34, 124.15, 123.02, 120.39, 119.90, 119.14, 118.24, 118.01, 95.55, 58.07, 56.37, 52.33, 47.35, 27.54, 26.29, 15.45, 0.54, 0.11.

Example 4 Transition metal catalyst compound 4 (R ⁹ = F, R ¹³ = R ¹⁴ = n-Bu), 73% yield, red solid. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.04 (m, 1H), 7.80 (m, 1H), 7.78 (m, 1H), 7.73 (m, 1H), 7.70 (m, 1H), 7.38 (m, 1H), 7.30-7.34 (m, 2H), 7.25 (m, 1H), 7.20 (m, 1H), 7.14-7.17 (m, 2H), 6.96 (m, 1H), 3.87 (m, 2H), 3.62 (m, 2H), 2.08 (s, 3H), 1.94-2.07 (m, 8H), 1.05-1.09 (m, 4H), 0.94-1.03 (m, 4H), 0.65-0.72 (m, 2H), 0.65 (s, 3H), 0.64 (m, 6H), 0.62 (s, 3H), 0.58 (s, 3H), 0.55-0.61 (m, 2H), -0.29 (s, 3H) ^.13 C NMR (CD ₂ Cl ₂ ): δ 160.72,158.91,157.31,151.46,150.98,141.46,140.62,140.40,137.87,133.16,133.14, 130.74,130.69,130.36,129.04,127.39,127.15,126.77,126.73,125.86,124.79,124.49,124.24.24. , 124.20,123.35,120.04,119.50,119.02,118.88,118.46,118.30,95.28,58.30,56.57,55.64,52.36,40.76,26.54,26.33,23.51,23.50,15.47,14.10,14.09,0.61,0.09.09.

[Example 5] Preparation of transition metal catalyst 5 according to the present invention

Compound B5, compound C5, and compound 5 were prepared using the methods of Examples 1 to 4 above.

Compound B5: quantitative yield. ¹ H NMR (400MHz, CDCl ₃ ): δ 7.74-7.79 (m, 2H), 7.57-7.61 (m, 2H), 7.25-7.39 (m, 9H), 7.14 (t, 2H, J = 7.9Hz), 7.06 (d, 1H, J = 2.2Hz), 7.02 (t, 1H, J = 7.4Hz), 5.73-5.83 (m, 1H), 5.28 (dd, 1H, J1 = 17.4Hz, J1 = 1.5Hz), 5.09 (dd, 1H, J1 = 10.7Hz, J2 = 1.2Hz), 1.74-1.77 (m, 2H), 1.61-1.64 (m, 2H), 4.07-4.10 (m, 3H), 2.39 (s, 3H) , 2.06 (s, 3H), 2.01 (t, 4H, J = 8.2Hz), 0.55-1.33 (m, 24H).

Compound C5: 62% yield, green solid. ¹ H NMR (400MHz, CDCl ₃ ): δ 8.40 (d, J = 8.8Hz, 1H), 7.60-7.70 (m, 4H), 7.52 (m, 1H), 7.27-7.45 (m, 11H), 5.67 ( d, J = 12.4Hz, 2H), 5.61 (d, J = 12.4Hz, 2H), 2.65 (s, 3H), 2.52 (s, 3H), 1.85-2.15 (m, 4H), 0.47-1.41 (m , 24H).

Transition metal catalyst compound 5: 91% yield, red solid. ¹ H NMR (400 MHz, C ₆ D ₆ ): δ 8.09 (m, 1H), 7.73-7.87 (m, 2H), 7.58 (m, 2H), 7.44 (m, 1H), 7.38 (m, 1H), 7.18-7.31 (m, 4H), 7.04-7.15 (m, 2H), 6.97 (m, 2H), 6.84 (m, 1H), 6.62 (m, 1H), 4.96 (d, J = 12.3Hz, 2H) , 4.66 (d, J = 12.0Hz, 2H), 2.31 (s, 3H), 2.18 (s, 3H), 2.00-2.13 (m, 4H), 0.80-1.34 (m, 21H), 0.60 (m, 6H ), 0.15 (s, 3H). ¹³ C { ¹ H} NMR (101MHz, CD ₂ Cl ₂ ): δ 163.2, 151.4, 150.8, 141.6, 140.0, 139.9, 139.0, 138.3, 135.0, 133.2, 132.3, 131.4, 130.4, 129.0, 128.9, 128.2, 127.4, 127.2, 127.1, 126.4, 125.1, 124.8, 124.3, 124.2, 123.3, 122.7, 119.9, 119.3, 96.2, 58.6, 58.4, 57.2, 55.5, 54.4, 54.1, 53.6, 53.3, 40.8, 40.7, 26.6, 26.5, 23.5, 23.5, 21.1, 15.3, 14.1, 7.9, 7.8, 5.7, 5.5.

