KR101165490B1 - Novel transition metal catalysts, and method for polymerization of olefin using the same - Google Patents

Abstract

The present invention provides ligand compounds having new two- and three-coordinating sites linked to dimine ligands or derivatives thereof with suitable bridging ligands. In addition, the present invention provides a novel transition metal compound wherein the transition compound of Group 3 to 12 of the periodic table is introduced into the nucleus or trinucleus. The transition metal compound may be used alone as a catalyst for polyolefin production, and may be used with a promoter such as alkylaluminoxane, alkylaluminum, Lewis acid, or the like.

Diimine ligands, transition metal compounds, polynuclear transition metal compounds, polyolefins

Description

New transition metal catalyst, and olefin polymerization method using the same {NOVEL TRANSITION METAL CATALYSTS, AND METHOD FOR POLYMERIZATION OF OLEFIN USING THE SAME}

The present invention relates to a novel transition metal catalyst, and an olefin polymerization method using the same. More specifically, the present invention relates to a ligand compound having a novel structure including an imine derivative composed of a ligand having a double or triple coordination reaction site, such as dimine or a derivative thereof. The present invention relates to a dinuclear or hetero-trinuclear transition metal compound in which transition metals of groups 12 to 12 are introduced, and an olefin polymerization method using the same.

In the polymerization of olefins such as ethylene, the metallocene catalyst system, which is a sandwich compound in which cyclopentadiene is introduced into a transition metal as a polymerization catalyst, has been mainstream. Thus, from the 1980s to the early 1990s, studies for patenting olefin polymerization catalysts focused on metallocene catalysts. Thus, since the mid-1990s, there has been a growing interest in new catalyst systems that can circumvent existing patents. As part of this research, the study of new catalysts in the form of nonmetallocenes rather than metallocenes has attracted great interest.

Representative compounds in which imine-based ligands are introduced as a non-metallocene catalyst system in which an anterior transition metal is introduced are a Group 4 transition metal compound reported by Fujita, T., et al. In 1999 of Mitsui Chemicals. There is a bis-salicylide imine catalyst system in which salicylide imine ligands having various substituents are added to the nitrogen element of the imine group. This catalyst system exhibits very high polymerization characteristics in activity and molecular weight of the produced polymer, compared to the conventional metallocene catalyst system. In addition, it is reported to show a living polymerization characteristic (living polymerization) that is not observed in the existing metallocene catalyst system. This result is disclosed in European Patent No. 0874005.

Research on olefin polymerization catalysts using post-transition metals has also been continuously conducted. An olefin polymerization method (Shell Higher Olefin Process, SHOP) for low molecular weight polyolefins using a nickel catalyst system which is a non-metallocene catalyst system in which a post-transition metal is introduced is known. Since the high activity of ethylene polymerization of nickel-based diimine compounds in the mid-1990s was reported by M. Brookhart, the study of catalyst systems introduced with post-transition metals has been of great interest (Johnson, LK; Killian, CM; Brookhart, M. J. Am . Chem . Soc . 1995, 117 , 6414.).

In the case of the non-metallocene catalyst system in which the post-transition metal is introduced, unlike the conventional metallocene catalyst system, the polymerization of various polyethylenes from the linear polyethylene to the branched polyethylene (Hyper branched polyethylene) in the ethylene polymerization depends on the electronic effect of the ligand. It is reported to be possible.

In addition, ligands having binding sites such as phosphoimine and hydroxyimine have been reported as diimine ligands as ligands of catalysts to which post-transition metals have been introduced. Post-transition metal compounds using these ligands are mostly those having one central metal in each ligand. For example, in the catalytic activity studies of core metals other than nickel and palladium, a catalyst system in which iron was introduced as a trimetallic ligand to a triimine ligand as a core metal was reported by Gibbson and Brookhart in 2000, respectively.

