KR102034133B1 - New transition metal complexes, catalysts composition containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same - Google Patents

Abstract

The invention cyclopenta [a] naphthalene (Cyclopenta [a] naphthalene) groups based novel transition metal compound, an ethylene homopolymer or of ethylene with a transition metal catalyst with one or more high catalytic activity for the production of α- olefin copolymer containing the same It relates to a composition and a method for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using the same. The metallocene compound according to the present invention and the catalyst composition including the same have excellent thermal stability of the catalyst, and maintain high catalytic activity even at high temperature, and have good copolymerization reactivity with other olefins and can produce a high molecular weight polymer in high yield. .

Description

New transition metal complexes, catalysts composition containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same}

The present invention relates to a novel transition metal compound, an ethylene homopolymer comprising the same or a transition metal catalyst composition having high catalytic activity for preparing a copolymer of ethylene and at least one α-olefin, and an air of ethylene homopolymer or ethylene and α-olefin using the same. It relates to a method for producing the coalescence.

Background Art In the past, so-called Ziegler-Natta catalyst systems composed of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkylaluminum compound have been generally used for preparing a homopolymer of ethylene or a copolymer of? -Olefin. However, the Ziegler-Natta catalyst system exhibits high activity against ethylene polymerization, but due to its heterogeneous catalytic activity, the molecular weight distribution of the resulting polymer is generally wide, and in particular, the composition distribution is not uniform in the copolymer of ethylene and α-olefin. There was this.

The metallocene catalyst system composed of a metallocene compound of Group 4 transition metal such as titanium, zirconium, and hafnium and methylaluminoxane as a promoter is a homogeneous catalyst having a single catalytic activity point. Compared to other catalyst system, polyethylene has narrower molecular weight distribution and uniform composition distribution. For example, in Japanese Patent Application Laid-Open No. 320,762, 372,632 or Japanese Patent Laid-Open No. 63-092621, Japanese Patent Laid-Open No. 02-84405, or Japanese Patent Laid-Open No. 03-2347, Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp ₂ ZrMeCl, Cp ₂ ZrMe ₂ , Ethylene (IndH ₄ ) ₂ ZrCl _2, etc., by activating the metallocene compound with the cocatalyst methylaluminoxane to polymerize ethylene with high activity so that the molecular weight distribution (Mw / Mn) ranges from 1.5 to 2.0. It has been announced that polyethylene can be prepared. However, it is difficult to obtain a high molecular weight polymer in the catalyst system. Especially, when applied to a solution polymerization method performed at a high temperature of 120 ° C. or higher, the polymerization activity decreases rapidly and the β-hydrogen desorption reaction predominates, resulting in a weight average molecular weight (Mw). It is known to be inadequate to produce high molecular weight polymers of 100,000 or more.

On the other hand, as a catalyst capable of producing a high catalytic activity and a high molecular weight polymer in ethylene homopolymerization or copolymerization of ethylene and α-olefin under solution polymerization conditions, so-called geometric nonmetallocene catalysts in which transition metals are linked in a ring form (Also known as single activity catalysts) have been published. In European Patent No. 0416815 and Patent No. 0420436, an example in which an amide group is linked to one cyclopentadiene ligand in the form of a ring is disclosed. In Patent No. 0842939, a phenol-based ligand is used as an electron donor compound and a cyclopentadiene ligand. An example of a catalyst connected in a cyclic form is shown. In the case of these geometric catalysts, the reactivity with higher alpha-olefins is remarkably improved due to the reduced steric hindrance effect of the catalyst itself, but there are many difficulties in commercial use. Therefore, it is important to secure a more competitive catalyst system based on the economical properties required for commercialization catalysts, that is, excellent high temperature activity, excellent reactivity with higher alpha-olefins, and high molecular weight polymer production ability.

European Patent No. 320,762 (1989.06.21) European Patent Publication 372,632 (1990.06.13) Japanese Patent Application No. 63-092621 (April 23, 1988) Japanese Patent Laid-Open No. 02-84405 (1990.03.26) Japanese Patent Laid-Open No. 03-2347 (1991.01.08) European Patent No. 0416815 (1991.03.13) European Patent No. 0420436 (1991.04.03) European Patent No. 0842939 (1998.05.20)

In order to overcome the problems of the prior art, the present inventors have conducted extensive research, and as a core metal, the Group 4 transition metal on the periodic table has a rigid planar structure and is a ligand rich in electrons and widely delocalized. A transition having a structure linked by a ligand in which a plurality of benzene rings are fused to a pentadiene ring; and an aryl or heteroaryl-substituted phenoxy group, in which a substituent to help improve solubility and performance can be easily introduced; It has been found that metal compounds exhibit excellent catalytic activity in the polymerization of ethylene and olefins. In view of this fact, a catalyst capable of producing high molecular weight ethylene homopolymer or copolymer of ethylene and α-olefin in a solution polymerization process performed at high temperature has been developed, and the present invention has been completed based on this.

Accordingly, it is an object of the present invention to provide a transition metal compound useful as a catalyst for the production of ethylene homopolymers or copolymers of ethylene and α-olefins, and also to provide catalyst compositions comprising the same.

Another object of the present invention is to provide a method for economically preparing an ethylene homopolymer or a copolymer of ethylene and an -olefin using a catalyst composition comprising the transition metal compound from a commercial point of view.

Another object of the present invention is a simple synthesis route, which is very economical in terms of catalytic synthesis, and has a high activity in olefin polymerization, and an ethylene homopolymer or ethylene and α- having various physical properties. An object of the present invention is to provide a polymerization method in which copolymers of olefins can be economically produced from a commercial standpoint.

One aspect of the present invention for achieving the above object relates to a novel transition metal compound based on a cyclopenta [ a ] naphthalene group represented by the following formula (1). More specifically, the electrons are goods rich and widely bipyeon-cyclopenta [a] naphthalene (Cyclopenta [a] naphthalene), which while having a Group 4 transition metal a hard (rigid) plane structure on the periodic table as a central metal group; and the solubility and A phenoxy group substituted with an aryl or heteroaryl which is easily introduced with a substituent to help improve the performance; a transition having a structure in which the cyclopenta [ a ] naphthalene group and the phenoxy group are connected by silyl; It relates to a metal compound.

[Formula 1]

In Chemical Formula 1,

M is a transition metal of Group 4 on the periodic table;

R ¹ to R ³ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, halogen, (C2-C20) alkenyl, (C3-C20) heteroaryl , (C3-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , wherein R ² and R ³ may or may not include an aromatic ring (C3-C7 May be linked to alkylene or (C3-C7) alkenylene to form a fused ring;

R ⁴ and R ⁵ 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 ⁴ and R ⁵ May be linked with (C 4 -C 7) alkylene to form a ring;

R ⁶ to R ⁸ are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl, (C3-C20) cycloalkyl, halogen, (C2-C20) Alkenyl, (C3-C20) heteroaryl, (C1-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6, or R ⁶ to R ⁸ are adjacent substituents May be linked to (C4-C7) alkenylene with or without aromatic rings to form fused rings;

Ar ¹ is (C6-C20) aryl or (C3-C20) heteroaryl, wherein the aryl or heteroaryl of Ar ¹ is halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C6-C20) Aryl, (C1-C20) alkyl (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 and -PR ^a5 R ^a6 May be further substituted with one or more selected from;

R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl;

Alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl of R ¹ to R ³ and R ⁶ to R ⁸ and alkyl or aryl of R ^a1 to R ^a6 are halogen, (C 1 -C 20) alkyl, halo (C 1-) C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy, nitro, cyano, -OSiR ^b1 R ^b2 R ^b3 , -SR ^b4 , -NR ^b5 R ^b6 and- May be further substituted with one or more selected from the group consisting of PR ^b7 R ^b8 ;

R ^b1 to R ^b8 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;

X ¹ and X ² are each independently halogen, (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) 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 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;

R ^e to R ^h are independently of each other (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;

Provided that if one of X ¹ or X ² is (C ¹ -C 50) alkylidene then the other is ignored;

The heteroaryl and heterocycloalkyl include one or more heteroatoms selected from N, O and S.

Another aspect of the present invention for achieving the above object is a transition metal compound of Formula 1; And a cocatalyst selected from an aluminum compound, a boron compound, or a mixture thereof. The present invention relates to a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin.

Another aspect of the present invention for achieving the above object relates to a method for producing an ethylene homopolymer or a copolymer of ethylene and α-olefin using the catalyst composition.

The transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by a simple method of high yield and economical method due to the simple synthesis process, and also has excellent thermal stability of the catalyst and high catalytic activity even at high temperature. While maintaining a good copolymerization reactivity with other olefins and can produce a high molecular weight polymer in high yield, it is commercially viable compared to the known metallocene and non-metallocene-based single-site catalyst. Therefore, the transition metal and the catalyst composition including the same according to the present invention can be usefully used for the preparation of ethylene homopolymer or copolymer with α-olefin having various physical properties.

Hereinafter, the present invention will be described in more detail. Unless otherwise defined in the technical terms and scientific terms used at this time, have a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs, unnecessarily obscure the subject matter of the present invention in the following description Description of known functions and configurations that may be omitted.

