Ligand compound, transition metal compound and catalyst composition containing the same

Abstract

The present invention relates to a ligand compound having a novel structure, a transition metal compound and a catalyst composition comprising the same.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to Korean Patent Application No. 2020-0046030, filed on Apr. 16, 2020, which is hereby incorporated by reference in its entirety. Technical Field

[0004] The present invention relates to a ligand compound having a novel structure, a transition metal compound and a catalyst composition comprising the same. Background Art

[0005] Transition metal pincer complexes have been widely used in the field of organometallic catalysis. The tridentate chelating pincer ligand binds to the metal to form a planar structure with the metal at the center. The ligand-metal interaction is rigid and non-flexible, thus providing high stability.

[0006] For homogeneous olefin polymerization, the initial Zr-based metallocene catalysts developed into Ti-based semi-metallocenes and finally into post-metallocenes with biscyclopentadienyl ligands. Among the post-metallocenes developed, the pincer-type [C 萘基 , N 吡啶 , N 酰胺 The HfMe2 complex is the main catalyst. This complex was developed through high-throughput screening in the early 2000s and has been extensively studied and applied in commercial processes.

[0007] Such complex can introduce a large amount of α-olefins in ethylene / α-olefin copolymerization, and can control the stereoregularity of propylene polymerization for preparing isotactic polypropylene. Another advantage of this complex is that there is no β-elimination process, which is an inevitable unique chain transfer reaction in the olefin polymerization using conventional Zr-based metallocenes and Ti-based semi-metallocene catalysts. Due to these characteristics, polyolefin chains can grow from Hf sites and transfer to chain transfer agents such as diethyl zinc (ET2Zn) to grow uniform polyolefin chains. Such a process is called coordinated chain transfer polymerization (CCTP). CCTP technology can be used for the commercial production of olefin block copolymers.

[0008] In addition, polyolefin-polystyrene block copolymers can be synthesized by anionic polymerization of styrene using the complex in a reaction after CCTP. As described above, transition metal compounds containing hafnium metal can be used as catalysts for producing olefin polymers, and a lot of research is being conducted to improve catalyst performance through modification.

[0009] [Prior art literature]

[0010] [Patent Document]

[0011] Korean Patent Application No. 10-2018-0055531 Summary of the invention

[0012] Technical issues

[0013] An object of the present invention is to provide novel transition metal compounds, ligand compounds and catalyst compositions comprising the same.

[0014] Technical Solution

[0015] In order to solve the above-mentioned task, the present invention provides a transition metal compound represented by the following formula 1:

[0016] [Formula 1]

[0017]

[0018] In formula 1

[0019] M is Ti, Zr or Hf,

[0020] R1 to R4 are each independently: hydrogen; an alkyl group of 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkyl group of 3 to 20 carbon atoms which may be substituted or unsubstituted; or an aryl group of 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein two or more adjacent groups thereof may be connected to each other to form a ring,

[0021] R5 and R6 are each independently: hydrogen; a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is carried out with an alkyl group of 1 to 12 carbon atoms,

[0022] Each R7 is independently: a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms,

[0023] n is 1 to 5, and

[0024] Y1 and Y2 are each independently: a halogen group; a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms; an alkenyl group of 2 to 20 carbon atoms; an alkynyl group of 2 to 20 carbon atoms; a cycloalkyl group of 3 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; an alkylaryl group of 7 to 20 carbon atoms; an arylalkyl group of 7 to 20 carbon atoms; a heteroaryl group of 5 to 20 carbon atoms; an alkoxy group of 1 to 20 carbon atoms; an aryloxy group of 5 to 20 carbon atoms which may be substituted; an alkylamino group of 1 to 20 carbon atoms; an arylamino group of 5 to 20 carbon atoms; an alkylthio group of 1 to 20 carbon atoms; an arylthio group of 5 to 20 carbon atoms; an alkylsilyl group of 1 to 20 carbon atoms; an arylsilyl group of 5 to 20 carbon atoms; a hydroxyl group; an amino group; a thiol group; a silyl group; a cyano group; or a nitro group.

[0025] In addition, an embodiment of the present invention provides a catalyst composition including a transition metal compound represented by Formula 1 and a co-catalyst.

[0026] In addition, an embodiment of the present invention provides a method for preparing an olefin polymer, which includes polymerizing an olefin monomer in the presence of the catalyst composition.

[0027] Beneficial effects

[0028] The novel transition metal compound of the present invention is useful as a polymerization catalyst for preparing an olefin polymer having a high molecular weight. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The embodiment 1 is shown 1 H NMR spectra and 13 C NMR spectrum.

[0030] Figure 2 Example 2 shows 1 H NMR spectra and 13 C NMR spectrum.

[0031] Figure 3 Example 3 shows 1 H NMR spectra and 13 C NMR spectrum.

[0032] Figure 4 Example 4 shows 1 H NMR spectra and 13 C NMR spectrum.

[0033] Figure 5 Example 5 shows 1 H NMR spectra and 13 C NMR spectrum.

[0034] Figure 6 Example 6 shows 1 H NMR spectra and 13 C NMR spectrum.

[0035] Figure 7 Example 7 shows 1 H NMR spectra and 13 C NMR spectrum.

[0036] Figure 8 Example 8 shows 1 H NMR spectra and 13 C NMR spectrum.

[0037] Fig. 9 A graph showing ethylene consumption over time for Example 2 and Comparative Example 1 using a mass flow controller (MFC) is shown. DETAILED DESCRIPTION

[0038] Hereinafter, the present invention will be explained in more detail to help understanding of the present invention.

[0039] It should be understood that the words or terms used in the specification and claims of the present invention should not be interpreted as the meanings defined in common dictionaries. It will also be understood that based on the principle that the inventor can appropriately define the meanings of words or terms to best explain the present invention, the words or terms should be interpreted as having a meaning consistent with the meaning in the technical idea of ​​the present invention.

[0040] In the present invention, "alkyl" refers to a linear or branched hydrocarbon residue.

[0041] In the present invention, "alkenyl group" refers to a linear or branched alkenyl group.

[0042] In the present invention, the "aryl group" preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilino, anisole and the like without limitation.

[0043] In the present invention, "alkylaryl group" refers to an aryl group substituted with an alkyl group.

[0044] In the present invention, "arylalkyl" refers to an alkyl group substituted with an aryl group.

[0045] In the present invention, the "alkylsilyl group" may be a silyl group substituted with an alkyl group having 1 to 20 carbon atoms, such as a trimethylsilyl group or a triethylsilyl group.

[0046] In the present invention, "alkylamino" refers to an amino group substituted with an alkyl group, and includes dimethylamino, diethylamino, etc., but is not limited thereto.

[0047] In the present invention, "hydrocarbon group" refers to a monovalent hydrocarbon group of 1 to 20 carbon atoms, regardless of its structure, consisting only of carbon and hydrogen, including alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl.

[0048] An embodiment of the present invention provides a transition metal compound represented by the following Formula 1:

[0049] [Formula 1]

[0050]

[0051] In formula 1

[0052] M is Ti, Zr or Hf,

[0053] R1 to R4 are each independently: hydrogen; an alkyl group of 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkyl group of 3 to 20 carbon atoms which may be substituted or unsubstituted; or an aryl group of 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein two or more adjacent groups thereof may be connected to each other to form a ring,

[0054] R5 and R6 are each independently: hydrogen; a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is carried out with an alkyl group of 1 to 12 carbon atoms,

[0055] Each R7 is independently: a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms,

[0056] n is 1 to 5, and

[0057] Y1 and Y2 are each independently: a halogen group; a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms; an alkenyl group of 2 to 20 carbon atoms; an alkynyl group of 2 to 20 carbon atoms; a cycloalkyl group of 3 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; an alkylaryl group of 7 to 20 carbon atoms; an arylalkyl group of 7 to 20 carbon atoms; a heteroaryl group of 5 to 20 carbon atoms; an alkoxy group of 1 to 20 carbon atoms; an aryloxy group of 5 to 20 carbon atoms which may be substituted; an alkylamino group of 1 to 20 carbon atoms; an arylamino group of 5 to 20 carbon atoms; an alkylthio group of 1 to 20 carbon atoms; an arylthio group of 5 to 20 carbon atoms; an alkylsilyl group of 1 to 20 carbon atoms; an arylsilyl group of 5 to 20 carbon atoms; a hydroxyl group; an amino group; a thiol group; a silyl group; a cyano group; or a nitro group.

[0058] If the polymerization reaction is carried out in the presence of an excess of a chain transfer agent (e.g., (Et)2Zn) relative to the catalyst, the olefin polymer chain can undergo rapid alkyl transfer between zinc (Zn) and hafnium (Hf), thereby uniformly propagating from the dialkyl zinc to complete the living polymerization, which is called coordination chain transfer polymerization (CCTP). Conventionally used metallocene catalysts exclude living polymerization due to the β-elimination process, and a small amount of catalysts known to be suitable for CCTP can only homopolymerize ethylene, but make the copolymerization of ethylene and α-olefins by CCTP very difficult. Therefore, it is difficult to prepare block copolymers by living polymerization using ordinary transition metal compounds as catalysts by CCTP.

[0059] The transition metal compound of the present invention is characterized in that a bulky functional group of R7 is included in Formula 1, thereby achieving high catalyst activity. In the case where a small-sized functional group (e.g., isopropyl) is configured for R7, the isopropyl group and the hafnium compound can react and a catalyst deactivation reaction can be performed, whereas the functional group located at R7 effectively reduces the deactivation reaction of the compound of the present invention and improves stability, while reducing activation energy in a polymerization reaction and showing excellent catalyst activity.

[0060] As described above, the transition metal compound of the present invention can be effectively used as a catalyst for producing olefin polymers, and this is an inherent characteristic achieved by the new structure of the compound newly developed in the present invention.

[0061] In particular, in Formula 1, M may be Hf.

[0062] In particular, in Formula 1, R1 to R4 are each independently: hydrogen; or an alkyl group of 1 to 20 carbon atoms with or without a substituent; wherein two or more adjacent ones of them may be connected to each other to form a ring, or R1 and R2 are each independently an alkyl group of 1 to 20 carbon atoms and are connected to each other to form an aromatic ring of 5 to 20 carbon atoms, and R3 and R4 may be hydrogen.

[0063] In particular, in Formula 1, R5 and R6 may each independently be: hydrogen; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is performed with an alkyl group of 1 to 6 carbon atoms.

[0064] In particular, in Formula 1, each R7 may independently be: a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms.

