KR102128569B1 - Novel transition metal compound - Google Patents

Abstract

The present invention relates to a novel transition metal compound represented by the formula (1), the transition metal compound according to the present invention can be usefully used as a catalyst for the polymerization reaction in the production of olefin polymers having high crystallinity, high density and high molecular weight have.

Description

Novel transition metal compound {NOVEL TRANSITION METAL COMPOUND}

The present invention relates to a novel transition metal compound.

Metallocene catalysts for olefin polymerization have been developed for a long time. 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 has been reported showing an effect such as an increase in catalyst activity.

Dow Corporation disclosed [Me ₂ Si(Me ₄ C ₅ )NtBu]TiCl ₂ (Constrained-Geometry Catalyst, CGC) in US Patent No. 5,064,802 in the early 1990s. The superior aspects compared to the known metallocene catalysts can be summarized into two main points:

(1) It produces high-molecular weight polymers while exhibiting high activity even at high polymerization temperatures.

(2) The copolymerization of alpha-olefins with large steric hindrances such as 1-hexene and 1-octene is also excellent.

In addition, in the polymerization reaction, various properties of CGC are gradually known, and efforts to synthesize their derivatives 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 are introduced with phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC structured silicon bridges, but are polymerized against 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 number of compounds composed of oxido ligands were synthesized instead of the amido ligands of CGC, and polymerization using them was also partially attempted.

In addition, various asymmetric non-crosslinked metallocenes have been developed. For example, metallocenes composed of (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene, (substituted indenyl) (cyclopentadienyl), etc. are known. have.

However, in terms of commercial use, the catalyst compositions of the non-crosslinkable metallocene do not sufficiently exhibit the polymerization activity of olefins, and are disadvantageous in that it is difficult to polymerize high molecular weight polyolefins.

U.S. Patent No. 5,064,802

The problem to be solved by the present invention is to provide a method for producing a novel transition metal compound.

In order to solve the above problems, the present invention

It provides a transition metal compound represented by the following formula (1).

[Formula 1]

In the above formula, Q ₁ to Q ₃ are each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkyl aryl having 6 to 20 carbons, 7 to 7 carbons Arylalkyl of 20, alkylamido of 1 to 20 carbon atoms, arylamido of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms; M is Ti, Zr or Hf;

R ₁ to R ₆ are each independently hydrogen, silyl, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, arylalkyl having 7 to 20 carbons Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; 2 or more of R ₄ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, or aryl having 6 to 20 carbons; n is 1 or 2.

The transition metal compound according to the present invention can be usefully used as a catalyst for a polymerization reaction in the production of an olefin-based polymer having high crystallinity, high density and high molecular weight.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the specification and claims should not be interpreted as being limited to ordinary or dictionary meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle that it should be interpreted as a meaning and a concept consistent with the technical idea of the present invention.

The transition metal compound according to the present invention is represented by Formula 1 below.

[Formula 1]

In the above formula, Q ₁ to Q ₃ are each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkyl aryl having 6 to 20 carbons, 7 to 7 carbons Arylalkyl of 20, alkylamido of 1 to 20 carbon atoms, arylamido of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms; M is Ti, Zr or Hf;

R ₁ to R ₆ are each independently hydrogen, silyl, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, arylalkyl having 7 to 20 carbons Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; 2 or more of R ₄ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, or aryl having 6 to 20 carbons; n is 1 or 2.

In addition, in Chemical Formula 1, Q ₁ to Q ₃ may each independently be hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, alkyl aryl having 6 to 20 carbons, or aryl alkyl having 7 to 20 carbons. have.

In addition, in Chemical Formula 1, R ₁ to R ₆ may be each independently hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, alkyl aryl having 7 to 20 carbons, or aryl alkyl having 7 to 20 carbons. There is; 2 or more of R ₄ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbons, or aryl having 6 to 20 carbons.

The compound of Formula 1 of the present invention may specifically be any one of the following compounds.