The transition metal compound according to the embodiment of the present invention solid the cyclopentadiene [a] naphthalene Group 4 transition metals on the periodic table as a transition metal compound, the central metal based groups (Cyclopenta [a] naphthalene) represented by the following general formula (1) ( rigid) cyclopentanone which electrons are abundant and widely delocalized while having a planar structure [a] naphthalene (cyclopenta [a] naphthalene) group; the solubility and the substituent that can help improve performance easily introduced available aryl or heteroaryl It is connected by a substituted phenoxy (phenoxy) group, and has a structure in which the cyclopenta [ a ] naphthalene group and the phenoxy group is connected by silyl, has an advantageous structural advantage in obtaining a high efficiency and high molecular weight ethylene polymer have.

[Formula 1]

In Chemical Formula 1,

M is a transition metal of Group 4 on the periodic table;

R ¹ to R ³ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, halogen, (C2-C20) alkenyl, (C3-C20) heteroaryl , (C3-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 , wherein R ² and R ³ may or may not include an aromatic ring (C3-C7 May be linked to alkylene or (C3-C7) alkenylene to form a fused ring;

R ⁴ and R ⁵ 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 ⁴ and R ⁵ May be linked with (C 4 -C 7) alkylene to form a ring;

R ⁶ to R ⁸ are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl, (C3-C20) cycloalkyl, halogen, (C2-C20) Alkenyl, (C3-C20), (C1-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6, or R ⁶ to R ⁸ are adjacent substituents and aromatic rings May be linked to (C4-C7) alkenylene with or without forming a fused ring;

Ar ¹ is (C6-C20) aryl or (C3-C20) heteroaryl, wherein the aryl or heteroaryl of Ar ¹ is halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C6-C20) Aryl, (C1-C20) alkyl (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 and -PR ^a5 R ^a6 May be further substituted with one or more selected from;

R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl;

Alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl of R ¹ to R ³ and R ⁶ to R ⁸ and alkyl or aryl of R ^a1 to R ^a6 are halogen, (C 1 -C 20) alkyl, halo (C 1-) C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy, nitro, cyano, -OSiR ^b1 R ^b2 R ^b3 , -SR ^b4 , -NR ^b5 R ^b6 and- May be further substituted with one or more selected from the group consisting of PR ^b7 R ^b8 ;

R ^b1 to R ^b8 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;

X ¹ and X ² are each independently halogen, (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) 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 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;

R ^e to R ^h are independently of each other (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;

Provided that if one of X ¹ or X ² is (C ¹ -C 50) alkylidene then the other is ignored;

The heteroaryl and heterocycloalkyl include one or more heteroatoms selected from N, O and S.

As used herein, the term “alkyl” refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, examples of which alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl , Pentyl, hexyl, octyl, nonyl, and the like.

As used herein, the term “aryl” refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, wherein a single or fused ring contains 4 to 7, preferably 5 or 6 ring atoms, as appropriate for each ring. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Fused ring systems can include aliphatic rings, such as saturated or partially saturated rings, and necessarily include one or more aromatic rings. In addition, the aliphatic ring may include nitrogen, oxygen, sulfur, carbonyl, and the like in the ring. Specific examples of the aryl radical include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, 9,10-dihydro Anthracenyl and the like.

As used herein, the term “heteroaryl” refers to an aryl group containing 1 to 4 heteroatoms selected from N, O and S as the aromatic ring skeleton atom, and wherein the remaining aromatic ring skeleton atom is carbon. Monocyclic heteroaryl and polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond. Examples of the heteroaryl group include pyrrole, quinoline, isoquinoline, pyridine, pyrimidine, oxazole, thiazole, thiadiazole, triazole, imidazole, benzoimidazole, isoxazole, benzoisoxazole, thiophene, Benzothiophene, furan, benzofuran and the like.

The term “cycloalkyl” herein refers to a monovalent saturated carbocyclic radical composed of one or more rings. Examples of cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

As used herein, the term "halo" or "halogen" refers to a fluorine, chlorine, bromine or iodine atom.

As used herein, the term "haloalkyl" refers to alkyl substituted with one or more halogens, and examples thereof include trifluoromethyl and the like.

As used herein, the terms "alkoxy" and "aryloxy" refer to -O-alkyl radicals and -O-aryl radicals, where "alkyl" and "aryl" are as defined above.

The transition metal compound of Formula 1 according to the present invention is a ethylene homopolymer synthesized because a ligand compound of a specific structure is bonded to the transition metal, has high catalytic activity, and can easily control the electronic / stereoscopic environment around the transition metal. Alternatively, properties such as chemical structure, molecular weight distribution and mechanical properties of the copolymer with α-olefin can be easily adjusted.

In one embodiment of the present invention, the transition metal compound of Formula 1 may be a transition metal compound represented by the following formula (2) or:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, M, R ⁴ , R ⁵ , R ⁷ , R ⁸ , Ar ¹ , X ¹ and X ² are the same as defined in Formula 1;

R ¹ to R ³ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, halogen, (C2-C20) alkenyl, (C3-C20) heteroaryl , (C3-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ;

R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl;

The alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl of R ¹ to R ³ and the alkyl or aryl of R ^a1 to R ^a6 are halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1 -C20) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy, nitro, cyano, -OSiR ^b1 R ^b2 R ^b3 , -SR ^b4 , -NR ^b5 R ^b6 and -PR ^b7 R ^b8 May be further substituted with one or more selected from the group;

R ^b1 to R ^b8 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl.

In one embodiment of the present invention, Ar ¹ is phenyl, biphenyl, naphthyl, fluorenyl, pyrrolyl, quinolyl, isoquinolyl, pyridyl, pyrimidyl or carbazolyl, and phenyl of Ar ¹ , Biphenyl, naphthyl, fluorenyl, pyrrolyl, quinolyl, isoquinolyl, pyridyl, pyrimidyl or carbazolyl is halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C6- C12) aryl, (C1-C10) alkyl (C6-C12) aryl, (C6-C12) aryl (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C12) aryloxy, (C1-C10) Consisting of alkylthio, (C6-C12) arylthio, di (C1-C10) alkylamino, di (C6-C12) arylamino, di (C1-C10) alkylphosphine and di (C6-C12) arylphosphine It may be further substituted with one or more selected from the group.

In one embodiment of the present invention, the transition metal compound of Formula 1 may be more preferably a transition metal compound represented by the following formula (4) or (5):

[Formula 4]

[Formula 5]

In Formulas 4 and 5, M, X ¹ and X ² are the same as the definition in Formula 1;

R ¹ to R ³ are each independently hydrogen, (C 1 -C 20) alkyl or halo (C 1 -C 20) alkyl;

R ⁴ and R ⁵ are each independently (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or (C 6 -C 20) aryl;

,

,

또는

으로 연결되어 융합고리를 형성할 수 있고;R ⁷ and R ⁸ are each independently hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or halogen, or R ⁷ and R ⁸ are

,

,

or

Connected to form a fused ring;

,

또는

이고;Ar ¹ is

,

or

ego;

m is an integer from 1 to 5 and R ¹¹ is (C1-C10) alkyl;

R ¹² and R ¹³ are each independently (C 1 -C 20) alkyl;

R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen or (C 1 -C 20) alkyl.

In one embodiment of the present invention, M of the transition metal compound is a transition metal of Group 4 on the periodic table, preferably titanium (Ti), zirconium (Zr) or hafnium (Hf).

,

,

또는

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the present invention, R ¹ to R ³ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl Neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, phenyl, pyridyl, methoxy, ethoxy, butyl Methoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenylamino, dimethylphosphine, diethylphosphine or diphenylphosphine, wherein R ² and R ³ are

,

,

or

Can be connected to form a fused ring.

,

,

또는

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the present invention, R ¹ , R ² and R ³ may be each independently hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or di (C 1 -C 20) alkylamino, Preferably R ¹ is hydrogen or (C ¹ -C 10) alkyl, (C 1 -C 10) alkoxy or di (C 1 -C 10) alkylamino, and R ² and R ³ are each independently hydrogen or (C 1 -C 10) alkyl, R ² and R ³ are

,

,

or

Can be connected to form a fused ring.

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the present invention, R ¹ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, methoxy, ethoxy, butoxy, Dimethylamino, methylethylamino or diethylamino, R ² and R ³ are each independently hydrogen, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl, or R ² and R ³

Can be connected to form a fused ring.

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the invention, R ¹ is hydrogen, R ² and R ³ is

Can be connected to form a fused ring.

In one embodiment of the invention, R ¹ is (C1-C10) alkyl, (C1-C10) alkoxy or di (C1-C10) alkylamino, and R ² and R ³ are each independently hydrogen or (C1- C10) alkyl.

In one embodiment of the invention, R ¹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, methoxy, ethoxy, butoxy, dimethylamino, Methylethylamino or diethylamino, and R ² and R ³ may each independently be hydrogen, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl.