Most non-metallocene forms of compounds that have previously been reported to be post-transition metals were mononuclear compounds with one central metal (Ittel, SD, Johnson, LK, Brookhart, M. Chem . Rev. 2000, 100, 1169 -1203). However, recent research results on a heteronuclear catalyst system having two core metals in a molecule have been reported, and there is an example in which such a catalyst system exhibits different polymerization characteristics from the existing mononuclear catalyst system. As an example of these results, a catalyst in which two central metals are bonded to one ligand has been reported in a catalyst system having a front transition metal as a central metal. Unlike conventional mononuclear catalyst systems, these polymerization catalysts are reported to produce polymers having side chains only by ethylene homopolymerization. However, these catalyst systems are also heteronuclear catalyst systems having the same type or the same group of core metals, and no studies have been made on the heterogeneous catalyst systems belonging to different groups.

The present invention synthesizes a ligand substance of a novel structure having a new double or triple coordination site in which a diimine ligand or a derivative thereof is linked with a suitable bridging ligand, wherein the transition metals of Group 3 to Group 12 of the periodic table are either binuclear or trinuclear. It is an object of the present invention to provide a novel transition metal compound introduced into the process, and a method for polymerizing olefins using the compound as a catalyst.

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In order to achieve the above object, the present invention provides a ligand compound represented by the following formula (1).

In Formula 1,

R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are the same as or different from each other, and each independently a hydrogen atom; An alkyl group having 1 to 11 carbon atoms; An aryl group unsubstituted or substituted with one or more selected from the group consisting of a fluoroalkyl group, a nitro group, a sulfonate group and a halogen group; Arylalkyl group; A halogen group; A nitro group; Sulfonate groups; -OSiZ ₃ ; Or-(G ¹ O) _n G ² , wherein Z is phenyl or straight or branched chain hydrocarbons having 1 to 4 carbon atoms, G ¹ is an alkylene or arylene group having 1 to 4 carbon atoms, and G ² is An alkyl group having 1 to 11 carbon atoms, a phenyl group, a biphenyl group, or a naphthyl group, n is an integer of 1 to 4,

R ⁴ and R ⁵ are the same as or different from each other, and each independently a hydrogen atom; An alkyl group having 1 to 11 carbon atoms; An aryl group unsubstituted or substituted with one or more selected from the group consisting of a fluoroalkyl group, a nitro group, a sulfonate group and a halogen group; Or an arylalkyl group,

Y is a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, aryl group, or at least one aryl group selected from the group consisting of hydroxy group, nitro group, sulfonate group and halogen group,

B is a linking group connecting the coordination ligand and the coordination ligand,-(C) _a- (D) _b- (E) _c- , wherein C and E are an arylene group, and D is a C1-C11 An alkylene group, a, b and c are each 0 or 1, and (a + b + c) is not zero.

The present invention also provides a dinuclear transition metal compound represented by the following Chemical Formula 2, which can be synthesized using the ligand compound represented by Chemical Formula 1.

In Formula 2,

R ¹ to R ¹¹ , Y, and B are the same as defined in Formula 1,

M ¹ and M ² are each independently a transition metal of Groups 3 to 12 of the periodic table,

X ¹ and X ² are each independently halogen or acetyl acetate anion, and the negative charges of X ¹ and X ² are the same as the oxidation number of the central metals M ¹ and M ² , respectively.

The present invention also provides a trinuclear transition metal compound represented by the following Chemical Formula 3, which can be synthesized using the ligand compound represented by Chemical Formula 1.

In Formula 3,

R ¹ to R ¹¹ , Y, and B are the same as defined in Formula 1,

M ¹ , M ² and M ³ are each independently a transition metal of Groups 3 to 12 of the periodic table,

X ¹ , X ² and X ³ are each independently halogen or acetyl acetate anion and the negative charges of X ¹ , X ² and X ³ are the same as the oxidation number of the central metals M ¹ , M ² and M ³ respectively. .

In addition, the present invention provides a method for producing a polyolefin using a transition metal compound represented by Formula 2 or Formula 3 and a polyolefin prepared by the method.

The multinuclear transition metal compound synthesized using the ligand compound represented by Formula 1 according to the present invention can be used as a catalyst for olefin polymerization, and exhibits the same or higher activity as compared to the conventional transition metal catalyst.

Hereinafter, the present invention will be described in detail.

The ligand compound represented by Formula 1 according to the present invention is a ligand compound in which diimine or a derivative thereof, which is a coordinating ligand and a coordinating ligand, is connected with appropriate linkers.

