KR100431444B1 - Catalyst for olefin polymerization and method for preparing polyolefins - Google Patents

Abstract

The present invention relates to a catalyst for polyolefin production and a polymerization method of olefins using the same, and more particularly, to a method for producing polyolefin using a compound obtained by activating a metalloenamine compound with Lewis acid as a catalyst.

C = CNM metal to the enamine compound having a skeleton of the structure is an alpha-I carbon has a high nucleophilic various Lewis acids (A) and the ^reaction is zwitterions (zwitterions) compounds having the structure of ACC = NM ⁺ Obtained. At this time, as the metal has a cationic character, it becomes active in olefin polymerization. The catalyst thus obtained can be used for various olefin polymerizations.

Description

Catalyst for polyolefin production and polyolefin production method using the same {Catalyst for olefin polymerization and method for preparing polyolefins}

The present invention relates to a catalyst system used to prepare polyolefins and to a polymerization method of olefins using the same.

Metallocene catalysts based on cyclopentadienyl ligands are widely used for the polymerization of olefins. Such metallocene catalysts require anionic co-catalysts as catalytic activators. In addition, the development of single-site homogeneous catalysts outside of the range of existing metallocene catalysts is being actively conducted in academic and industrial fields (GJP Britovsek, VC Gibson, DF Wass, Angew. Chem., Int. Ed. Eng. 38 (1999) 429). The structural features of almost all single site catalysts, as well as metallocene catalysts, consist of ion pairs of cations and anions. Indeed, where the polymerization takes place is cationic central metal, which is cationic due to its electrophilicity, increasing the bond of ethylene. In order to exhibit high polymerization activity, the anion should not be coordinated with the cationic core metal. As the anion active catalyst, mainly bulky compounds such as methylaluminoxane (MAO) or tris (petatafluorophenyl) boron are used, which is the center when using anions derived from these compounds. It is not coordinating with metal, and thus high activity can be obtained.

However, catalysts in which cations and anions exist as ion pairs can inhibit the polymerization process by preventing the anion from circulating the central metal and the monomers from accessing the central metal.

Recently, several attempts have been made to prepare zwitterions catalysts having both cations and anions in a molecule to overcome this. Representative examples thereof are shown in Schemes 1 and 2. Scheme 1 is an activated catalyst of zwitterions by reacting tris (pentafluorophenyl) boron in which a part of the substituent of cyclopentadienyl is bonded by zirconium and methylene group. (WE Piers, et al. J. Am Chem. Soc. 1997, 5132). The structure of this catalyst is similar to that of a metallocene catalyst having a cyclopentadienyl structure as a basic skeleton except that the anion is in a molecule by a covalent bond.

Scheme 1

Scheme 2 shows that the Lewis acid B (C ₆ F ₅ ) ₃ is a ligand when B (C ₆ F ₅ ) ₃ is used as a ligand for caboxamidato-Nickel (II). It is attached to an oxygen atom of carbonyl to provide an activated catalyst in the form of an amphoteric ionic compound (Lee, BY et al. J. Am. Chem. Soc. 2001, 123, 5352).

Scheme 2

However, conventional catalysts composed of complex salts mainly use MAO or tris (pentafluorophenyl) boron in the activation step, which is a cost increase factor due to their high cost.

Accordingly, an object of the present invention is to provide a catalyst in the form of zwitterions of various structures by a new reaction, and to provide an olefin polymerization method using the same.

That is, an object of the present invention is to provide a catalyst having a new molecular structure, and thereby to provide a polymer having a new molecular structure.

In order to achieve the above object, the present invention provides a catalyst system composed of a metalloenamine compound and a Lewis acid. This provides a new concept of chemical reaction for activating a metal compound, a metalloenamine compound. That is, the Lewis acid is reacted with the metalloenamine compound as shown in Schemes 3 and 4 to provide an activated catalyst having zwitterions.

Scheme 3

Scheme 4

Metalloenamine compound refers to all the molecules which have a structure of C = C-N-M as a basic skeleton. Where M is a metal element, N is a nitrogen element, and C is a carbon element.