[0065] Particularly, in Formula 1, n may be 1 to 3, preferably 2.

[0066] Particularly, in Formula 1, Y1 and Y2 may each independently be an alkyl group of 1 to 20 carbon atoms.

[0067] More specifically, the transition metal compound represented by Formula 1 may be a compound represented by the following Formula 1a:

[0068] [Formula 1a]

[0069]

[0070] In formula 1a,

[0071] M, R5 to R7, Y1 and Y2 are the same as defined above.

[0072] The transition metal compound represented by Formula 1 may be particularly selected from the compounds described below, but all transition metal compounds corresponding to Formula 1 are included in the present invention without limitation.

[0073]

[0074] In addition, the present invention provides a ligand compound represented by the following formula 2:

[0075] [Formula 2]

[0076]

[0077] In formula 2,

[0078] R1 to R4 are each independently: hydrogen; an alkyl group of 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkyl group of 3 to 20 carbon atoms which may be substituted or unsubstituted; or an aryl group of 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein two or more adjacent groups thereof may be connected to each other to form a ring,

[0079] R5 and R6 are each independently hydrogen; a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms; a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is carried out with an alkyl group of 1 to 12 carbon atoms,

[0080] Each R7 is independently: a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms; and

[0081] n is 1 to 5.

[0082] In other words, the transition metal compound of the present invention can be prepared by a process comprising reacting a ligand compound represented by the following Formula 2 with a compound represented by the following Formula 3:

[0083] [Formula 2]

[0084]

[0085] [Formula 3]

[0086] M(Y1Y2)2

[0087] In the above formula,

[0088] R1 to R7, M, Y1 and Y2 are the same as defined above.

[0089] Meanwhile, when preparing the transition metal compound represented by Formula 1 of the present invention, the reaction may be performed through the following process.

[0090] [Reaction 1]

[0091]

[0092] [Reaction 2]

[0093]

[0094] The catalyst composition of the present invention is characterized by including a transition metal compound represented by Formula 1 and a co-catalyst.

[0095] In the present invention, a "composition" includes a mixture of materials, including the corresponding composition and reaction products and decomposition products formed from the materials of the corresponding composition.

[0096] The co-catalyst may be any one known in the art, for example, one or more selected from the following formulae 4 to 6 may be used as the co-catalyst:

[0097] [Formula 4]

[0098] -[Al(R a )-O] m -

[0099] [Formula 5]

[0100] D(R a )3

[0101] [Formula 6]

[0102] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0103] In the above formula,

[0104] Each R a are independently: a halogen group; a hydrocarbon group of 1 to 20 carbon atoms; or a halogen-substituted hydrocarbon group of 1 to 20 carbon atoms,

[0105] m is an integer greater than or equal to 2,

[0106] D is aluminum or boron,

[0107] L is a neutral or cationic Lewis acid,

[0108] Z is an element in group 13,

[0109] Each A is independently an aryl group of 6 to 20 carbon atoms or an alkyl group of 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with a substituent, and

[0110] The substituent of A is: a halogen group; a hydrocarbon group of 1 to 20 carbon atoms; an alkoxy group of 1 to 20 carbon atoms; or an aryloxy group of 6 to 20 carbon atoms.

[0111] The compound represented by Formula 4 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples may include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is particularly preferred.

[0112] The compound represented by Formula 5 is not particularly limited, and preferred examples thereof may include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and is particularly preferably selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0113] Examples of the compound represented by Formula 6 may include: if Z is boron, for example, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -, dioctadecylmethylammonium tetra(phenyl)borate, dioctadecylmethylammonium tetra[3,5-bis(trifluoromethyl)phenyl]borate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetra(pentafluorophenyl)borate, diethylammonium tetra(pentafluorophenyl)borate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate , trimethylammonium tetra(o,p-xylyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, triphenylcarbonium tetra(pentafluorophenyl)borate, or a combination thereof; if Z is aluminum, for example, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethyl)aluminum The invention can be any of the following: triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or a combination thereof, without limitation.

[0114] In particular, the co-catalyst used in the present invention may be a compound represented by Formula 6, particularly dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

[0115] In addition, the transition metal compound represented by Formula 1 and the co-catalyst may be used in a supported type through a carrier. Silica or alumina may be used as the carrier without limitation.

[0116] The method for preparing an olefin polymer of the present invention is characterized by comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition.

[0117] In the present invention, "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. This general term for polymers includes the term homopolymer used to refer to polymers prepared from only one monomer and the term interpolymer specified below.

[0118] In the present invention, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different monomers. Thus, the general term of interpolymer refers to a polymer prepared from two different monomers, and includes commonly used copolymers and polymers prepared from two or more different monomers.

[0119] In the present invention, the olefin monomer may be one or more selected from the group consisting of ethylene, 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 and 1-eicosene, without limitation.

[0120] In particular, the olefin polymer of the present invention can be an olefin homopolymer or an olefin-α-olefin copolymer according to the type of the olefin monomer, and can preferably be an ethylene / α-olefin copolymer. In this case, those skilled in the art can appropriately select the amount of the α-olefin monomer as a comonomer according to the use, purpose, etc. of the olefin polymer, and it can be about 1 to 99mol%.

[0121] The catalyst composition can be injected after being dissolved or diluted in an aliphatic hydrocarbon solvent of 5 to 12 carbon atoms (e.g., pentane, hexane, heptane, nonane, decane, isomers thereof), an aromatic hydrocarbon solvent (e.g., toluene and benzene), or a hydrocarbon solvent substituted with a chlorine atom (e.g., dichloromethane and chlorobenzene) suitable for an olefin polymerization process. The solvent used herein can be preferably used after removing a small amount of water or air (which acts as a catalyst poison) by treating with a small amount of alkylaluminum, and can be treated by further using a co-catalyst.

[0122] The most preferred preparation method using the catalyst composition is a solution process, and if the composition is used with an inorganic support such as silica, it can also be applied to a slurry process or a gas phase process.

[0123] The polymerization may be performed by homopolymerizing one olefin monomer or copolymerizing two or more olefin monomers using one of a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

[0124] In addition, in order to remove moisture in the reactor during the polymerization reaction, an organic aluminum compound may be further injected, and the polymerization reaction may be carried out in the presence thereof. Specific examples of such organic aluminum compounds may include trialkylaluminum, dialkylaluminum halides, alkylaluminum dihalides, dialkylaluminum hydrides, or alkylaluminum sesquihalides, and more specific examples thereof may include Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(i-C4H9)2H, Al(C8H 17 )3、Al(C 12 H25 )3、Al(C2H5)(C 12 H 25 )2、Al(i-C4H9)(C 12 H 25 )2, Al(i-C4H9)2H, Al(i-C4H9)3, (C2H5)2AlCl, (i-C3H9)2AlCl or (C2H5)3Al2Cl3. Such an organoaluminum compound may be continuously injected into the reactor, or may be injected at a rate of about 0.1 to 10 mol per 1 kg of the reaction medium, which is injected into the reactor so as to properly remove moisture.

[0125] According to one embodiment of the present invention, the polymerization of olefin polymers can be carried out at a temperature of about 80-200°C (particularly a temperature of about 90-200°C, or a temperature of about 130-200°C) and a pressure of about 20-100 bar (particularly a pressure of about 20-50 bar, or a pressure of about 20-40 bar) for about 8 minutes to 2 hours.

[0126] Example

[0127] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[0128] Reagents and experimental conditions

[0129] All experiments were performed under an inert atmosphere using a standard glove box and Schlenk techniques. Toluene, hexane, and tetrahydrofuran (THF) were used after distillation from benzophenone ketal. Methylcyclohexane (anhydrous grade) for polymerization was purchased from Tokyo Chemical Industry (TCI) and used after purification using Na / K alloy. Sublimation grade HfCl4 was purchased from Streme and used as is. Ethylene-propylene gas mixtures were purified and used in a steel bomb reactor (2.0 L) using trioctyl aluminum (0.6 M in a mineral system).

[0130] Recorded using ECZ 600 equipment (JOEL) 1 H NMR (600 MHz) and 13 C NMR (150 MHz) spectrum.

[0131] Elemental analysis was performed at the Analytical Center of Asia University.

[0132] GPC data were analyzed using a PL-GPC 220 system equipped with a refractive index detector and two columns (Plarian Mixed-B 7.5 x 300 mm Varian [Polymer Lab]) at 160°C in 1,2,4-trichlorobenzene.

[0133] Preparation of transition metal compounds

[0134] Example 1

[0135]

[0136] (i) Preparation of ligand compound

[0137]

[0138] 2,6-Dicycloheptylaniline (1.94 g, 6.78 mmol) and 6-bromo-2-pyridinecarboxaldehyde (1.26 g, 6.78 mmol) were dissolved in toluene (8 mL) and molecular sieves were injected therein. The mixture was heated to 70 ° C overnight while stirring. After filtration, the solvent was removed in a rotary evaporator. A yellow solid (2.35 g, 77%) was obtained.

[0139] 1 H NMR (C6D6): δ8.42(s,1H,NCH),8.11(d,J=6.6Hz,1H),7.14(m,3H),6.84(d,J=8.4Hz, 1H), 6.64 (t, J = 7.2Hz, 1H), 2.94 (m, 2H), 1.92 (m, 4H), 1.62 (m, 8H), 1.45 (m, 12H) ppm.

[0140] 13 C NMR (C6D6): δ27.79,28.21,36.54,40.95,119.38,124.24,125.36,129.83,138.79,138.82,142.56,147.48,156.00,162.28ppm.

[0141] HRMS (EI): m / z calculated: ([M + ]C 26 H 33 BrN2) 452.1827. Found: 452.1830.

[0142] Under nitrogen, the above compound (2.35 g, 5.18 mmol), 1-naphthaleneboronic acid (0.936 g, 5.44 mmol), Na2CO3 (1.45 g, 13.6 mmol) and toluene (10 mL) were loaded into a Schlenk flask. A solution of (Ph3P)4Pd (16.2 mg, 0.0140 mmol) in a degassed H2O-EtOH mixture (1:1 [v / v], 5 mL) and toluene (2 mL) was injected. The two-phase solution was heated to 70 ° C overnight while stirring. After cooling to room temperature, water (15 mL) was added and the product was extracted with toluene (3×10 mL). The collected organic phase was dried over anhydrous MgSO4 and the solvent was removed in a rotary evaporator. A yellow solid (2.17 g, 84%) was obtained.

