WO2018122693A1

WO2018122693A1 - NOVEL CYCLOPENTA[B]THIOPHENYL TRANSITION METAL COMPOUND, TRANSITION METAL CATALYST COMPOSITION COMPRISING SAME, AND METHOD FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND α-OLEFINS USING SAME

Info

Publication number: WO2018122693A1
Application number: PCT/IB2017/058243
Authority: WO
Inventors: 한용규; 오연옥; 김명일; 함형택
Original assignee: 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
Priority date: 2016-12-30
Filing date: 2017-12-21
Publication date: 2018-07-05

Abstract

The present invention relates to a novel transition metal compound based on a cyclopenta[b]thiophenyl group, a transition metal catalyst composition, comprising same and having a high catalytic activity, for preparing ethylene homopolymers or copolymers of ethylene and one or more α-olefins, and a method for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using same.

Description

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

The invention cyclopenta [b] thiophenyl (cyclopenta [b] thiophenyl) groups based novel transition metal compound, the transition with the ethylene homopolymer or ethylene and one or more high catalytic activity for the production of α- olefin copolymer containing the same It relates to a metal catalyst composition and a method for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using the same.

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.

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 rich in electrons and is widely delocalized. b] a thiophenyl (cyclopenta [b] thiophenyl) group; and a substituent to help improve solubility and performance is linked by a fluorenyl or phenoxy group substituted with a carbazole, which can be easily introduced; It has been found that a transition metal compound having a structure in which a cyclopenta [b] thiophenyl group and a phenoxy group are connected by silyl shows 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 point of view.

One aspect of the present invention for achieving the above object relates to a novel transition metal compound based on a cyclopenta [b] thiophenyl group represented by the following formula (1). More specifically, a cyclopenta [b] thiophenyl group, in which the Group 4 transition metal on the periodic table as a central metal has a rigid planar structure and is rich in electrons and widely delocalized; and Fluorenyl or carbazole-substituted phenoxy groups, which are easily introduced with substituents that help improve solubility and performance, are linked by the cyclopenta [b] thiophenyl group and phenoxy group by silyl It relates to a transition metal compound having a linked structure.

[Formula 1]

In Chemical Formula 1,

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

R ¹ to R ⁴ 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 ⁵ and R ⁶ are each independently (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) Aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) heteroaryl, -OR ^a1 , -SR ^a2 , -NR ^a3 R ^a4 or -PR ^a5 R ^a6, or R ⁵ and R ⁶ May be linked with (C 4 -C 7) alkylene to form a ring;

R ⁷ to R ⁹ 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 ⁷ to R ⁹ can be linked to a (C4-C7) alkenylene with or without adjacent substituents and an aromatic ring to form a fused ring;

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

Ar ¹ is fluorenyl or N-carbazole, wherein the fluorenyl or carbazole of Ar ¹ may be further substituted with (C1-C20) alkyl;

X ¹ and X ² are each independently halogen, (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 (C 1 -C 20) 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 includes one or more hetero atoms 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.

1-Production of 100 mg of polymer using the catalyst of Example 1 (1), Example 2 (2), Example 3 (3) and Example 4 (4) and Comparative Example 1 (□) of the present invention A diagram showing the reaction rate of each catalyst with ethylene

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 one embodiment of the present invention is a transition metal compound based on a cyclopenta [b] thiophenyl group represented by the following Chemical Formula 1, and a Group 4 transition metal on the periodic table as a central metal is Fluent, which has a rigid planar structure, an electron-rich, widely delocalized cyclopenta [b] thiophenylyl group, and a substituent which can easily introduce a substituent to improve solubility and performance. Orenyl or carbazole is substituted by a phenoxy (phenoxy) group; the cyclopenta [b] thiophenyl group has a structure in which the phenoxy group is connected by silyl, high efficiency and high molecular weight ethylene polymer It has an advantageous structural advantage in obtaining.

[Formula 1]

In Chemical Formula 1,

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

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

The heteroaryl includes one or more hetero atoms 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.