In Formula 1, an alkyl group having 1 to 11 carbon atoms of R ¹ to R ¹¹ is preferably a linear or branched hydrocarbon having 1 to 5 carbon atoms, but is not limited thereto.

In Chemical Formula 1, an aryl group of R ¹ to R ¹¹ is preferably a phenyl group, a biphenyl group, a naphthyl group, anthracyl group, an phenanthracyl group, or the like, but is not limited thereto.

In Formula 1, the halogen group of R ¹ to R ¹¹ is preferably a chloro group, a bromo group, etc., but is not limited thereto.

The ligand compound represented by Chemical Formula 1 according to the present invention may be represented by Chemical Formula 4 as an embodiment.

In Chemical Formula 4,

R ¹ to R ¹¹ are the same as defined in Formula 1,

R ^A and R ^B are each independently a hydrogen atom, an aryl group, an alkyl group having 1 to 11 carbon atoms, a halogen group, an aromatic hydrocarbon group, or a cycloalkyl group.

In Formula 4, an alkyl group having 1 to 11 carbon atoms of R ¹ to R ¹¹ is preferably a linear or branched hydrocarbon having 1 to 5 carbon atoms, but is not limited thereto.

In Chemical Formula 4, an aryl group of R ¹ to R ¹¹ is preferably a phenyl group, a biphenyl group, a naphthyl group, anthracyl group, an phenanthracyl group, or the like, but is not limited thereto.

In Chemical Formula 4, a halogen group of R ¹ to R ¹¹ is preferably a chloro group, a bromo group, or the like, but is not limited thereto.

In Formula 4, R ^A and R ^B are preferably an aryl group, a branched alkyl group having 3 to 6 carbon atoms, an alkoxyalkyl group, and a phenyl group, anthracyl group, phenanthracel group, terphenyl group, or tertiary butyl group (tert). Substituents with large steric hindrance, such as -butyl), are more preferred, but are not limited thereto.

The preparation method of the ligand compound represented by Chemical Formula 1 according to the present invention is described in detail in the following Examples.

The transition metal compound represented by Formula 2 or 3 according to the present invention is prepared by introducing a transition metal of Group 3 to 12 of the Periodic Table into a nucleus or trinucleus into a ligand compound represented by Formula 1.

In Formulas 2 and 3, M ¹ , M ² and M ² is preferably cobalt, iron, nickel, chromium, vanadium, but is not limited thereto.

The transition metal compound represented by Chemical Formula 2 according to the present invention may be represented by Chemical Formula 5 as an embodiment.

In Formula 5, M ¹ , M ² , X ¹ and X ² are the same as defined in Formula 2.

The transition metal compound represented by Chemical Formula 3 according to the present invention may be represented by Chemical Formula 6 as an embodiment.

In Formula 6, M ¹ , M ² , M ³ , X ¹ , X ² and X ³ are the same as defined in Formula 3.

The transition metal compound represented by Chemical Formula 2 or Chemical Formula 3 according to the present invention may be prepared by reacting a ligand compound represented by Chemical Formula 1 in which two kinds of diimine ligands are connected as bridge ligands with a chlorine salt of a metal.

In addition, the present invention provides an olefin polymerization method using a transition metal compound represented by Formula 2 or Formula 3.

In the olefin polymerization method according to the present invention, the transition metal compound represented by the formula (2) or (3) can be used alone as a catalyst, and at least one tank selected from the group consisting of alkylaluminoxane, alkylaluminum and weakly coordinated Lewis acid. It can also be used with a catalyst.

The alkylaluminoxane may be represented by the following formula (7).

In Chemical Formula 7,

R ¹² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group, or an arylalkyl group,

m is an integer from 1 to 100.

The alkyl aluminum may be represented by the following formula (8).

In Chemical Formula 8,

R ¹³ , R ¹⁴ , and R ¹⁵ are the same as or different from each other, and each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, It is a C6-C40 aryl group, an alkylaryl group, or an arylalkyl group, At least one of said R <^13> , R <^14> , and R <^15> contains an alkyl group.

