KR102121437B1 - Novel ligand compound and transition metal compound comprising the same - Google Patents

Abstract

The present invention relates to a novel ligand compound and a transition metal compound containing the same, and the novel structured transition metal compound according to the present invention can be used as a polymerization reaction catalyst in preparing an oliphine-based polymer.

Description

A novel ligand compound and a transition metal compound containing the same {NOVEL LIGAND COMPOUND AND TRANSITION METAL COMPOUND COMPRISING THE SAME}

The present invention relates to a novel ligand compound and a transition metal compound comprising the ligand compound.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process of conventional polyolefins. Although the Ziegler-Natta catalyst has a high activity, the molecular weight distribution of the resulting polymer is wide and the comonomer is a multi-activation catalyst. There was a limitation in securing the desired physical properties because the composition distribution of was not uniform.

Accordingly, recently, metallocene catalysts in which ligands including transition metals such as titanium, zirconium, and hafnium and cyclopentadiene functional groups are combined have been developed and widely used. Metallocene compounds are generally activated by using aluminoxane, borane, borate or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. In the case of substituting the chloride group of the metallocene compound with another ligand (for example, benzyl or trimethylsilylmethyl group (-CH ₂ SiMe ₃ )), an example showing an effect such as an increase in catalytic activity has been reported.

Dow Corporation [Me ₂ Si(Me ₄ C ₅ )N t Bu]TiCl ₂ (Constrained-Geometry Catalyst, CGC) was disclosed in U.S. Patent No. 5,064,802, in the early 1990s. The superior aspect compared to the known metallocene catalysts can be broadly summarized as follows: (1) It produces high-molecular weight polymers with high activity even at high polymerization temperatures, and (2) 1-hexene And that the copolymerization of alpha-olefin having a large steric hindrance such as 1-octene is also excellent. In addition, in the polymerization reaction, various properties of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.

As one of the approaches, synthesis of a metal compound in which various other bridges and nitrogen substituents were introduced instead of a silicon bridge and polymerization using the same were attempted. Representative metal compounds known until recently have introduced phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges, but polymerized in comparison to CGC when applied to ethylene polymerization or copolymerization of ethylene and alpha olefins It did not show excellent results in terms of activity or copolymerization performance.

As another approach, a large number of compounds composed of oxido ligands have been synthesized instead of the amido ligands of CGC, and polymerization using them has been partially attempted.

However, among all these attempts, catalysts that are actually applied to commercial plants are only a few, and there is still a need for a catalyst that exhibits improved polymerization performance.

The present invention is to provide a novel ligand compound capable of producing an olefin-based polymer with high catalytic activity and selectivity, and a transition metal compound containing the same.

In order to solve the above problems, the present invention provides a ligand compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₁₉ are each independently hydrogen; C _1-20 alkyl; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _7-20 alkylaryl; C _7-20 arylalkyl; Or C _2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.

The compound according to the present invention can be used as a ligand of a transition metal compound that can be used as a catalyst for preparing an olefinic polymer. More specifically, the compound represented by Chemical Formula 1 has a structure in which two biphenyl-2-ols are each connected to pyridine by methylene. At this time, the oxygen atom of biphenyl-2-ol is covalently bonded to the transition metal in the transition metal compound to be described later, and the nitrogen atom of pyridine may be coordinated with the transition metal.

In Chemical Formula 1, R ₁ to R ₁₉ are each independently hydrogen; C _1-10 alkyl; C _6-10 aryl; Or it may be a C _2-20 heteroaryl containing one or more N atoms.

Specifically, R ₁ to R ₁₉ may each independently be hydrogen, tert-butyl, phenyl, or carbazole.

More specifically, R ₁ , R ₃ , R ₁₇ and R ₁₉ are each independently tert-butyl, phenyl, or carbazolyl, and R ₂ , R ₄ to R ₁₆ and R ₁₈ can be hydrogen.

At this time, R ₁ and R ₁₉ are the same as each other, and R ₃ and R ₁₇ may be the same as each other.

For example, R ₁ and R ₁₉ can each independently be phenyl or carbazolyl, and R ₃ and R ₁₇ can be tert-butyl.

Specifically, for example, R ₁ and R ₁₉ may each independently be phenyl or 9H-carbazole-9-yl, and R ₃ and R ₁₇ may be tert-butyl.

The compound represented by Formula 1 may be represented by the following Formula 1A:

[Formula 1A]

In Formula 1A,

Description of R ₁ , R ₃ , R ₁₇ and R ₁₉ is as defined in Formula 1 above.

In addition, a typical example of the compound represented by Formula 1 may be the following Compound 1-1 or 1-2:

Meanwhile, the compound represented by Chemical Formula 1 may be prepared as shown in Reaction Scheme 1 below, but is not limited thereto. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In Reaction Scheme 1, the description of R ₁ to R ₁₉ is as defined in Formula 1 above.

In steps 1 and 2, n-butyllithium and ZnBr ₂ are sequentially added to the compound represented by Chemical Formula A-1 to generate a compound represented by Chemical Formula A-2 as an intermediate, and then in Chemical Formula A- in the presence of a platinum catalyst. This is a step for preparing a compound represented by Chemical Formula A-4 by adding a compound represented by 3. Specifically, a step for introducing a biphenyl-based compound represented by Formula A-1 at positions 2 and 6 of the pyridine derivative represented by Formula A-2, wherein the reaction in Step 1 is -78°C and an argon atmosphere It is preferably carried out under, and the reaction of step 2 is preferably carried out by refluxing for about 24 hours.