[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 equivalent) 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 was slowly added thereto (NIS) (62.0 g, 277 mmol, 1 equivalent) was added over 30 minutes, and the reaction solution was stirred for 12 hours. After stirring for 12 hours, the same volume of distilled water was added. The formed product was extracted with diethyl ether (200 mL × 2), the recovered organic matter was treated with an aqueous Na ₂ SO ₃ solution and distilled water, and dried over anhydrous Na ₂ SO ₄ to remove the solvent. The obtained compound (2-iodo-4-methylphenol; 56.5 g, yield 87%) was used in the next reaction without further purification.

Under a nitrogen atmosphere, 2-iodo-4-methylphenol (56.5 g, 240 mmol, 1 equivalent) was dissolved in anhydrous THF (250 mL). N, N-diisopropylethylamine (DIPEA) (62.7 mL, 360 mmol, 1.5 equivalents) and chloromethyl methyl ether (MOMCl) (27.5 mL, 360 mmol, 1.5 equivalents) were sequentially added to the reaction solution. 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, thereby obtaining a crude product. The crude product was purified by flash chromatography (diluent: hexane) using a column packed with silica gel 60 (40-63 μm) to obtain the title compound D6 (65.9 g, 99% yield) as a yellow oil. .

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 equivalent), compound D6 (29.6 g, 107 mmol, 1.2 equivalents), CuI (3.4 g, 18.0 mmol, 0.2 equivalents) K ₃ PO ₄ (57.0 g, 267 mmol, 3 eq) and N, N'-dimethyl-1,2-ethylenediamine (2.35 g, 26.7 mmol, 0.3 eq) were dissolved in anhydrous toluene (180 mL), And stirred at 120 ° C for 12 hours. Then, distilled water (500 mL) was added to stop the reaction. The organic layer was extracted with toluene (100 mL × 3), treated with distilled water and anhydrous Na ₂ SO _{4 in this order} , and dried to obtain a crude product. The crude product was purified via Kugelrohr distillation to obtain the title compound E6 as a black oil (32.2 g, 85% yield).

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

At room temperature, n-BuLi (58.0 mL, 145 mmol, 2 equivalents) was slowly added to an anhydrous ether solution (850 mL) of compound E6 (31.1 g, 72.0 mmol, 1 equivalent), and the mixture was stirred at room temperature for 2 hours . 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 stop the reaction. The organic layer was recovered, treated with anhydrous Na ₂ SO ₄ and dried to obtain the product (9- {3-bromo-5-methyl-2- (methoxymethoxy) phenyl} -2,7-di -Tertiary butyl-9H-carbazole; 32.1 g, 88% yield), and used in the next reaction without further purification.

9- {3-Bromo-5-methyl-2- (methoxymethoxy) phenyl} -2,7-di-tert-butyl-9H-carbazole (32.1 g, 75.0 mmol) was added To a mixed solution of methanol (220 mL) and THF (220 mL) and hydrochloric acid (12 M, 2.5 mL), 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 obtain an organic layer, and the organic layer was treated with anhydrous Na ₂ SO ₄ and dried to obtain a crude product. The crude product was purified by flash chromatography (diluent: hexane / dichloromethane) using a column packed with silica gel 60 (40-63 μm) to obtain the title compound F6 (22.2 g, 64 %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 = 8.2Hz, J ₂ = 1.7Hz, 2H), 7.15 (dd, J ₁ = 2.1Hz, J ₂ = 0.7Hz, 1H), 7.08 (d, J = 1.2Hz, 2H), 5.42 (s, 1H), 2.37 (s, 3H), 1.36 (s, 18H).