In one embodiment of the present invention, R ⁴ and R ⁵ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl, neo Pentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoromethyl, trifluoromethyl, perfluoroethyl, Perfluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl , n-butylphenyl, sec -butylphenyl, tert -butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, biphenyl ), Fluorenyl, triphenyl, naphthyl, anthracenyl, benzyl, naphthylmethyl, anthracenylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethyl thi , Is dimethyl amino, methyl ethylamino, diethylamino, diphenylamino, dimethyl phosphine, diethyl phosphine, or diphenyl or phosphine, wherein R ⁴ and R ⁵ are connected to butylene or pentylene to form a ring Can be.

In one embodiment of the invention, R ⁴ and R ⁵ are each independently (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl, halo (C 1 -C 20) alkyl, preferably halo (C 1) -C10) alkyl or (C6-C20) aryl, preferably (C6-C12) aryl.

In one embodiment of the present invention, R ⁴ and R ⁵ may be each independently methyl, ethyl or phenyl.

,

,

또는

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the present invention, R ⁶ to R ⁸ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl , Neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoromethyl, trifluoromethyl, perfluoro Ethyl, perfluoropropyl, chloro, fluoro, bromo, phenyl, biphenyl, fluorenyl, triphenyl, naphthyl, anthracenyl, benzyl, naphthylmethyl, anthracenylmethyl, pyridyl, metha Methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenylamino, dimethylphosphine, diethylphosphine or diphenylphosphine, wherein R ⁷ and R ⁸ are

,

,

or

Can be connected to form a fused ring.

In one embodiment of the invention, R ⁶ to R ⁸ are each independently hydrogen, (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl, halo (C 1 -C 20) alkyl, preferably halo It may be (C1-C10) alkyl or halogen.

In one embodiment of the present invention, R ⁶ to R ⁸ may be each independently hydrogen, methyl, ethyl, tert -butyl or fluoro.

,

,

또는

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the invention, R ⁶ is hydrogen, R ⁷ and R ⁸ are each independently hydrogen, (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl, halo (C 1 -C 20) Alkyl, preferably halo (C1-C10) alkyl or halogen, wherein R ⁷ and R ⁸ are

,

,

or

Can be connected to form a fused ring.

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the present invention, R ⁶ and R ⁸ is hydrogen, R ⁷ is (C1-C10) alkyl or halogen, or R ⁷ and R ⁸ is

Can be connected to form a fused ring.

로 연결되어 융합고리를 형성할 수 있다.In one embodiment of the invention, R ⁶ and R ⁸ is hydrogen, R ⁷ may be methyl, ethyl, tert -butyl or fluoro, wherein R ⁷ and R ⁸ is

Can be connected to form a fused ring.

,

또는

이고, m은 1 내지 5의 정수이고, R¹¹은 (C1-C10)알킬이고, R¹² 및 R¹³ 는 각각 독립적으로 (C1-C20)알킬이고, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소 또는 (C1-C20)알킬일 수 있다.In one embodiment of the present invention, Ar ¹ is

,

or

M is an integer from 1 to 5, R ¹¹ is (C1-C10) alkyl, R ¹² and R ¹³ are each independently (C1-C20) alkyl, and R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently Hydrogen or (C1-C20) alkyl.

In one embodiment of the present invention, R ¹¹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl, neopentyl, amyl, n- Hexyl or n-octyl, R ¹² and R ¹³ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl, neopentyl, amyl , n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadecyl; R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl, neopentyl, amyl, n -Hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadedecyl.

In one embodiment of the invention, preferably R ¹¹ is (C1-C10) alkyl, R ¹² and R ¹³ are (C1-C20) alkyl, and R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen Or (C1-C10) alkyl.

In one embodiment of the invention, R ¹¹ is (C1-C10) alkyl, R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ are each independently (C1-C20) alkyl, preferably (C1-C15) ) Alkyl, more preferably (C1-C10) alkyl; R ¹⁴ may be hydrogen.

In one embodiment of the present invention, X ¹ and X ² are each independently fluoro, chloro, bromo, methyl, ethyl, isopropyl, amyl, cyclopropyl, cyclobutyl, cyclopentyl, cichlorohexyl, phenyl , Naphthyl, benzyl, methoxy, ethoxy, isopropoxy, tert -butoxy, phenoxy, 4-tert-butylphenoxy, trimethylsiloxy, tert -butyldimethylsiloxy, dimethylamino, diphenylamino, Dimethylphosphine, diethylphosphine, diphenylphosphine, ethylthio or isopropylthio.

In one embodiment of the invention, X ¹ and X ² may be (C ¹ -C 20) alkyl, preferably (C 1 -C 10) alkyl or halogen, more preferably X ¹ and X ² are (C 1 -C10) alkyl.

In one embodiment of the present invention, X ¹ and X ² may be methyl or chloro, preferably methyl.

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

 (M is titanium, zirconium or hafnium.)

On the other hand, the transition metal compound according to the present invention is preferably X ¹ and X in the transition metal complex in order to be an active catalyst component used in the preparation of an ethylene polymer selected from ethylene homopolymers and copolymers of ethylene and α-olefins. ² Ligands can be catalyzed to the central metal and catalyze the counterion with weak binding ability, that is, an aluminum compound, a boron compound, or a mixture thereof, which can act as an anion, and act as a cocatalyst. A catalyst composition comprising a is also within the scope of the present invention.

In the catalyst composition according to an embodiment of the present invention, the aluminum compound which may be used as a promoter may be specifically an aluminoxane compound of Formula 6 or 7, an organoaluminum compound of Formula 8 or an organoaluminum oxide of Formula 9 or Formula 10 It may be one or two or more selected from compounds.

[Formula 6]

(-Al (R ⁵¹ ) -O-) _n

[Formula 7]

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

[Formula 8]

(R ⁵² ) _r Al (E) _{3 -r}

[Formula 9]

(R ⁵³ ) ₂ AlOR ⁵⁴

[Formula 10]

R ⁵³ Al (OR ⁵⁴ ) ₂

[In Formulas 6 to 10, R ⁵¹ is (C1-C20) alkyl, preferably methyl or isobutyl, and n 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; R ⁵⁴ is (C1-C20) alkyl or (C6-C20) aryl.]

Specific examples of the aluminum compound which may be used include methyl aluminoxane, improved methyl aluminoxane and tetraisobutyl aluminoxane; Examples of organoaluminum compounds are trialkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutyl, including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum Dialkylaluminum chloride, including aluminum chloride, and dihexyl aluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and alkylaluminum dichloride, including hexylaluminum dichloride, And dialkyl aluminum hydrides including dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride.

In one embodiment of the present invention, the aluminum compound is preferably one or two or more mixtures selected from alkylaluminoxane compounds and trialkylaluminum, more preferably methylaluminoxanes, improved methylaluminoxanes, tetraisobutylalumina Or a mixture of two or more selected from noxic acid, trimethylaluminum, triethylaluminum, trioctylaluminum and triisobutylaluminum.

Boron compounds that can be used as cocatalysts in the present invention have been known in US Pat. No. 5,198,401, and may be selected from boron compounds represented by the following Chemical Formulas 11 to 13.

[Formula 11]

B (R ⁴¹ ) ₃

[Formula 12]

[R ⁴² ] ⁺ [B (R ⁴¹ ) ₄ ] ^-

[Formula 13]

[(R ⁴³ ) _p ZH] ⁺ [B (R ⁴¹ ) ₄ ] ^-

In Formulas 11 to 13, B is a boron atom; R ⁴¹ is phenyl, said phenyl being 3 to 5 substituents selected from fluoro, (C1-C20) alkyl unsubstituted or substituted with fluoro, and (C1-C20) alkoxy unsubstituted or substituted with fluoro; May be further substituted; R ⁴² represents a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical, a (C6-C20) aryl (C1-C20) alkyl radical, for example triphenylmethylium Radical; Z is nitrogen or phosphorus atom; R ⁴³ is a (C1-C50) alkyl radical or an anninium radical substituted with two (C1-C10) alkyl with a nitrogen atom; And p is an integer of 2 or 3.

Preferred examples of the boron-based cocatalysts include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro Phenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4 , 5-tetrafluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate or tetrakis (3,5-bistrifluoromethylphenyl) borate Can be mentioned. Moreover, as a specific compounding example thereof, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'- dimethyl ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, and triphenyl Methylinium tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis ( Pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N- Dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (Pentafluorofe ) Borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluoro Phenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate, the most preferred of which is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylmethyllinium tetrakis (pentafluorophenyl) borate or tris (pentafluorophenyl) bore It is phosphorus.

Meanwhile, the cocatalyst may serve as a scavenger to remove impurities that act as poisons to the catalyst in the reactants.

In one embodiment according to the present invention, in the case where the aluminum compound is used as a promoter, the preferred range of the ratio between the transition metal compound and the promoter of the present invention is based on the molar ratio ratio of the transition metal (M) to the aluminum atom (Al). 1: 10 to 5,000.