In addition, step 3 is a step of preparing a compound represented by the formula (1) by reacting the compound represented by the formula (A-4) in the presence of boron tribromide, by introducing a hydroxyl group at the methoxy group position by a hydrolysis reaction can do.

In addition, the present invention provides a transition metal compound represented by Formula 2:

[Formula 2]

In Chemical Formula 2,

M is a transition metal of group 4,

L ₁ and L ₂ are each independently halogen, C _1-20 alkyl; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _7-20 alkylaryl; C _7-20 arylalkyl; C _1-20 alkylamino; C _6-20 arylamino; Or C _6-20 alkylidene,

R ₁ to R ₁₉ are each independently hydrogen; C _1-20 alkyl; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _7-20 alkylaryl; C _7-20 arylalkyl; Or C _2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

Here, → means coordination bond.

Specifically, M may be Ti, Zr, or Hf.

Further, L ₁ and L ₂ may be each independently C _1-10 alkyl. For example, L ₁ and L ₂ may be methyl.

In addition, R ₁ to R ₁₉ are each independently hydrogen; C _1-10 alkyl; C _6-10 aryl; Or it may be a C _2-20 heteroaryl containing one or more N atoms.

Specifically, R ₁ to R ₁₉ may each independently be hydrogen, tert-butyl, phenyl, or carbazole.

More specifically, R ₁ , R ₃ , R ₁₇ and R ₁₉ are each independently tert-butyl, phenyl, or carbazolyl, and R ₂ , R ₄ to R ₁₆ and R ₁₈ can be hydrogen.

At this time, R ₁ and R ₁₉ are the same as each other, and R ₃ and R ₁₇ may be the same as each other.

For example, R ₁ and R ₁₉ can be phenyl or carbazolyl, and R ₃ and R ₁₇ can be tert-butyl.

Specifically, for example, R ₁ and R ₁₉ may be phenyl or 9H-carbazole-9-yl, and R ₃ and R ₁₇ may be tert-butyl.

The compound represented by Chemical Formula 2 may be represented by Chemical Formula 2A:

[Formula 2A]

In Formula 2A,

The description of M, L ₁ , L ₂ , R ₁ , R ₃ , R ₁₇ and R ₁₉ is as defined in Chemical Formula 2.

In addition, a typical example of the compound represented by Formula 2 may be one of the following compounds 2-1 to 2-4:

Meanwhile, the compound represented by Chemical Formula 2 may be prepared as Reaction Scheme 2 below, but is not limited thereto. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 2]

In Reaction Scheme 2, the description of M, L ₁ , L ₂ and R ₁ to R ₁₉ is as defined in Formula 2 above.

Specifically, the compound represented by Chemical Formula 2 may be prepared through the reaction in which the compound represented by Chemical Formula 1 is introduced as a ligand of the transition metal M.

Meanwhile, a transition metal catalyst composition including the above-described transition metal compound is provided. More specifically, the transition metal compound may be used alone or in the form of a catalyst composition further comprising a co-catalyst in addition to the transition metal compound, and may be used as a catalyst for a polymerization reaction for preparing an olefin-based polymer. At this time, the cocatalyst used is an organometallic compound containing a Group 13 metal, and is generally not particularly limited as long as it can be used when polymerizing an olefin under a catalyst of a transition metal compound.

Specifically, the transition metal catalyst composition may further include any one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5:

[Formula 3]

-[Al(R ₂₁ )-O] _c-

In Chemical Formula 3,

R ₂₁ are each independently halogen, C _1-20 alkyl or C _1-20 haloalkyl,

c is an integer greater than or equal to 2,

[Formula 4]

D(R ₂₂ ) ₃

In Chemical Formula 4,

D is aluminum or boron,

R ₂₂ are each independently hydrogen, halogen, C _1-20 hydrocarbyl or C _1-20 hydrocarbyl substituted with halogen,

[Formula 5]

^{[LH] + [Q (E} ) 4] - or ^{[L] + [Q (E} ) 4] -

In Chemical Formula 5,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is Br ³⁺ or Al ³⁺ ,

E are each independently C _6-20 aryl or C _1-20 alkyl, wherein the C _6-20 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, C _1-20 alkoxy and It is substituted with one or more substituents selected from the group consisting of phenoxy.

The compound represented by Chemical Formula 3 may be, for example, modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like.

Examples of the alkyl metal compound represented by Chemical Formula 4 include, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, and diethyl. Chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p- Tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like.

Examples of the compound represented by Formula 5 include, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammoniumtetra(p -Tolyl) boron, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron, trimethyl ammonium tetra (o, p-dimethylphenyl) boron, tributyl ammonium Tetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenyl boron, N ,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphonium Tetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tripropylammonium Tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapenta Florophenyl aluminum, diethyl ammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triphenylcarbonium tetraphenyl boron, triphenylcarbonium tetraphenyl aluminum, tri Phenylcarbonium tetra(p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like.

More specifically, the catalyst composition may use methyl aluminoxane, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, or methyl alumoxane (MAO) as a cocatalyst.

The use content of the co-catalyst can be appropriately adjusted according to the properties or effects of the desired catalyst composition.

The catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier. The transition metal compound represented by Chemical Formula 2 has the above structural characteristics and can be stably supported on a carrier. In addition, the supported catalyst on which such a transition metal compound is supported may exhibit high activity in olefin polymerization.

As the carrier, a carrier containing a hydroxy group or a siloxane group on the surface may be used. Specifically, as the carrier, a carrier containing a hydroxy group or a siloxane group having high reactivity may be used by drying at a high temperature to remove moisture on the surface. More specifically, as the carrier, silica, alumina, magnesia or a mixture thereof can be used. The carrier may be dried at a high temperature, and these may typically include oxides, carbonates, sulfates, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

On the other hand, in the presence of a catalyst composition comprising the transition metal compound, a method for producing an olefin-based polymer comprising the step of polymerizing an olefin-based monomer is provided.

Examples of the synthesized olefin-based polymer are not particularly limited, but may be, for example, an olefin homopolymer, an olefin copolymer, or an ethylene/alpha-olefin copolymer.

Specific examples of the olefinic monomer include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomer or triene olefin monomer having two or more double bonds can also be polymerized. Specific examples of the monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-atocene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and may be copolymerized by mixing two or more of these monomers.

The polymerization reaction of the olefin monomer may be performed without limitation in a continuous solvent polymerization process, a bulk polymerization process, a suspension polymerization process, or an emulsion polymerization process, but for example, a solution polymerization reaction or a supported copolymerization reaction performed in a single reactor. Can be by The solution copolymerization reaction consists of dissolving the transition metal catalyst composition directly in a solvent in a solution state, and the supported copolymerization reaction is carried by preparing the supported catalyst by supporting the transition metal catalyst composition on the above-described carrier, and then the supported catalyst is solvent. It can be made into a slurry state by putting in.

The polymerization reaction of the olefinic monomer may be performed at a temperature of 45 to 200, or 60 to 150, for 0.1 hour to 2.5 hours, or 0.1 hour to 1.3 hours. In addition, the pressure can be carried out at 1 bar to 50 bar, or 2 bar to 45 bar. Specifically, the solution copolymerization reaction may be performed at a pressure of 1 bar to 50 bar, a temperature of 60 to 150 for 0.1 hour to 1 hour, and the supported copolymerization reaction may be performed at a pressure of 1 bar to 50 bar, and a temperature of 60 to 90 0.5 hour to 2.5 hours.

The reactor used in the polymerization reaction is not particularly limited, but for example, a continuous stirred reactor (CSTR) or a continuous flow reactor (PFR) may be used. In the polymerization reaction, two or more reactors may be arranged in series or in parallel, and may further include a separator for continuously separating solvent and unreacted monomers from the reaction mixture.

The novel ligand compound of the present invention and the transition metal compound containing the same can be usefully used as a catalyst for polymerization reaction in the production of olefin-based polymers.

1 is a ¹ H NMR spectrum of the transition metal compound 2-1 synthesized in Example 3.
Figure 2 shows the ¹ H NMR spectrum of the transition metal compound 2-2 synthesized in Example 4.
Figure 3 shows the ¹ H NMR spectrum of the transition metal compound 2-3 synthesized in Example 5.
Figure 4 shows the ¹ H NMR spectrum of the transition metal compound 2-4 synthesized in Example 6.

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited thereby.

Example 1: Synthesis of Compound 1-1

Step (a): 2- Bromo -4- tert - Butylphenol (2- bromo -4- tert - butylphenol )

4-tert-butylphenol dissolved in 1:1 v/v chloroform:carbon tetrachloride (30 mL) at 0° C. and argon in a solution of bromine (10 g, 62.5 mmol) dissolved in chloroform (15 mL). (8.48 g, 56.5 mmol) solution was slowly added over 2 hours. The reaction mixture was stirred overnight. The reaction mixture was diluted with dichloromethane (50 mL) and washed with 1% Na ₂ SO ₃ aqueous solution and brine. The combined organic layers were treated with Na ₂ SO ₄ , filtered, and evaporated. The residue was purified by flash chromatography (eluent: normal-hexane) to obtain 2-bromo-4-tert-butylphenol. Yield 8.04 g (62%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.29 (s, 9 H), 6.96 (d, J=8.47 Hz, 1 H), 7.25 (dd, J=9.04, 1.64 Hz, 1 H), 7.45 (d, J=2.22 Hz, 1 H).

Step (b): 2- Bromo -4- tert -Butyl-1- Methoxybenzene (2- bromo -4- tert -butyl-1-methoxybenzene)

Methyl iodide (6.23 g) in a mixture of 2-bromo-4-tert-butylphenol (8.04 g), anhydrous K ₂ CO ₃ (11.6 g) and acetone anhydrous (120 mL) prepared in step (a) above. ) Was added slowly. The reaction mixture was refluxed overnight, then cooled to room temperature and filtered. After evaporating the filtrate, it was purified by column chromatography (eluent: normal-hexane) to obtain 2-bromo-4-tert-butyl-1-methoxybenzene. Yield 8.27 g (97%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.31 (s, 10 H), 3.89 (s, 3 H), 6.85 (d, J=8.55 Hz, 1 H), 7.29 (dd, J=8.55, 2.38 Hz, 1 H), 7.56 (d, J=2.38 Hz, 1 H).