Lewis acids provide R _5- [Al (R ₅ ) -O] _a -AlR ⁵ ₂ , AlX _n (R ⁵ ) _3-n or BX _n (R ⁵ ) _3-n and the like. X is hydrogen, halogen, alkoxy or aryloxy, R ⁵ is a halogen radical, hydrocarbyl or hydrocarbyl substituted with halogen, a is an integer of at least 1 and n is an integer from 0 to 3. When _n of X _n is 2 or more, X may be the same as or different from each other, and when a is 2 or more or (R ⁵ ) ₃ n is 0 or 1, R ⁵ may be the same or different.

In addition, the present invention can use the catalyst system in the polymerization process of the olefin. Polymerization can be accomplished by contacting the catalyst system with olefin monomers at temperatures and pressures sufficient to produce polyolefins.

Metalloenamine compounds in which the metal is lithium or magnesium in organic chemistry have been studied. In other words, alpha carbon is rich in electrons and can be used as a nucleophile, which is useful when reacting with various electrophiles to form new carbon carbon bonds (Scheme 5, W. Carruthers by Some modern methods of organic). synthesis 3rd edition pp 26 38).

Scheme 5

When the metalloenamine compound is described in detail, the metalloenamine compound means all compounds having a basic structure of MNC = C, and specific examples of the metalloenamine compound are as follows (Formulas 1 and 2) . However, the structure of the metalloenamine compound is not limited by this example.

Structural Formula 1

(1) (2)

In formula (1), M is Ni, Pd, or Pt, R, R ′, R ″ are each hydrogen radical, hydrocarbyl, substituted hydrocarbyl, A is π-allyl, substituted π-allyl, π-benzyl or Substituted π-benzyl, L is a neutral monodentate ligand which may be substituted by an olefin, L 'is a monodentate ligand of anion, and L and L' are linked to each other May be a bidentate ligand.

More specifically, for example, the metalloenamine compound having the structure of Structural Formula 1 is illustrated as follows.

Structural Formula 2

In formula 2 M is Ti, Zr, Hf, V, or Sc and L is an anionic or neutral ligand and x is 0 or 1 or 2. When x is 2, each L may be the same or different from each other. R, R 'is a hydrogen radical, hydrocarbyl or substituted hydrocarbyl and X is a halogen radical, alkoxy radical, aryl oxy radical, hydrocarbyl or substituted hydrocarbyl and y is 1 or 2. When y is 2, each X may be the same or different.

More specific examples of the metalloenamine compound having the structure of Structural Formula 1 are as follows.

Such a metalloenamine compound may be prepared by reacting a ketiminate anion ligand with a halometal compound. Ketimate anion ligands can be prepared by deprotonation of an imine compound having hydrogen on alpha carbon with an appropriate base (Scheme 6).

Scheme 6

The catalyst for olefin polymerization may be prepared by activating the metalloenamine compound thus prepared with Lewis acid.

As Lewis acid, the following compounds can be used individually or in mixture. However, this does not limit the Lewis acids that can be used.

(1) Aluminoxane compound represented by Structural Formula 3

R ^5- [Al (R ⁵ ) -O] _a -AlR ⁵ ₂ or (Structure 3)

Wherein R ⁵ is the same or different halogen radical, hydrocarbyl radical or hydrocarbyl radical substituted by halogen and a is an integer of 1 or more. When a is 2 or more, R ⁵ may be the same or different. This compound can exist in linear, circular or mesh form. Examples of this compound include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like.

(2) An organoalkylaluminum represented by AlX _n (R ⁵ ) _3-n .

Wherein X is hydrogen, halogen, alkoxy or aryl oxy and R ⁵ is as defined in formula 3 above. n is an integer of 0-3. For X _n n is 2 or more, X may be the same or different from each other, (R ⁵⁾ _3-n, if n is 0 or 1 of R ⁵ may be the same or different from each other. Examples of such compounds are tris (pentafluorophenyl) aluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloro Aluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl Aluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide and the like.

(3) Boron compound represented by BX _n (R ⁵ ) _3-n .

Wherein X, R ^5, n is as defined in (2) above, wherein, and in the case of X _n n is 2 or more, X may be the same or different from each _{^{other, (R 5) 3-n}} n is 0 or 1, of R ⁵ may be the same as or different from each other. Examples of this compound include tris (pentafluorofluorophenyl) boron, bis (pentafluoroboron), trifluoroboron, trichloroboron, triiodoboron and the like.

(4) transition metals such as anhydrous ZnCl ₂ , FeCl ₃ , TiCl ₄ , TiCl ₃ .

(5) The Lewis acid described in (1)-(4) above is supported on a suitable carrier such as silica.