In one embodiment according to the present invention, when the aluminum compound and the boron compound are simultaneously used as a promoter, the preferred range of the ratio between the transition metal compound and the promoter of the present invention is a transition metal (M): boron atom on a molar ratio basis. The molar ratio of (B): aluminum atom (Al) may be in the range of 1: 0.1 to 100: 10 to 3,000, more preferably in the range of 1: 0.5 to 5: 100 to 3,000.

When the ratio between the transition metal compound and the promoter of the present invention is out of the above range, the amount of the promoter is relatively small so that the activation of the transition metal compound may not be completed, and thus the catalytic activity of the transition metal compound may not be sufficient, or more than necessary. The use of cocatalysts can lead to a significant increase in production costs. It shows excellent catalytic activity for producing ethylene homopolymer or copolymer of ethylene and α-olefin within the above range, and the range of the ratio will vary depending on the purity of the reaction.

As another aspect of the present invention, a method for preparing an ethylene polymer using the transition metal catalyst composition may be carried out by contacting the transition metal catalyst, the promoter, and ethylene or, if necessary, an α-olefin comonomer in the presence of a suitable organic solvent. . At this time, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or each component may be previously mixed and introduced into the reactor, and mixing conditions such as the order of input, temperature or concentration are not particularly limited.

Preferred organic solvents that can be used in the preparation method are (C3-C20) hydrocarbons, specific examples of which are butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclo Hexane, benzene, toluene, xylene, etc. are mentioned.

Specifically, when preparing the ethylene homopolymer, ethylene is used alone as a monomer, wherein a suitable pressure of ethylene is 1 to 1000 atm and more preferably 10 to 150 atm. Moreover, it is effective that polymerization temperature is performed at 25-200 degreeC, Preferably it is 50-180 degreeC, More preferably, it is 100-180 degreeC.

In addition, when preparing a copolymer of ethylene and an α-olefin, at least one selected from C3 to C18 α-olefins, C5 to C20 cycloolefins, styrene and derivatives of styrene may be used as a comonomer together with ethylene. Preferred examples of the α-olefin of ˜C18 include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, It may be selected from the group consisting of 1- tetradecene, 1- hexadecene and 1-octadecene, preferred examples of C5-C20 cycloolefins are cyclopentene, cyclohexene, norbonene and phenylnorbornene Styrene and its derivatives may be selected from styrene, alpha-methylstyrene, p-methylstyrene and 3-chloromethylstyrene. In the present invention, ethylene may be polymerized alone or copolymerized with two or more kinds of olefins, and more preferably 1-butene, 1-hexene, 1-octene or 1-decene and ethylene may be copolymerized. In this case, the preferred ethylene pressure and polymerization temperature may be the same as in the case of preparing the ethylene homopolymer, and the copolymer prepared according to the method of the present invention usually contains 30 wt% or more of ethylene, and preferably 60 wt%. It contains at least% ethylene, more preferably in the range of 60 to 99% by weight.

  As described above, when the catalyst of the present invention is used, it has a density of 0.850 g / cc to 0.960 g / cc and a melt flow rate of 0.001 to 15 dg / min using ethylene and a C-C18 α-olefin as a comonomer. It can be easily and economically produced from the elastomer having a high density polyethylene (HDPE) region.

In addition, hydrogen may be used as a molecular weight regulator to control the molecular weight in the preparation of the ethylene homopolymer or copolymer according to the present invention, and generally has a weight average molecular weight (Mw) in the range of 5,000 to 1,000,000 g / mol.

Since the catalyst composition presented in the present invention is present in a uniform form in the polymerization reactor, it is preferable to apply to the solution polymerization process carried out at a temperature above the melting point of the polymer. However, as disclosed in US Pat. No. 4,752,597, it may be used in slurry polymerization or gas phase polymerization in the form of a heterogeneous catalyst composition obtained by supporting the transition metal catalyst and the promoter on a porous metal oxide support.

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

Except where noted, all ligand and catalyst synthesis experiments were performed using standard Schlenk or glovebox techniques under nitrogen atmosphere and the organic solvent used in the reaction was refluxed under sodium metal and benzophenone to remove moisture Distilled immediately before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was performed using Bruker 500 MHz at room temperature.

Cyclohexane, a polymerization solvent, was used after passing through a tube filled with molecular sieve 5Å and activated alumina and bubbling with high purity nitrogen to sufficiently remove moisture, oxygen, and other catalyst poisons. The polymerized polymer was analyzed by the method described below.

1. Molecular Weight and Molecular Weight Distribution

Freeslate Rapid GPC was used to measure the solvent at 1,2,3-trichlorobenzene at 135 ° C. at a rate of 1.0 mL / min, and molecular weight was corrected using PL polystyrene standards.

2. α-olefin content in the copolymer (mol%)

The Bruker Avance400 nuclear magnetic resonance spectrometer was used to measure ¹³ C-NMR mode at 120 ° C. using a 1,2,4-trichlorobenzene / C ₆ D ₆ (7/3 weight fraction) mixed solvent at 125 MHz. (Reference: Randal, JC JMS- Rev. Macromol . Chem . Phys . 1980 , C29 , 201)

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

3. Crystallinity of the polymer

PolymerChar A-CEF was used to measure the AF (amorphous fraction) of the polymer by branching distribution analysis of the polymer.

[Examples 1 to 5] Preparation of the transition metal catalysts 1 to 5 according to the present invention

Preparation of Compound B

2-Methyl-9bH-cyclopenta [a] naphthalene (30.08 mmol) was added to THF (112 mL), followed by the slow addition of a hexane solution of n-BuLi (2.5 M, 31.58 mmol) at -78 ° C. After the n-BuLi addition was completed, the temperature was slowly raised to room temperature and stirred for 2 hours. When stirring is complete, cool down to -78 ° C and then (2- (allyloxy) -5-substituted-3- (9,9-disubstituted-9H-fluoren-7-yl) phenyl) chlorodimethyl Toluene (14 mL) solution of silane (Compound A, 33.09 mmol) was slowly added dropwise and the reaction mixture was allowed to warm to room temperature. After further stirring at room temperature for 3 hours, the reaction mixture was added to distilled water (200 mL) to terminate the reaction. The organic layer was extracted with toluene (2 x 50 mL) to remove moisture with Na ₂ SO ₄ , and the yellow oily residue obtained by removing the solvent with a vacuum distiller was filtered through a column filled with silica gel 60 (40-63 μm). Purification by flash chromatography (eluent: dichlroromethane / hexane (1:10 vol)) afforded Compound B as the target compound.

Compound B1 (R ⁷ = Me, R ¹² = R ¹³ = Me): Yield 53%. ¹ H NMR (CDCl ₃ ): δ 8.18 (m, 1H), 7.90 (m, 1H), 7.84 (m, 1H), 7.80-7.82 (m, 2H), 7.62-7.65 (m, 1H), 7.36- 7.54 (m, 7H), 7.30 (m, 1H), 7.23 (m, 1H), 7.08 (m, 1H), 5.83 (m, 1H), 5.31 (d, 1H), 5.13 (d, 1H), 4.36 (m, 1H), 4.14 (s, 1H), 2.40 (s, 3H), 2.18 (s, 3H), 1.57 (s, 6H), 0.23 (s, 3H), 0.09 (s, 3H).

Compound B2 (R ⁷ = Me, R ¹² = R ¹³ = n-Bu): yield 44%. ¹ H NMR (CDCl ₃ ): δ 8.16 (m, 1H), 7.88 (m, 1H), 7.80 (m, 1H), 7.76 (m, 1H), 7.66 (m, 1H), 7.61 (m, 1H) , 7.48-7.52 (m, 2H), 7.43 (m, 1H), 7.32-7.38 (m, 4H), 7.29 (m, 1H), 7.21 (m, 1H), 7.07 (m, 1H), 5.81 (m , 1H), 5.32 (m, 1H), 5.13 (m, 1H), 4.35 (m, 1H), 4.14 (m, 1H), 2.39 (s, 3H), 2.15 (s, 3H), 2.03 (m, 4H), 1.08-1.14 (m, 4H), 0.68 (m, 6H), 0.60-0.67 (m, 4H), 0.21 (s, 3H), 0.06 (s, 3H).

Compound B3 (R ⁷ = F, R ¹² = R ¹³ = Me): yield 60%. ¹ H NMR (CDCl ₃ ): δ 8.13 (m, 1H), 7.87 (m, 1H), 7.81 (m, 1H), 7.75-7.78 (m, 2H), 7.59 (m, 1H), 7.34-7.52 ( m, 7H), 7.20-7.25 (m, 2H), 6.93 (m, 1H), 5.79 (m, 1H), 5.28 (m, 1H), 5.11 (m, 1H), 4.29 (m, 1H), 4.10 (m, 1H), 2.14 (s, 3H), 1.53 (s, 6H), 0.18 (s, 3H), 0.06 (s, 3H).