Step (c): 5- tert -Butyl-2- Methoxybiphenyl (5- tert -butyl-2- methoxybiphenyl )

2-bromo-4-tert-butyl-1-methoxybenzene (6.8 g), phenylboronic acid (3.6 g), NaHCO ₃ (7.2 g), tetrabutylammonium bromide (860) prepared in step (b) above mg), (6Dipp)Pd(cinn)Cl (90 mg) was added to distilled water (42 mL) and refluxed for 1 hour. The reaction solution was extracted with dichloromethane (50 mL x 3 times), the organic layers were collected and evaporated, and the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane = 1:1) to 5-tert-butyl. 2-Methoxybiphenyl was obtained. Yield 6.31 g (94%).

¹ H NMR (600 MHz, DMSO- d ₆ , ppm): 1.29 (s, 9 H), 3.73 (s, 3 H), 7.02 (d, J=8.63 Hz, 1 H), 7.24 (d, J= 2.55 Hz, 1 H), 7.29-7.36 (m, 2 H), 7.39 (t, J=7.60 Hz, 2 H), 7.46 (d, J=7.89 Hz, 2 H).

Step (d): 3- Bromo -5- tert -Butyl-2- Methoxybiphenyl (3- bromo -5- tert -butyl-2-methoxybiphenyl)

The 5-tert-butyl-2-methoxybiphenyl (9.22 g, 38 mmol) prepared in step (c) was dissolved in dichloromethane (200 mL) and cooled to 0° C., followed by dichloromethane (40 mL). The dissolved bromine (6.3 g) solution was slowly added for 2 hours. Thereafter, an aqueous NaHCO ₃ solution (100 mL) was added to terminate the reaction, extracted with dichloromethane (100 mL x 3 times), and the organic layers were collected and evaporated. The residue was purified by column chromatography (eluent: dichloromethane:normal-hexane = 1:5) to obtain 3-bromo-5-tert-butyl-2-methoxybiphenyl. Yield 10.2 g (83%).

¹ H NMR (600 MHz, DMSO- d ₆ , ppm): 1.28 (s, 9 H) 3.31 (s, 3 H) 7.30 (d, J=2.48 Hz, 1 H) 7.36-7.41 (m, 1 H) 7.45 (t, J=7.57 Hz, 2 H) 7.50-7.54 (m, 2 H) 7.57 (d, J=2.38 Hz, 1 H).

Step (e): 3-(4- Tolyl )-5- tert -Butyl-2- Methoxybiphenyl (3-(4-tolyl) -5- tert -butyl-2-methoxybiphenyl)

3-bromo-5-tert-butyl-2-methoxybiphenyl (1 g, 3.13 mmol), 4-tolylboronic acid (500 mg, 3.67 mmol), NaHCO ₃ (790) prepared in step (d) above. mg, 9.4 mmol), tetrabutylammonium bromide (100 mg, 0.31 mmol), (6Dipp)Pd(cinn)Cl (10 mg, 0.015 mmol) was added to distilled water (3 mL) and refluxed for 1 hour. The reaction solution was extracted with dichloromethane (50 mL x 3 times), the organic layers were collected and evaporated, and the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane = 10:1) to 3-(4- Tolyl)-5-tert-butyl-2-methoxybiphenyl was obtained. Yield 0.98 g (95%).

¹ H NMR (600 MHz, DMSO- d ₆ , ppm): 1.31 (s, 9 H) 2.17 (s, 3 H) 2.98 (s, 3 H) 7.13 (d, J=2.57 Hz, 1 H) 7.19- 7.33 (m, 5 H) 7.35 (t, J=7.38 Hz, 1 H) 7.44 (t, J=7.70 Hz, 2 H) 7.53-7.57 (m, 2 H).

Step (f): 2-( Bromomethyl )-5'-( tert -Butyl)-2'- Methoxy -1,1':3',1''- Terphenyl(2-(bromomethyl)-5'- Preparation of (tert-butyl)-2'-methoxy-1,1':3',1''-terphenyl)

3-(4-tolyl)-5-tert-butyl-2-methoxybiphenyl (4.15 g, 12.6 mmol) and N -bromosuccinimide (2.46 g, 13.8 mmol) prepared in step (e) above. Was dissolved in carbon tetrachloride (100 mL), heated to reflux, and benzoyl peroxide (140 mg, 0.58 mmol) was added several times. The reaction mixture was refluxed for 2 hours, and then evaporated to remove the solvent. The residue was purified by column chromatography (eluent: normal-hexane) to 2-(bromomethyl)-5'-(tert-butyl)-2'-methoxy-1,1':3',1''-Terphenyl was obtained. Yield 4.06 g (79%).

¹ H NMR (600 MHz, DMSO- d ₆ , ppm): 1.33 (s, 9 H), 3.00 (s, 3 H), 4.43 (d, J=9.72 Hz, 1 H), 4.71 (d, J= 9.81 Hz, 1 H), 7.28-7.48 (m, 8 H), 7.53-7.71 (m, 3 H).