[Formula 1a]

[Formula 1b]

In the above formula, Bn represents benzyl.

Each substituent defined in this specification will be described in detail as follows.

As used herein, the term'halogen' means fluorine, chlorine, bromine or iodine, unless stated otherwise.

The term'alkyl', as used herein, unless otherwise indicated, refers to a straight or branched chain hydrocarbon residue.

As used herein, the term'alkenyl' means a straight or branched alkenyl group, unless stated otherwise.

The branched chain is alkyl having 1 to 20 carbons; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.

According to an example of the present invention, the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris( Trimethylsilyl)silyl, and the like, but is not limited to these examples.

According to an example of the present invention, the aryl group is preferably 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited to these examples.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing one or more heteroatoms, and may be a single ring or a condensed ring of two or more rings. Also, the heterocyclic group may or may not be substituted with an alkyl group. Examples of these include indoline, tetrahydroquinoline, and the like, but the present invention is not limited to these.

The alkyl amino group means an amino group substituted by the alkyl group, and includes dimethylamino group, diethylamino group, and the like, but is not limited to these examples.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, there are phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, etc., but are limited to these examples no.

The transition metal compound of the present invention may be prepared through the following manufacturing method, specifically, the transition metal compound of the present invention (1) preparing a compound of formula 3 by reacting a compound of formula 2 with peroxide; And (2) reacting a compound of Formula 3 with a compound of Formula 4 to prepare a compound of Formula 1 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In the above formula, Q ₁ to Q ₃ , R ₁ to R ₆ , M and n are as defined in Formula 1, respectively.

(1) preparing a compound of formula 3 by reacting a compound of formula 2 with peroxide

[Scheme 1]

In step (1), a compound of Formula 2 is reacted with a peroxide to prepare a compound of Formula 3.

In step (1), the compound of Formula 2 and the peroxide may be reacted with a molar ratio of 1:5 to 1:20, and specifically, a molar ratio of 1:5 to 1:15.

The reaction of step (1) may be performed under an organic solvent such as tetrahydrofuran, and may be performed by adding the peroxide to the compound of Formula 2 under an organic solvent.

The peroxide may be at least one selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumyl hydroperoxide, propionyl peroxide, lauryl peroxide, and acetyl peroxide, specifically hydrogen peroxide. Can.

The reaction of step (1) is a method of reacting for 1 to 48 hours after adding the peroxide to the compound of Formula 2 in a temperature range of 0° C. to 30° C., after raising the temperature to a temperature range of 0° C. to 140° C. It can be carried out, specifically after adding the peroxide to the compound of Formula 2 in the temperature range of 20 ℃ to 30 ℃, and then heated to a temperature range of 20 ℃ to 30 ℃, and reacted for 1 to 48 hours It can be carried out by a method.

At this time, the compound of Formula 2 may be prepared through the reaction represented by Scheme 2 below.

[Scheme 2]

In the above reaction formula, R ₆ to R ₉ and n are as defined in Chemical Formula 2.

The compound of Formula 2-1 is placed in an organic solvent such as hexane, and n-BuLi is added in a temperature range of -80°C to 0°C. At this time, the n-BuLi may be reacted with a molar ratio of 1:1 to 1:2 with respect to the compound of Formula 2-1, specifically, with a molar ratio of 1:1.1 to 1:1.2. After adding n-BuLi, after reacting at room temperature for 1 to 48 hours, filtering it, adding a solvent to the obtained compound, bubbling and adding CO ₂ at a temperature of -160°C to -20°C to add Chemical Formula 2 A compound of -2 can be obtained. When t-BuLi is added to the obtained compound of Formula 2-2 and reacted in a temperature range of -80°C to 0°C, the compound of Formula 2-3 can be obtained. After the compound of Formula 2-4 is added to the compound of Formula 2-3 at a temperature of -150°C to -20°C, the reaction is performed by gradually raising the temperature to room temperature to obtain the compound of Formula 2. At this time, distilled water (H ₂ O) may be added, and the organic layer may be separated with an organic solvent such as diethyl ether, and then a process of drying moisture using Na ₂ SO ₄ may be performed.