Preparation of compound G6

K ₂ CO ₃ (30 mmol) and bromopropene (30 mmol) were added to anhydrous acetone (200 mL) and phenol (20 mmol), followed by refluxing for 16 hours. The acetone was removed in vacuo, 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 resulting residue was purified by flash chromatography (dipping solution: hexane) using a column packed with silica gel 60 (40-63 μm) to obtain the 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 = 1.3Hz, 2H), 5.40-5.50 (m, 1H), 4.76-4.84 (m, 2H), 3.85 (d, J = 6.0Hz, 2H), 2.41 (s, 3H), 1.40 (s, 18H).

Preparation of compound H6

N-BuLi (2.5M in hexane, 91 mmol) was slowly added to a solution of compound G6 (70 mmol) in toluene (200 mL) at -78 ° C, and then the temperature was raised to -20 ° C. The reaction solution was cooled to -78 ° C again, dichlorodiethylsilane (210 mmol) was quickly added, the temperature was raised to room temperature, and the mixture was stirred for 5 hours. The inorganic salts were removed by filtration through diatomaceous earth. After removing the solvent, excess dichlorodiethylsilane was removed in vacuo to obtain the title compound H6 (99% yield) and used in the next reaction without further purification.

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

Preparation of compound I6

At -78 ° C, n-BuLi (2.5M in hexane, 31.6 mmol) was slowly added dropwise to 2- (2-metal inden-1-yl) isodihydroindole (30.1 mmol) in THF (112 mL). ) In solution. The reaction mixture was warmed to room temperature and further stirred for 2 hours. When 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, and 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 the solvent was removed by vacuum distillation to obtain a crude product. Then, using a column packed with silica gel 60 (40-63 μm), the crude product was purified by flash chromatography (diluent: hexane / dichloromethane, 10/1 volume) to obtain the title compound I6 (75 %Yield).

¹ H NMR (400MHz, CDCl ₃ ): δ. 7.99 (d, 2H), 7.61 (s, 1H), 7.40 (s, 1H), 7.34 (d, 2H), 7.28 (s, 2H), 7.15-7.06 (m, 6H), 6.13-6.09 (m, 2H), 5.48 (s, 1H), 5.29-5.39 (m, 1H), 4.80 (d, 1H), 4.65 (d, 1H), 4.62 (s, 4H ), 3.59 (d, 2H), 2.44 (s, 3H), 2.29 (s, 3H), 1.38 (s, 18H), 1.03-1.31 (m, 10H)

Preparation of compound J6

A solution of Et ₃ N (45 mmol) and compound 16 (10 mmol) in toluene (70 mL) was cooled to -78 ° C, and n-BuLi (2.5M in hexane, 22 mmol) was slowly added. The reaction mixture was warmed to room temperature, stirred for 20 hours, cooled again to -78 ° C, and then a solution of TiCl ₄ (15 mmol) in toluene (22 mL) was slowly added dropwise through a syringe. After the addition of TiCl ₄ was completed, the reaction mixture was warmed to room temperature and stirred at 90 ° C. for 16 hours. The mixture was cooled to room temperature and the solvent was removed in vacuo. After the solvent was removed, hot methylcyclohexane was added to remove insoluble inorganic salts through a celite filter. The solvent of the filtrate was concentrated in vacuo, and then recrystallized from a mixed solvent of methylcyclohexane and hexane to obtain the title compound J6 (25% yield).

¹ H NMR (400MHz, CDCl ₃ ): δ 7.99 (d, 2H), 7.61 (s, 1H), 7.40 (s, 1H), 7.34 (d, 2H), 7.28 (s, 2H), 7.23-7.06 ( m, 6H), 6.43-6.20 (m, 2H), 4.62 (s, 4H), 2.44 (s, 3H), 2.29 (s, 3H), 1.38 (s, 18H), 1.03-1.31 (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, stirred for 22 hours, and then the solvent was removed in vacuo. Hot hexane was added to the reaction, and insoluble inorganic salts were removed through a celite filter. The filtrate was dried under vacuum, dissolved in hexane (70 mL), and the insoluble inorganic salt was removed again through a celite filter. The obtained filtrate was stored at -30 ° C for 12 hours to obtain Compound 6 (54% yield) as a yellow solid.

¹ H NMR (400MHz, CDCl ₃ ): δ 7.99 (d, 2H), 7.61 (s, 1H), 7.40 (s, 1H), 7.34 (d, 2H), 7.28 (s, 2H), 7.23-7.06 ( m, 6H), 6.43-6.20 (m, 2H), 4.62 (s, 4H), 2.44 (s, 3H), 2.29 (s, 3H), 1.38 (s, 18H), 1.03-1.31 (m, 10H) , -0.50 (s, 3H),-0.62 (s, 3H).

