KR101384321B1 - Non-metallocene catalysts having tetrazol group for olefin polymerization and polymerizing method of olefin using the same - Google Patents

Abstract

The present invention is to provide a non-metallocene-based transition metal compound comprising a tetrazole group, which is easy to manufacture and has high polymerization activity and high temperature stability in polymerization of olefins, and a catalyst composition comprising the transition metal compound and a promoter. do. In addition, an object of the present invention is to provide a method for efficiently preparing an olefinic homopolymer or copolymer using the catalyst composition.

Transition metal, tetrazole, catalyst composition, olefin polymerization

Description

Non-metallocene catalysts having tetrazol group for olefin polymerization including tetrazole group and olefin polymerization method using the same

The present invention relates to a catalyst for non-metallocene olefin polymerization using a transition metal compound containing a tetrazole group, a method for preparing the same, and a method for producing an olefin polymer using the catalyst for olefin polymerization.

The production and application of polyolefins has advanced dramatically with the invention of a catalyst called Ziegler-Natta catalyst, and the production process and the use of the product have been variously developed. In particular, the development of polyolefin products using various single-site catalysts, together with the remarkable improvement in the activity of the Ziegler-Natta catalyst, has also attracted much attention in the art. Such single-site catalysts include metallocene catalysts, Dow's Constrained-Geometry-Catlyst (CGC), and catalysts using post-transition metals.

In the copolymerization reaction between ethylene and alpha-olefin, CGC is superior to metallocene catalysts known to the prior art in two main ways: (1) high molecular weight with high activity even at high polymerization temperature It produces a polymer of (2) and the copolymerizability of alpha-olefin with high steric hindrance such as 1-hexene and 1-octene is also excellent. In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.

One approach has been to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known to date are listed as compounds (1) to (4) (Chem. Rev. 2003, 103, 283).

Compounds (1) to (4) have phosphorus (1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges instead of CGC-structured silicon bridges, respectively, but ethylene polymerization Or, when the copolymerization with alpha-olefin is applied, no improved results were obtained in terms of activity or copolymerization performance compared to CGC.

In addition, as another approach, many compounds composed of oxido ligands instead of the amido ligands of CGC have been synthesized, and some polymerization has been attempted. The examples are summarized as follows.

Compound (5) was reported by T. J. Marks et al. Characterized in that the Cp (cyclopentadiene) derivative and the oxido ligand were crosslinked by ortho-phenylene groups (Organometallics 1997, 16, 5958). Compounds with the same crosslinks and polymerizations using them have also been reported by Mu et al. (Organometallics 2004, 23, 540). In addition, it was reported by Rothwell et al. That an indenyl ligand and an oxido ligand were crosslinked by the same ortho-phenylene group (Chem. Commun. 2003, 1034). Compound (6), reported by Whitby et al., Is characterized by the piercing of cyclopentanienyl and oxido ligands by three carbons (Organometallics 1999, 18, 348). These catalysts are syndiotactic. ) Have been reported to be active in polystyrene polymerization. Similar compounds have also been reported by Hessen et al. (Organometallics 1998, 17, 1652).

Compound (7), reported by Rau et al., Is characterized by its activity in ethylene polymerization and ethylene / 1-hexene copolymerization at high temperatures and pressures (210 ° C, 150 MPa) (J. Organomet. Chem. 2000, 608, 71). . In addition, a catalyst synthesis 8 having a similar structure and high temperature and high pressure polymerization using the same have been patented by Sumitomo (US Pat. No. 6,548,686).

Ligands having an anionic skeleton in the form of two cyclopentadienes have a high activity in olefin polymerization by a catalyst using a transition metal compound of Group 4 of the periodic table (so-called metallocene) and a methylaluminoxane or a specific boron compound as a promoter. It has also been reported to exhibit commercially useful features, such as producing polymers having narrow molecular weight distributions and composition distributions.

In addition, in the nonmetallocene system, in 1999, Mitsui Chemicals, Fujita, T., et al. Introduced salicylidamine imine ligands having various substituents on amine elements, and thus, were very effective for olefins such as ethylene and propylene. It was disclosed in European Patent No. 0874005 that a catalyst system exhibiting high polymerization activity. In the same year, a catalyst system showing polymerization activity in olefins was introduced by reducing group salicylate imine ligand to introduce a Group 4 transition metal into a hydroxybenzylamine ligand. Published in 158189.