Step (g): 2,6-bis((5'-tert-butyl)-2'-methoxy-[1,1':3',1''-terphenyl]-2-yl)methyl)pyridine Preparation of (2,6-bis((5'-(tert-butyl)-2'-methoxy-[1,1':3',1''-terphenyl]-2-yl)methyl)pyridine)

2-(bromomethyl)-5'-(tertbutyl)-2'-methoxy-1 prepared in step (f) above dissolved in anhydrous tetrahydrofuran (20 mL) at -78 °C and argon, To a solution of 1':3',1''-terphenyl (1.19 g, 2.91 mmol) was slowly added a 2.5 M normal-butyllithium solution (1.4 mL, 3.5 mmol) dissolved in normal-hexane. Thereafter, the reaction solution was stirred at the same temperature for one hour. Then, a solution of ZnBr ₂ (920 mg, 4.1 mmol) dissolved in anhydrous tetrahydrofuran (6 mL) was slowly added. The reaction solution was stirred at -78°C for 10 minutes, then warmed to room temperature and stirred for an additional hour. After adding 2,6-dibromopyridine (344 mg, 1.45 mmol) and PdCl ₂ (PPh ₃ ) ₂ (21 mg, 0.03 mmol), the mixture was refluxed overnight. After cooling to room temperature, distilled water (50 mL) was added to terminate the reaction. After extraction with ethyl acetate (100 mL x 3 times), the organic layer was collected and evaporated, and the residue was purified by column chromatography (eluent: normal-hexane: dichloromethane = 5:1) to obtain 2,6-bis((5 '-tert-Butyl)-2'-methoxy-[1,1':3',1''-terphenyl]-2-yl)methyl)pyridine was obtained. Yield 860 mg (80%).

Step (h): Preparation of compound 1-1

2,6-bis((5'-tertbutyl)-2'-methoxy-[1,1':3',1''-terphenyl]-2-yl)methyl prepared in step (g) above ) Pyridine (850 mg, 1.15 mmol) was dissolved in anhydrous dichloromethane (20 mL) and then cooled to -78 °C. A solution of BBr ₃ (2.36 g, 9.44 mmol) in dichloromethane (5 mL) was added slowly. The reaction mixture was warmed to room temperature, stirred overnight, and distilled water (50 mL) was slowly added to terminate the reaction. The mixture was extracted with dichloromethane (100 mL x 3 times), and the combined organic layers were evaporated, and the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane = 4:1) to obtain compound 1-1. Yield 623 mg (76%)

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.37 (d, J=4.95 Hz, 18 H), 2.61-2.80 (m, 4 H), 4.83 (s, 1 H), 4.87 (s, 1 H ), 6.86 (dd, J=16.05, 7.34 Hz, 2 H), 7.15 (d, J=1.56 Hz, 2 H), 7.20-7.32 (m, 6 H), 7.35-7.42 (m, 4 H), 7.47 (dt, J=11.94, 7.65 Hz, 4 H), 7.60 (dd, J=16.51, 7.34 Hz, 4 H).

Example 2: Synthesis of Compound 1-2

Step (a): 9-(5- tert -Butyl-2- Methoxyphenyl )-9 H - Carbazole (9-(5- tert -butyl-2-methoxyphenyl)-9 H -carbazole)

2-bromo-4-tert-butyl-1-methoxybenzene (8.2 g, 33.75 mmol), carbazole (6.75 g, 40.5 mmol), K ₃ PO ₄ (12.52 g), CuI (320 mg) and 1 ,2-Diaminocyclohexane (770 mg) was dissolved in anhydrous 1,4-dioxane (100 mL) and refluxed in an argon atmosphere for 3 days. The reaction mixture was cooled to room temperature, extracted with distilled water (100 mL) and ethyl acetate (100 mL), and the organic layer was separated. The water layer was washed with ethyl acetate (100 mL x 3 times). After the combined organic layers evaporated The residue was purified by column chromatography (eluent: n-hexane: ethyl acetate = 10: 1) to give 9- (5-tert- butyl-2-methoxy-phenyl) -9 H-carbazole Got a sol. Yield 11.0 g (99%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.37 (s, 9 H), 3.70 (s, 3 H), 7.12 (d, J=8.55 Hz, 1 H), 7.19 (m, J=8.14 Hz , 2 H), 7.27-7.31 (m, 2 H), 7.39-7.44 (m, 2 H), 7.48-7.52 (m, 2 H), 8.17 (m, J=7.73 Hz, 2 H).

Step (b): 5'-tert-butyl-3'-(9 H -Carbazole-9-yl)-2'-methoxybiphenyl-2-carbaldehyde(5'-tert-butyl-3'-(9 H Preparation of -carbazol-9-yl)-2'-methoxybiphenyl-2-carbaldehyde)

After dissolving 9-(5-tert-butyl-2-methoxyphenyl)-9 H -carbazole (1.64 g, 4.97 mmol) prepared in step (a) with anhydrous diethyl ether (15 mL), argon Under an atmosphere, a 2.5 M normal-butyllithium solution (2.4 mL, 6 mmol) dissolved in normal-hexane was slowly added and stirred overnight. After drying under vacuum to remove the solvent, anhydrous ZnBr2 (1.67 g, 7.4 mmol) solution dissolved in anhydrous tetrahydrofuran (20 mL) was added. After stirring for 1 hour, 2-bromobenzaldehyde (0.92 g, 5 mmol), Pd(dba) ₂ (29 mg, 0.05 mmol), and SPhos (41 mg, 0.1 mmol) were added and refluxed for 4 hours. The reaction mixture was cooled to room temperature, and distilled water (100 mL) was added to terminate the reaction. After extraction with ethyl acetate (150 mL x 3 times), the organic layers were collected and evaporated, and the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane = 4:1) to 5'-tert-butyl-3. '-(9 H -carbazole-9-yl)-2'-methoxybiphenyl-2-carbaldehyde was obtained. Yield 1.05 g (49%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.43 (s, 9 H), 2.86 (s, 3 H), 7.33 (t, J=7.52 Hz, 4 H), 7.48 (d, J=2.48 Hz , 3 H), 7.54-7.58 (m, 2 H), 7.59 (d, J=2.48 Hz, 1 H), 7.71 (t, J=7.52 Hz, 1 H), 8.09 (d, J=8.16 Hz, 1 H), 8.18 (d, J=8.44 Hz, 2 H), 10.14 (s, 1 H).