(2) preparing a compound of formula 1 by reacting a compound of formula 3 with a compound of formula 4

[Scheme 2]

In step (2), the compound of formula 2 is reacted with the compound of formula 4 to prepare the compound of formula 1.

In step (2), the compound of Formula 3 and the compound of Formula 4 may be reacted with a molar ratio of 1:0.8 to 1:1.8, and specifically, a molar ratio of 1:1 to 1:1.2. .

The reaction of step (2) may be performed by a method of reacting for 1 to 48 hours after adding the compound of Formula 4 to the compound of Formula 3 in a temperature range of -20°C to 60°C, specifically After adding the compound of Formula 4 to the compound of Formula 3 in the temperature range of 0 ℃ to 30 ℃, it may be carried out by a method of reacting for 4 to 12 hours.

The compound of Formula 1 prepared through the above steps (1) and (2) may additionally be subjected to (3) a recrystallization step, and thus the method of preparing a transition metal compound according to an example of the present invention is after the above step (2). , (3) may further include the step of recrystallization of the compound of formula (1).

The recrystallization may be performed using an organic solvent such as ether, such as a reaction solvent, and purified through recrystallization to obtain a pure compound of Formula 1.

The transition metal compound represented by Chemical Formula 1 according to the present invention is activated by reacting with an additional cocatalyst and then applied to olefin polymerization to produce polyolefin having high crystallinity, high density, and high molecular weight even at high polymerization temperature. It is possible.

In particular, using the catalyst composition containing the transition metal compound, it is possible to manufacture a polymer having a narrow MWD compared to CGC, excellent copolymerizability, and high molecular weight even in a low density region.

More specifically, the transition metal compound according to the present invention, alone or in addition to the transition metal compound, in the form of a composition further comprising at least one of the following cocatalyst compounds represented by the following Chemical Formulas 5, 6 and 7, polymerization reaction It can be used as a catalyst.

<Formula 5>

-[Al(R ₇ )-O] _m-

In Chemical Formula 5,

R ₇ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer greater than or equal to 2;

<Formula 6>

J(R ₇ ) ₃

In Chemical Formula 6,

R ₇ is as defined in Formula 5 above;

J is aluminum or boron;

<Formula 7>

_{^{[EH] + [ZA 4]}} - or _{^{[E] + [ZA 4]}} -

In Chemical Formula 7,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

A may be the same or different from each other, and each independently one or more hydrogen atoms are halogen, a hydrocarbon having 1 to 20 carbons, an alkoxy or phenoxy substituted or unsubstituted aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. .

Examples of the compound represented by the formula (5) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and more preferred compounds are methyl aluminoxane.

Examples of the compound represented by Chemical Formula 6 are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl 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, and more preferred compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Chemical Formula 7 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, and trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -Diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilium tetrakis(pentafluorophenyl) borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , Tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentanetraphenylaluminum, triphenyl Phosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl ) Boron or triphenyl carbon tetrapentafluorophenyl boron.

Specifically, aluminoxane may be used, and more specifically, it may be alkylaluminoxane, methylaluminoxane (MAO).

The catalyst composition, as a first method, 1) obtaining a mixture by contacting the compound represented by Formula 5 or Formula 6 with the transition metal compound represented by Formula 1; And 2) adding the compound represented by Chemical Formula 7 to the mixture.

In addition, the catalyst composition may be prepared by contacting a transition metal compound represented by Chemical Formula 1 with a compound represented by Chemical Formula 5 as a second method.