Compound B4 (R ⁷ = F, R ¹² = R ¹³ = n-Bu): Yield 59%. ¹ H NMR (CDCl ₃ ): δ 8.13 (m, 1H), 7.87 (m, 1H), 7.80 (m, 1H), 7.75 (m, 1H), 7.64 (m, 1H0, 7.59 (m, 1H), 7.48-7.52 (m, 2H), 7.43 (m, 1H), 7.32-7.38 (m, 3H), 7.26 (m, 1H), 7.20-7.23 (m, 2H), 6.94 (m, 1H), 5.79 ( m, 1H), 5.31 (m, 1H), 5.14 (m, 1H), 4.30 (m, 1H), 4.13 (m, 1H), 2.15 (s, 3H), 2. 02 (m, 4H), 1.03 -1.14 (m, 4H), 0.68 (m, 6H), 0.60-0.67 (m, 4H), 0.19 (s, 3H), 0.06 (s, 3H).

Compound B5 (R ⁷ = Me, R ¹² = R ¹³ = n-Tetradecyl): Yield 59%. ¹ H NMR (CDCl ₃ ): δ 8.18 (m, 1H), 7.90 (m, 1H), 7.84 (m, 1H), 7.80-7.82 (m, 2H), 7.62-7.65 (m, 1H), 7.36- 7.54 (m, 7H), 7.30 (m, 1H), 7.23 (m, 1H), 7.08 (m, 1H), 5.79 (m, 1H), 5.31 (d, 1H), 5.14 (d, 1H), 4.30 (m, 1H), 4.13 (s, 1H), 2.40 (s, 3H), 2.18 (s, 3H), 1.27-0.20 (m, 61H), 0.09 (s, 3H).

Preparation of Compound C

Toluene (70 mL) in which Compound B (10 mmol) and Et ₃ N (45 mmol) was dissolved was cooled to −78 ° C., and a hexane solution of n-BuLi (2.5 M, 22 mmol) was added thereto. After the n-BuLi charge was completed, the reaction mixture was warmed to room temperature and stirred at room temperature for 20 hours. The reaction mixture was again cooled to -78 ° C, and then a solution of toluene (22 mL) of TiCl ₄ (15 mmol) was slowly added dropwise. After completion of the TiCl _{4 addition} , the reaction mixture was slowly warmed to room temperature, and the reaction mixture was further stirred at 90 ° C. The reaction was cooled to room temperature and then the solvent was removed in vacuo under a nitrogen atmosphere. After removal of the solvent, warm methylcyclohexane was added to separate the byproducts through a celite filter. The filtrate obtained from the filter was dried in vacuo and a mixed solvent of methylcyclohexane and hexane was added to give a reddish brown precipitate at −30 ° C. to obtain the title compound C in solid form.

Compound C1 (R ⁷ = Me, R ¹² = R ¹³ = Me): yield 71%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.31 (m, 1H), 7.84 (m, 1H), 7.72 (m, 1H), 7.62-7.68 (m, 4H), 7.56 (m, 1H), 7.44 ( m, 1H), 7.39-7.42 (m, 2H), 7.31-7.35 (m, 3H), 7.28 (m, 2H), 2.50 (s, 3H), 2.49 (s, 3H), 1.41 (s, 3H) , 1.43 (s, 3H), 0.83 (s, 3H), 0.77 (s, 3H).

Compound C2 (R ⁷ = Me, R ¹² = R ¹³ = n-Bu): Yield 71%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.31 (m, 1H), 7.83 (m, 1H), 7.73 (m, 1H), 7.63-7.66 (m, 3H), 7.60 (m, 1H), 7.49- 7.54 (m, 2H), 7.38-7.44 (m, 2H), 7.32 (m, 3H), 7.26 (m, 2H), 2.51 (s, 3H), 2.49 (s, 3H), 1.89-1.99 (m, 4H), 0.94-1.05 (m, 4H), 0.82 (s, 3H), 0.75 (s, 3H), 0.57-0.61 (m, 6H), 0.42-0.70 (m, 4H).

Compound C3 (R ⁷ = F, R ¹² = R ¹³ = Me): yield 62%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.31 (m, 1H), 7.84 (m, 1H), 7.72 (m, 1H), 7.64-7.67 (m, 4H), 7.58 (m, 1H), 7.41 ( m, 2H), 7.33-7.35 (m, 2H), 7.28-7.31 (m, 3H), 7.25-7.28 (m, 1H), 2.51 (s, 3H), 1.41 (s, 3H), 1.44 (s, 3H), 0.85 (s, 3H), 0.79 (s, 3H).

Compound C4 (R ⁷ = F, R ¹² = R ¹³ = n-Bu): Yield 74%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.32 (m, 1H), 7.85 (m, 1H), 7.74 (m, 1H), 7.68 (m, 1H), 7.65 (m, 1H), 7.63 (m, 1H), 7.55 (m, 1H), 7.51 (m, 1H), 7.37 (m, 1H), 7.28-7.36 (m, 6H), 7.26 (m, 1H), 2.53 (s, 3H), 1.91-1.99 (m, 4H), 0.96-1.07 (m, 4H), 0.84 (s, 3H), 0.78 (s, 3H), 0.58-0.63 (m, 6H), 0.42-0.70 (m, 4H).

Compound C5 (R ⁷ = Me, R ¹² = R ¹³ = n-Tetradecyl): yield 54%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.30 (d, 1H), 7.81 (d, 1H), 7.74-7.24 (m, 14H), 2.43 (s, 3H), 2.02 (m, 3H), 1.93 ( s, 3H), 1.27-0.60 (m, 64H).

Preparation of Compounds 1-5

Dissolved compound C (10 mmol) was dissolved in diethyl ether (100 mL), and a solution of MeMgBr (2.9 M in ether, 22 mmol) was slowly added at -30 ° C. The reaction mixture was slowly warmed to room temperature and stirred for 22 hours, after which the solvent was removed in vacuo under nitrogen atmosphere. The solvent was removed under vacuum under a nitrogen atmosphere after the filtrate obtained by adding warm hexane to celite filter. The obtained solid was dissolved in hexane (70 mL) and treated again with a celite filter, and the filtrate was cooled to -30 ° C to give target compounds 1 to 5 as a yellow solid.

Example 1 Transition Metal Catalyst Compound 1 (R ⁷ = Me, R ¹¹ = R ¹² = Me), yield 10%. ¹ H NMR (C ₆ D ₆ ): δ 8.15 (m, 1H), 8.04 (m, 1H), 7.81 (m, 1H), 7.73 (m, 1H), 7.57 (m, 2H), 7.40 (m, 1H), 7.34-7.38 (m, 3H), 7.14-7.27 (m, 6H), 2.31 (s, 3H), 1.77 (s, 3H), 1.45 (m, 3H), 1.39 (m, 3H), 0.78 (s, 3H), 0.57 (s, 3H), 0.55 (m, 3H), -0.08 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 162.62, 154.40, 153.75, 139.54, 138.90, 138.09, 134.39, 133.10, 132.14, 131.88, 130.85, 130.43, 129.76, 129.08, 128.94, 128.51, 127.58, 127.46, 127.46. , 124.74, 124.43, 123.85, 122.99, 120.29, 119.81, 111.45, 103.53, 60.30, 51.83, 41.30, 27.56, 21.01, 15.72, 0.84, -0.75.

Example 2. Transition Metal Catalyst Compound 2 (R ⁷ = Me, R ¹² = R ¹³ = n- Bu ), yield 36%. ¹ H NMR (C ₆ D ₆ ): δ 8.08 (m, 1H), 8.04 (m, 1H), 7.84 (m, 1H), 7.72 (m, 1H), 7.54-7.58 (m, 2H), 7.41 ( m, 1H), 7.32-7.35 (m, 3H), 7.25 (m, 1H), 7.18-7.22 (m, 5H), 2.28 (s, 3H), 1.94-2.11 (m, 4H), 1.79 (s, 3H), 0.94-1.05 (m, 4H), 0.85-0.92 (m, 2H), 0.83 (s, 3H), 0.73-0.81 (m, 2H), 0.56 (t, J = 7.2 Hz, 3H), 0.55 (s, 3H), 0.53 (s, 3H), 0.52 (t, J = 7.4 Hz, 3H), -0.07 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 162.63, 151.35, 150.90, 141.56, 140.11, 138.87, 138.13, 134.30, 133.33, 132.02, 131.86, 130.94, 130.60, 129.67, 129.08, 129.16, 128.40, 127.58.127 , 126.90, 126.85, 124.56, 124.55, 123.83, 123.29, 119.90, 119.35, 111.62, 103.34, 60.26, 55.54, 52.08, 40.77, 40.62, 26.54, 26.47, 23.44, 20.99, 15.88, 14.06, 14.02, 0.79.0.7.

Example 3. Transition Metal Catalyst Compound 3 (R ⁷ = F, R ¹² = R ¹³ = Me), Yield 8%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.27 (m, 1H), 7.96 (m, 1H), 7.83 (m, 1H), 7.77 (m, 1H), 7.73 (m, 1H), 7.60-7.63 ( m, 2H), 7.49-7.56 (m, 3H), 7.43 (m, 1H), 7.38 (m, 1H), 7.30-7.33 (m, 2H), 7.21 (m, 1H), 7.17 (m, 1H) , 1.94 (s, 3H), 1.50 (s, 6H), 0.66 (s, 6H), 0.49 (s, 3H), -0.53 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 160.62, 159.54, 157.13, 154.41, 153.85, 139.31, 138.68, 138.26, 137.67, 131.86, 130.80, 130.56, 129.11, 128.95, 128.59, 127.63, 127.64, 127.36, 127.127. , 124.52, 124.34, 123.83, 123.00, 120.38, 119.93, 119.26, 119.06, 118.44, 118.21, 111.56, 103.01, 61.17, 52.60, 47.33, 27.50, 15.69, 0.47, -1.02.