Step (c): (5'-tert-butyl-3'- (9 H - Carbazole -9-Sun)-2'- Methoxybiphenyl -2 days) Methanol (5'-tert-butyl-3'- (9 H Preparation of -carbazol-9-yl)-2'-methoxybiphenyl-2-yl)methanol

5'-tert-butyl-3'-(9 H -carbazole-9-yl)-2'-methoxybiphenyl-2-carbaldehyde (1.047 g, 2.42 mmol) prepared in step (b) above Dissolved with anhydrous tetrahydrofuran (50 mL), cooled to 0° C., stirred, and NaBH ₄ (0.54 g, 14.5 mmol) was added in portions. Methanol (15 mL) was added slowly at the same temperature. Thereafter, the mixture was stirred at 0°C for 1 hour and at room temperature for 1 hour. After removing the solvent by vacuum drying, the residue was extracted with distilled water (100 mL) and dichloromethane (100 mL x 3 times). After the combined organic layers evaporated The residue was purified by column chromatography (eluent: n-hexane: dichloromethane = 3: 1) to give (5'-tert- butyl -3 '- (9 H-carbazole-9- 1)-2'-methoxybiphenyl-2-yl)methanol was obtained. Yield 843 mg (80%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.39 (s, 9 H) 1.60 (s, 1 H) 2.88 (s, 3 H) 4.56 (d, J=8.53 Hz, 1 H) 4.61-4.72 ( m, 1 H) 7.31-7.39 (m, 4 H) 7.40-7.51 (m, 6 H) 7.54 (s, 1 H) 7.63 (d, J=8.80 Hz, 1 H) 8.18 (d, J=7.61 Hz , 2 H).

Step (d): 9-(2'- Bromomethyl )-5- tert -Butyl-2- Methoxybiphenyl -3-day)-9 H - Carbazole (9-(2'-(bromomethyl) -5-tert-butyl-2-methoxybiphenyl-3-yl)-9 H -carbazole)

Prepared in Step (c) (5'-tert- butyl -3 '- (9 H - carbazol-9-yl) -2'-methoxy-biphenyl-2-yl) methanol (843 mg, 1.93 mmol ) And PPh ₃ (560 mg, 2.13 mmol) were dissolved with anhydrous tetrahydrofuran (20 mL) and then placed under an argon atmosphere and -78°C. After stirring vigorously, N -bromosuccinimide (380 mg, 2.13 mmol) was added little by little, followed by stirring at this temperature for 30 minutes and warming slowly to room temperature. After removing the solvent by vacuum drying, the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane = 8:1) to give 9-(2'-bromomethyl)-5-tert-butyl-2- methoxy-biphenyl-3-yl) -9 H - to give the carbazole. Yield 761 mg (79%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.43 (s, 9 H), 2.91 (s, 3 H), 4.53-4.68 (m, 2 H), 7.34 (t, J=7.47 Hz, 3 H ), 7.37-7.46 (m, 4 H), 7.47-7.52 (m, 2 H), 7.55 (dd, J=11.78, 2.52 Hz, 2 H), 7.58-7.63 (m, 1 H), 8.20 (d , J=7.70 Hz, 2 H).

Step (e): 2,6-bis((5'-tert-butyl-3'-(9 H -Carbazole-9-yl)-2'-methoxybiphenyl-2-yl)methyl)pyridine(2,6-bis((5'-tert-butyl-3'-(9 H Preparation of -carbazol-9-yl)-2'-methoxybiphenyl-2-yl)methyl)pyridine)

Said step (d) a 9- (2'-bromomethyl) -5-tert- butyl-2-methoxy-biphenyl-3-yl) -9 H prepared in-carbazole (671 mg, 1.35 mmol) to After dissolving with anhydrous tetrahydrofuran (15 mL) and argon atmosphere and -78°C, a 2.5 M normal-butyllithium solution (0.7 mL, 1.75 mmol) dissolved in normal-hexane was slowly added. After stirring at the same temperature for 1 hour, a solution of ZnBr2 (450 mg, 2 mmol) dissolved in anhydrous tetrahydrofuran (5 mL) was added. After slowly warming to room temperature, 2,6-dibromopyridine (160 mg, 0.675 mmol), Pd(dba) ₂ (11 mg, 0.014 mmol), and SPhos (11 mg, 0.027 mmol) were added. After the reaction solution was refluxed overnight, the solvent was removed by evaporation, and the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane 5:1) to give 2,6-bis((5'-tert-butyl) -3 '- (9 H - carbazol-9-yl) -2'-methoxy-biphenyl-2-yl) methyl) pyridine. Yield 540 mg (87.5%).