[0143] 1 H NMR (C6D6): δ8.70(s,1H,NCH),8.44(d,J=7.8Hz,1H),8.35(d,J=9.0Hz,1H),7.68(d,J=7.2Hz,1H),7.65(d,J=8.4 Hz,1H),7.53(d,J=7.2Hz,1H),7.28(m,4H),7.18(m,4H),3.11(m,2H),2.00(m,4H),1.66(m,8H),1.52(m,12H)ppm.

[0144] 13 C NMR(C6D6): δ27.87,28.23,36.66,40.94,119.14,124.22,125.13,125.49,126.16,126.27,126.61,126.7 3,128.35,128.74,129.39,131.83,134.54,137.18,138.54,139.06,147.97,155.11,159.84,164.29ppm.

[0145] HRMS (EI): m / z calculated: ([M + ]C 36 H 40 N2) 500.3191. Measured value: 500.3188.

[0146] To a Schlenk flask containing the above compound (1.00 g, 2.00 mmol) in diethyl ether (20 mL) was added dropwise 2-isopropylphenyl lithium (0.436 g, 3.46 mmol) dissolved in diethyl ether (8 mL). After stirring for 3 hours, an aqueous solution (10 mL) of ammonium chloride (0.30 g) was added thereto, and the product was extracted with diethyl ether (3×10 mL). The resulting oil was dried overnight at 60° C. in a high vacuum. A yellow solid (0.912 g, 74%) was obtained.

[0147] 1 H NMR (C6D6): δ8.24(m,1H),7.82(m,1H),7.63(m,1H),7.61(d,J=8.4Hz,1H),7.56(d,J =7.2Hz,1H),7.23(m,8H),7.11(m,4H),5.72(s,1H,NCH),4.46(s,1H,NH),3.27(septe t,J=7.2Hz,1H,CH),2.89(m,2H),1.82(m,2H),1.74(m,2H),1.58(m,8H),1.39(m,8H) ,1.24(m,2H),1.14(m,2H),1.00(d,J=6.6Hz,3H,CH3),0.98(d,J=6.0Hz,3H,CH3)ppm.

[0148] 13 C NMR (C6D6): δ23.60,24.53,27.83,27.95,27.98,29.10,37.22,37.50,40.34,67.23,119.93 122.91,124.31,124.59,125.34,125.77,126.03,126.53,126.58,126.72,127.56,128.53,1 29.34,131.84,134.63,136.97,138.74,142.09,142.95,144.24,146.46,159.23,164.01ppm.

[0149] HRMS (EI): m / z calculated: ([M + ]C 45 H 52 N2) 620.4130. Measured value: 620.4128.

[0150] (ii) Preparation of transition metal compounds

[0151] A Schlenk flask was charged with the ligand compound (0.241 g, 0.388 mmol) in toluene (1.5 g), and n-BuLi (0.25 mL, 1.6 M solution in hexane, 0.41 mmol) was added dropwise thereto at room temperature. After stirring for 1 hour, HfCl4 (0.125 g, 0.390 mmol) was added thereto as a solid. The reaction mixture was heated at 100°C and stirred for 2 hours. After cooling, MeMgBr (0.44 mL, 3.1 M solution in ether, 1.4 mmol) was injected, followed by stirring at room temperature overnight. The volatiles were removed via a vacuum tube, and the product was extracted with toluene (12 mL). The extract was obtained by filtration through diatomaceous earth. After removing the solvent by a vacuum tube, the residue was softened in hexane (2 mL) to obtain a yellow solid (0.211 g, 66%). Analysis 1 H NMR spectra and 13 C NMR spectrum, the results are shown in Figure 1 middle.

[0152] 1 H NMR (C6D6): δ8.59(d,J=7.2Hz,1H),8.34(d,J=8.4Hz,1H),7.78(d,J=8.4Hz,1H),7.69(d,J=6.6Hz,1H),7.58(d,J=7.2Hz,1H),7.47(m, 1H),7.32(m,1H),7.27(t,J=7.2Hz,1H),7.18(m,1H),7.09(m,5H),6.90(d,J=7.8Hz,1H),6.64(d,J=7.8Hz,1H),6.44(s,1H,NCH),3.49 (m,1H),3.04(t,J=10.2Hz,1H),2.89(septet,J=7.2Hz,1H,CH),2.32(m,1H),2.10(m,2H),1.90(m,1H),1.80(m,1H),1.62(m,10H),1.2 4(m,6H),1.19(d,J=7.2Hz,3H,CH3),1.13(m,2H),0.98(s,3H,HfCH3),0.79(d,J=6.6Hz,3H,CH3),0.69(s,3H,HfCH3),0.56(m,1H)ppm.

[0153] 13C NMR(C6D6): δ23.17,25.27,27.17,27.45,27.50,27.62,28.15,28.37,28.89,28.93,29.20, 37.01,38.22,39.24,39.57,40.30,41.05,62.44,66.71,77.22,119.61,120.23,124.18,12 5.30,125.43,125.51,126.04,126.97,127.14,129.94,130.04,130.20,130.85,134.31,13 5.81,140.70,141.02,143.95,144.35,146.27,147.83,148.19,164.39,171.96,206.43ppm.

[0154] Analytical calculation value (C 47 H 56 HfN2): C, 68.22; H, 6.82; N, 3.39%. Measured value: C, 68.44; H, 6.95; N, 3.07%.

[0155] Example 2

[0156]

[0157] (i) Preparation of ligand compound

[0158]

[0159] Prepared by the same method as in Example 1 using 2,6-dicyclohexylaniline (0.772 g, 3.00 mmol), 6-bromo-2-pyridinecarboxaldehyde (0.558 g, 3.00 mmol) and toluene (5 mL). A yellow solid (1.07 g, 84%) was obtained.

[0160] 1 H NMR (C6D6): δ8.41(s,1H,NCH),8.09(d,J=7.8Hz,1H),7.53(m,3H),6.85(d,J=7.8Hz,1H),6.63(t,J=7.8Hz,1H),2.74(m, 2H), 1.87 (d, J = 12Hz, 4H), 1.64 (d, J = 12.6Hz, 4H), 1.54 (d, J = 10.8Hz, 2H), 1.39 (quartet, J = 10.2Hz, 4H), 1.11 (m, 6H) ppm.

[0161] 13C NMR (C6D6): δ26.55,27.33,34.25,39.30,119.42,124.32,125.21,129.83,136.68,138.82,142.54,148.94,155.95,162.06ppm.

[0162] HRMS(EI): m / z calculated ([M + ]C 24 H 29 BrN2) 424.1514. Found: 424.1516.

[0163] The above compound (1.07 g, 2.51 mmol), 1-naphthaleneboronic acid (0.453 g, 2.64 mmol), Na2CO3 (0.700 g, 6.60 mmol), toluene (5 mL), degassed H2O / EtOH (1 mL, v / v, 1:1) and (Ph3P)4Pd (7.83 mg, 0.00678 mmol) in toluene (1 mL) were prepared by the same method as in Example 1. A lemon yellow oil (0.712 g, 60%) was obtained by column chromatography on silica gel using hexane and ethyl acetate (v / v, 90:3:1) containing a small amount of triethylamine.

[0164] 1 H NMR (C6D6): δ8.70(s,1H,NCH),8.41(d,J=7.8Hz,1H),8.31(d,J=7.8Hz,1H),7.68(d,J=7.2Hz,1H),7.65(d,J=7.8Hz,1H),7.54(d,J=7.2Hz,1H ),7.27(m,4H),7.20(m,4H),2.93(m,2H),1.90(d,J=12Hz,4H),1.61(d,J=13.2Hz,4H),1.50(d,J=12.6Hz,2H),1.38(m,4H),1.11(m,6H),ppm.

[0165] 13 C NMR(C6D6): δ26.63,27.38,34.35,39.36,119.21,124.32,124.98,125.50,126.15,126.21,126.64,126.7 5,128.15,128.73,129.38,131.81,134.52,136.94,137.14,138.52,149.48,155.13,159.79,164.05ppm.

[0166] HRMS(EI): m / z calculated ([M + ]C 34 H 36 N2)472.2878. Measured value: 472.2878.

[0167] The preparation was carried out by the same method as in Example 1 using the above compound (0.247 g, 0.523 mmol) and 2-isopropylphenyllithium (0.114 g, 0.904 mmol). A yellow solid (0.257 g, 83%) was obtained.

[0168] 1 H NMR (C6D6): δ8.24(m,1H),7.90(m,1H),7.64(m,1H),7.62(d,J=7.8Hz,1H),7.56(d,J=7.2Hz,1H),7 .26(m,3H),7.22(m,4H),7.11(m,5H),5.62(d,J=5.4Hz,1H,NCH),4.59(d,J=5.4Hz,1H,NH),3.31(se ptet,J=7.2Hz,1H,CH),2.74(m,2H),1.79(d,J=7.8Hz,2H),1.64(m,4H),1.54(m,4H),1.32(m,4H), 1.08(m,2H),1.03(d,J=6.6Hz,3H,CH3),1.00(m,1H),0.980(d,J=6.6Hz,3H,CH3),0.921(m,3H)ppm.

[0169] 13 C NMR(C6D6): δ23.78,24.45,26.63,27.42,27.54,28.96,34.77,35.08,39.01,67.64,119.99,122.89,124.13,124.80,125.36,125.77,126. 08,126.46,126.56,126.71,127.58,128.55,129.35,131.84,134.64, 136.94,138.77,141.88,142.24,144.97,146.32,159.28,163.74ppm.

[0170] HRMS(EI): m / z calculated ([M + ]C 43 H 48 N2) 592.3817. Measured value: 592.3819.

[0171] (ii) Preparation of transition metal compounds

[0172] The preparation was carried out by the same method as in Example 1 using the ligand compound (0.150 g, 0.253 mmol), n-BuLi (0.17 mL, 1.6 M hexane solution, 0.27 mmol), HfCl4 (0.0814 g, 0.254 mmol), MeMgBr (0.29 mL, 3.1 M ether solution, 0.89 mmol) and toluene (1.5 g). A yellow solid (0.128 g, 63%) was obtained. Analysis 1 HNMR spectra and 13 C NMR spectrum, the results are shown in Figure 2 middle.