(6) Silica dehydrated at 600 degreeC or more.

The silica thus treated forms a siloxane group with a large ring strain on its surface, which can be directly used as a Lewis acid.

When the metalloenamine compound is reacted with Lewis acid, as shown in Scheme 4, Lewis acid attacks electron-rich alpha carbon to obtain an activated catalyst species of zwitterions.

The catalyst obtained by activating the metalloenamine compound with the Lewis acid can be used for producing polyolefin. Solvents used in the preparation of olefinic polymers include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane and their isomers and aromatic hydrocarbon solvents such as toluene, benzene, dichloromethane, Hydrocarbon solvents substituted with chlorine atoms such as chlorobenzene may be used respectively, or two or more may be used in combination. Or may be polymerized in the gas phase without solvent.

Examples of the olefin monomer that can be polymerized using the metalloenamine compound and the Lewis acid activator include ethylene, alpha olefin, cyclic olefin, and the like, and a diene olefin monomer or triene olefin having two or more double bonds. The monomers and the like can also be polymerized. Examples of such monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetra Decene, 1-hexadecene, 1-icocene, norbornene, norbornadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6- Hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, and the like can be mixed and copolymerized by mixing two or more kinds of these monomers.

The polymerization method of the olefin according to the present invention can be carried out by a conventional method. That is, in a dry box, an appropriate amount of catalyst, cocatalyst, and organic solvent are added to a glass reactor, and the reactor is assembled. The polymerization can be carried out by stirring. The polymerization is carried out at a temperature in the range from 25 to 500 ° C. and a pressure in the range from 15 to 1500 psi, and is polymerized by adding 1 to 30000 times the number of moles of Lewis acid to the number of moles of metallocene. In the present invention, the contact order and the addition order of the catalyst, the promoter, the solvent and the monomer are not particularly limited.

The present invention is described in detail with reference to the following examples, but the present invention is not limited thereto.

EXAMPLE

Example 1

Nickel-Based Metalloenamine Compound Synthesis

(1) Compound 3 Synthesis

Compound 1 (1.62g, 4.00mmol), KH (0.160g, 4.0mmol), THF (20g) was quantitated in a dry box, and then stirred at room temperature for 2 days in a flask. As the reaction proceeded, hydrogen gas was generated, and finally all KH in the slurry disappeared and a dark orange solution was obtained. When a little amount was taken to remove the solvent, ¹ H NMR analysis confirmed that the desired compound 2 was obtained almost quantitatively. NMR spectra were obtained using a 200 MHz device manufactured by Varian Corporation or a 300 MHz device manufactured by Brooker Corporation.

¹ H NMR (300 MHz, C ₆ D ₆ / THF-d ₈ (10: 1)): 7.35 (d, J = 7.6 Hz, 2 H, ph-H ^3,5 ), 7.12 (d, J = 7.6 Hz, 2H, ph-H ^3,5 ), 7.12 (t, J = 7.6 Hz, 1H, ph-H ⁴ ), 7.03 (t, J = 7.6 Hz, 1H, ph-H ⁴ ), 4.22 (d, J = 1.0 Hz, 1 H, = CH ₂ ), 3.85 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 3.59 (d, J = 1.0 Hz, 1 H, = CH ₂ ) , 3.05 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 2.13 (s, 3 H, CH ₃ ), 1.59 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.33 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.18 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.15 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ )

After removing all solvents by using a vacuum pump, B (C ₆ F ₅ ) ₃ (2.05g, 4.0mmol) and toluene 20mL was added and stirred for about 30 minutes. After removing some suspended matter by filtration, 40 mL of pentane was added to the filtered solution. When left at room temperature overnight, off-white crystals settled, and the precipitate was filtered to give Compound 3. NMR structure analysis showed that one molecule of toluene was contained. The yield was 3.30 g (79%).