Example 4. Transition Metal Catalyst Compound 4 (R ⁷ = F, R ¹² = R ¹³ = n- Bu ) , Yield 7%. ¹ H NMR (C ₆ D ₆ ): δ 8.02 (m, 1H), 7.98 (m, 1H), 7.72 (m, 1H), 7.65 (m, 1H), 7.54-7.56 (m, 2H), 7.30- 7.35 (m, 2H), 7.17-7.27 (m, 8H), 1.94-2.05 (m, 4H), 1.20-1.25 (m, 4H), 0.94-1.03 (m, 4H), 0.82 (s, 6H), 0.56 (t, J = 7.3 Hz, 3H), 0.51 (t, J = 7.3 Hz, 3H), 0.43 (s, 3H), 0.37 (s, 3H), -0.08 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 160.68, 159.47, 157.06, 151.38, 151.09, 141.35, 140.69, 138.29, 137.69, 131.87, 131.19, 130.91, 130.75, 129.13, 129.06, 128.50, 127.68, 127.40, 127.40. , 124.36, 124.11, 123.85, 123.33, 120.03, 119.49, 119.17, 118.97, 118.69, 118.46, 111.77, 102.87, 61.21, 55.60, 52.94, 40.73, 40.59, 26.53, 26.46, 23.42, 15.87, 0.4 14.05-14.14 0.92.

Example 5. Transition Metal Catalyst Compound 5 (R ⁷ = Me, R ¹² = R ¹³ = n- Tetradecyl ) , Yield 5%. ¹ H NMR (CD ₂ Cl ₂ ): δ 8.30 (d, 1H), 7.81 (d, 1H), 7.74-7.24 (m, 14H), 2.43 (s, 3H), 2.02 (m, 3H), 1.93 ( s, 3H), 1.27-0.60 (m, 64H), 0.48 (s, 3H), -0.57 (s, 3H). ¹³ C NMR (CD ₂ Cl ₂ ): δ 163.18, 151.36, 150.92, 141.56, 140.06, 138.89, 138.29, 135.07, 133.26, 135.07, 033.26, 130.94, 130.91, 130.85, 130.81, 129.19, 129.02, 128.15, 127.05, 127.15. , 126.97, 126.82, 124.72, 124.23, 123.78, 123.29, 119.90, 119.31, 111.78, 102.32, 60.23, 55.60, 52.08, 40.81, 34.57, 32.38, 30.42, 30.11, 30.02, 29.81, 24.37, 24.24, 23.05. , 15.88, 14.34, 7.84, 5.75, 4.87

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 equiv) was dissolved in MeCN (3000 mL). p-TSA (p-Toluenesulfonic acid monohydrate) (52.8 g, 277 mmol, 1 equiv) was added to the reaction solution, stirred for 15 minutes, and then N-iodosuccinimide (NIS) (62.0 g, 277 mmol, 1 equiv) was added to 30 Slowly added over minutes, and stirred for 12 hours with the reaction solution. After stirring for 12 hours, the same volume of distilled water was added. The formed product was extracted with ether (200 mL × 2), and the recovered organics were treated with aqueous Na ₂ SO ₃ solution and distilled water, and then dried over anhydrous Na ₂ SO ₄ to remove the solvent. The resulting compound (2-iodo-4-methylphenol; 56.5 g, 87% yield) was used for the next reaction without further purification.

2-iodo-4-methylphenol (56.5 g, 240 mmol, 1 equiv) was dissolved in anhydrous THF (250 mL) under a nitrogen atmosphere. DIPEA (N, N-Diisopropylethylamine) (62.7 mL, 360 mmol, 1.5 equiv) and MOMCl (Chloromethyl methyl ether) (27.5 mL, 360 mmol, 1.5 equiv) were added sequentially 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. Extracted with hexane (200 mL x 2), the organic layer obtained 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 on a column packed with silica gel 60 (40-63 μm) to obtain the target compound D6 as a yellow oil (65.9 g, 99% yield).

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

Preparation of Compound E6

2,7-di- t -butyl-9 H -carbazole (24.8 g, 89.0 mmol, 1 equiiv), compound D6 (29.6 g, 107 mmol, 1.2 equiv), CuI (3.4 g, 18.0 mmol, 0.2 equiiv), K A mixture of ₃ PO ₄ (57.0g, 267mmol, 3equiv) and N, N'-dimethyl-1,2-ethylenediamine (2.35g, 26.7mmol, 0.3equiv) was dissolved in anhydrous toluene (180mL) and then at 120 ° C. After stirring for 12 hours, distilled water (500 mL) was added to terminate the reaction. The organic layer was extracted with toluene (100 mL × 3), then treated with distilled water and anhydrous Na ₂ SO ₄ , and dried to obtain a crude product. The crude product was purified by Kugelrohr distillation to give the target compound Compound E6 as a black oil (32.2g, 85% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.05 (d, J = 8.2 Hz, 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

N - BuLi (58.0 mL, 145 mmol, 2 equiv) was slowly added to anhydrous ether solution (850 mL) of Compound E6 (31.1 g, 72.0 mmol, 1 equiv) at room temperature, followed by stirring at room temperature for 2 hours. 1,2-dibromotetrafluoroethane (74.8 g, 288 mmol, 4 equiv) 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, treated with anhydrous Na ₂ SO ₄ and dried to give the product (9- {3-bromo-5-methyl-2- (methoxymethoxy) phenyl} -2,7-di- t -butyl- 9 H - carbazole; have gained 32.1 g, 88% yield) which was used in the next reaction without further purification.

9- {3-bromo-5-methyl-2- (methoxymethoxy) phenyl} -2,7-di- t -butyl-9 H -carbazole (32.1 g, 75.0 mmol) was dissolved in methanol (220 mL ), THF (220 mL) and hydrochloric acid (12 M, 2.5 mL) were added to the mixture, and the mixture was stirred at 60 ° C. for 12 hours, and distilled water (1000 mL) was added to terminate the reaction. The organic layer obtained by treatment with ether (200 mL × 2) was treated with anhydrous Na ₂ SO ₄ and dried to afford the crude product. The crude product was purified by flash chromatography on a column packed with silica gel 60 (40-63 μm) to give compound F6 as a white solid (22.2 g, 64% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.00 (dd, J ₁ = 8.3 Hz, J ₂ = 0.5 Hz, 2H), 7.51 (dd, J ₁ = 2.1 Hz, J ₂ = 0.6 Hz, 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, 1 H), 2.37 (s, 3 H), 1.36 (s, 18 H).

Preparation of Compound G6

K ₂ CO ₃ (30 mmol) and allyl bromide (30 mmol) were added to anhydrous acetone (200 mL) and phenol (20 mmol), refluxed for 16 hours, acetone was removed in vacuo, distilled water was added, and dichloromethane ( Extracted with 50 mL x 3). The organic layer was treated with anhydrous Na ₂ SO ₄ , and the residue was purified by flash chromatography (eluent: hexane) on a column packed with silica gel 60 (40-63 μm) to obtain the title compound G6 (yield 99%). .

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.00 (d, J = 8.2 Hz, 2H), 7.57 (d, J = 1.9 Hz, 2H), 7.35 (dd, J ₁ = 8.2 Hz, J ₂ = 1.6 Hz, 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 hexanes, 91 mmol) was slowly added to a solution of compound G6 (70 mmol) toluene (200 mL) at -78 ° C, and then heated to -20 ° C. The reaction solution was cooled to −78 ° C., and then dichlorodiethylsilane (210 mmol) was added rapidly, and the reaction mixture was stirred for 5 hours after warming to room temperature. The inorganic salts were removed through celite filtration, and after removing the solvent, excess dichlorodiethylsilane was removed in vacuo to obtain the target compound H6 (99% yield), which was used in the next reaction without further purification.

¹ H NMR (400 MHz, 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 = 10.5 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 hexanes, 31.6 mmol) was slowly added dropwise to a THF (112 mL) solution of 2-methyl-9bH-cyclopenta [a] naphthalene (30.1 mmol) at -78 ° C. The reaction mixture was raised to room temperature and then stirred for 2 hours. After stirring was complete, the mixture was cooled to -78 ° C, and then a toluene (14 mL) solution of compound H6 (33.1 mmol) was added through a syringe. The reaction mixture solution was raised to room temperature, stirred for 3 hours, and added to distilled water (200 mL) to terminate the reaction. The organic layer was extracted with toluene (2 x 50 mL) and then water was removed with Na ₂ SO ₄ , and the crude product obtained by removing the solvent by vacuum distillation was subjected to flash chromatography using a column filled with silica gel 60 (40-63 μm). Purification with (eluent: hexane / dichloromethane, 10/1, vol) gave the target compound I6 (65% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.21 (d, J = 8.2 Hz, 1H), 8.10 (d, J = 8.2 Hz, 2H), 7.94 (d, J = 8.0 Hz, 1H), 7.54- 7.60 (m, 2H), 7.37-7.50 (m, 7H), 7.30 (br.s, 2H), 5.49-5.59 (m, 1H), 4.86-4.94 (m, 2H), 4.42 (s, 1H), 3.74-3.84 (m, 2H), 2.48 (s, 3H), 2.30 (s, 3H), 1.47 (s, 9H), 1.45 (s, 9H), 0.75-1.19 (m, 10H).