Step (f): Preparation of compound 1-2

2,6-bis((5'-tert-butyl-3'-(9 H -carbazole-9-yl)-2'-methoxybiphenyl-2-yl)methyl prepared in step (e) above )Pyridine (540 mg, 0.59 mmol) was dissolved in anhydrous dichloromethane (20 mL), placed under an argon atmosphere and -78°C, and then a solution of BBr ₃ (0.79 g, 3.16 mmol) in anhydrous dichloromethane (5 mL) Apply slowly. The reaction mixture was warmed to room temperature, stirred overnight, and distilled water (50 mL) was carefully added to terminate the reaction. After extracting with dichloromethane (100 mL x 3 times), the organic layers were collected and evaporated, and the residue was purified by column chromatography (eluent: normal-hexane:dichloromethane = 4:1) to obtain compound 1-2. Yield 390 mg (75%).

¹ H NMR (600 MHz, CDCl ₃ , ppm): 1.39 (s, 9 H), 1.43 (s, 9 H), 2.77-2.99 (m, 4 H), 4.92 (br.s., 2 H), 7.05 (t, J=8.07 Hz, 2 H), 7.23 (d, J=7.52 Hz, 2 H), 7.28-7.47 (m, 19 H), 7.47-7.55 (m, 4 H), 8.13-8.29 ( m, 4 H).

Example 3: Synthesis of Compound 2-1

Compound 1-1 (708 mg, 1 mmol) prepared in Example 1 was added to a 100 mL Schlenk flask substituted with argon and dissolved by adding toluene anhydrous (50 mL), and then dissolved in diethyl ether, 3.0 M methyl Magnesium bromide solution (1.37 mL, 4.1 mmol), 1.0 M titanium tetrachloride solution (1 mL, 1 mmol) dissolved in toluene was added. The solution was stirred overnight at room temperature. After removing the solvent by vacuum drying, anhydrous normal-hexane (50 mL) was added, stirred for 10 minutes, and the resultant was extracted and filtered. The filtrate was dried under vacuum to obtain compound 2-1. Yield 434 mg (55%).

¹ H NMR spectrum (500 MHz, C ₆ D ₆ , ppm) of Compound 2-1 synthesized in Example 3 is shown in FIG. 1.

Example 4: Synthesis of Compound 2-2

In a 100 mL Schlenk flask substituted with argon, Compound 1-2 (886 mg, 1 mmol) prepared in Example 2 was added and dissolved by adding anhydrous toluene (50 mL), and then dissolved in diethyl ether, 3.0 M methyl Magnesium bromide solution (1.37 mL, 4.1 mmol), 1.0 M titanium tetrachloride solution (1 mL, 1 mmol) dissolved in toluene was added. The solution was stirred overnight at room temperature. After removing the solvent by vacuum drying, anhydrous normal-hexane (50 mL) was added, stirred for 10 minutes, and the resultant was extracted and filtered. The filtrate was dried under vacuum to obtain compound 2-2. Yield 127 mg (13%).

The ¹ H NMR spectrum (500 MHz, C ₆ D ₆ , ppm) of Compound 2-2 synthesized in Example 4 is shown in FIG. 2.

Example 5: Synthesis of Compound 2-3

Compound 1-1 (500 mg, 0.706 mmol) and zirconium tetrachloride (165 mg, 0.706 mmol) prepared in Example 1 were added to a 100 mL Schlenk flask substituted with argon, and dissolved in anhydrous toluene (30 mL). Then a 3.0 M methylmagnesium bromide solution (1.37 mL, 4.1 mmol) dissolved in diethyl ether was added. The solution was stirred overnight at room temperature. After removing the solvent by vacuum drying, anhydrous normal-hexane (30 mL) was added, stirred for 10 minutes, and the resultant was extracted and filtered. The filtrate was dried under vacuum to obtain compound 2-3. Yield 200 mg (34%).

The ¹ H NMR spectrum (500 MHz, C ₆ D ₆ , ppm) of compound 2-3 synthesized in Example 5 is shown in FIG. 3.

Example 6: Synthesis of Compound 2-4

Compound 1-2 (886 mg, 1 mmol) and zirconium tetrachloride (233 mg, 1 mmol) prepared in Example 2 were added to a 100 mL Schlenk flask substituted with argon, and dissolved in anhydrous toluene (30 mL). Then a 3.0 M methylmagnesium bromide solution (1.37 mL, 4.1 mmol) dissolved in diethyl ether was added. The solution was stirred overnight at room temperature. After removing the solvent by vacuum drying, anhydrous toluene (50 mL) was added, stirred for 10 minutes, and the resultant was extracted and filtered. The residue obtained by vacuum drying the filtrate was recrystallized under anhydrous normal-hexane to obtain compound 2-4. Yield 590 mg (59%).

The ¹ H NMR spectrum (500 MHz, C ₆ D ₆ , ppm) of Compound 2-4 synthesized in Example 6 is shown in FIG. 4.