The weakly coordinated Lewis acid may be represented by the following Formula 9.

In Chemical Formula 9,

M is a transition metal of group 3 to 11 of the periodic table,

R ¹⁶ is C1-20 hydrocarbon,

l is an integer from 2 to 4.

In Formula 9, M is preferably a post-transition metal such as iron or nickel, but is not limited thereto.

In Formula 9, R ¹⁶ is preferably cyclooctadiene, but is not limited thereto.

In the olefin polymerization method according to the present invention, the polymerization may be carried out by a slurry phase polymerization, liquid phase polymerization, gas phase polymerization, or bulk polymerization method. When the polymerization is carried out in a slurry or liquid phase, a solvent may be used as the polymerization medium, and preferred solvents include 4 carbon atoms such as butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, methylcyclopentane, and cyclohexane. Alkanes or cycloalkane solvents of from 20 to 20; Aromatic hydrocarbon solvents having 6 to 20 carbon atoms such as benzene, toluene, xylene, and mesitylene; Dichloromethane, chloromethane, chloroform, carbon tetrachloride, chloroethane, 1,2-dichloroethane, 1,1,2,2, -tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichloro C1-C20 halogenated alkane, halogenated aromatic hydrocarbon solvent, etc., such as robenzene. The solvent may be used alone or in combination at a constant ratio.

In the olefin polymerization method according to the present invention, the reaction pressure during olefin polymerization is preferably 0.01 to 1,000 atm. When the reaction pressure is less than 0.01 atm, the reaction rate is low, the productivity is low, there is a problem due to the vaporization of the solvent used, etc., if the reaction pressure exceeds 1,000 atm there is a problem of equipment cost increase, such as equipment costs according to the high pressure .

In the olefin polymerization method according to the present invention, examples of the olefin monomers usable in the olefin polymerization include ethylene, alpha-olefins, cyclic olefins, and the like, and diene olefin monomers or triene olefins having two or more double bonds. System monomers and the like can also be used, and comonomers can be added.

Specific examples of the monomers include 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-aitocene, norbornene, nobornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. More specifically, the monomer is preferably ethylene.

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

< Ligand  Synthesis of Compounds>

< Synthetic example  1> 1- (6-((E) -1- (2,6- Diisopropylphenylimino ) Ethyl) pyridin-2-yl) Ethanone  Synthesis [1- (6-((E) -1- (2,6-) diisopropylphenylimino ) ethyl ) pyridin -2- yl ) ethanone , Ligand  Compound (1)]

[Ligand compound (1)]

Methanol solution of 2,6-diacetylpyridine (1,630 g, 10.0 mmol) and 2,6-diisopropylaniline (2,6-diisopropylaniline, 1.70 mL, 1.596 g, 9.0 mmol) (15 mL ) Was added at room temperature. After 12 hours, a yellow solid was formed, which was washed 3-4 times with cold methanol (0 ° C.). After the resulting solid was refluxed in ethanol, the dissolved solution was filtered to reduce the solvent, and a yellow solid was obtained in a yield of 67% (2.17 g, 6.73 mmol).

Mp 182-184 ° C. IR: ν (C = N) 1648 cm ⁻¹ , ν (C = O) 1698 cm ⁻¹ .

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.16 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 1.17 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 2.28 [s, 3H, C (NAr) CH ₃ ], 2.74 [sept, 2H, CH (CH ₃ ) (CH ₃ )], 2.81 [s, 3H, C (O) CH ₃ ], 7.08- 7.22 (m, 3H, CH Ar), 7.96 (t, 1H, CH Ar), 8.16 (d, 1.2 Hz, 1 H, CH Ar), 8.58 (d, 1.2 Hz, 1 H, CH Ar) ppm .

¹³ C-NMR (300 MHz, CDCl ₃ ): δ 17.7 [1 C, C (NAr) CH ₃ ], 23.5 [2 C, CH (CH ₃ ) (CH ₃ )], 23.9 [2 C, CH (CH ₃ ) (CH ₃ )], 26.4 [1 C, C (O) CH ₃ ], 29.0 [2 C, CH (CH ₃ ) (CH ₃ )], 123.2 (1 C, CH Ar), 123.7 (2 C , CH Ar), 124.4 (1 C, CH Ar), 125.2 (1 C, CH Ar), 136.4 (2 C, C Ar), 138.4 (1 C, CH Ar), 142.9 (1 C, C Ar), 153.1 (1 C, CH Ar), 156.2 (1 C, C Ar), 167.8 [1 C, C (NAr) CH ₃ ], 200.8 [1 C, C (O) CH ₃ ] ppm.