In one embodiment of the present invention, the transition metal compound based on the cyclopenta [b] thiophenyl group of Chemical Formula 1 may be a transition metal compound represented by the following Chemical Formula 2 or 3:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, M, R ¹ to R ⁴ , X ¹ and X ² are the same as defined in Formula 1;

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

R ⁸ and R ⁹ are each independently hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or halogen, or R ⁸ and R ⁹ are

,

or

Connected to form a fused ring;

R ¹¹ and R ¹² are each independently (C 1 -C 20) alkyl;

R ¹³ , R ¹⁴ and R ¹⁵ 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), more preferably Titanium.

In one embodiment of the present invention, R ¹ to R ⁴ 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.

In one embodiment of the invention, R ¹ is (C ¹ -C 20) alkyl, preferably (C 1 -C 10) alkyl, R ² is hydrogen, R ³ and R ⁴ are each independently hydrogen, (C 1 -C20) alkyl, preferably (C1-C10) alkyl, (C1-C20) alkoxy, preferably (C1-C10) alkoxy or di (C1-C20) alkylamino, preferably di (C1-C10) Alkylamino.

In one embodiment of the present invention, R ¹ , R ³ and R ⁴ are each independently (C 1 -C 10) alkyl, R ² may be hydrogen.

In one embodiment of the present invention, R ¹ , R ³ and R ⁴ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl, R ² is hydrogen Can be.

In one embodiment of the invention, R ¹ is (C1-C10) alkyl, R ² and R ³ are hydrogen, R ⁴ is (C1-C10) alkyl, (C1-C10) alkoxy or di (C1) -C10) alkylamino.

In one embodiment of the invention, R ¹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl, R ² and R ³ are hydrogen, R ⁴ is a methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl may be a methoxy, ethoxy, butoxy, dimethylamino, methyl-ethylamino or diethylamino-butyl, tert .

In one embodiment of the invention, R ¹ is (C ¹ -C 10) alkyl, R ² and R ⁴ are hydrogen, R ³ is (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or di (C 1) -C10) alkylamino.

In one embodiment of the invention, R ¹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl, R ² and R ⁴ are hydrogen, R ³ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, methoxy, ethoxy, butoxy, dimethylamino, methylethylamino or diethylamino .

In one embodiment of the present invention, the R ⁵ and R ⁶ are each independently selected from 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 ⁵ and R ⁶ are connected with butylene or pentylene to form a ring Can be.

In one embodiment of the invention, R ⁵ and R ⁶ 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 ⁵ and R ⁶ may be each independently methyl, ethyl or phenyl.

In one embodiment of the present invention, R ⁷ to R ⁹ 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 ⁸ and R ⁹ are

,

or

Can be connected to form a fused ring.

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

In one embodiment of the invention, R ⁷ is hydrogen, R ⁸ and R ⁹ 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 ⁸ and R ⁹ are

,

or

Can be connected to form a fused ring.

In one embodiment of the present invention, R ⁷ and R ⁹ are hydrogen, R ⁸ is (C1-C10) alkyl or halogen, or R ⁸ and R ⁹ is

Can be connected to form a fused ring.

In one embodiment of the present invention, R ⁷ and R ⁹ are hydrogen, R ⁸ may be methyl, ethyl, tert -butyl or fluoro, wherein R ⁸ and R ⁹ are

Can be connected to form a fused ring.

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

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.

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

In one embodiment of the invention, R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ are each independently (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl; R ¹³ may be hydrogen.

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 4 or 5, an organoaluminum compound of Formula 6 or an organoaluminum oxide of Formula 7 or Formula 8 It may be one or two or more selected from compounds.

[Formula 4]

(-Al (R ⁵¹ ) -O-) _m

[Formula 5]

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

[Formula 6]

(R ⁵² ) _r Al (E) _3-r

[Formula 7]

(R ⁵³ ) ₂ AlOR ⁵⁴

[Formula 8]

R ⁵³ Al (OR ⁵⁴ ) ₂

[In Formulas 4 to 8, R ⁵¹ is (C1-C20) alkyl, preferably methyl or isobutyl, 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; 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 include trialkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum Dialkyl aluminum chloride, including diisobutyl aluminum chloride, and dihexyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, and alkyl including hexyl aluminum dichloride Dialkyl aluminum hydrides including aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride De.