[0173] 1 H NMR (C6D6): δ8.58(d,J=7.8Hz,1H),8.29(d,J=8.4Hz,1H),7.79(d,J=7.8Hz,1H),7.71(d,J=7.2Hz,1H),7.54(d,J=7.8Hz,1 H),7.46(m,1H),7.30(m,2H),7.15(m,3H),7.09(m,3H),6.88(t,J=7.8Hz,1H),6.62(d,J=8.4Hz,1H),6.48(s,1H,NCH),3.39 (m,1H),2.92(m,2H),2.15(d,J=13.8Hz,1H),2.10(d,J=13.8Hz,2H),1.80(m,2H),1.65(m,3H),1.29(m,6H),1.17(d,J=7.2 Hz,3H,CH3),1.07(m,3H),0.99(s,3H,HfCH3),0.95(m,2H),0.73(d,J=7.2Hz,3H,CH3),0.70(s,3H,HfCH3),0.23(m,1H)ppm.

[0174] 13C NMR(C6D6): δ23.31,25.04,26.63,26.74,27.70,27.76,27.81,28.29,28.89,35.00,35. 66,36.62,37.02,38.13,40.88,62.53,67.00,77.27,119.30,120.30,124.29,125.52,1 25.60,125.97,126.95,127.06,127.73,129.91,130.00,130.09,130.85,134.36,135.8 0,140.73,140.89,144.02,145.12,146.31,146.38,146.49,164.46,170.79,206.40ppm.

[0175] Analytical calculation value (C 45 H 52 HfN2): C, 67.61; H, 6.56; N, 3.50%. Measured value: C, 67.98; H, 6.88; N, 3.19%.

[0176] Example 3

[0177]

[0178] (i) Preparation of ligand compound

[0179]

[0180] Prepared by the same method as in Example 1 using 2,6-dicyclopentylaniline (1.69 g, 7.36 mmol), 6-bromo-2-pyridinecarboxaldehyde (1.37 g, 7.36 mmol) and toluene (12 mL). Obtained a yellow solid (1.07 g, 84%). Obtained an analytically pure compound by recrystallization in hexane and toluene at -30°C.

[0181] 1 H NMR(C6D6): δ8.36(s,1H,NCH),8.03(d,J=7.8Hz,1H),7.13(m,3H),6.84(d,J=7.8Hz ,1H),6.60(t,J=7.2Hz,1H),3.13(m,2H),1.91(m,4H),1.59(m,8H),1.40(m,4H)ppm. 13CNMR(C6D6): δ26.05,34.72,40.82,119.55,124.11,125.21,129.78,135.28,138.79,142.45,150.38,155.90,162.32ppm.

[0182] HRMS(EI): m / z calculated ([M + ]C 22 H 25 BrN2) 396.1201. Found: 396.1203.

[0183] Prepared by the same method as in Example 1 using the above compound (1.63 g, 4.09 mmol), 1-naphthaleneboronic acid (0.739 g, 4.30 mmol), NaCO (1.14 g, 10.8 mmol), toluene (8 mL), degassed HO / EtOH (3.5 mL, v / v, 1:1) and (pH3P)4Pd (12.8 mg, 0.0111 mmol) in toluene (1 mL). Analytically pure compound was obtained by recrystallization in hexane and toluene at -30°C. Obtained a yellow solid (1.24 g, 68%).

[0184] 1 H NMR (C6D6): δ8.66(s,1H,NCH),8.39(d,J=7.2Hz,1H),8.28(m,1H),7.68(m,1H),7.65(d,J=8.4Hz,1H),7.56(d,J=7.2Hz,1H) ,7.24(m,6H),7.17(s,1H),7.14(d,J=8.4Hz,1H),3.30(quintet,d,J=7.2Hz,2H),2.00(m,4H),1.64(m,8H),1.44(m,4H)ppm.

[0185] 13 C NMR(C6D6): δ26.07,34.78,40.94,119.31,124.12,124.98,125.53,126.16,126.18,126.65,126. 77,128.74,129.38,131.79,134.51,135.47,137.07,138.57,150.98,155.14,159.73,164.32ppm.

[0186] HRMS(EI): m / z calculated ([M + ]C 32 H 32N2)444.2565. Measured value: 444.2561.

[0187] The preparation was carried out by the same method as in Example 1 using the above compound (1.20, 2.70 mmol) and 2-isopropylphenyllithium (0.589 g, 4.66 mmol). A lemon yellow solid (1.38 g, 91%) was obtained.

[0188] 1 H NMR (C6D6): δ8.22(m,1H),7.77(d,J=8.4Hz,1H),7.65(m,1H),7.61(d,J=8.4Hz,1H),7.53(d,J=7.2 Hz,1H),7.27(m,3H),7.19(m,1H),7.13(m,6H),7.07(d,J=7.8Hz,1H),7.03(d,J=7.2Hz,1H),5.74( s,1H,NCH),4.95(s,1H,NH),3.34(septet,J=7.2Hz,1H,CH),3.26(m,2H),1.87(m,2H),1.71(m,2H) ,1.61(m,4H),1.48(m,4H),1.32(m,4H),1.03(d,J=6.6Hz,3H,CH3),0.981(d,J=6.6Hz,3H,CH3)ppm.

[0189] 13 C N-MR(C6D6): δ23.83,24.39,26.06 26.08,28.94,35.54,35.62,40.58,67.19,120.19,122.87,124.25,124.69,125.39,125.89,126.10,126.30,126.58,126. 60,127.65,128.59,128.63,129.31,131.86,134.60,136.86,138.87,140.76,141.40,145.93,146.72,159.08,163.23ppm.

[0190] HRMS(EI): m / z calculated ([M + ]C 41 H 44 N2) 564.3504. Measured value: 564.3507.

[0191] (ii) Preparation of transition metal compounds

[0192] The preparation was carried out by the same method as in Example 1 using the ligand compound (0.300 g, 0.531 mmol), N-BuLi (0.348 mL, 1.6 M hexane solution, 0.560 mmol), HfCl4 (0.171 g, 0.533 mmol), MeMgBr (0.60 mL, 3.1 M ether solution, 1.9 mmol) and toluene (3.0 g). A yellow solid (0.278 g, 68%) was obtained.

[0193] 1 H NMR (C6D6): δ8.59(d,J=7.8Hz,1H),8.24(d,J=8.4Hz,1H),7.81(d,J=7.2Hz,1H),7.71(d,J=7.8Hz,1H),7.47(d,J=8.4Hz,1H), 7.30(m,3H),7.21(m,2H),7.11(m,2H),7.01(m,2H),6.80(t,J=7.8Hz,1H),6.62(s,1H,NCH),6.52(d,J=7.8Hz,1H),3.74(m,1H) ,3.55(quintet,J=8.4Hz,1H),2.90(septet,J=6.6Hz,1H,CH),2.38(m,1H),2.28(m,1H),2.13(m,1H),1.69(m,8H),1.29(m,3H ),1.19(d,J=7.2Hz,3H,CH3),1.04(m,1H),0.92(s,3H,HfCH3),0.72(d,J=6.6Hz,3H,CH3),0.70(s,3H,HfCH3),0.29(m,1H)ppm.

[0194] 13 C NMR(C6D6): δ23.22,25.23,26.23,26.31,27.15,27.45,28.66,36.27,37.46,38.06,38.54 ,40.40,41.01,62.13,66.83,119.52,120.37,124.24,125.09,125.26,125.51,125.61,125 .86,126.17,126.50,126.63,126.95,129.88,129.97,130.00,130.78,134.11,134.30,135 .73,140.79,140.87,144.06,144.80,145.93,146.96,146.99,164.46,170.79,206.11ppm.

[0195] Analytical calculation value (C 43 H 48 HfN2): C, 66.96; H, 6.27; N, 3.63%. Measured value: C, 67.12; H, 6.59; N, 3.42%.

[0196] Example 4

[0197]

[0198] (i) Preparation of ligand compound

[0199]

[0200] Prepared by the same method as in Example 1 using 2,6-di(3-pentyl)aniline (2.2 g, 9.42 mmol), 6-bromo-2-pyridinecarboxaldehyde (1.75 g, 9.42 mmol) and toluene (15 mL). A yellow solid (3.30 g, 87%) was obtained.

[0201] 1 H NMR (C6D6): δ8.42(s,1H,NCH),8.03(d,J=7.2Hz,1H),7.11(m,1H),7.03(d,J=7.8Hz,2H),6.89(d,J=8.4Hz,1H),6.6 6(t,J=8.4Hz,1H), 2.66(quintet,J=7.8Hz,2H), 1.54(quintet,J=7.2Hz,8H,CH2), 0.80(t,J=7.2Hz,12H,CH3)ppm.

[0202] 13 C NMR (C6D6): δ12.37,29.61,42.74,119.42,124.35,125.20,129.79,134.12,138.81,142.50,151.86,155.93,162.63ppm.

[0203] HRMS(EI): m / z calculated ([M + ]C 22 H 29 BrN2) 400.1514. Measured value: 400.1512.

[0204] Prepared by the same method as in Example 1 using compound (1.06 g, 2.63 mmol), 1-naphthaleneboronic acid (0.475 g, 2.76 mmol), Na2CO3 (0.733 g, 6.92 mmol), toluene (5 mL), degassed H2O / EtOH (2.3 mL, v / v, 1:1) and a toluene (1 mL) solution of (Ph3P)4Pd (8.21 mg, 0.0711 mmol). Obtained a yellow solid (1.00 g, 85%).

[0205] 1 H NMR (C6D6): δ8.71(s,1H,NCH),8.37(d,J=7.2Hz,1H),8.31(m,1H),7.67(t,J=4 .2Hz,1H),7.65(d,J=8.4Hz,1H),7.58(d,J=7.2Hz,1H),7.28(m,4H),7.21(d,J= 7.8Hz,1H),7.14(d,J=7.2Hz,1H),7.07(d,J=7.8Hz,2H),2.84(quintet,J=6.6Hz,2H,CH),1.60(quintet,J=7.8Hz,8H,CH2),0.867(t,J=7.2Hz,12H,CH3)ppm.

[0206] 13 C NMR(C6D6): δ12.44,29.69,42.80,119.18,124.33,124.96,125.53,126.17,126.66,126.75,128. 21,128.73,129.37,131.79,134.34,134.51,137.05,138.58,152.45,155.10,159.75,164.66ppm.

[0207] HRMS(EI): m / z calculated ([M + ]C 32 H 36 N2) 448.2878. Measured value: 448.2881.

[0208] The preparation was carried out by the same method as in Example 1 using the above compound (0.763 g, 1.70 mmol) and 2-isopropylphenyllithium (0.371 g, 2.94 mmol). A lemon yellow solid (0.878 g, 91%) was obtained.