Calcd for C ₂₁ H ₂₆ N _{2 O} (322.45): C 78.22, H 8.13, N 8.69, O 4.96; Found C 78.39, H 8.17, N 8.84, O 4.6.

< Synthetic example  2> 4-((4E) -4- (1- (6-((E) -1- (2,6- Diisopropylphenylimino ) Ethyl) pyridin-2-yl) Ethyleneamino ) -3,5- Diisopropylbenzyl ) -2,6- Diisopropyl  Benzeneamine [4-((4E) -4- (1- (6-((E) -1- (2,6-diisopropylphenylimino) ethyl) pyridine -2-yl) ethyleneamino) -3,5-diisopropylbenzyl) -2,6-diisopropyl benzenamine , Ligand  Compound (2)]

[Ligand compound (2)]

Ligand Compound (1) prepared in Synthesis Example 1 (1.6 g, 5 mmol) and 4,4'-methylenebis (2,6-diisopropylaniline) (4,4'-methylenebis (2,6-diisopropylaniline) , 5.5 g, 15 mmol) was dissolved in 15 ml of xylene and the solution was stirred at 100 ° C. until the solution became clear. Acetic acid (100 μL) was added to the solution and stirred for 5 days. After the solution was removed under reduced pressure, methanol was added to obtain a solid at low temperature. The resulting solid was washed several times with cold methanol. Methanol was removed and purified by column chromatography [5% ethyl acetate (EA) / n- hexane-alumina] to give the compound (2) in a yield of 60%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 1.27 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 1.28 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 2.30 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 1.32 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 1.38 [d, 6 H, CH (CH ₃ ) (CH ₃ ) )], 1.40 [d, 6 H, CH (CH ₃ ) (CH ₃ )], 2.2 [s, 6 H, C (NAr) CH ₃ ], 2.68 [sept, 2 H, CH (CH ₃ ) (CH ₃ )], 2.72 [sept, 2 H, CH (CH ₃ ) (CH ₃ )], 2.86 [sept, 2 H, CH (CH ₃ ) (CH ₃ )], 3.56 (s, 2 H, NH ₂ ) , 3.88 (s, 2H, CH ₂ ), 6.82 (s, 2H, CHAr), 6.94 (s, 2H, CHAr), 7.09 (m, 3H, CHAr), 7.84 (t, 1H, CHAr ), 8.42 (dd, 1 H, CHAr) ppm.

¹³ C-NMR (300 MHz, CDCl ₃ ): δ = 16.13, 21.51, 21.99, 22.20, 26.83, 26.95, 27.17, 27.28, 122.21, 122.58, 122.80, 130.32, 131.47, 134.54, 134.71, 135.29, 136.92, 143.20, 145.44, 154.02, 154.20, 165.88, 166.09. Anal. Calcd for C ₄₆ H ₆₂ N ₄ (671.01): C 82.34, H 9.31, N 8.35; Found C 82.34, H 9.31, N 8.35.

< Synthetic example  3> Vis -[4-((4E) -4- (1- (6-((E) -1- (2,6- Diisopropylphenylimino ) Ethyl) pyridin-2-yl) Ethyleneamino ) -3,5- Diisopropylbenzyl ) -2,6- Diisopropylimino ] Ah Cenaphthalenequinone [bis- [4-((4E) -4- (1- (6-((E) -1- (2,6-) diisopropylphenylimino ) ethyl ) pyridine -2- yl ) ethyleneamino ) -3,5-diisopropylbenzyl) -2,6-diisopropyl imino ] acenaphthalenequinone , Ligand  Compound (3)]

[Ligand compound (3)]