¹ H NMR (300 MHz, C ₆ D ₆ / THF-d ₈ (10: 1)): 7.2 7.0 (m, 8 H, toluene, ph-H ^3,4,5 ), 6.91 (br d, J = 7.6 Hz, 2H, ph-H ^3,5 ), 6.81 (br d, J = 7.6 Hz, 2H, ph-H ⁴ ), 3.47 (br s, 2H, CH ₂ -B), 2.89 (br septet , J = 6 Hz, 2 H, i Pr-CH), 2.37 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 2.12 (s, toluene), 1.78 (br s, 3 H, CH ₃ ), 1.23 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.10 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.09 (br d, J = 6 Hz, 6 H, i Pr-CH ₃ ), 1.00 (br d, J = 6 Hz, 6 H, i Pr-CH ₃ ). ¹³ C NMR (C ₆ D ₆ / THF-d ₈ (10: 1)): 176.13, 170.85 ( C = N), 150 (dm, J = 960 Hz, p - C F), 148.32, 145.78 (ipso- C ), 139.3 (dm, J = 480 Hz, o - C F), 138.24 (toluene), 137.67, 137.09 (ph-C ² ), 136.9 (dm, J = 560 Hz, m - C F), 129.67 ( toluene), 128.89 (toluene), 126.02 (toluene), 124.43, 123.81 (ph- C ⁴ ), 123.81, 123.39 (ph- C ³ ), 32.72 (m, B-CH ₂ ), 28.31, 28.00 ( i Pr- C H), 25.06, 24.87, 24.16, 23.08 ( i Pr- C H ₃ ), 21.74 (toluene), 19.52 ( C H ₃ )

(2) Compound 4 Synthesis

In a dry flask, Compound 3 (0.523 g, 0.500 mmol), Ni (η ³ -CH ₂ C ₆ H ₅ ) Cl (PMe ₃ ) (0.131 g), and toluene (4 g) were added and stirred overnight at room temperature. Filter removes byproduct KCl, and then removes all solvents by vacuum depressurization. Add about 10 mL of pentane and filter over celite to get a dark red solution. All solvents were removed to give a red solid. ¹ H NMR structure analysis showed that almost pure compounds were obtained, and in deuterated benzene, two rotomers were present at about 4: 1 ratio depending on the position of η ³ -benzyl ligand. there was. However, by changing the solvent to deuterated acetonitrile, η ³ -benzyl was converted into η ¹ -benzyl and was found to be converted into one compound. The yield was 0.255 g (81%). The darker peaks in the following NMR data are interpreted as derived from minor isomers.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 7.4 6.9 (m, 6 H, ph-H ^3,4,5 ), 6.58 and 6.76 (t, J = 7.6 Hz, benyl- p -H) , 6.27 and 6.42 (t, J = 7.6 Hz, benyl-mH), 6.06 and 5.96 (d, J = 7.6 Hz, benyl- o -H), 4.15 and 3.72 (septet, J = 6.8 Hz, 2H, i Pr-C H ), 4.13 and 4.19 (s, 1 H, C = CH ₂ ), 3.83 and 3.76 (s, 1 H, C = CH ₂ ), 3.10 and 3.52 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 1.54 and 1.36 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.52 and 1.57 (s, 3 H, CH ₃ ), 1.49 and 1.20 (s, 2 H, benzyl -CH ₂ ), 1.46 and 1.36 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.12 and 1.02 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.90 and 1.02 (d, J = 6.8 Hz, 6H, i Pr-CH ₃ ). ¹ H NMR (300 MHz, CD ₃ CN): 7.3 6.8 (m, 11H, ph-H and benzyl), 4.07 (s, 1H, C = CH ₂ ), 4.05 (br septet, J = 7 Hz, 2 H, i Pr-CH), 3.52 (br septet, J = 7 Hz, 2 H, i Pr-CH), 3.13 (s, 1 H, C = CH ₂ ), 1.82 (s, 3 H, CH ₃ ), 1.43 (br d, J = 7 Hz, 6 H, i Pr-CH ₃ ), 1.40 (br d, J = 7 Hz, 6 H, i Pr-CH ₃ ), 1.34 (s, 2 H, benzyl -CH ₂ ), 1.32 (br d, J = 7 Hz, 6H, i Pr-CH ₃ ). ¹³ C NMR (75 MHz, CD ₃ CN): 176.47 ( C = N), 161.33 (CH ₂ C -N), 154.99, 147.79 (ph- C ¹ ), 147.57, 140.08 (ph- C ² ), 143.88 ( benzyl -ipso-C ), 128.38, 127.93, 126.82 (benzyl), 124.72, 121.79 (ph- C ⁴ ), 124.06, 123.94 (ph- C ³ ), 87.22 ( C H ₂ -CN), 29.25, 28.59 ( i Pr- C H), 25.82, 24.39, 23.78, 23.64 ( i Pr- C H ₃ ), 20.02, 17.83 ( C H ₃ , benzyl- C H ₂ )