In the case of the first method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1/compound represented by Formula 5 or Formula 6 is preferably 1/5,000 to 1/2, and more It is preferably 1/1,000 to 1/10, and most preferably 1/500 to 1/20. When the molar ratio of the transition metal compound represented by Chemical Formula 1/the compound represented by Chemical Formula 5 or Chemical Formula 6 exceeds 1/2, there is a problem that the alkylation of the metal compound is not completely progressed because the amount of the alkylating agent is very small. , When the molar ratio is less than 1/5,000, alkylation of the metal compound is performed, but there is a problem in that activation of the alkylated metal compound is not completely achieved due to a side reaction between the remaining excess alkylating agent and the activator of the compound of Formula 7 . In addition, the molar ratio of the transition metal compound represented by Formula 1/compound represented by Formula 7 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5. It is 1 to. When the molar ratio of the transition metal compound represented by the formula (1) / the compound represented by the formula (7) exceeds 1, the amount of the activator is relatively small so that the activation of the metal compound is not completely achieved and thus the activity of the catalyst composition generated There is a problem of falling, and when the molar ratio is less than 1/25, the metal compound is completely activated, but there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is lowered with the remaining excess activator.

In the case of the second method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Chemical Formula 1/compound represented by Chemical Formula 5 is preferably 1/10,000 to 1/10, and more preferably 1 /5,000 to 1/100, most preferably 1/3,000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activator is relatively small, and thus the activation of the metal compound is not completely achieved, resulting in a decrease in the activity of the resulting catalyst composition, and when it is less than 1/10,000, the metal compound Although activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the remaining excess of activator.

When preparing the catalyst composition, a hydrocarbon-based solvent such as pentane, hexane, heptane, or the like, or an aromatic-based solvent such as benzene and toluene may be used.

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.

Specifically, the polymerization reaction for polymerizing an olefinic monomer in the presence of a catalyst composition containing the transition metal compound is a solution polymerization process, using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor, etc. It can be carried out by a slurry process or a gas phase process. In addition, it may be carried out by homopolymerization with one olefin monomer or by copolymerization with two or more monomers.

The polymerization of the polyolefin may be performed by reacting at a temperature of about 25 to about 500°C and about 1 to about 100 kgf/cm ² .

Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 to about 500 °C, preferably about 25 to 200 °C, more preferably about 50 to 100 °C. In addition, the reaction pressure can be carried out at about 1 to about 100 kgf/cm ² , preferably about 1 to about 50 kgf/cm ² , more preferably about 5 to about 40 kgf/cm ² .

In addition, examples of the polymerizable olefin-based monomer using the transition metal compound and the cocatalyst according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin having two or more double bonds. Polymeric monomers or triene olefinic monomers and the like can also be polymerized.

In the polyolefin prepared according to an example of the present invention, specific examples of the olefinic monomer include 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, 1-atocene, and the like, and may be a copolymer obtained by mixing two or more of them.

The polyolefin may be a propylene polymer, but is not limited thereto.

The polymer may be either a homopolymer or a copolymer. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer are composed of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene. It is preferred that it is at least one comonomer selected from the group.

Hereinafter, preferred embodiments will be described to assist in understanding the present invention. The following examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich and Merck and purified by standard methods. Blocking the contact of air and moisture at all stages of synthesis increased the reproducibility of the experiment. To demonstrate the structure of the compound, a spectrum and a schematic were obtained using a 500 MHz nuclear magnetic resonator (NMR), respectively.