[Comparative Example 1] Preparation of Comparative Catalyst 1

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

¹ H NMR (CDCl ₃ ): δ 7.73 (dt, 1H), 7.51 (dt, 1H), 7.32-7.35 (m, 3H), 6.89 (m, 1H), 5.48 (m, 1H), 3.41 (m, 2H, N (CH ₂ CH ₂ ) ₂ ), 2.32 (s, 3H, Ar-Me), 3.24 (m, 2H, N (CH ₂ -CH ₂ ) ₂ ), 1.51 (s, 9H, C (CH ₃ ) ₃ ), 1.39-1.42 (m, 4H, N (CH ₂ CH ₂ ) ₂ ), 0.76 (s, 3H, TiCH _3a ), 0.63 (s, 3H, SiCH ₃ , C10), 0.59 (s, 3H, SiCH ₃ , C11), 0.08 (s, 3H, TiCH _3b ).

[Comparative Example 2] Preparation of Comparative Catalyst 2

Comparative Catalyst 2 was prepared using the methods of Examples 1 to 5 described 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 equivalents) 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 equivalents) was quickly added thereto, and the mixture was stirred for 1 hour and warmed to room temperature, and stirred for another 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 were sequentially added thereto. (40), 13028-13032] (1.92 g, 4.00 mmol, 0.04 equivalent) and 2-bromo-1- (methoxymethoxy) -4-methylbenzene (23.7 g, 103 mmol, 1 equivalent). 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 stop 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 the solvent was removed in vacuo. The obtained product was solidified with ethanol and the obtained solid was separated to obtain 2 ', 6'-diisopropyl-2-methoxymethoxy-5-methylbiphenyl (23.1 g, 72% yield), as White crystalline solid. The obtained white solid (23.1 g, 74.0 mmol) was dissolved in a mixed solution of methanol (220 mL) and THF (220 mL). Then, HCl (aq) (12M, 2.2 mL) was added thereto, the mixture was stirred at 60 ° C for 12 hours, and distilled water (1000 mL) was added to stop the reaction. After the reaction was completed, the product was extracted with diethyl ether (200 mL × 2), treated with distilled water, dried over anhydrous Na ₂ SO ₄ , and then the solvent was removed to obtain compound a as a white solid (19.3 g, 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 = 8.3Hz, 1H), 6.82 (s, 1H), 4.45 (s, 1H), 2.62 (m, 2H), 2.30 (s, 3H), 1.10 (d, J = 6.9Hz, 6H), 1.07 (d, J = 6.8Hz, 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 = 6.9Hz, 6H), 1.09 (d, J = 6.9Hz, 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 = 5.4Hz, 2H), 2.53-2.63 (m, 2H), 2.32 (s, 3H), 1.18 (d, J = 6.9Hz, 6H), 1.05 (d, J = 6.8Hz, 6H).

Preparation of compound d

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

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 = 5.6Hz, J2 = 1.4Hz, 2H), 2.67 (m, 2H), 2.35 (s, 3H) , 1.16 (d, J = 6.9Hz, 6H), 0.98-1.10 (m, 16H).

Preparation of compound e

Compound e (77% yield) was prepared in the same manner as Compound 16 of Example 6.

¹ H NMR (400MHz, CDCl ₃ ): δ 7.47-7.48 (m, 1H), 7.33-7.37 (m, 1H), 7.15-7.30 (m, 6H), 7.05-7.15 (m, 2H), 6.93-7.05 (m, 2H), 6.88 (m, 1H), 6.03 (m, 1H), 5.57 (m, 1H), 5.29 (m, 1H), 4.56-4.70 (m, 2H), 4.49-4.62 (m, 2H) ), 4.35-4.49 (m, 2H), 3.96 (s, 1H), 2.75-2.62 (m, 2H), 2.27 (s, 3H), 1.90 (s, 3H), 0.88-1.05 (m, 22H).

Preparation of compound f

Compound f (65% yield) was prepared in the same manner as Compound J6 of Example 6.