Example 2

compound 4 And reaction with Lewis acid

(1) Reaction with B (C ₆ F ₅ ) ₃

Compound 4 (13.8 mg, 0.025 mmol) and B (C ₆ F ₅ ) ₃ (12.8 mg, 0.025 mmol) were dissolved in C ₆ D ₆ and subjected to ¹ H NMR analysis. Two rotomers by η ³ -benzyl were present at a ratio of about 3: 1. The hydrogens of CH ₂ = C, which appeared as a pair, appear as one, indicating that B (C ₆ F ₅ ) ₃ reacted with a double bond carbon.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 7.16 (t, J = 7.6 Hz, 1 H, ph-H ⁴ ), 7.02 (t, J = 7.6 Hz, 1 H, ph-H ⁴ ) , 7.02 and 6.93 (d, J = 7.6 Hz, 2H, ph-H ³ ), 6.83 and 6.91 (d, J = 7.6 Hz, 2H, ph-H ³ ), 6.60 and 6.61 (t, J = 7.6 Hz, 1 H, benyl- p -H), 6.01 and 6.03 (t, J = 7.6 Hz, 2 H, benyl- m -H), 5.82 and 5.88 (d, J = 7.6 Hz, 2 H, benyl- o -H), 3.33 and 3.24 (br d, J = 7.2 Hz, 1 H, CH ₂ -B), 3.30 and 3.20 (br d, J = 7.2 Hz, 1 H, CH ₂ -B), 2.90 and 2.99 ( septet, J = 6.8 Hz, 2 H, i Pr-CH), 2.60 and 2.72 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 1.46 and 1.40 (s, 2 H, benzyl-CH ₂ ) , 1.32 and 1.21 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.20 and 1.10 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.95 and 1.08 (s, 3 H, CH ₃ ), 0.90 and 0.98 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.85 and 0.92 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ).

(2) reaction with BF ₃

Compound 4 (13.8 mg, 0.025 mmol) in benzene (about 0.3 mL) and BF ₃ (3.6 mg, 0.025 mmol) in benzene (about 0.3 mL) were added slowly with stirring. All volatiles were removed with a vacuum pump and dissolved in C ₆ D ₆ for ¹ H NMR analysis. Two rotomers with η ³ -benzyl were present in the ratio of about 3: 2.

¹ H NMR (200 MHz, C ₆ D ₆ ): δ 7.2 6.8 (m, 6 H, ph-H ^3,4,5 ), 6.63 and 6.67 (t, J = 7.8 Hz, 1 H benyl- p- H), 6.18 and 6.22 (t, J = 7.8 Hz, 2 H, benyl- m -H), 5.94 and 5.91 (d, J = 7.8 Hz, 2 H, benyl- o -H), 3.28 and 3.66 (septet and br septet , J = 6.8 Hz, 2 H, i Pr-CH), 2.86 and 2.43 (septet and br septet, J = 6.8 Hz, 2 H, i Pr-CH), 2.3 2.0 (br, 2 H, CH ₂ -B), 2.08 and 2.15 (s, 3 H, CH ₃ ), 1.51 and 1.42 (s, 2 H, benzyl-CH ₂ ), 1.42 and 1.28 (d, J = 6.8 Hz, 6 H, i Pr- CH ₃ ), 1.40 and 1.25 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.00 and 1.06 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.94 and 1.06 ( d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ).

(3) Reaction with Al (C ₆ F ₅ ) ₃

Compound 4 (13.8 mg, 0.025 mmol) and Al (C ₆ F ₅ ) ₃ toluene (15.5 mg, 0.025 mmol) were dissolved in C ₆ D ₆ and subjected to ¹ H NMR analysis. Two rotomers with η ³ -benzyl were present in the ratio of about 3: 2. The hydrogens of CH ₂ = C, which appeared as a pair, appear as one, indicating that Al (C ₆ F ₅ ) ₃ has reacted with the carbon having a double bond.