< Example >

Example 1

Synthesis of 8-(dicyclohexylphosphanyl)-2-methyl-1,2,3,4-tetrahydroquinoline

2-Methyl tetrahydroquinoline (6.12 g, 41.6 mmol) and hexane (0.536 M, 77.5 mL) were added to a 250 mL Schlenk flask. N-BuLi (1.1 eq, 18.3 mL) was added at -20°C and left overnight at room temperature. Filtration with a glass frit (G4) and vacuum drying afforded phosphine-amide lithium. Phosphine-amide lithium (1.83 g, 11.9 mmol) was added to diethyl ether (0.423 M, 28.2 mL), and CO ₂ bubbling was performed at -78°C for 1 hour. After slowly heating, the reaction was performed at room temperature overnight, and THF (1.1 eq, 1.07 mL) and t-BuLi (1.1 eq, 8.4 mL) were added at -20°C and maintained for 2 hours. Chlorodicyclohexylphosphine (0.85 eq, 2.36 g) and diethyl ether (0.359 M, 28.2 mL) were added at the same temperature and maintained at the same temperature for 1 hour. After reacting overnight at room temperature while slowly raising, 50 mL of distilled water was added at 0°C, and then stirred at room temperature for 30 minutes. After work-up with diethyl ether and drying the moisture with MgSO ₄ , 1.86 g of a pale yellow solid was obtained in 45.3% yield through a hexane and diethyl ether 50:1 column.

¹ H-NMR (C6D6): 7.18 (d, 1H), 6.97 (d, 1H), 6.75 (t, 1H), 5.70 (d, 1H), 3.16 (m, 1H), 2.65 (m, 1H), 2.55 (m, 1H), 2.02 (m, 5H) 1.80 (m, 5H), 1.59 (m, 6H), 1.28 (m, 6H), 0.98 (d, 3H)

Example 2

Synthesis of 8-(diisopropylphosfanyl)-2-methyl-1,2,3,4-tetrahydroquinoline

2-Methyl THQ (7.0 mL, 48.5 mmol) and hexane (0.536 M, 90.5 mL) were added to a 250 mL Schlenk flask. Insert n-BuLi (1.1 eq, 21.3 mL) at -20°C and leave overnight at room temperature. Filtration with a glass frit (G4) and vacuum drying afforded phosphine-amide lithium. Phosphine-amide lithium (3.0 g, 19.6 mmol) and diethyl ether (0.423 M, 46.3 mL) were added, and CO ₂ bubbling was performed at -78°C for 1 hour. After slowly raising the reaction at room temperature overnight, THF (1.1 eq, 1.75 mL) and t-BuLi (1.1 eq, 12.7 mL) were added at -20°C and maintained for 2 hours. Chlorodiisopropylphosphine (0.85 eq, 2.54 g) and diethyl ether (0.359 M, 46.3 mL) were added at the same temperature and maintained at the same temperature for 1 hour. After slowly heating, the mixture was reacted overnight at room temperature, and 50 mL of distilled water was added at 0°C, followed by stirring at room temperature for 30 minutes. After work-up with diethyl ether and drying the moisture with MgSO ₄ , 3.1 g of a yellow solid was obtained in 60% yield through a hexane and diethyl ether 50:1 column.

¹ H-NMR (C6D6): 7.07 (d, 1H), 6.94 (d, 1H), 6.70 (t, 1H), 5.60 (d, 1H), 3.12 (m, 1H), 2.63 (m, 1H), 2.55 (m, 1H), 2.04 (m, 2H) 1.53 (m, 1H), 1.15 (d, 3H), 1.12 (d, 3H), 1.00 (m, 9H)

Example 3

Dicyclohexyl (2- methyl -1,2,3,4- Tetrahydroquinoline -8-day) Phosphine oxide synthesis

To a 100 mL Schlenk flask was added 8-(dicyclohexylphosphanyl)-2-methyl-1,2,3,4-tetrahydroquinoline (0.70 g, 2.04 mmol) and THF (10.0 mL). 30 drops of H ₂ O ₂ (28%) were added at room temperature and left overnight at room temperature. After the reaction, the product was dried in vacuo to obtain a ligand in quantitative yield.