¹ H NMR (400MHz, CDCl ₃ ): δ 8.19 (d, J = 8.0Hz, 1H), 7.71 (d, J = 7.8Hz, 1H), 7.63 (t, J = 7.60Hz, 1H), 7.55 (t , J = 7.5Hz, 1H), 7.47-7.48 (m, 2H), 7.33-7.37 (m, 3H), 7.26-7.29 (m, 2H), 7.16 (t, J = 7.7Hz, 1H), 7.08 ( d, J = 7.8Hz, 1H), 6.98 (d, J = 2.1Hz, 1H), 6.94 (d, J = 7.8Hz, 1H), 2.75-2.62 (m, 2H), 2.53 (s, 3H), 2.45 (s, 3H), 2.37-2.44 (m, 1H), 2.23-2.30 (m, 1H), 1.00-1.39 (m, 14H), 0.88-1.07 (m, 23H) 0.70 (d, J = 6.8Hz , 1H).

Preparation of Comparative Catalyst 3

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

¹ H NMR (600MHz, CD ₂ Cl ₂ ): ¹ H NMR (400MHz, CDCl ₃ ): δ 8.21 (d, 1H), 7.70 (d, 1H), 7.63 (t, 1H), 7.57 (t, 1H) , 7.47-7.48 (m, 2H), 7.33-7.37 (m, 3H), 7.26-7.30 (m, 2H), 7.18 (t, 1H), 7.12 (d, 1H), 6.95 (d, 1H), 6.94 (d, 1H), 2.75-2.60 (m, 2H), 2.56 (s, 3H), 2.43 (s, 3H), 2.37-2.40 (m, 1H), 2.23-2.30 (m, 1H), 1.00-1.39 (m, 14H), 0.88-1.07 (m, 23H) 0.70 (d, 1H), 0.25 (s, 3H), -0.79 (s, 3H). ¹³ C { ¹ H} NMR (151MHz, CD ₂ Cl ₂ ): Δ 186.6, 170.8, 170.2, 160.9, 160.1, 158.2157.5.157.8, 157.3, 156.8, 154.9, 154.3, 153.9, 153.7, 152.1, 151.4, 151.0, 150.7, 150.6, 150.1, 149.9, 147.7, 147.0, 145.6, 134.7, 145.6, 134.7 , 125.2, 82.9, 77.4, 77.2, 76.8, 76.6, 74.5, 54.1, 54.0, 48.3, 48.1, 46.8, 46.4, 44.2, 38.6, 31.0, 30.8, 29.2, 28.4.

[Examples 7 to 20 and Comparative Examples 4 to 11] Copolymerization of ethylene and 1-hexene

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

The polymerization was carried out in a temperature-controlled continuous polymerization reactor equipped with a mechanical stirrer. TiBA / BHT (triisobutylaluminum / 2,6-di-tertiary-butyl-4-methylphenol as a scavenger, with a molar ratio of 1: 1, 30 μmol, 120 μL, 0.25M toluene solution), 1-hexene (120 μL, 180 μL, 200 μL, 250 μL, 300 μL, 350 μL or 400 μL) and toluene were added to this reactor so that the total volume was 5 mL. The temperature of the reactor was adjusted to the polymerization temperature (110 ° C or 150 ° C), and then the stirring rate was set to 800 rpm. Depending on the polymerization temperature, ethylene was added at 220 psi at 150 ° C and 200 psi at 110 ° C to keep ethylene constant. The amount of the catalyst used was 10 nmol, 15 nmole, or 20 nmole, and the amount of the co-catalyst was fixed to 5 equivalents relative to the polymerization catalyst. A polymerization catalyst was added to the reactor, and then 5 equivalents of a co-catalyst (pentafluorophenyl) triphenylmethyl borate (TTB) was added to start polymerization. The time during which the polymerization reaction proceeds is shown in Table 1 below.

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

As shown in Table 1, it can be understood that the activity of ethylene / 1-hexene copolymerization of Examples 7 to 20 is higher than the activity of ethylene / 1-hexene copolymerization of Comparative Examples 4 to 11.

It can be understood that the activity of Example 9, Example 11, Example 12, Example 14, Example 17, Example 18, and Example 20 at the polymerization temperature of 150 ° C is higher than that of Comparative Example 6, Comparative Example 7, Comparative Example 9, and Comparative Example 11 activity. In particular, when the amounts of the polymerization catalysts were the same, the polymerization activity of Example 18 was 63 to 67 times or more higher than that of Comparative Examples 6 and 7. In addition, it was confirmed that the polymerization activity of the catalysts of these examples at a polymerization temperature of 110 ° C was 2.5 times or more higher than that of Comparative Example 4, Comparative Example 5, and Comparative Example 8.