[0209] 1H NMR (C6D6): δ8.28(m,1H),7.70(d,J=7.8Hz,1H),7.64(m,1H),7.61(d,J=8.4Hz,1H),7.52(d,J=7.8Hz,1H),7.27(m,3H),7. 18(m,4H),7.11(m,3H),7.01(d,J=7.8Hz,2H),5.72(d,J=7.8Hz,1H,NCH),4.83(d,J=7.8Hz,1H,NH),3.37(septet,J=6.6Hz, 1H,CH),2.81(m,2H),1.60(d,J=7.2Hz,2H,CH2),1.54(d,J=7.2Hz,2H,CH2),1.41(d,J=7.2Hz,2H,CH2),1.32(d,J=7.2Hz,2H ,CH2),1.01(d,J=6.6Hz,3H,CH3),0.940(d,J=6.6Hz,3H,CH3),0.793(t,J=6.6Hz,6H,CH3),0.700(t,J=6.6Hz,6H,CH3)ppm.

[0210] 13 C NMR(C6D6): δ12.22,12.41,23.80,24.42,28.98,29.41,29.72,42.01,67.19,120.14,122.83,124.31,125.32,126.04,126.42,126. 59,126.72,127.67,128.55,128.74,129.36,131.89,134.63,136.96,138.74,140.66,141.51,146.78,146.85,159.04,163.40ppm.

[0211] HRMS(EI): m / z calculated ([M + ]C 41 H 48 N2) 568.3817. Measured value: 568.3820.

[0212] (ii) Preparation of transition metal compounds

[0213] The preparation was carried out by the same method as in Example 1 using the ligand compound (0.205 g, 0.361 mmol), N-BuLi (0.24 mL, 1.6 M hexane solution, 0.38 mmol), HfCl4 (0.116 g, 0.362 mmol), MeMgBr (0.41 mL, 3.1 M ether solution, 1.3 mmol) and toluene (2.0 g). A dark yellow solid (0.167 g, 60%) was obtained.

[0214] 1 H NMR (C6D6): δ8.61(d,J=7.8Hz,1H),8.28(d,J=8.4Hz,1H),7.81(d,J=7.8Hz,1H),7.72(d,J=8.4Hz,1H),7.50(m,2H),7.31(m ,2H),7.12(m,3H),7.05(m,3H),6.84(t,J=7.8Hz,1H),6.62(d,J=8.4Hz,1H),6.53(s,1H,NCH),3.55(m,1H,CH),2.92(septe t,J=7.2Hz,1H,CH),2.76(m,1H,CH),1.94(m,1H),1.77(m,5H),1.48(m,1H),1.18(d,J=6.6Hz,3H,CH3),1.05(t,J=7.8Hz,3H ,CH3),1.02(s,3H,HfCH3),0.98(t,J=7.2Hz,3H,CH3),0.80(m,6H,HfCH3,CH3),0.73(t,J=7.8Hz,3H,CH3),0.56(m,4H)ppm.

[0215] 13 C NMR(C6D6): δ11.31,12.37,13.39,13.58,23.35,25.33,27.89,28.25,28.77,31.11, 39.90,43.27,63.34,67.51,77.52,119.33,120.26,124.25,124.95,125.49,125.53, 125.67,125.79,126.93,127.02,129.92,129.99,130.18,130.78,134.48,135.74,1 40.77,141.35,143.89,144.80,144.89,146.21,147.87,164.29,170.75,205.95ppm.

[0216] Analytical calculation value (C 43 H52 HfN2): C, 66.61; H, 6.76; N, 3.61%. Measured value: C, 66.54; H, 6.88; N, 3.80%.

[0217] Example 5

[0218]

[0219] (i) Preparation of ligand compound

[0220]

[0221] Prepared by the same method as in Example 1 using 2,6-diphenylaniline (2.00 g, 8.15 mmol), 6-bromo-2-pyridinecarboxaldehyde (1.52 g, 8.15 mmol) and toluene (10 mL).

[0222] 1 H NMR (C6D6): δ8.09(s,1H,NCH),7.63(d,J=7.8Hz,1H),7.38(d,J=7.2Hz,4H),7.29(d,J=7.8H z, 2H), 7.07 (m, 5H), 6.97 (t, J = 7.8Hz, 2H), 6.64 (d, J = 7.2Hz, 1H), 6.42 (t, J = 7.2Hz, 1H) ppm.

[0223] 13 C NMR (C6D6): δ119.44,125.53,127.06,128.34,129.47,130.42,130.46,133.86,138.36,140.34,142.02,148.13,155.59,164.42ppm.

[0224] HRMS(EI): m / z calculated ([M + ]C 24 H 17 BrN2) 412.0575. Found: 412.0572.

[0225] Prepared by the same method as in Example 1 using the above compound (2.08 g, 5.04 mmol), 1-naphthaleneboronic acid (0.910 g, 5.29 mmol), Na2CO3 (1.40 g, 13.3 mmol), toluene (8 mL), degassed H2O / EtOH (4.6 mL, v / v, 1:1) and a toluene (2 mL) solution of (Ph3P)4Pd (15.7 mg, 0.0136 mmol). Obtained a yellow solid (2.08 g, 90%).

[0226] 1 H NMR (C6D6): δ8.35(s,1H,NCH),8.04(m,1H),7.98(d,J=7.8Hz,1H),7.65(m,1H),7.60(d,J=7.8Hz,1H),7.49(d, J=7.8Hz,4H),7.34(d,J=7.8Hz,2H),7.32(d,J=7.2Hz,1H),7.28(m,2H),7.20(t,J=7.8Hz,1H),7.08(m,9H)ppm.

[0227] 13 C NMR(C6D6): δ119.22,125.37,126.01,126.38,126.56,126.94,128.33,128.58,129.21,130.50 ,130.60,131.71,134.10,134.44,136.75,138.41,140.65,148.55,154.69,159.29,166.55ppm.

[0228] HRMS(EI): m / z calculated ([M + ]C 34 H 24 N2) 460.1939. Measured value: 460.1938.

[0229] The compound (0.459 g, 0.996 mmol) and 2-isopropylphenyllithium (0.217 g, 1.72 mmol) were used to prepare by the same method as in Example 1. A white solid (0.428 g, 74%) was obtained.

[0230] 1 H NMR (C6D6): δ8.05(d,J=8.4Hz,1H),7.68(d,J=8.4Hz,1H),7.64(d,J=8.4Hz,1H),7. 42(d,J=8.4Hz,4H),7.27(m,5H),7.14(d,J=7.2Hz,2H),7.01(m,10H),6.89(m,2H),6 .71(d,J=7.8Hz,1H),5.82(d,J=10.8Hz,1H,NCH),5.22(d,J=10.8Hz,1H,NH),2.97(s eptet,J=6.0Hz,1H,CH),1.01(d,J=6.0Hz,3H,CH3),0.872(d,J=6.0Hz,3H,CH3)ppm.

[0231] 13C NMR(C6D6): δ23.96,24.65,28.57,61.56,119.97,120.91,122.67,125.36,125.52,125.94,126.19,126.48,162.87,127.11,127.34,127.7 1,128.44,128.67,129.03,129.71,130.99,131.84,133.29,134.51, 136.40,138.97,140.04,141.43,143.23,146.44,158.85,162.62ppm.

[0232] HRMS(EI): m / z calculated ([M + ]C 43 H 36 N2) 580.2878. Measured value: 580.2881.

[0233] (ii) Preparation of transition metal compounds

[0234] The preparation was carried out by the same method as in Example 1 using the ligand compound (0.199 g, 0.343 mmol), N-BuLi (0.226 mL, 1.6 M hexane solution, 0.362 mmol), HfCl4 (0.110 g, 0.345 mmol), MeMgBr (0.39 mL, 3.1 M ether solution, 1.2 mmol) and toluene (2.0 g). A dark yellow solid (0.178 g, 66%) was obtained.

[0235] 1 H NMR (C6D6): δ8.54(d,J=7.2Hz,1H),8.33(d,J=9.6Hz,1H),7.76(d,J=8.4Hz,1H),7.71(d,J=8.4Hz ,1H),7.57(d,J=7.8Hz,2H),7.51(d,J=7.8Hz,1H),7.27(m,6H),7.11(m,4H),7.01(t,J=7.2Hz,1H) ,6.96(d,J=4.2Hz,2H),6.76(m,3H),6.68(m,2H),6.34(s,1H,NCH),6.11(d,J=7.8Hz,1H),3.15(s eptet,J=6.6Hz,1H),1.22(d,J=6.6Hz,3H,CH3),0.93(m,6H,HfCH3,CH3),-0.08(s,3H,HfCH3)ppm.

[0236] 13C NMR(C6D6): δ23.31,25.55,29.13,64.26,65.18,74.07,118.94,119.86,123.91, 124.29,125.49,125.74,126.78,126.91,126.94,127.16,128.52,129.69,130.00 ,130.72,130.75,131.44,131.58,131.95,134.36,135.72,138.33,139.89,140. 88,141.19,141.51,143.09,143.65,146.42,147.03,163.90,170.58,206.23ppm.

[0237] Analytical calculation value (C 45 H 40 HfN2): C, 68.65; H, 5.12; N, 3.56%. Measured value: C, 68.37; H, 5.49; N, 3.25%.

[0238] Example 6

[0239]

[0240] (i) Preparation of ligand compound

[0241]

[0242] Under nitrogen, 2,6-dibromopyridine (7 g, 29.5 mmol), 1-naphthaleneboric acid (2.54 g, 14.8 mmol), Na2CO3 (3.91 g, 36.9 mmol) and toluene (23 mL) were loaded into a Schlenk flask. Then, a degassed H2O-EtOH mixture (1:1 [v / v], 4.67 mL) and a toluene (5 mL) solution of (Ph3P)4Pd (85.3 mg, 0.0739 mmol) were injected therein. The two-phase solution was heated to 70 ° C and stirred vigorously overnight. After cooling to room temperature, the organic phase was collected and washed with H2O (20 mL). The product was extracted with toluene (3×20 mL). The organic phase thus collected was dried with anhydrous MgSO4 and the solvent was removed in a rotary evaporator. The product was separated by silica gel column chromatography using a mixture of hexane and toluene (1:2, v / v). A white solid (3.1 g, 74%) was obtained.

[0243] 1H NMR (C6D6): δ8.18(d,J=8.4Hz,1H),7.64(d,J=8.4Hz,1H),7.62(d,J=8.4Hz,1H),7.44(d,J=6. 6Hz, 1H), 7.23 (m, 3H), 6.97 (d, J = 8.4Hz, 1H), 6.92 (d, J = 7.2Hz, 1H), 6.68 (t, J = 7.8Hz, 1H) ppm.