Ligand compound (2) (1.5 g, 2.2 mmol) and acenaphthalenequinone (0.18 g, 1 mmol) prepared in Synthesis Example 2 were dissolved in 10 ml of xylene at 100 ° C. Acetic acid (100 μL) was added and the solution stirred for 5 days. The resulting solution was purified by an auto column (CombiFlash-companion autocolumn) using hexane (solvent B) and ethyl acetate (solvent A) as eluents. An orange solid was obtained at a yield of 0.5 g (33%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ 0.873 [d, 12 H, CH (CH ₃ ) (CH ₃ )], 0.90 [d, 12 H, CH (CH ₃ ) (CH ₃ )], 1.09 [d, 12 H, CH (CH ₃ ) (CH ₃ )], 1.11 [d, 12 H, CH (CH ₃ ) (CH ₃ )], 1.14 [d, 12 H, CH (CH ₃ ) (CH ₃ ) )], 1.16 [d, 12 H, CH (CH ₃ ) (CH ₃ )], 2.21 [s, 6 H, C (NAr) CH ₃ ], 2.25 [s, 6 H, C (NAr) CH ₃ ] , 2.71 [sept, 4 H, CH (CH ₃ ) (CH ₃ )], 2.73 [sept, 4 H, CH (CH ₃ ) (CH ₃ )], 2.96 [sept, 4 H, CH (CH ₃ ) ( CH ₃ )], 4.07 (s, 2H, CH ₂ ), 6.73 (m, 4H, CHAr), 7.00 (m, 4H, CHAr), 7.08 (m, 6H, CHAr), 7.87 (m, 2 H, CHAr), 8.44 (m, 4H, CHAr) ppm.

¹³ C-NMR (300 MHz, CDCl ₃ ): δ = 16.16, 21.92, 22.10, 22.18, 22.31, 22.47, 27.24, 27.54, 40.42, 121.16, 121.96, 122.39, 123.49, 127.77, 128.58, 130.06, 134.19, 134.60, 134.74, 135.60, 135.82, 143.21, 144.35, 145.43, 154.03, 154.16, 160.06, 165.92, 166.19, 178.47. Anal. Calcd for C ₁₀₄ H ₁₂₆ N ₈ (1487.01): C 83.94, H 8.53, N 7.53; Found C 83.94, H 8.53, N 7.53.

<Production of Transition Metal Compound>

< Manufacturing example  1> Preparation of mononuclear transition metal compound represented by the following structural formula ( catalyst  One)

12 hours after adding the ligand compound (1) prepared in Synthesis Example 1 (0.15 g, 0.1 mmol) and (DME) NiBr ₂ (0.03 g, 0.1 mmol) under nitrogen conditions to a solvent of CH ₂ Cl ₂ (20 mL) Was stirred. After filtering the reaction solution, the solvent was removed under reduced pressure from the filter solution. Ether was then added to precipitate the solid product, filtered and dried under vacuum at 60 ° C. A brown solid can be obtained at a yield of 90%.

< Manufacturing example  2> Preparation of the binuclear transition metal compound represented by the following structural formula ( catalyst  2)

Ligand compound (2) prepared in Synthesis Example 1 (0.3 g, 0.2 mmol) and FeCl _{2 in} a reactor containing 20 ml of THF under nitrogen conditions ? 4H ₂ O (0.08 g, 0.4 mmol) was added and stirred at room temperature for 12 hours. The compound precipitated by addition of ether was filtered and dried in vacuo at 60 ° C. A dark green compound was obtained with a yield of 90% or more. The low solubility and paramagnet nature made it difficult to analyze using NMR spectroscopy, and the product was identified by IR.

< Manufacturing example  3> Preparation of a trinuclear transition metal compound represented by the following structural formula ( catalyst  3)

In a reactor at 30 ° C., a binary nucleus transition metal compound catalyst 2 (0.2 g, 0.11 mmol) and (DME) NiBr ₂ (0.04 g, 0.13 mmol) prepared in Preparation Example 2 were added to the reactor using CH ₂ Cl ₂ as a solvent. . The reaction was stirred for 24 hours. Ether was added to precipitate the product which was then obtained through a filter and dried in vacuo. A dark green compound was obtained with a high yield of 90% or more. The low solubility and paramagnet nature made it difficult to analyze using NMR spectroscopy, and the product was identified by IR.