In Table 1, A-CEF is a value showing the amorphousness of the prepared polymer, where 100% represents a completely amorphous (amorphous) polymer, and when more comonomer is included, the polymer becomes non-crystalline Crystal (amorphous). From the polymerization results, it can be seen that in Comparative Examples 4 to 7 using the catalyst of Comparative Example 1, it is necessary to add 400 μL of 1-hexene as a comonomer to prepare an amorphous polymer, and an example of the present invention is used In the case of Examples 7 to 18 and Example 20 of the catalyst of 1 to Example 5, even if a small amount (180 μL to 350 μL) of a comonomer is added, an amorphous polymer can be prepared. It can be understood that the polymer obtained by polymerizing by using the catalyst of Comparative Example 2 has a reduced polymer compared to the polymer obtained by polymerizing at a high temperature of 150 ° C using the catalysts of Examples 1 to 5. Crystallinity. That is, it can be confirmed that the catalysts of Examples 1 to 5 exhibit higher comonomer reactivity at a high temperature of 150 ° C. or higher compared to the catalysts of Comparative Examples 1 to 3. That is, regarding the reactivity of the catalyst with respect to the comonomer, that is, 1-hexene in the polymerization reaction, in Comparative Examples 4 to 7 using the catalyst of Comparative Example 1, it is necessary to add 400 μL of comonomer to the polymerization. The content of 1-hexene in the copolymer was made about 10 mol%, and in Examples 7 to 18 and Example 20 using the catalysts of Examples 1 to 5, even if a comonomer of 180 μL to 350 μL was added to the copolymer, It also contains an equivalent level of comonomer content. It can be confirmed that, compared to the concentration of the comonomer added in Comparative Examples 4 to 7, in Polymerization Examples 13 and 14, even at a concentration of about 62.5%, it is possible to prepare Co-monomer copolymer. In addition, it can be understood that in Comparative Example 9, when 200 μL of 1-hexene was added and polymerization was performed at 150 ° C., the non-crystallinity was 98.9 wt%, and in the catalyst of Example 5, as in Example 20 It is shown that in the polymerization results, when 180 μL of 1-hexene was added, 100% by weight of an amorphous polymer can be prepared at 150 ° C. That is, it can be understood that when the catalysts of Examples 1 to 5 of the present invention are used as the polymerization catalyst, compared with the case where the catalyst of Comparative Example 1 is used, even if the content of the comonomer added is as low as about From 12% to 38%, amorphous polymers can also be prepared. In addition, it can be understood that when the catalyst of Example 5 of the present invention is used as a polymerization catalyst, compared with the case where the catalyst of Comparative Example 2 is used, even if the content of the comonomer added is as low as about 10%, Amorphous polymers can be prepared. Therefore, it can be understood that when the catalyst of the present invention is used as a polymerization catalyst, a polymer having a high comonomer content can be prepared even if the content of the comonomer used is small.

This feature indicates that, compared with the catalysts of Comparative Examples 1 to 3, the catalysts of Examples 1 to 5 of the present invention are structurally highly reactive to comonomers, and have a smaller content of comonomers. Products with lower densities can be prepared at concentrations. In addition to the comonomer content in the prepared polymer, as a factor that may affect the physical properties of the polymer, the molecular weight distribution of the polymer may be considered.

It can be confirmed that when the polymerization is performed using the catalyst of Comparative Example 1, the molecular weight distribution is 2.5 to 2.8 (Comparative Examples 4 to 7), and when the polymerization is performed using the catalyst of Examples 1 to 5, the molecular weight distribution is 2.4. Or smaller, which is a relatively very narrow molecular weight distribution (Examples 7 to 20). This indicates that the copolymers prepared from the catalysts of Examples 1 to 5 of the present invention have a uniform molecular weight compared to the copolymers prepared from the catalyst of Comparative Example 1, and exhibit properties such as tensile strength, impact strength, and the like. Out of better characteristics.