Example 7: Preparation of ethylene/1-octene copolymer

Anhydrous n -hexane (1 L), 1-octene (230 mL), and triisobutylaluminum solution (1.0 M in n -hexane, 0.3 mL) were added to a 2 L autoclave reactor at a temperature of about 100° C. or lower, and then the pressure inside the reactor. Vented to 10 psi or less. After preheating the temperature of the reactor to 120°C, ethylene was injected at 500 psi. Dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst solution (5 x 10 ^-3 M in toluene, 1.5 mL) was placed in a catalyst storage tank, and a high pressure argon pressure was added to the reactor, and the triisobutyl aluminum compound was added. After adding the transition metal compound catalyst solution (2 ｘ 10 ^-3 M in toluene, 2.5 mL) of Example 3 to the reactor, a high pressure argon pressure of about 30 bar was applied to initiate a polymerization reaction. The polymerization reaction proceeded for 10 minutes. The heat of reaction was removed through a cooling coil inside the reactor to keep the polymerization temperature as constant as possible. After the polymerization reaction was performed for 10 minutes, the remaining gas was removed, and the polymer solution was discharged to the bottom of the reactor, and excess ethanol was added to cool it to induce precipitation. The obtained polymer was washed 2-3 times with ethanol and acetone, respectively, and then dried in a vacuum oven at 90° C. for at least 12 hours, and then measured for physical properties.

Example 8: Preparation of ethylene/1-octene copolymer

The ethylene/1-octene copolymer was prepared in the same manner as in Example 7, except that the transition metal compound prepared in Example 4 was used instead of the transition metal compound prepared in Example 3 in Example 7. Did.

Example 9: Preparation of ethylene/1-octene copolymer

An ethylene/1-octene copolymer was prepared in the same manner as in Example 7, except that the transition metal compound prepared in Example 5 was used instead of the transition metal compound prepared in Example 3 in Example 7. Did.

Example 10: Preparation of ethylene/1-octene copolymer

An ethylene/1-octene copolymer was prepared in the same manner as in Example 7, except that the transition metal compound prepared in Example 6 was used instead of the transition metal compound prepared in Example 3 in Example 7. Did.

Experimental Example: Measurement of physical properties of ethylene/1-octene copolymer

The weight and melting temperature of the ethylene/1-octene copolymers prepared in Examples 7 to 10 were measured. At this time, the melting temperature (Tm) of the copolymer was measured using Q100 manufactured by TA, and the measured value was obtained through a second melting in which the temperature was raised to 10 per minute in order to eliminate the thermal history of the polymer.

In addition, the activity of the catalyst used in preparing the ethylene/1-octene copolymers in Examples 7 to 10 was measured. At this time, the catalyst activity was calculated using the number of moles of the transition metal compound and the polymerization time relative to the total yield of the copolymer.

After measuring the physical properties in the same manner as described above for Examples 7 to 10, the results are shown in Table 1 below.

catalyst
(Transition metal compound) Polymer weight
(Unit: g) Melt temperature
(Unit: ℃) Catalyst activity
(Unit: g·mol ^-1 hr ^-1 ) Example 7 Compound 2-1 0.12 119.5 144 Example 8 Compound 2-2 1.98 122.1 2,376 Example 9 Compound 2-3 2.14 117.9 2,568 Example 10 Compound 2-4 2.73 121.5 3,276

As shown in Table 1, it was confirmed that the transition metal compound according to the present invention can be used as a polymerization reaction catalyst in preparing an oliphine-based polymer.

Claims (15)

Compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₁₉ are each independently hydrogen; C _1-20 alkyl; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _7-20 alkylaryl; C _7-20 arylalkyl; Or C _2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.
According to claim 1,
R ₁ to R ₁₉ are each independently hydrogen, tert-butyl, phenyl, or carbazolyl.
According to claim 2,
R ₁ , R ₃ , R ₁₇ and R ₁₉ are each independently tert-butyl, phenyl, or carbazolyl,
R ₂ , R ₄ to R ₁₆ and R ₁₈ are hydrogen.
According to claim 1,
R ₁ and R ₁₉ are the same as each other,
R ₃ and R ₁₇ are the same as each other, a compound.
The method of claim 4,
R ₁ and R ₁₉ are phenyl or carbazolyl,
R ₃ and R ₁₇ are tert-butyl.
The method of claim 5,
R ₁ and R ₁₉ are phenyl or 9H-carbazole-9-yl,
R ₃ and R ₁₇ are tert-butyl.
According to claim 1,
The compound is a compound represented by the following formula 1A, a compound:
[Formula 1A]

In Formula 1A,
The description of R ₁ , R ₃ , R ₁₇ and R ₁₉ is as defined in claim 1.
According to claim 1,
The compound is a compound 1-1 or 1-2,

Transition metal compound represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
M is a transition metal of group 4,
L ₁ and L ₂ are each independently halogen, C _1-20 alkyl; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _7-20 alkylaryl; C _7-20 arylalkyl; C _1-20 alkylamino; C _6-20 arylamino; Or C _6-20 alkylidene,
R ₁ to R ₁₉ are each independently hydrogen; C _1-20 alkyl; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _7-20 alkylaryl; C _7-20 arylalkyl; Or C _2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.
The method of claim 9,
M is Ti, Zr, or Hf, a transition metal compound.
The method of claim 9,
L ₁ and L ₂ are methyl, a transition metal compound.
The method of claim 9,
The transition metal compound is a compound represented by the following formula 2A, a transition metal compound:
[Formula 2A]

In Formula 2A,
Descriptions of M, L ₁ , L ₂ , R ₁ , R ₃ , R ₁₇ and R ₁₉ are as defined in claim 9.
The method of claim 9,
The transition metal compound is one of the following compounds 2-1 to 2-4, a transition metal compound:

A transition metal catalyst composition comprising the transition metal compound of claim 9.
A method for producing an olefin-based polymer, comprising the step of polymerizing an olefin-based monomer in the presence of the transition metal catalyst composition of claim 14.

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