¹ H-NMR (C6D6): 8.08 (s, 1H), 6.90 (d, 1H), 6.64 (t, 1H), 6.47 (t, 1H), 3.26 (m, 1H), 2.55 (m, 2H), 2.20 (d, 1H), 2.03 (d, 2H) 1.94 (m, 2H), 1.66 (m, 5H), 1.53 (m, 7H), 1.14 (m, 6H), 1.02 (m, 3H)

Example 4

Diisopropyl (2- methyl -1,2,3,4- Tetrahydroquinoline -8-day) Phosphine oxide synthesis

To a 100 mL Schlenk flask was added 8-(diisopropylphosphanyl)-2-methyl-1,2,3,4-tetrahydroquinoline (0.95 g, 3.60 mmol) and THF (10.0 mL). 30 drops of H ₂ O ₂ (28%) were added at room temperature and left overnight at room temperature. After the reaction, the mixture was dried in vacuo to obtain a ligand in quantitative yield.

¹ H-NMR (C6D6): 8.93 (s, 1H), 6.90 (d, 1H), 6.53 (t, 1H), 6.44 (m, 1H), 3.19 (m, 1H), 2.53 (m, 2H), 1.94 (m, 2H), 1.47 (m, 1H), 1.27 (m, 1H), 1.14 (m, 9H), 0.98 (m, 3H), 0.86 (m, 3H)

Example 5

8-( Dicyclohexylphosphoryl )-2- methyl -3,4- Dihydroquinoline -1(2H)-day) Tribenzyl Synthesis of zirconium

Dicyclohexyl(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)phosphine oxide (0.51 g, 1.42 mmol), Zr(CH ₂ Ph) ₄ (1.0) in a 100 mL Schlenk flask eq, 0.646 g) and toluene (0.154 M, 9.3 mL) were added and reacted at 25°C overnight. After the reaction, toluene was removed and extracted with pentane (15 mL*3) to obtain a chocolate solid, 197 mg.

¹ H-NMR (C6D6): As the peaks are broad, it is difficult to assign the peaks

Example 6

(8-( Diisopropylphosphoryl )-2- methyl -3,4- Dihydroquinoline -1(2H)-day) Tribenzyl Synthesis of zirconium

Diisopropyl (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)phosphine oxide (0.66 g, 2.36 mmol), Zr(CH ₂ Ph) ₄ (1.0) in a 100 mL Schlenk flask eq, 1.07 g), toluene (0.154 M, 15.3 mL) was added and reacted at 25°C overnight. After the reaction, toluene was removed and extracted with pentane (15 mL*3) to obtain 226 mg of an ocher solid.

¹ H-NMR (C6D6): As the peaks are broad, it is difficult to assign the peaks

Example 7

<Preparation of ethylene-octene copolymer>

After adding hexane solvent (1.0 L), octene (280 mL), and ethylene (35 bar) to the 2L autoclave reactor, the pressure was adjusted to 500 psi under a high pressure argon pressure, and the reactor temperature was preheated to 120°C. The transition metal compound of Example 5, treated with a triisobutylaluminum compound, was added to a reactor by applying 10 equivalents of a high pressure argon pressure of 5 x 10 ^-6 M of dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst ( 1×10 ^-6 M, 2.0 mL) was placed in a catalyst storage tank, and then a high pressure argon pressure was added to the reactor. 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 proceeded 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 12 hours or more to prepare an ethylene-octene copolymer.

Example 8

<Preparation of ethylene-octene copolymer>

Example 7, except that the transition metal compound of Example 6 treated with a triisobutylaluminum compound was used in place of the transition metal compound of Example 5 treated with a triisobutylaluminum compound in Example 7 Ethylene-octene copolymer was prepared in the same manner as.

Claims (8)

A transition metal compound represented by the following Chemical Formula 1a or 1b.
[Formula 1a]

[Formula 1b]

delete delete delete Catalyst composition comprising a transition metal compound according to claim 1.
A supported catalyst in which the catalyst composition according to claim 5 is supported on a carrier.
A polymer prepared using the catalyst composition according to claim 5.
The method of claim 7,
The polymer is a polyolefin-based polymer.