¹ H NMR (200 MHz, C ₆ D ₆ ): δ 7.2 6.8 (m, 6 H, ph-H ^3,4,5 ), 6.61 and 6.59 (t, J = 7.8 Hz, 1 H benyl- p- H), 6.10 and 6.09 (t, J = 7.8 Hz, 2 H, benyl- m -H), 5.86 and 5.82 (d, J = 7.8 Hz, 2 H, benyl- o -H), 3.24 and 3.21 (septet , J = 6.8 Hz, 2 H, i Pr-CH), 2.78 and 2.95 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 2.74 (br s, 2 H, CH ² -Al), 1.65 and 1.67 (s, 3H, CH ₃ ), 1.43 and 1.40 (s, 2H, benzyl-CH ₂ ), 1.24 and 1.27 (d, J = 6.8 Hz, 6H, i Pr-CH ₃ ), 1.10 and 1.07 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.99 and 0.96 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.90 and 0.87 (d, J = 6.8 Hz , 6 H, i Pr-CH ₃ ).

Example 3

Zirconium-Based Metalloenamine Compound Synthesis

By the following synthesis method it was possible to synthesize a metalloenamine compound including an early transition metal (early transition metal).

(1) Compound 5 Synthesis

Compound 1 (7.00 g, 17.3 mmol) and KH (3.47 g, 86.5 mmol) were stirred for 6 days while removing hydrogen gas generated during the reaction in anhydrous THF (50 ml) under an argon stream through a mercury bubbler. Unreacted KH was filtered using Celite, concentrated by distillation under reduced pressure. White crystals precipitated when the concentrated THF solution was stored in a refrigerator at -30 ° C. THF was decanted and excess THF was removed with a vacuum pump. The obtained solid was powdered with pentane and then filtered and washed three times with pentane to give compound 5 as a yellow powder (6.74 g, 75.3%, including 1 / 2THF).

¹ H-NMR (200 MHz, C ₆ D ₆ / THF-d ₈ (10: 1)): δ 7.22 (d, J = 7.6 Hz, 4H, ph-H ³ ), 6.95 (t, J = 7.6 Hz , 2H,, ph-H ⁴ ), 3.92 (septet, J = 6.7 Hz, 4 H, i Pr-CH), 3.09 (d, J = 3.7 Hz, 2 H, C = CH ₂ ), 2.49 (d, J = 3.5 Hz, 2 H, C = CH ₂ ), 1.48 (d, J = 6.7 Hz, 12 H, i Pr-CH ₃ ), 1.31 (d, J = 6.7 Hz, 12 H, i Pr-CH ₃ ). ¹³ C NMR (75 MHz, C ₆ D ₆ / THF-d ₈ (10: 1)): δ 170.65 (CH ₂ -C -N), 156.20 (ph-C ¹ ), 142.49 (ph-C ³ ), 122.71 (ph-C ⁴ ) 118.12 (ph-C ² ), 67.77 ( C H2 = C), 27.75 ( i Pr- C H), 25.78 ( i Pr- C H ₃ ), 25.11 ( i Pr- C H ₃ ).

(2) Compound 6 Synthesis

To compound 5 (0.283 g, 0.588 mmol) and CpZrCl ₃ (0.155 g. 0.588 mmol) were added anhydrous THF (7 ml) cooled to −30 ° C. and stirred at room temperature under nitrogen stream for 12 hours. To remove the resulting salt, the solid obtained by filtration using Celite and distillation under reduced pressure was extracted with pentane, concentrated by distillation under reduced pressure, and recrystallized at -30 ° C to obtain Compound 6 as a red acicular crystal (0.190). g, 54%).

¹ H-NMR (200 MHz, C ₆ D ₆ ): δ 7.3 7.6 (m, 6 H, ph-H ^3,4,5 ), 5.95 (s, 5 H, Cp), 4.69 (s, 2 H, C = CH ₂ ), 3.62 (s, 2H, C = CH ₂ ), 3.51 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 3.46 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 1.38 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.29 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.29 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.25 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ). ¹³ C NMR (75 MHz, C ₆ D ₆ ) 151.89 (CH ₂ -C -N), 145.57, 144.28, 142.72 (ph-C ^1,3,5 ), 126.99, 124.92, 124.16 (ph-C ^{2,4 , 6} ), 116.28 (Cp), 92.20 ( C H ₂ = C), 28.90, 28.57 ( i Pr- C H), 26.25, 25.94, 25.49, 24.73 ( i Pr- C H ₃ ).