Although the examples of the present invention have been described in more detail as described above, those having ordinary knowledge in the technical field to which this application belongs will understand that various modifications can be made to the present invention without departing from the scope of the appended patent application of the present invention. Therefore, further modifications in the examples of the present invention will not depart from the technology of the present 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 in the periodic table; R ¹ to R ⁵ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl , -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ¹ to R ⁴ can pass through (C4-C7) alkylene or (C4-C7) with or without aromatic ring ) Alkenyl groups are linked to adjacent substituents to form a fused ring; R ⁶ and R ⁷ 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) heteroaryl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , or R ⁶ and R ⁷ can be extended through (C4-C7) alkyl groups to form a ring; R ⁸ to R ¹⁰ are each 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 ⁸ to R ¹⁰ may form a condensed ring through (C4-C7) alkenyl group with or without aromatic ring to form a fused ring; R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl; R ¹¹ and R ¹² are each independently hydrogen, (C1-C2 0) alkyl or (C6-C20) aryl, or R ¹¹ and R ¹² may be linked to each other to form an aromatic ring; Ar ¹ is a fluorenyl or N-carbazole, and the fluorenyl or carbazole of Ar ¹ may be further Substituted by (C1-C20) alkyl; X ¹ and X ² are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl (C1-C20) alkane ((C1-C20) alkyl (C6-C20) aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20) alkane (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; each of ^Ra to ^{Rd is} 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 ) Ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl, (C3-C20) cycloalkyl, tri (C1-C20) alkylsilyl or tri (C6-C20 ) Arylsilyl; its limitation is that when one of X ¹ and X ² is (C1-C50) alkylene, the other is ignored; and the heteroaryl includes at least one selected from N, O and Heteroatom of S. The transition metal compound according to claim 1, wherein the transition metal compound is represented by the following Chemical Formula 2, Chemical Formula 3, Chemical Formula 4, or Chemical Formula 5: In Chemical Formulas 2 to 5, M, R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , X ¹ and X ² are the same as defined in Chemical Formula 1 of claim 1; R ¹ to R ⁵ are each independently hydrogen , (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ; R ^a1 to R ^a6 each independently (C1-C20) alkyl or (C6-C20) aryl; R ¹¹ and R ¹² are each independently hydrogen, and R ¹¹ and R ¹² may link with each other to form a benzene ring; R ¹³ and R ¹⁴ are each independently (C1-C20) alkyl; and R ^15, R ¹⁶ and R ¹⁷ 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 following compounds: Where M is titanium, zirconium or hafnium.     A transition metal catalyst composition for preparing 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 co-catalyst selected from an aluminum compound, a boron compound, or a mixture 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 alkylalumoxane and organoaluminum, and includes One or a mixture of methylalumoxane, modified methylalumoxane, tetraisobutylalumoxane, trimethylaluminum, triethylaluminum, and triisobutylaluminum.         The transition metal catalyst composition according to claim 4 or 5, wherein the aluminum compound used as the cocatalyst has a transition metal (M) and an aluminum atom (Al) (M: Al) of 1:10 to 5,000. Ear ratio.         The transition metal catalyst composition according to claim 4, wherein the boron compound used as the co-catalyst includes a member selected from the group consisting of (pentafluorophenyl) boronic acid-N, N-dimethylaniline, and (pentafluorobenzene) One of triphenylmethyl borate and gins (pentafluorophenyl) borane or a mixture thereof.         The transition metal catalyst composition according to claim 4 or 7, wherein the molar ratio of the transition metal compound to the co-catalyst is Moore of the transition metal (M): boron atom (B): aluminum atom (Al) The ratio ranges from 1: 0.1 to 100: 10 to 3,000.         The transition metal catalyst composition according to claim 8, wherein the molar ratio of the transition metal compound to the cocatalyst is the molar ratio of the transition metal (M): boron atom (B): aluminum atom (Al). The range is 1: 0.5 to 5: 100 to 3,000.         A method for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin by using the transition metal catalyst composition according to claim 4.         The method according to 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-icosene, 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 an α-olefin has an ethylene content of 30 to 99% by weight.         The method according to claim 11, wherein the pressure in the reactor used for the ethylene homopolymerization reaction or the copolymerization reaction of the ethylene monomer and the α-olefin is 1 atm to 1000 atm, and the polymerization reaction temperature is 25 ° C to 200 ° C.         The method according to claim 12, wherein the pressure in the reactor for ethylene homopolymerization reaction or copolymerization reaction of ethylene monomer and α-olefin is 10 atm to 150 atm, and the polymerization reaction temperature is 50 ° C to 180 ° C.