Preparation of Compound J6

Toluene (70 mL) solution of Et ₃ N (45 mmol) and compound I6 (10 mmol) was cooled to -78 ° C, and n-BuLi (2.5 M in hexanes, 22 mmol) was slowly added. The reaction mixture was warmed to room temperature, stirred for 20 hours, cooled to -78 ° C, and then slowly added dropwise to a toluene (22 mL) solution of TiCl ₄ (15 mmol) through a syringe. After the addition of TiCl ₄ , the reaction mixture was heated to room temperature and stirred at 90 ° C. for 16 hours. After cooling to room temperature, the solvent was removed in vacuo. After removal of the solvent, hot methylcyclohexane was added to remove the insoluble inorganic salts through a celite filter. The solvent was concentrated in vacuo and then recrystallized from a mixed solution of methylcyclohexane and hexane to obtain the target compound J6 (61%). yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.06 (d, J = 7.5 Hz, 1H), 7.85 (d, J = 8.2 Hz, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.62 ( d, J = 8.0 Hz, 1H), 7.53 (td, J1 = 7.5 Hz, J2 = 1.4 Hz, 1H), 7.45-7.49 (m, 2H), 7.36-7.40 (m, 3H), 7.20-7.23 (m , 2H), 7.12 (dd, J1 = 8.2 Hz, J2 = 1.7 Hz, 1H), 6.95 (dd, J1 = 6.2 Hz, J2 = 1.2 Hz, 1H), 2.55 (s, 3H), 2.36 (s, 3H ), 1.32 (s, 9H), 1.27 (s, 9H), 1.11-1.40 (m, 10H).

Preparation of Compound 6

Compound J6 (10 mmol) was dissolved in diethyl ether (100 mL) and then MeMgBr (2.9 M in ether, 22 mmol) solution was slowly added at -30 ° C. The reaction mixture was slowly warmed to room temperature and stirred for 22 hours, after which the solvent was removed in vacuo. The reaction was added hot hexanes to remove insoluble inorganic salts through a celite filter. The filtrate was dried in vacuo and then dissolved in hexane (70 mL) and then insoluble inorganic salts were removed through a celite filter. The filtrate obtained was stored at −30 ° C. for 12 hours to obtain Compound 6 in the form of a yellow solid (30% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.00-8.09 (m, 1H), 7.91 (t, J = 8.4 Hz, 2H), 7.67 (d, J = 7.3 Hz, 1H), 7.33-7.48 (m , 5H), 7.18-7.27 (m, 4H), 7.11 (m, 1H), 7.02 (m, 1H), 2.51 (s, 3H), 1.79 (s, 3H), 1.32 (s, 9H), 1.25 ( s, 9H), 1.00-1.23 (m, 10H), -0.29 (s, 6H), -1.13 (s, 6H). ¹³ C {1H} NMR (101 MHz, CDCl ₃ ): δ 162.2, 148.4, 148.3, 142.8, 142.7, 137.4, 134.9, 131.7, 131.1, 130.6, 130.4, 128.5, 127.8, 127.5, 127.0, 126.6, 126.3, 124.4 , 123.8, 123.1, 121.1, 120.8, 119.2, 119.0, 117.1, 117.0, 110.4, 106.7, 105.9, 101.7, 77.3, 77.2, 76.7, 61.5, 52.6, 35.0, 35.0, 31.8, 31.7, 21.0, 15.4, 7.7, 7.7 , 5.7, 4.8.

Comparative Example 1 Preparation of Comparative Catalyst 1

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

¹ H NMR (CDCl ₃ ): δ 7.21 (m, 1H, Ar-H), 7.17 (m, 1H, Ar-H), 2.31 (s, 3H, Ar-Me), 2.02 (s, 6H, C ₅ Me ₄ ), 1.95 (s, 6H, C ₅ Me ₄ ), 1.36 (s, 9H, Ar-tBu), 0.62 (s, 3H, Si-Me), 0.58 (s, 3H, Si-Me), 0.21 (s, 3H), 0.07 (s, 3H)

Comparative Example 2 Preparation of Comparative Catalyst 2

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

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

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.39 (t, J = 7.8 Hz, 1H), 7.27 (d, J = 7.7 Hz, 1H), 7.08 (d, J = 8.3 Hz, 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 was prepared in the same manner as compound 6F of Example 6 (95% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.41 (t, J = 7.8 Hz, 1H), 7.35 (s, 1H), 7.27 (d, J = 7.8 Hz, 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 was prepared in the same manner as compound G6 of Example 6 (79% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.40 (s, 1H), 7.35 (t, J = 7.7 Hz, 1H), 7.20 (d, J = 7.7 Hz, 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 was prepared in the same manner as compound H6 of Example 6 (79% yield).

¹ H NMR (400 MHz, 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 was prepared in the same manner as compound I6 of example 6 (77% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 7.9 Hz, 1H), 7.48-7.52 (m, 2H), 7.38-7.45 (m , 2H), 7.25-7.32 (m, 3H), 7.19 (s, 1H), 7.09 (d, J = 7.9 Hz, 1H), 7.02 (d, J = 1.8 Hz, 1H), 5.68-5.78 (m, 1H), 5.06-5.15 (m, 2H), 4.31 (s, 1H), 4.06 (dd, J1 = 5.5 Hz, J2 = 1.1 Hz, 2H), 2.83-2.94 (m, 2H), 2.34 (s, 3H ), 2.13 (s, 3H), 1.24 (d, J = 8.9 Hz, 3H), 1.22 (d, J = 8.9 Hz, 3H), 1.17 (d, J = 6.8 Hz, 3H), 1.11 (d, J = 6.8 Hz, 3H), 0.62-1.09 (m, 10H).

Preparation of Compound f

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

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.19 (d, J = 8.0 Hz, 1H), 7.71 (d, J = 7.8 Hz, 1H), 7.63 (t, J = 7.60 Hz, 1H), 7.55 ( t, J = 7.5 Hz, 1H), 7.45 (s, 1H), 7.35-7.37 (m, 2H), 7.26-7.29 (m, 1H), 7.16 (t, J = 7.7 Hz, 1H), 7.08 (d , J = 7.8 Hz, 1H), 6.98 (d, J = 2.1 Hz, 1H), 6.94 (d, J = 7.8 Hz, 1H), 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), 0.97 (d, J = 6.8 Hz, 1H), 0.70 (d, J = 6.8 Hz, 1H).

Comparison  3, manufacturing

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

¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ 8.25 (d, J = 7.8 Hz, 1H), 7.79 (d, J = 7.6 Hz, 1H), 7.59 (t, J = 7.3 Hz, 1H), 7.49-7.53 (m, 2H), 7.42 (d, J = 9.0 Hz, 1H), 7.25-7.32 (m, 3H), 7.19 (d, J = 8.1 Hz, 1H), 7.16 (d, J = 7.9 Hz , 1H), 7.00 (br. S., 1H), 2.69 (m, 1H), 2.61 (m, 1H), 2.40 (s, 3H), 1.98 (s, 3H), 1.00-1.21 (m, 19H) , 0.95 (t, J = 7.7 Hz, 3H), 0.25 (s, 3H), -0.79 (s, 3H). ¹³ C { ¹ H} NMR (151 MHz, CD ₂ Cl ₂ ): δ 186.9, 170.9, 170.5, 160.9, 160.1, 157.8, 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, 125.2, 82.9, 77.4, 77.2, 76.8, 76.6, 74.6, 54.1, 54.0, 48.4, 48.2, 46.8, 46.7, 44.3, 38.8, 31.0, 30.9, 29.3, 28.5.

[Examples 7 to 20 and Comparative Examples 4 to 9] Copolymerization of ethylene and 1-hexene

The ethylene / 1-hexene copolymerization process is as follows:

The polymerization was carried out in a temperature controlled continuous polymerization reactor equipped with a mechanical stirrer. TiBA / BHT as scavenger in this reactor (triisobutylaluminum / 2,6-di-tert-butyl-4-methylphenol = 1/1 molar ratio, 30 μmol, 120 μL, 0.25 M toluene solution), 1-hexene (120 μL, 150 μL, 180 μL, 200 μL or 400 μL)) and toluene were added to bring the total volume to 5 mL. The temperature of the reactor was adjusted to the polymerization temperature (110 ° C. or 150 ° C.), and then the stirring speed was set to 800 rpm. Ethylene was added at 220 psi for 150 ° C. and 200 psi for 110 ° C. in order to keep the ethylene constant according to the polymerization temperature. The catalyst used was 5 nmole, 8 nmole, 10 nmole, 15 nmole or 20 nmole, and the amount of promoter was adjusted to 5 equivalents relative to the polymerization catalyst. After the polymerization catalyst was introduced into the reactor, polymerization was initiated while adding 5 equivalents of a co-catalyst, TTB (triphenylmethylium-tetrakis (pentafluorophenyl) borate). The polymerization reaction proceeded for 45 seconds to 5 minutes, or the polymerization was terminated at a time when the resulting polymer did not exceed 100 to 200 mg.