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 formulas (9) to (11).

[Formula 9]

B (R ⁴¹ ) ₃

[Formula 10]

[R ⁴² ] ⁺ [B (R ⁴¹ ) ₄ ] ^-

[Formula 11]

[(R ⁴³ ) _p ZH] ⁺ [B (R ⁴¹ ) ₄ ] ^-

In Formulas 9 to 11, 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 reaction temperature is 25-200 degreeC, Preferably it is 50-180 degreeC, More preferably, it is 100-180 degreeC, More preferably, it is 130-180 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%)

It was measured in 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 using a Bruker Avance400 nuclear magnetic resonance spectrometer. (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

2,4,5-trimethyl-6H-cyclopenta [b] thiophene (30.08 mmol) was added to THF (112 mL), and the hexane solution of n-BuLi (2.5 M, 31.58 mmol) was slowly added at -78 ° C. Was added. After the n-BuLi addition was completed, the temperature was slowly raised to room temperature and stirred for 2 hours. After stirring was complete, the mixture was cooled to -78 ° C, and then slowly added dropwise a solution of Compound A (33.09 mmol) toluene (14 mL), and then 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), followed by water removal with Na ₂ SO ₄ , and a yellow oily residue obtained by removing the solvent with a vacuum distiller was 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 ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = Me): yield 80%. ¹ HNMR (CDCl ₃ ): δ 7.81 (m, 1H), 7.80 (m, 1H), 7.77 (m, 1H), 7.60 (m, 1H), 7.47 (m, 1H), 7.33-7.40 (m, 3H ), 7.11 (m, 1H), 6.66 (m, 1H), 5.76 (m, 1H), 5.24 (m, 1H), 5.07 (m, 1H), 4.06 (m, 2H), 3.92 (s, 1H) , 2.50 (s, 3H), 2.40 (s, 3H), 2.07 (s, 3H), 1.93 (s, 3H), 1.54 (m, 6H), 0.18 (s, 6H).

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

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

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

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

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

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

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

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

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

화합물 1 내지 5의 제조Preparation of Compounds 1-5

Compound C (10 mmol) was dissolved in diethyl ether (100 mL), and a 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 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 ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = Me), Yield 64%. ¹ HNMR (CD ₂ Cl ₂ ): δ 8.01 (m, 1H), 7.83 (m, 1H), 7.78 (m, 1H), 7.71 (m, 1H), 7.49 (m, 1H), 7.31-7.38 (m , 3H), 7.25 (m, 1H), 6.87 (m, 1H), 2.57 (s, 3H), 2.42 (s, 3H), 2.36 (s, 3H), 1.66 (s, 3H), 1.61 (s, 3H), 1.56 (m, 3H), 0.59 (s, 3H), 0.48 (s, 3H), 0.28 (s, 3H), 0.05 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 162.73, 154.44, 153.77, 148.4, 142.01, 139.62, 139.06, 138.10, 136.15, 135.48, 134.64, 133.24, 131.72, 129.15, 128.87, 127.47, 127.31, 124. 119.80, 118.11, 116.59, 99.79, 57.96, 55.34, 47.35, 27.63, 20.97, 16.84, 13.11, 12.75, -0.69, -1.69.

Example 2. Transition Metal Catalyst Compound 2 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-Bu), yield 40%. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.80 (m, 1H), 7.78 (m, 1H), 7.73 (m, 1H), 7.71 (m, 1H), 7.37 (m, 1H), 7.33 (m, 1H ), 7.30 (m, 1H), 7.27 (m, 1H), 7.20 (m, 1H), 6.86 (m, 1H), 2.55 (s, 3H), 2.38 (s, 3H), 2.33 (s, 3H) , 2.00-2.08 (m, 4H), 1.62 (s, 3H), 1.01-1.06 (m, 4H), 0.71-0.77 (m, 1H), 0.62 (t, J = 7.25 Hz, 6H), 0.56 (s , 3H), 0.50-0.58 (m, 3H), 0.44 (s, 3H), 0.24 (s, 3H), 0.00 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 162.75, 151.41, 150.88, 148.24, 141.87, 141.66, 140.12, 139.04, 136.21, 135.65, 134.52, 133.47, 131.61, 129.14, 129.11, 128.124, 127.20, 127.10, 127.10. 119.92, 119.40, 118.24, 116.69, 99.53, 57.99, 55.61, 55.46, 40.93, 40.66, 26.67, 26.51, 23.54, 23.50, 20.95, 16.85, 14.13, 14.09, 13.21, 12.76, -0.68, -1.71.