[0244] 13 C NMR (C6D6): δ 123.76, 125.41, 125.81, 126.21, 126.30, 126.94, 128.35, 128.70, 129.68, 131.41, 134.35, 137.31, 138.37, 142.22, 160.41 ppm. Calculated value (C 15 H 10 BrN): C, 63.40; H, 3.55; N, 4.93%. Found: C, 63.39; H, 3.66; N, 4.62%.

[0245] The above compound (0.609 g, 2.14 mmol) was dissolved in THF (8 mL) and cooled to about -78 ° C. t-BuLi (2.52 mL, 1.7 M hexane solution, 4.3 mmol) was introduced, and the mixture was stirred at about -78 ° C for 2 hours. Then, a THF (16 mL) solution of 2,6-(cycloheptyl) 2C6H3N=C(H)Ph (0.800 g, 2.14 mmol) was added thereto. After stirring at about -78 ° C for 3 hours, the temperature of the resulting solution was slowly raised to room temperature. After stirring overnight, water (10 mL) was added and the product was extracted with ethyl acetate (3×10 mL). The organic phase was collected and dried with MgSO4. The solvent was removed in a rotary evaporator. A lemon yellow solid (0.412 g, 63%) was obtained by column chromatography on silica gel using hexane and toluene (v / v, 75:25:1) containing a small amount of triethylamine.

[0246] 1 H NMR (C6D6): δ8.27(m,1H),7.67(m,2H),7.60(d,J=7.2Hz,3H),7.28(m,3H),7.18(m,2H),7.10(m,6H),6.89(m,1H),5.3 2(d,J=7.2Hz,1H,NCH),5.18(d,J=7.8Hz,1H,NH),3.04(m,2H),1.81(m,4H),1.55(m,8H),1.37(m,8H),1.18(m,4H)ppm.

[0247] 13 C NMR(C6D6): δ27.65,27.84,27.99,37.20,37.54,40.48,70.57,120.30,123.23,124.06,124.56,125.34,126.15,126.59 ,126.75,127.17,128.58,128.63,129.40,131.86,134.65,137.10,138.82,142.71,144.07,144.87,159.43,162.82ppm.

[0248] HRMS(EI): m / z calculated ([M + ]C 42 H 46 N2) 578.3661. Measured value: 578.3660.

[0249] (ii) Preparation of transition metal compounds

[0250] The preparation was carried out by the same method as in Example 1 using the ligand compound (0.120 g, 0.207 mmol), N-BuLi (1.6 M hexane solution, 0.129 mL, 0.219 mmol), HfCl4 (66.7 mg, 0.208 mmol) and MeMgBr (0.24 mL, 3.0 M ether solution, 0.73 mmol). A yellow solid (0.106 g, 65%) was obtained.

[0251] 1 H NMR (C6D6): δ8.58(d,J=7.2Hz,1H),8.32(d,J=8.4Hz,1H),7.78(d,J=7.2Hz,1H),7.69(d,J=7.8Hz,1 H),7.57(d,J=7.2Hz,1H),7.32(m,1H),7.27(m,1H),7.20(m,3H),7.05(m,5H),6.87(t,J=7.8Hz,1H), 6.47(d,J=7.2Hz,1H),5.74(s,1H,NCH),3.46(m,1H),2.92(m,1H),2.33(m,1H),2.11(m,2H),1.89(m, 1H),1.82(m,1H),1.62(m,9H),1.25(m,9H),0.97(s,3H,HfCH3),0.66(s,3H,HfCH3),0.63(m,1H)ppm.

[0252] 13C NMR(C6D6): δ27.23,27.44,27.84,28.12,28.28,28.90,29.02,37.49,37.68,39.8 5,39.93,40.29,41.19,62.50,66.67,84.17,119.73,120.33,124.12,125.33,125. 46,125.52,126.16,127.00,128.93,129.16,129.94,130.03,130.80,134.27,135 .78,140.78,143.84,143.92,143.95,148.04,148.32,164.51,170.22,206.25ppm.

[0253] Analytical calculation value (C 44 H 50 HfN2): C, 67.29; H, 6.42; N, 3.57%. Measured value: C, 67.18; H, 6.44; N, 3.31%.

[0254] Example 7

[0255]

[0256] (i) Preparation of ligand compound

[0257]

[0258] The product was prepared by the same method as in Example 6 using 2-bromo-6-(naphthalen-1-yl)pyridine (0.156 g, 0.548 mmol), t-BuLi (0.65 mL, 1.7 M hexane solution, 1.1 mmol), 2,6-(cyclohexyl)2C6H3N=C(H)Ph (0.189 g, 0.548 mmol) and THF (7 mL). A pale yellow solid (0.208 g, 69%) was obtained by column chromatography on silica gel using hexane and toluene (v / v, 75:25:1) containing a small amount of triethylamine.

[0259] 1H NMR (C6D6): δ8.30(m,1H),7.67(m,2H),7.61(d,J=7.8Hz,3H),7.28(m,3H),7.19(m,2 H),7.10(m,6H),6.83(quintet,J=4.2Hz,1H),5.31(s,1H,NCH),5.24(s,1H,NH),2.89 (m,2H),1.75(d,J=12.6Hz,2H),1.70(d,J=12.6Hz,2H),1.59(d,J=13.2Hz,2H),1.55( d,J=12.6Hz,2H),1.50(d,J=12.6Hz,2H),1.32(m,4H),1.09(m,2H),0.922(m,4H)ppm.

[0260] 13 C NMR (C6D6): δ 26.63, 27.18, 27.49, 34.75, 35.12, 38.98, 70.71, 120.32, 123.19, 123.81, 124.75, 125.38, 126.18, 126.59, 126.71, 127.19, 127.78, 128.60, 129.40, 131.85, 134.64, 137.11, 138.88, 141.90, 144.69, 144.94, 159.38, 162.73 ppm. HRMS (EI): m / z calculated ([M + ]C 40 H 42 N2) 550.3348. Measured value: 550.3350.

[0261] (ii) Preparation of transition metal compounds

[0262] Prepared by the same method as in Example 6 using HfCl4 (0.124 g, 0.387 mmol), MeMgBr (0.51 mL, 3.0 M ether solution, 1.6 mmol) and ligand compound (0.142 g, 0.258 mmol). Obtained a yellow solid (0.140 g, 72%).

[0263] 1H NMR (C6D6): δ8.56(d,J=8.4Hz,1H),8.29(d,J=7.8Hz,1H),7.78(d,J=7.8Hz,1H),7.70(d,J=7.8Hz,1H),7.54(d, J=7.2Hz,1H),7.30(m,2H),7.19(m,2H),7.17(m,1H),7.06(m,5H),6.88(t,J=7.8Hz,1H),6.43(d,J=7.2Hz,1H), 5.79(s,1H,NCH),3.37(m,1H),2.77(m,1H),2.18(d,J=12.6Hz,1H),2.07(m,2H),1.84(d,J=12.0Hz,1H),1.77(d ,J=12.0Hz,1H),1.54(m,8H),1.14(m,3H),0.96(s,3H,HfCH3),0.89(m,3H),0.65(s,3H,HfCH3),0.34(m,1H)ppm.

[0264] 13 C NMR(C6D6): δ26.65,26.74,27.77,28.28,35.17,35.59,36.23,38.00,38.21,4 0.83,62.51,66.95,84.22,119.46,120.38,124.19,125.52,125.61,125.79,12 6.05,126.97,127.76,128.92,129.11,129.92,130.00,130.81,134.33,135.78 ,140.78,143.87,144.00,145.33,145.79,146.65,164.58,170.16,206.09ppm.

[0265] Analytical calculation value (C 42 H 46 HfN2): C, 66.61; H, 6.12; N, 3.70%. Measured value: C, 66.89; H, 6.45; N, 3.51%.

[0266] Example 8

[0267]

[0268] (i) Preparation of ligand compound

[0269]

[0270] The product was prepared by the same method as in Example 6 using 2-bromo-6-(naphthalen-1-yl)pyridine (0.493 g, 1.74 mmol), t-BuLi (2.0 mL, 1.7 M hexane solution, 3.5 mmol), 2,6-(cyclopentyl)2C6H3N=C(H)Ph (0.551 g, 1.74 mmol) and THF (20 mL). A pale yellow solid (0.637 g, 70%) was obtained by column chromatography on silica gel using hexane and toluene (v / v, 75:25:1) containing a small amount of triethylamine.

[0271] 1 H NMR (C6D6): δ8.24(m,1H),7.67(m,2H),7.63(d,J=7.2Hz,2H),7.56(d,J=6.6Hz ,1H),7.31(d,J=8.4Hz,1H),7.27(m,2H),7.18(m,2H),7.12(d,J=6.6Hz,2H),7. 05(m,4H),6.75(m,1H),5.60(d,J=7.2Hz,1H,NCH),5.36(d,J=8.4Hz,1H,NH),3. 37(m,2H),1.87(m,2H),1.78(m,2H),1.58(m,4H),1.49(m,4H),1.26(m,4H)ppm.

[0272] 13 C NMR(C6D6): δ25.93,25.98,35.46,35.53,40.64,70.33,120.66,123.17,123.59,124.68,125.42,126.18,126.53,126.61,12 7.21,127.68,127.83,128.59,128.63,129.35,131.79,134.59,136.94,138.95,139.70,144.67,146.13,159.25,162.51ppm.

[0273] HRMS(EI): m / z calculated ([M + ]C 38 H 38 N2) 522.3035. Measured value: 522.3033.

[0274] (ii) Preparation of transition metal compounds

[0275] Prepared by the same method as in Example 6 using HfCl4 (0.184 g, 0.587 mmol), MeMgBr (0.76 mL, 3.0 M ether solution, 2.4 mmol) and ligand compound (0.200 g, 0.383 mmol). Obtained a yellow solid (0.226 g, 81%).

[0276] 1 H NMR (C6D6): δ8.57(d,J=7.8Hz,1H),8.24(d,J=8.4Hz,1H),7.80(d,J=7.8Hz,1H),7.71(d,J=7.2Hz,1H),7.4 7(d,J=8.4Hz,1H),7.27(m,3H),7.19(t,J=7.8Hz,1H),7.14(m,1H),7.01(m,5H),6.80(t,J=4.2Hz,1H),6.4 0(d,J=7.8Hz,1H),5.93(s,1H,NCH),3.74(m,1H),3.43(quintet,J=9.6Hz,1H),2.40(m,1H),2.20(m,1H),2 .10(m,1H),1.69(m,8H),1.33(m,3H),1.06(m,1H),0.91(s,3H,HfCH3),0.66(s,3H,HfCH3),0.34(m,1H)ppm.