(3) Compound 7 Synthesis

Compound 2 (0.166 g, 0.345 mmol) and Cp * ZrCl ₃ (0.115 g, 0.345 mmol) were stirred in anhydrous toluene (5 ml) at room temperature under nitrogen stream for 12 hours. To remove the resulting salt, the solid obtained by filtration and distillation under reduced pressure using Celite was extracted with pentane and distilled under reduced pressure to obtain Compound 3 as a red solid (180 mg, 79%).

¹ H-NMR (200 MHz, C ₆ D ₆ ): δ 7.3 7.1 (m, 6 H, ph-H ^3,4,5 ), 4.83 (s, 2 H, C = CH ₂ ), 3.72 (s, 2 H, C = CH ₂ ), 3.39 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 3.20 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 1.66 (s, 15 H, Cp * -CH ₃ ), 1.39 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.34 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.33 (d , J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.31 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ).

(4) Compound 8 Synthesis

Compound 6 (150 mg, 0.252 mmol) was dissolved in 5 g of diethyl ether and 1.0 equivalent of MeMgBr was added at room temperature. The red solution turns dark yellow. After stirring for 2 hours at room temperature, it is filtered. After all solvents have been removed, the remaining oil is extracted again with pentane. Removal of the pentane with a vacuum pump yields a dark yellow sticky solid. NMR analysis showed that a fairly pure compound was obtained. Yield 130 mg (90%).

¹ H NMR (200 MHz, C6D6): 7.3 7.1 (m, ^6H , ph-H ^3,4,5 ), 5.85 (s, 5H, Cp), 4.73 (s, 2H, CH ₂ = C) , 3.58 (s, 2H, CH ₂ = C), 3.58 (septet, J = 6.8 Hz, 2H, i Pr-CH), 3.33 (septet, J = 6.8 Hz, 2H, i Pr-CH), 1.38 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.34 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.35 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 1.19 (d, J = 6.8 Hz, 6 H, i Pr-CH ₃ ), 0.67 (s, Zr-CH ₃ ). ). ¹³ C NMR (75 MHz, C ₆ D ₆ ) 153.49 (CH ₂ -C -N), 145.14, 143.67, 143.21 (ph-C ^1,3,5 ), 126.56, 124.77, 123.91 (ph-C ^{2,4 , 6} ), 114.72 (Cp), 89.64 ( C H ₂ = C), 30.54 (Zr- C H ₃ ), 28.68, 28.37 ( i Pr- C H), 26.16, 26.04, 25.60, 24.56 ( i Pr- C H ₃ ).

(4) Compound 9 Synthesis

Prepared under the same conditions as in compound 8 . Purification by recrystallization from pentane solution at 30 ℃. Yield 63% if obtained with red crystals.

¹ H-NMR (200 MHz, C ₆ D ₆ ): δ 7.3 7.1 (m, 6 H, ph-H ^3,4,5 ), 4.88 (s, 2 H, C = CH ₂ ), 3.70 (s, 2 H, C = CH ₂ ), 3.51 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 3.03 (septet, J = 6.8 Hz, 2 H, i Pr-CH), 1.60 (s, 15 H, Cp * -CH ₃ ), 1.42 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.39 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.28 (d , J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 1.27 (d, J = 6.8 Hz, 12 H, i Pr-CH ₃ ), 0.63 (s, Zr-CH ₃ ).

Example 4

Ethylene polymerization

In a 100 mL high-pressure glass reactor, an appropriate amount of catalyst and a Lewis acid cocatalyst were dissolved in 30 mL toluene, introduced into a dry box, and a dry box was taken out to add ethylene under an appropriate pressure to prepare a polymer. The obtained polymer solution or slurry was poured into a flask containing 100 mL acetone, and the white polymer obtained herein was filtered and then vacuum reduced to remove the solvent to obtain a polymer.

(1) Compound 4 (0.025 mmol) was activated with B (C ₆ F ₅ ) 3 (0.025 mmol) to polymerize at room temperature under 100 psi pressure for 10 minutes to obtain 0.083 g of polymer.

(2) Compound 4 (0.025 mmol) was activated with Al (C ₆ F ₅ ) 3 (0.025 mmol) to polymerize at room temperature under 100 psi pressure for 10 minutes to obtain 0.083 g of polymer.

(3) Compound 4 (0.010 mmol) was activated with methylaluminoxane (5.00 mmol), and polymerized at room temperature under 100 psi pressure for 5 minutes to obtain 0.227 g of polymer.