Example 3. Transition Metal Catalyst Compound 3 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = Me), yield 43%. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.99 (m, 1H), 7.82 (m, 1H), 7.77 (m, 1H), 7.68 (m, 1H), 7.47 (m, 1H), 7.32-7.37 (m , 3H), 7.21 (m, 1H), 6.86 (m, 1H), 2.55 (s, 3H), 2.34 (s, 3H), 1.64 (s, 3H), 1.58 (s, 3H), 1.54 (m, 3H), 0.57 (s, 3H), 0.47 (s, 3H), 0.26 (s, 3H), 0.06 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 160.79, 159.31, 156.92, 154.47, 153.88, 148.59, 142.10, 139.40, 138.65, 137.83, 136.34, 135.68, 130.95, 129.05, 127.65, 127.38, 124.39, 120, 39. 119.48, 119.27, 118.56, 118.33, 116.65, 99.31, 58.79, 56.07, 47.38, 27.56, 16.82, 13.11, 12.74, -1.07, -1.92.

Example 4. Transition Metal Catalyst Compound 4 (R ⁵ = R ⁶ = Me, R ⁸ = F, R ¹¹ = R ¹² = n-Bu), Yield 71%. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.89-7.82 (m, 2H), 7.74 (m, 2H), 7.31-7.39 (m, 3H), 7.18 (m, 1H), 7.10 (m, 1H), 6.87 (m, 1H), 2.55 (s, 3H), 2.35 (s, 3H), 2.02-2.08 (m, 4H), 1.64 (s, 3H), 1.03-1.08 (m, 4H), 0.72-0.79 (m , 1H), 0.63 (t, J = 7.43 Hz, 6H), 0.57 (s, 3H), 0.51-0.59 (m, 3H), 0.47 (s, 3H), 0.27 (s, 3H), 0.05 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 160.81, 159.25, 156.86, 151.43, 151.05, 148.45, 141.99, 141.43, 140.67, 137.82, 136.39, 135.84, 129.07, 127.40, 127.14, 124.23, 123.36, 120.04, 37.37, 120.04 119.17, 118.80, 118.56, 118.48, 116.75, 99.07, 58.88, 56.24, 55.63, 40.87, 40.61, 26.62, 26.46, 23.50, 23.46, 14.10, 14.06, 13.19, 12.74, -1.06, -1.94.

Example 5. Transition Metal Catalyst Compound 5 (R ⁵ = R ⁶ = Me, R ⁸ = Me, R ¹¹ = R ¹² = n-Tetradecyl), Yield 92% ¹ HNMR (CD ₂ Cl ₂ ): δ 7.73-7.80 (m, 4H), 7.28-7.38 (m, 4H), 7.18 (m, 1H), 6.86 (m, 1H), 2.56 (s, 3H), 2.40 (s, 3H), 2.34 (s, 3H), 2.02-2.10 (m, 4H), 1.61 (s, 3H), 1.09-1.38 (m, 34H), 0.97-1.09 (m, 17H), 0.88-0.92 (m, 9H), 0.58-0.84 (m, 4H ), 0.24 (s, 3H), 0.02 (s, 3H). ¹³ CNMR (CD ₂ Cl ₂ ): δ 163.22, 154.42, 150.93, 148.19, 142.03, 141.64, 140.05, 139.04, 136.26, 136.05, 135.23, 133.39, 131.28, 129.17, 127.15, 127.08, 126.49, 124.30. 119.34, 118.10, 116.62, 98.45, 57.81, 55.65, 55.59, 41.05, 40.81, 32.39, 30.47, 30.12, 30.02, 29.81, 24.44, 24.28, 23.15, 21.01, 16.83, 14.35, 13.23, 12.82, 7.72, 7.50, 4.74, 4.74 4.33.