After completion of the polymerization, the reactor temperature was cooled to room temperature and ethylene in the reactor was slowly evacuated to remove. The resulting polymer was then dried in vacuo.

The polymerization reaction conditions and physical properties of the polymers obtained in Examples and Comparative Examples are shown in Table 1 below.

As shown in Table 1, it can be seen that the ethylene / 1-hexene copolymerization activity of Examples 7 to 20 is equally higher than or equal to the ethylene / 1-hexene copolymerization activity of Comparative Examples 4 to 9.

In particular, in the case of Example 20 at the polymerization temperature 150 ℃ it can be seen that the activity is 15 times or more, 34.5 times or more and 6.7 times higher than Comparative Examples 5, 7 and 9, respectively. In addition, in the case of the embodiments at the polymerization temperature 110 ° C, the polymerization activity of the catalysts was higher than 2.7 times, 44 times, and 1.7 times higher than Comparative Examples 4, 6, and 8, respectively, showing high polymerization characteristics.

In addition, in Comparative Examples 4 to 7 of the polymerization results using the catalysts of Comparative Examples 1 to 2 in the polymerization property to 1-hexene, which is a comonomer, in order that the 1-hexene content in the copolymer was about 10 mol%, the polymerization was performed. 200 μL to 400 μL of comonomer should be added. However, in the case of polymerization Examples 7 to 20 using the catalysts of Examples 1 to 5, even if 120 μL to 150 μL of comonomer was added, the same comonomer content was contained in the copolymer. .

That is, when the polymerization catalysts of Examples 1 to 5 were used, the amount of comonomers added was about 30 to 75% of the comonomers, compared to the case of using the catalysts of Comparative Examples 1 to 2. It was found that one copolymer could be prepared. This characteristic means that the catalysts of Examples 1 to 5 structurally have a higher reactivity to comonomers than the catalysts of Comparative Examples 1 to 2, and can produce products of lower density at lower concentrations of comonomers. It means that there is.

In addition, the molecular weight distribution of the polymer may be considered as a factor that may affect the polymer properties as well as the comonomer content in the prepared polymer. When the polymerization was carried out using the catalyst of Comparative Example 1, the molecular weight distribution was in the range of 2.4 to 2.8 (Comparative Examples 4 and 5), whereas when the polymerization was performed using the catalysts of Examples 1 to 5, the polymerization was relatively very high. It can be confirmed that it has a molecular weight distribution of 1.9-2.3 which is a narrow molecular weight distribution (Examples 7-20). In the case of the copolymer prepared by the catalysts of Examples 1 to 5, it is possible to prepare a polymer having a uniform molecular weight compared to the copolymer prepared by the catalyst of Comparative Example 1, and in terms of properties such as tensile strength and impact strength It means that it can show excellent characteristics.

Although described in detail with respect to embodiments of the present invention as described above, those of ordinary skill in the art, the present invention without departing from the scope of the invention defined in the appended claims Various modifications may be made. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

Claims (15)

delete A transition metal compound represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
M is a transition metal of Group 4 on the periodic table;
R ¹ to R ³ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, halogen, (C2-C20) alkenyl, (C3-C20) heteroaryl , (C3-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6 ;
R ⁴ and R ⁵ 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 ;
R ⁶ to R ⁸ are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl, (C3-C20) cycloalkyl, (C2-C20) alkenyl , (C3-C20) heteroaryl, (C1-C20) heterocycloalkyl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6, or R ⁶ to R ⁸ are adjacent substituents and aromatic rings May be linked to (C4-C7) alkenylene with or without forming a fused ring;
Ar ¹ is fluorenyl or carbazolyl, and the fluorenyl or carbazolyl of Ar ¹ is halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C6-C12) aryl, (C1-C10 ) Alkyl (C6-C12) aryl, (C6-C12) aryl (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C12) aryloxy, (C1-C10) alkylthio, (C6-C12) At least one further selected from the group consisting of arylthio, di (C1-C10) alkylamino, di (C6-C12) arylamino, di (C1-C10) alkylphosphine and di (C6-C12) arylphosphine Can be substituted;
R ^a1 to R ^a6 are each independently (C1-C20) alkyl or (C6-C20) aryl;
Alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl of R ¹ to R ³ and R ⁶ to R ⁸ and alkyl or aryl of R ^a1 to R ^a6 are halogen, (C 1 -C 20) alkyl, halo (C 1-) C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy, nitro, cyano, -OSiR ^b1 R ^b2 R ^b3 , -SR ^b4 , -NR ^b5 R ^b6 and- May be further substituted with one or more selected from the group consisting of PR ^b7 R ^b8 ;
R ^b1 to R ^b8 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;
X ¹ and X ² are each independently halogen, (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) 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 independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;
R ^e to R ^h are independently of each other (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;
Provided that if one of X ¹ or X ² is (C ¹ -C 50) alkylidene then the other is ignored;
The heteroaryl and heterocycloalkyl include one or more heteroatoms selected from N, O and S.
delete The method of claim 2,
The transition metal compound is a transition metal compound represented by the following formula (4):
[Formula 4]

In Formula 4, M, X ¹ and X ² are the same as defined in Formula 2 of claim 2;
R ¹ to R ³ are each independently hydrogen, (C 1 -C 20) alkyl or halo (C 1 -C 20) alkyl;
R ⁴ and R ⁵ are each independently (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or (C 6 -C 20) aryl;
R ⁷ and R ⁸ are each independently hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or halogen, or R ⁷ and R ⁸ are

,

,

or

Connected to form a fused ring;
Ar ¹ is

or

ego;
R ¹² and R ¹³ are each independently (C 1 -C 20) alkyl;
R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen or (C 1 -C 20) alkyl. The method of claim 4, wherein
The transition metal compound is selected from the following compounds.

(M is titanium, zirconium or hafnium.) A transition metal compound according to any one of claims 2, 4 and 5; And
A promoter selected from aluminum compounds, boron compounds or mixtures thereof;
Ethylene homopolymer or a transition metal catalyst composition for producing a copolymer of ethylene and α-olefin comprising a. The method of claim 6,
The aluminum compound used as the cocatalyst is one or two or more mixtures selected from alkylaluminoxane or organoaluminum, and includes methylaluminoxane, improved methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutyl A transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin, which is one or a mixture thereof selected from aluminum. The method of claim 6,
The aluminum compound promoter is a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin having a transition metal (M): aluminum atom (Al) ratio of 1: 10 to 5,000. The method of claim 6,
The boron compound used as the cocatalyst is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylmethyllinium tetrakis (pentafluorophenyl) borate and tris (pentafluorophenyl) borane Transition metal catalyst composition for preparing ethylene homopolymer or copolymer of ethylene and α-olefin which is a single or a mixture thereof. The method of claim 6,
The ratio of the transition metal compound and the promoter is ethylene homopolymer or ethylene, wherein the molar ratio of transition metal (M): boron atom (B): aluminum atom (Al) is in the range of 1: 0.1 to 100: 10 to 3,000. Transition metal catalyst composition for preparing a copolymer of α-olefin. The method of claim 10,
The ratio of the transition metal compound and the promoter is ethylene homopolymer, characterized in that the molar ratio of transition metal (M): boron atom (B): aluminum atom (Al) is in the range of 1: 0.5 to 5: 100 to 30,00. Or a transition metal catalyst composition for preparing a copolymer of ethylene and an α-olefin. Method for producing ethylene homopolymer or copolymer of ethylene and α-olefin using the transition metal catalyst composition according to claim 6. The method of claim 12,
Α-olefin copolymerized with ethylene is 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-atocene, cyclopentene, cyclohexene, norbonene, phenylnorbornene, styrene, alpha-methylstyrene, p At least one selected from -methyl styrene and 3-chloromethyl styrene, the ethylene content of the copolymer of ethylene and α-olefin is 30 to 99% by weight of the ethylene homopolymer or ethylene and α-olefin Copolymer production method. The method of claim 13,
The ethylene homopolymer or copolymerization of ethylene monomer and α-olefin in the reactor is 1 to 1000 atm, the polymerization temperature is 25 to 200 ℃ ethylene homopolymer or a copolymer of ethylene and α-olefin How to manufacture. The method of claim 14,
The ethylene homopolymerization or copolymerization of ethylene monomers and α-olefins in the reactor is a pressure of 10 to 150 atm, polymerization reaction temperature is 50 to 180 ℃ prepared ethylene homopolymer or copolymer of ethylene and α-olefin Way.