[0277] 13 C NMR(C6D6): δ26.18,26.22,26.86,27.19,36.74,37.53,39.17,40.67,41.0 4,62.26,66.85,84.05,119.56,120.49,124.17,125.10,125.51,125.85,12 6.26,126.96,128.91,129.04,129.91,129.98,130.74,134.15,135.73,14 0.82,143.94,144.04,145.01,145.67,146.68,164.60,170.03,205.87ppm.

[0278] Analytical calculation value (C 40 H 42 HfN2): C, 65.88; H, 5.80; N, 3.84%. Measured value: C, 65.94; H, 5.72; N, 3.75%.

[0279] Comparative Example 1

[0280]

[0281] The above compounds are prepared according to known methods.

[0282] Comparative Example 2

[0283]

[0284] (i) Preparation of ligand compound

[0285]

[0286] Prepared by the same method as in Example 1 using 2,6-diethylaniline (1.50 g, 10.1 mmol), 6-bromo-2-pyridinecarboxaldehyde (1.87 g, 10.1 mmol) and toluene (15 mL). A lemon yellow solid (2.51 g, 79%) was obtained.

[0287] 1 H NMR (C6D6): δ8.23(s,1H,NCH),7.96(d,J=7.2Hz,1H),7.01(s,3H),6.87(d,J=7.8Hz,1H) ,6.62(t,J=8.4Hz,1H),2.44(quartet,J=7.2Hz,4H,CH2),1.06(t,J=7.8Hz,6H,CH3)ppm.

[0288] 13 C NMR (C6D6): δ14.88,25.13,119.46,125.02,126.84,129.70,132.90,138.73,142.29,149.89,155.89,162.16ppm.

[0289] HRMS(EI): m / z calculated ([M + ]C 16 H 17 BrN2) 316.0575. Found: 316.0574.

[0290] Use above-mentioned compound (2.34g, 7.02mmol), 1-naphthaleneboronic acid (1.27g, 7.37mmol), NaCO (1.96g, 18.5mmol), toluene (10mL), degassed HO / EtOH (6.5mL, v / v, 1:1) and (pH3P)4Pd (21.9mg, 0.0190mmol) in toluene (2mL) solution to prepare by the same method as in Example 1. Analytically pure compound was obtained by recrystallization in hexane and toluene at -30°C. Obtain yellow solid (2.35g, 92%).

[0291] 1 H NMR (C6D6): δ8.56(s,1H,NCH),8.33(d,J=7.2Hz,1H),8.29(m,1H),7.69(t,J=2.4Hz,1H),7.67(d,J=8.4Hz,1H),7 .58(d,J=6.6Hz,1H),7.26(m,5H),7.04(m,3H),2.56(quartet,J=7.2Hz,4H,CH2),1.14(t,J=7.2Hz,6H,CH3)ppm.

[0292] 13 C NMR(C6D6): δ14.93,25.26,119.24,124.76,125.54,126.17,126.19,126.69,126.83,128.17, 128.76,129.37,131.80,133.06,134.53,136.97,138.69,150.49,155.13,159.66,164.12ppm.

[0293] HRMS(EI): m / z calculated ([M + ]C 26 H 24 N2) 364.1939. Measured value: 364.1938.

[0294] The compound (0.400 g, 1.10 mmol) and 2-isopropylphenyllithium (0.239 g, 1.90 mmol) were used to prepare by the same method as in Example 1. A lemon yellow solid (0.432 g, 82%) was obtained.

[0295] 1 H NMR (C6D6): δ8.18(m,1H),7.79(m,1H),7.66(m,1H),7.64(d,J=7.8Hz,1H),7.50(d,J=7.8Hz,1H),7.27(m,3H),7.18(m,2H),7.14 (m,2H),7.01(m,5H),5.83(s,1H,NCH),4.78(s,1H,NH),3.33(septet,J=6.6Hz,1H,CH),2.50(m,4H,CH2),1.02(m,12H,CH3)ppm.

[0296] 13C NMR(C6D6): δ14.95,23.99,24.84,25.05,28.93,65.42,120.00,122.97,123.18,125.40,125.86,126.07,126.37,126.60,126.62 ,127.09,127.69,127.84,128.58,129.28,131.88,134.57,136.90,137.01,138.95,141.42,145.44,146.52,159.21,163.41ppm.

[0297] HRMS(EI): m / z calculated ([M + ]C 35 H 36 N2) 484.2878. Measured value: 484.2876.

[0298] (ii) Preparation of transition metal compounds

[0299] HfCl4 (0.189 g, 0.588 mmol) and toluene (5 mL) were loaded into a Schlenk flask. Under nitrogen, the temperature was reduced to about -78 ° C, and MeMgBr (0.78 m, 3.1 M ether solution, 2.4 mmol) was added dropwise thereto. The mixture was stirred at -40 ° C to -35 ° C for 1 hour to precipitate a white solid. The temperature was reduced to about -78 ° C again, and a toluene (5 mL) solution of a ligand compound (0.190 g, 0.392 mmol) was added dropwise thereto. After the resulting mixture was stirred at -40 ° C to -35 ° C for 2 hours, the temperature was slowly raised to room temperature. After stirring overnight, all volatile substances were removed by vacuum tube. The product was extracted with toluene (10 mL). The extract was filtered and collected on diatomaceous earth. After removing the solvent by vacuum tube, the residue was softened in hexane (2 mL). A yellow solid (0.170 g, 63%) was obtained.

[0300] 1H NMR (C6D6): δ8.58(d,J=7.2Hz,1H),8.35(d,J=9.0Hz,1H),7.82(d,J=8.4Hz,1H),7.73(d,J=7.8Hz,1H),7.56(d,J=7.8Hz,1H),7.36 (t,J=7.2Hz,1H),7.30(t,J=6.6Hz,1H),7.22(d,J=7.8Hz,1H),7.14(d,J=7.8Hz,1H),7.09(t,J=7.8Hz,2H),7.04(m,2H),6.93(t,J= 7.8Hz,1H),6.84(t,J=7.8Hz,1H),6.60(s,1H,NCH),6.47(d,J=7.8Hz,1H),2.83(m,4H,CH2),2.41(m,1H,CH),1.30(t,J=7.8Hz,3H, CH3),1.14(d,J=6.6Hz,3H,CH3),0.82(s,3H,HfCH3),0.68(d,J=6.6Hz,3H,CH3),0.62(t,J=7.2Hz,3H,CH3),0.56(s,3H,HfCH3)ppm.

[0301] 13 C NMR(C6D6): δ14.88,15.20,22.85,24.20,24.34,25.57,28.61,63.61,64.75 ,74.63,120.14,120.30,124.20,125.33,125.54,126.01,126.42,126.71,1 26.85,127.01,129.91,130.05,130.57,130.70,134.30,135.76,140.67,14 0.76,142.33,143.79,143.83,144.26,147.16,164.52,171.23,205.38ppm.

[0302] Analytical calculation value (C 37 H 40 HfN2): C, 64.29; H, 5.83; N, 4.05%. Measured value: C, 64.41; H, 6.05; N, 3.86%.

[0303] Comparative Example 3

[0304]

[0305] (i) Preparation of ligand compound

[0306]

[0307] The product was prepared by the same method as in Example 6 using 2-bromo-6-(naphthalen-1-yl)pyridine (0.220 g, 0.774 mmol), t-BuLi (0.91 mL, 1.7 M hexane solution, 1.6 mmol), 2,6-Et2C6H3N=C(H)Ph (0.184 g, 0.774 mmol) and THF (10 mL). A pale yellow solid (0.210 g, 61%) was obtained by column chromatography on silica gel using hexane and toluene (v / v, 75:25:1) containing a small amount of triethylamine.

[0308] 1 H NMR (C6D6): δ8.21(m,1H),7.68(m,2H),7.54(d,J=7.2Hz,1H),7.51(d,J=8 .4Hz,2H),7.30(t,J=7.2Hz,1H),7.26(m,2H),7.11(t,J=7.8Hz,2H),7.05( m,2H),7.00(m,3H),6.93(m,1H),6.80(m,1H),5.59(d,J=8.4Hz,1H,NCH), 5.52 (d, J = 8.4Hz, 1H, NH), 2.62 (m, 4H, CH2), 1.06 (t, J = 6.6Hz, 6H, CH3) ppm.

[0309] 13 C NMR (C6D6): δ 14.82, 25.47, 68.09, 120.75, 122.56, 123.35, 125.48, 126.16, 126.50, 126.63, 127.09, 127.24, 127.73, 127.81, 128.60, 128.65, 129.28, 131.84, 134.54, 136.08, 136.94, 139.08, 144.24, 144.89, 159.17, 162.33 ppm. HRMS (EI): m / z calculated ([M + ]C 32 H 30 N2) 442.2409. Measured value: 442.2408.

[0310] (ii) Preparation of transition metal compounds

[0311] Prepared by the same method as in Example 6 using HfCl4 (0.0709 g, 0.221 mmol), MeMgBr (0.29 mL, 3.0 M ether solution, 0.91 mmol) and ligand compound (0.0653 g, 0.148 mmol). Obtained a yellow solid (0.0628 g, 66%).

[0312] 1 H NMR (C6D6): δ8.57(d,J=7.2Hz,1H),8.35(d,J=8.4Hz,1H),7.82(d,J=7.8Hz,1H),7.73(d,J=8.4Hz,1H),7.56(d,J=8.4Hz,1H),7.36( t,J=7.2Hz,1H),7.30(t,J=7.8Hz,1H),7.23(d,J=7.2Hz,1H),7.18(m,1H),7.12(d,J=7.8Hz,1H),6.96(m,3H),6.83(m,3H),6.36(d, J=7.8Hz,1H),5.93(s,1H,NCH),2.84(sextet,J=7.2Hz,1H,CH2),2.78(sextet,J=7.8Hz,1H,CH2),2.69(sextet,J=6.6Hz,1H,CH2), 2.38(sextet,J=6.6Hz,1H,CH2),1.32(t,J=7.8Hz,3H,CH3),0.80(s,3H,HfCH3),0.61(t,J=7.2Hz,3H,CH3),0.55(s,3H,HfCH3)ppm.