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

Preparation of Compound D6

p-cresol (30.0 g, 277 mmol, 1 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 NIS (N-iodosuccinimide) (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. It was. 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 ) And 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 filled with silica gel 60 (40-63 μm) to obtain the title compound G6 (99% yield). ).

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 2,4,5-trimethyl-6H-cyclopenta [b] thiophene (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 by chromatography (eluent: hexane / dichloromethane, 10/1, vol) gave the target compound I6 (65% yield).

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

Preparation of Compound J6

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 warmed 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%). Soul).

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

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 for 12 hours at -30 ° C to give compound 6 in the form of a yellow solid (54% yield).

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

Comparative Example 1 Preparation of Comparative Catalyst 1

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

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

Comparative Example 2 Preparation of Comparative Catalyst 2

Comparative catalyst 2 was prepared using the 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). After stirring the reaction solution at 100 ° C. for 12 hours, distilled water (150 mL) was added to terminate the reaction, followed by extraction with ether (200 mL) twice. 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 7.37 (t, J = 7.7 Hz, 1H), 7.22-7.26 (m, 2H), 7.13 (d, J = 2.2 Hz, 1H), 6.98 (d, J = 2.2 Hz, 1H), 6.64 (s, 1H), 5.59-5.68 (m, 1H), 4.99-5.06 (m, 2H), 3.98 (d, J = 5.32 Hz, 2H), 3.89 (s, 1H) , 2.77-2.91 (m, 2H), 2.50 (s, 3H), 2.36 (s, 3H), 2.04 (s, 3H), 1.90 (s, 3H), 1.21 (d, J = 6.7 Hz, 3H), 1.19 (d, J = 6.7 Hz, 3H), 1.14 (d, J = 6.8 Hz, 3H), 1.08 (d, J = 6.8 Hz, 3H), 0.68-0.93 (m, 10H).

Preparation of Compound f

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

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.26 (s, 1H), 7.24-7.26 (m, 1H), 7.09-7.12 (m, 1H), 6.99 (s, 1H), 6.78 (s, 1H) , 2.51 (s, 3H), 2.45 (s, 3H), 2.41 (s, 3H), 2.41-2.45 (m, 2H), 2.12 (s, 3H), 1.00-1.24 (m, 22H).

Preparation of Comparative Solvent 3

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

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

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

The ethylene / 1-hexene copolymerization process was 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-tert-butyl-4-methylphenol = 1/1 molar ratio, n Al = 30 μmol, 120 μL, 0.25 M toluene solution), 1-hexene as scavenger in this reactor μL, 270 μL or 300 μL) and toluene were added to bring the total volume to 5 mL. The temperature of the reactor was adjusted to the polymerization temperature (130 ° C. or 150 ° C.), and then the stirring speed was set to 800 rpm. Ethylene was added at 200 psi or 220 psi for 150 ° C. and 175 psi or 180 psi for 130 ° C. to maintain constant ethylene depending on the polymerization temperature. 10 nmole or 15 nmole was used as the polymerization catalyst, and the amount of the promoter was fixed at 5 equivalents relative to the polymerization catalyst. After the polymerization catalyst was introduced into the reactor, polymerization was initiated while adding 5 equivalents of the cocatalyst TTB (triphenylmethylium tetrakis (pentafluorophenyl) borate). The polymerization reaction proceeded for 1 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.

TABLE 1 Ethylene / 1-hexene copolymerization conditions and results

As shown in Table 1, the copolymerization of ethylene and 1-hexene using the catalyst of Examples 1 to 5 of the present invention has a copolymerization characteristic compared to the case of using the catalyst of Comparative Examples 1, 2 and 3 Can be. In particular, in the case of the embodiment at the polymerization temperature 130 ℃ it can be seen that the activity is higher than the comparative example. However, in the case of Example 20 using the catalyst of Example 5, the catalytic activity is slightly lower than that of Comparative Example 4, but it is found that the copolymerization characteristics are very excellent compared to Comparative Example 4 due to the very high content of comonomer 1-hexene in the copolymer. Can be. In addition, the Example at the polymerization temperature of 150 ℃ showed about 2 to 45 times higher than the catalyst of Comparative Example 1, about 10 to 213 times compared to the catalyst of Comparative Example 2, about 1.7 to 33 times higher than the catalyst of Comparative Example 3 .