<Ethylene polymerization>

< Example  1 to 14

Ethylene polymerization was performed after a magnetic stirrer and thermometer were installed in a 250 mL round bottom flask. 80 ml of toluene and a catalyst were added to the reactor, and the reactor temperature was adjusted to the polymerization temperature. After the reactor temperature reached a certain temperature, ethylene monomer was started to be injected into the reactor. After the ethylene pressure was constant, ethylene polymerization was started with the addition of a promoter to the reactor. After 30 minutes of polymerization, the reaction was terminated with methanol of 10% HCl. The resulting polymer was washed with excess methanol and dried in vacuo at 50 ° C. The catalyst and polymerization conditions used for the ethylene polymerization are shown in Table 1 below.

* MAO: methylaluminoxane,

  EAS: Ethyl Aluminum Sesquichloride,

  TEA: Triethyl aluminum,

  M: center metal (Ni or Fe).

<Ethylene polymerization result>

The ethylene polymerization results of Examples 1 to 14 are shown in Table 2 below.

In the results of Table 2, the yield was measured by the weight of the obtained polymer, M _n (number average molecular weight) and PDI (polydispersity, polydispersity) was measured by GPC (gel permeation chromatography), T _m is DSC (differential scanning) calorimeter, heating rate: 10 ℃ / min) and the number of branches (branch) was measured using a polymer ¹³ C-NMR.

Claims (28)

Formula 11 comprising 1- (6-((E) -1- (2,6-diisopropylphenylimino) ethyl) pyridin-2-yl) ethanone represented by Formula 10 as a ligand compound A bidentate mononuclear transition metal catalyst for the polymerization of polyolefins in the presence of an aluminum promoter [Formula 10]

[Formula 11]

(Wherein Z1 is Ni, L is each independently halogen or acetyl acetate anion, and the negative charge of L is the same as the oxidation number of the central metal Z1.) delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete React the transition metal catalyst and the aluminum-containing promoter with the olefin, As a transition metal catalyst, a bidentate mononuclear transition metal catalyst represented by Formula 11 of claim 1 is used, As the aluminum-containing promoter, one selected from alkylaluminoxanes represented by the following formula (7), alkylaluminum represented by the following formula (8), and weakly coordinated Lewis acids represented by the following formula (9) is used. A polymerization method of olefins, characterized in that the olefinic monomers are polymerized under the condition that the molar ratio of Al / Z1 is 300. [Formula 11]

(Wherein Z1 is Ni, L is each independently halogen or acetyl acetate anion, and the negative charge of L is the same as the oxidation number of the central metal Z1.) [Formula 7]

In Chemical Formula 7, R ¹² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group, or an arylalkyl group, m is an integer from 1 to 100. [Formula 8]

In Chemical Formula 8, R ¹³ , R ¹⁴ , and R ¹⁵ are the same as or different from each other, and each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, It is a C6-C40 aryl group, an alkylaryl group, or an arylalkyl group, At least one of said R <^13> , R <^14> , and R <^15> contains an alkyl group. [Chemical Formula 9]

In Chemical Formula 9, M is aluminum, R ¹⁶ is C1-20 hydrocarbon, l is an integer from 2 to 4. delete delete delete delete The olefin polymerization method according to claim 18, wherein the polymerization is performed by slurry phase polymerization, liquid phase polymerization, gas phase polymerization, or bulk polymerization. The method according to claim 18, Alkanes or cycloalkane solvent having 4 to 20 carbon atoms in the polymerization; Aromatic hydrocarbon solvents having 6 to 20 carbon atoms; And at least one solvent selected from the group consisting of halogenated alkane or halogenated aromatic hydrocarbon solvent having 1 to 20 carbon atoms. The olefin polymerization method according to claim 18, wherein the polymerization pressure is 0.01 to 1,000 atm, and the reaction temperature is 30 ° C. The olefin polymerization method according to claim 18, wherein the olefin monomer is selected from the group consisting of ethylene, alpha-olefin, cyclic olefin, diene olefin monomer, and triene olefin monomer. delete delete