[0313] 13 C NMR(C6D6): δ15.28,15.68,24.37,63.72,64.58,81.45,120.29,120.49,124.13,125.56,126.09,126.69,126.74,127.05,127.82,12 8.76,129.38,129.90,130.06,130.65,134.32,135.74,140.68,142.53,143.15,143.73,144.00,144.24,164.59,170.07,205.27ppm.

[0314] Analytical calculation value (C 34 H 34 HfN2): C, 62.91; H, 5.28; N, 4.32%. Measured value: C, 63.13; H, 5.50; N, 4.41%.

[0315] Comparative Example 4

[0316]

[0317] (i) Preparation of ligand compound

[0318]

[0319] The product was prepared by the same method as in Example 6 using 2-bromo-6-(naphthalen-1-yl)pyridine (0.220 g, 0.774 mmol), T-BuLi (0.91 mL, 1.7 M hexane solution, 1.6 mmol), 2,6-Et2C6H3N=C(H)Ph (0.184 g, 0.774 mmol) and THF (10 mL). A pale yellow solid (0.210 g, 61%) was obtained by column chromatography on silica gel using hexane and toluene (v / v, 75:25:1) containing a small amount of triethylamine.

[0320] 1 H NMR (C6D6): δ8.21(m,1H),7.68(m,2H),7.54(d,J=7.2Hz,1H),7.51(d,J=8 .4Hz,2H),7.30(t,J=7.2Hz,1H),7.26(m,2H),7.11(t,J=7.8Hz,2H),7.05( m,2H),7.00(m,3H),6.93(m,1H),6.80(m,1H),5.59(d,J=8.4Hz,1H,NCH), 5.52 (d, J = 8.4Hz, 1H, NH), 2.62 (m, 4H, CH2), 1.06 (t, J = 6.6Hz, 6H, CH3) ppm.

[0321] 13 C NMR (C6D6): δ 14.82, 25.47, 68.09, 120.75, 122.56, 123.35, 125.48, 126.16, 126.50, 126.63, 127.09, 127.24, 127.73, 127.81, 128.60, 128.65, 129.28, 131.84, 134.54, 136.08, 136.94, 139.08, 144.24, 144.89, 159.17, 162.33 ppm. HRMS (EI): m / z calculated ([M + ]C 32 H 30 N2) 442.2409. Measured value: 442.2408.

[0322] (ii) Preparation of transition metal compounds

[0323] Prepared by the same method as in Example 6 using HfCl4 (0.0709 g, 0.221 mmol), MeMgBr (0.29 mL, 3.0 M in ether, 0.91 mmol) and 31 (0.0653 g, 0.148 mmol). Obtained as a yellow solid (0.0628 g, 66%).

[0324] 1 H NMR (C6D6): δ8.57(d,J=7.2Hz,1H),8.35(d,J=8.4Hz,1H),7.82(d,J=7.8Hz,1H),7.73(d,J=8.4Hz,1H),7.56(d,J=8.4Hz,1H),7.36( t,J=7.2Hz,1H),7.30(t,J=7.8Hz,1H),7.23(d,J=7.2Hz,1H),7.18(m,1H),7.12(d,J=7.8Hz,1H),6.96(m,3H),6.83(m,3H),6.36(d, J=7.8Hz,1H),5.93(s,1H,NCH),2.84(sextet,J=7.2Hz,1H,CH2),2.78(sextet,J=7.8Hz,1H,CH2),2.69(sextet,J=6.6Hz,1H,CH2), 2.38(sextet,J=6.6Hz,1H,CH2),1.32(t,J=7.8Hz,3H,CH3),0.80(s,3H,HfCH3),0.61(t,J=7.2Hz,3H,CH3),0.55(s,3H,HfCH3)ppm.

[0325] 13 C NMR(C6D6): δ15.28,15.68,24.37,63.72,64.58,81.45,120.29,120.49,124.13,125.56,126.09,126.69,126.74,127.05,127.82,12 8.76,129.38,129.90,130.06,130.65,134.32,135.74,140.68,142.53,143.15,143.73,144.00,144.24,164.59,170.07,205.27ppm.

[0326] Analytical calculation value (C 34 H 34HfN2): C, 62.91; H, 5.28; N, 4.32%. Measured value: C, 63.13; H, 5.50; N, 4.41%.

[0327] Polymerization of ethylene / α-olefin copolymers

[0328] A steel bomb reactor (125 mL) was evacuated at 60°C for 1 hour. After charging the steel bomb reactor with ethylene gas under atmospheric atmosphere, a solution of Me3Al (28.8 mg, 200 μmol-Al) in methylcyclohexane (15.5 g) was added to the reactor. The mixture thus obtained was stirred at 100°C for 1 hour using a jacket and then the solution was removed using a loop. The reactor was evacuated again to remove the remaining solvent and charged with ethylene gas again under atmospheric atmosphere. This procedure was performed to remove catalyst poisons.

[0329] The reactor was charged with methylcyclohexane (15.5 g) containing MMAO (AkzoNobel, 6.7 wt% Al in heptane, 20 mg, 50 μmol-Al). A solution of (1-hexyl)2Zn (150 μmol) in methylcyclohexane (10.0 g) was provided. Then, a solution containing [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] - A methylcyclohexane solution (0.30 g) of each transition metal compound (1.0 μmol-Hf) of the activated examples or comparative examples (1.0 eq).

[0330] Ethylene / propylene mixed gas (15 bar / 10 bar, 25 bar in total) was charged into the reactor at 23 bar in a tank, and polymerization was carried out for 70 minutes at 80-90° C. The remaining ethylene / propylene mixed gas was evacuated, and an ethylene / propylene copolymer was obtained by drying in a vacuum oven at 160° C. overnight.

[0331] Experimental Example 1

[0332] (1) Output (g)

[0333] The weight of the ethylene / α-olefin copolymer prepared by the experimental example was measured, and the yield was calculated.

[0334] (2) Propylene content

[0335] Depend on 1 H NMR spectrum was measured.

[0336] (3) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MWD)

[0337] The measurement is performed by GPC by using trichlorobenzene at 160° C. and by standardization by polystyrene. Using the Mw and Mn thus measured, the MWD is calculated by dividing the Mw value by the Mn value.

[0338] Table 1

[0339] catalyst <![CDATA[(Hexyl)2Zn (μmol)]]> Yield (g) <]]> Mn(kDa) MWD Example 1 150 10.2 20 28 1.9 Example 2 150 10.0 20 33 1.7 Example 3 150 8.1 18 25 1.4 Example 4 150 9.0 18 18 1.8 Example 5 150 8.8 19 22 1.5 Example 6 150 7.0 14 22 1.6 Example 7 150 7.7 16 19 1.5 Example 8 150 6.2 16 19 1.4 Comparative Example 1 150 6.0 20 27 1.8 Comparative Example 2 150 5.8 18 19 1.4 Comparative Example 3 150 5.3 16 19 1.4 Comparative Example 4 150 3.9 14 14 1.5

[0340] According to the polymerization results, the transition metal compounds of the Examples generally showed higher catalyst activity than the transition metal compounds of the Comparative Examples, and ethylene / α-olefin copolymers could be prepared in excellent yield.

[0341] For example, the transition metal compounds of Examples 1 and 2 can be used for polymerization for a longer period of time than Comparative Example 1. In particular, it can be found that in Comparative Example 1, the monomer is almost not consumed after 40 minutes, whereas in Examples 1 and 2, the monomer is stably consumed until about 70 minutes.

[0342] In addition, refer to Fig. 9 , an experiment was conducted using a mass flow controller to observe the consumption rate of ethylene by providing ethylene at a constant pressure (10 bar) instead of the ethylene-propylene gas mixture, and it was confirmed that the transition metal compound of Example 2 maintained the catalyst activity for a longer time when compared with the transition metal compound of Comparative Example 1.

Claims

1. A transition metal compound, the transition metal compound is represented by the following formula 1a: [Formula 1a] In formula 1a M is Ti, Zr or Hf, R5 is an aromatic group having 6 to 20 carbon atoms and having a substituent, wherein Substituted with an alkyl group of 1 to 12 carbon atoms, R6 is: hydrogen; or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the aryl group may be substituted with an alkyl group having 1 to 12 carbon atoms, Each R7 is independently a cycloalkyl group of 6 to 20 carbon atoms, and Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms.

2. The transition metal compound according to claim 1, wherein M is Hf, R5 is an aromatic group having 6 to 20 carbon atoms and having a substituent, wherein Substituted with an alkyl group of 1 to 6 carbon atoms, R6 is: hydrogen; or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms, Each R7 is independently a cycloalkyl group of 6 to 20 carbon atoms, and Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms.

3. The transition metal compound according to claim 1, wherein The transition metal compound represented by Formula 1a is selected from the following compounds:

4. A ligand compound, the ligand compound is represented by the following formula 2: [Formula 2] In formula 2, R5 is an aromatic group having 6 to 20 carbon atoms and having a substituent, wherein Substituted with an alkyl group of 1 to 12 carbon atoms, R6 is: hydrogen; or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the aryl group may be substituted with an alkyl group having 1 to 12 carbon atoms, and Each R7 is independently a cycloalkyl group of 6 to 20 carbon atoms.

5. A catalyst composition comprising the transition metal compound according to claim 1 and a co-catalyst.

6. The catalyst composition according to claim 5, wherein The co-catalyst comprises one or more selected from the following formulas 4 to 6: [Formula 4] <h2 style=";text-align:left;direction:ltr">-[Al(R<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> )-O]<h2 style=";text-align:left;direction:ltr"> m <h2 style=";text-align:left;direction:ltr"> - [Formula 5] D(R a )3 [Formula 6] [L-H] + [Z(A)4] - or [L] + [Z(A)4] - In the above formula, Each R a are independently: a halogen group; a hydrocarbon group of 1 to 20 carbon atoms; or a halogen-substituted hydrocarbon group of 1 to 20 carbon atoms, m is an integer greater than or equal to 2, D is aluminum or boron, L is a neutral or cationic Lewis acid, Z is an element in group 13, Each A is independently an aryl group of 6 to 20 carbon atoms or an alkyl group of 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with a substituent, and The substituent of A is: halogen; a hydrocarbon group of 1 to 20 carbon atoms; an alkoxy group of 1 to 20 carbon atoms; or an aryloxy group of 6 to 20 carbon atoms.

7. A method for preparing an olefin polymer, the method comprising: Olefin monomers are polymerized in the presence of the catalyst composition of claim 5.

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