In addition, in the polymerization properties for the comonomer 1-hexene, when the catalysts of Comparative Examples 1 to 3 were used, the 1-hexene content in the copolymer was very low compared to the case of using the catalysts of Examples 1 to 5, and thus the copolymerization characteristics were very low. You can see bad. On the other hand, when the catalyst of Comparative Example 2 was used, the content of 1-hexene in the copolymer was similar to that of the catalysts of Examples 1 to 5, but the polymerization activity was poor.

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

1-hexene ([1-C6] = 450 μL), polymerization temperature (T = 150 ° C.), ethylene pressure ( pE = 220 psi), the polymerization was carried out in the same manner as in the above examples using the catalyst used (15 nmol), the polymerization was terminated at a time not more than 100mg. The copolymerization characteristics of the catalysts of Examples 1 to 4 of the present invention were confirmed through the reactivity of each catalyst to ethylene up to 100 mg of the copolymer, and the results are shown in FIG. 1, and the steeper the slope, the better. Activity. As shown in Table 1 from Figure 1 it was confirmed that the polymerization activity is good in the order of polymerization catalysts of Examples 4, 3, 2, 1 and Comparative Example 1. That is, in case of using the polymerization catalysts of Examples 4, 3, and 2, it was necessary to add about 70 seconds of ethylene to produce 100 mg of copolymer, while using the catalysts of Example 1 and Comparative Example 1, It could be confirmed that input was necessary. However, when the catalysts of Example 1 and Comparative Example 1 are used, the same level of activity is expected, but it can be confirmed that ethylene consumption of up to about 150 seconds is better at the initial stage of the reaction. That is, in the case of using the catalysts of Examples 1, 2, 3 and 4 of the present invention in the ethylene / 1-hexene copolymer, it has higher activity than the catalyst of Comparative Example 1, and also in the reactivity of the comonomer It was confirmed that it has a high reactivity.

Claims

The transition metal compound of Formula 1

[Formula 1]

In Chemical Formula 1,

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

R 1 to R 4 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 5 and R 6 are each independently (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) Aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 5 and R 6 May be linked with (C 4 -C 7) alkylene to form a ring;

R 7 to R 9 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 7 to R 9 can be linked to a (C4-C7) alkenylene with or without adjacent substituents and an aromatic ring to form a fused ring;

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

Ar 1 is fluorenyl or N-carbazole, wherein the fluorenyl or carbazole of Ar 1 may be further substituted with (C1-C20) alkyl;

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 includes one or more hetero atoms selected from N, O and S.
The method of claim 1,

The transition metal compound is a transition metal compound represented by Formula 2 or 3 below:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, M, R 1 to R 4 , X 1 and X 2 are the same as defined in Formula 1 of claim 1;

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

R 8 and R 9 are each independently hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or halogen, or R 8 and R 9 are
,
,
or
Connected to form a fused ring;

R 11 and R 12 are each independently (C 1 -C 20) alkyl;

R 13 , R 14 and R 15 are each independently hydrogen or (C 1 -C 20) alkyl.
The method of claim 2,

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 1 to 3; 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 4, wherein

The aluminum compound used as the cocatalyst is one or two or more mixtures selected from aluminoxane and organoaluminum, and includes methylaluminoxane, improved methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum, trioctylaluminum and A transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an -olefin, which is a single or a mixture thereof selected from triisobutylaluminum.
The method according to claim 4 or 5,

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 4, wherein

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 according to claim 4 or 7,

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 5,

The ratio of the transition metal compound and the promoter is ethylene homopolymer or ethylene, 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 3,000. Transition metal catalyst composition for preparing a copolymer of α-olefin.
Method for producing an ethylene homopolymer or copolymer of ethylene and α-olefin using the transition metal catalyst composition according to claim 4.
The method of claim 10,

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 11,

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 12,

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.