(4) Compound 6 (0.00050 mmol) was activated with methylaluminoxane (2.50 mmol) and polymerized for 15 minutes at 60 ° C. under 60 psi pressure to obtain 1.389 g of polymer.

As mentioned above, the metalloenamine compounds disclosed in the present invention are rarely synthesized and since no attempt has been made to activate such metalloenamine compounds with Lewis acids for use in polyolefin polymerization, metalloenamine compounds By varying the structure of and the Lewis acid, which is also an activator, it is possible to open the way to prepare a catalyst to achieve the desired properties.

In addition, the catalyst prepared by this method can be expected in the following aspects compared to the catalyst in the existing (ion pair). First, it is possible to exclude the anion and the cation in one molecule and the anion of the molecule is coordinated to the central metal of the cation. For this reason, it is possible to avoid the requirement of using bulky and expensive methylaluminoxane (MAO) or tris (petnatafluorophenyl) boron as Lewis acid, and lower the cost of BX ₃ (X Is a halogen) or a commonly used alkylaluminum compound (AlR _n X _m , n + m = 3, R is hydrocarbyl or aryl, X is halogen or alkoxy or aryloxy). Second, in the case of catalysts composed of complex salts, the anion may hinder the access of the monomers to the central metal during polymerization by the anion circulating in the central metal, but in the case of zwitterions catalysts, the anion is behind the central metal. No need to do Third, if the Lewis acid supported on a suitable carrier is used, the supported catalyst can be easily prepared, and thus it can be easily applied to a gas phase process or a slurry process requiring the supported catalyst.

Claims (6)

C = CNM (M is a metal element) with a metal having a skeleton of the structure yen is composed of an amine compound and a Lewis acid (A), the metal to enamine compound and the acid in the ^Lewis-both having the ACC = NM ⁺ structure Performing olefin polymerization at a temperature of 25 to 500 ° C. and a pressure of 15 to 1500 psi in the presence of a catalyst system forming an ionic compound. The method according to claim 1, wherein the olefin is at least one selected from the group consisting of R1CH = CH2, cyclopentene, norbornene, H2C = CH (CH2) CO2R2, wherein R1, R2 Is hydrogen, hydrocarbyl or substituted hydrocarbyl, and s is an integer from 1 to 10). The method of claim 1, wherein the metalloenamine compound is a compound represented by Structural Formula 1-1 or Structural Formula 1-2. [Structure 1-1] [Structure 1-2] Where M is Ni, Pd, or Pt and R, R ′, R ″ are each hydrogen radical, hydrocarbyl, substituted hydrocarbyl, and A is π-allyl, substituted π-allyl, π-benzyl or substituted π-benzyl, L is a neutral monodentate ligand which may be substituted by an olefin, L 'is a monodentate ligand of an anion, and L and L' are linked to each other so that bidentate). The method of claim 1, wherein the metalloenamine compound is a method of producing a polyolefin, characterized in that the compound represented by the formula (2). [Formula 2] Wherein M is Ti, Zr, Hf, V, or Sc, L is an anionic or neutral ligand, x is 0 or 1 or 2. If x is 2, then each L may be the same or different. R, R 'is a hydrogen radical, hydrocarbyl or substituted hydrocarbyl, X is a halogen radical, alkoxy radical, aryloxy radical, hydrocarbyl or substituted hydrocarbyl and y is 1 or 2. When y is 2 Each X may be the same or different from each other.) 5. The compound of claim 4, wherein L in formula 2 is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, or substituted fluorenyl and X is halogen or alkyl. Method for producing a polyolefin, characterized in that. The compound of claim 1, wherein the Lewis acid is a compound of Formula 3: AlX _n (R ⁵ ) _3-n ; BX _n (R ⁵ ) _3-n ; Transition metals selected from anhydrous ZnCl ₂ , FeCl ₃ , TiCl ₄ , or TiCl ₃ ; Method for producing a polyolefin at least one selected from the group consisting of silica dehydrated at 600 ℃ or more: [Formula 3] R ^5- [Al (R ⁵ ) -O] _a -AlR ⁵ ₂ or Wherein R ⁵ is a halogen radical, hydrocarbyl or hydrocarbyl substituted with halogen and a is an integer of at least 1. If a is 2 or more, R ⁵ may be the same or different. X is hydrogen, halogen, alkoxy or aryloxy. And n is an integer from 0 to 3. When n is 2 or more, X may be the same or different.)