Further, a polymerization catalyst comprising a transition metal compound of Group 4 of the periodic table having an anionic skeleton in the form of one cyclopentadiene and having a ligand in which a nitrogen atom is crosslinked with a silicon group and methylaluminoxane or a specific boron compound Also, it has been reported that high molecular weight polymers can be produced with high activity in olefin polymerization (JP Publication No. 1991-163088, JP Publication No. 1991-188092). However, in the case of the transition metal compound, in particular, having a crosslinked structure, not only the synthesis of the ligand is difficult, but also a plurality of steps are required, and the complexing step is not easy.

Among the reported catalysts for olefin polymerization as described above, only a few of the catalysts actually applied to commercial plants. Therefore, there is still a need to develop a catalyst having a new structure and to prepare a polymer using the same. In particular, in the case of the conventional heteronuclear catalyst compound does not deviate significantly from the structure of the existing CGC form, the production method is complicated and the yield is not high. Therefore, there is still a need for a new structure of a heteronuclear transition metal compound which can be expected to have high catalytic activity, and a method of simply manufacturing the same at a high yield.

The present invention is to provide a non-metallocene-based transition metal compound containing a tetrazole group having easy polymerization, high polymerization activity and high temperature stability in the polymerization of olefins, and a catalyst composition comprising the transition metal compound and a promoter. . In addition, an object of the present invention is to provide a method for efficiently preparing an olefinic homopolymer or copolymer using the catalyst composition.

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

[Chemical Formula 1]

In Formula 1,

R ₀ is hydrogen or alkyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; A cycloalkyl having 5 to 20 carbon atoms unsubstituted or substituted with an alkyl or halogen group, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or phenyl unsubstituted or substituted with an alkyl or halogen group,

R ₁ to R ₃ each independently represent a hydrogen atom; Alkyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms unsubstituted or substituted with fluoroalkyl, nitro, sulfonate or halogen; Alkenyl having 2 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; A halogen group; A nitro group; Sulfonate groups; Siloxane groups (-OSiZ ₃ , wherein Z is an aryl having 6 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, respectively); Or a hydrocarbylene group (-(RO) zR 'wherein R is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, R' is an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms, z Is 1 to 4), and R ₁ and R ₂ may be connected to each other to form a ring,

A represents an electron donor,

X may be the same or different, respectively, halogen or alkyl group having 1 to 20 carbon atoms, allyl group, benzyl group, nitro group, amido group (-N (R) ₂ ), alkylsilyl group having 1 to 20 carbon atoms, 1 carbon Or an alkoxy group or sulfonate group or a derivative thereof,

M may be selected from transition metals from Groups 3 to 11 of the Periodic Table.

In particular, R ₁ is an aryl, a derivative thereof, or a crushed alkyl group or an alkoxyalkyl group having 3 to 6 carbon atoms, a phenyl, anthrasyl group, phenanthrasyl group, terphenyl or tert-butyl It is preferable that such a steric hindrance is a large substituent.

In the hydrocarbylene group (-(RO) zR '), R is preferably an alkylene group having 2 to 3 carbon atoms and a phenyl group, and R' is preferably a hydrocarbon having 1 to 3 carbon atoms.

In addition, A is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a NO ₂ , a halogen group, a persulfonate (SO ₃ ⁻ ) group, a sulfonyl ester (SO ₂ R), a carboxyl group ( COO-), perfuluro alkyl groups, alkoxy groups, sulfonates and carboxylates containing cations of alkali or alkaline earth metals are preferred.

In addition, M is preferably a Group 4 transition metal such as titanium, zirconium, and hafnium.

As another exemplary embodiment of the present invention, a transition metal compound of Chemical Formula 1 prepared by adding a compound containing a transition metal to a reaction solution containing a tetrasol-containing compound and a strong base compound such as butyllithium ( n- BuLi) It provides a method of manufacturing.

As another exemplary embodiment of the present invention, a catalyst composition for olefin polymerization comprising a) a transition metal compound according to claim 1 and b) at least one cocatalyst compound selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4 Provides:

(2)

^{- [Al (R 4) -O} ] a -

Wherein R ⁴ is each independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen;

a is an integer of 2 or more;

(3)

J (R ⁵ ) ₃

Wherein J is aluminum or boron; Each R ⁵ is independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen;

[Chemical Formula 4]

^{[LH] + [Z (R} 6) 4] - or ^{[L] + [Z (R} 6) 4] -

Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; Each R ⁶ is independently one or more hydrogen atoms is halogen; Hydrocarbyl having 1 to 20 carbon atoms; Or an aryl or alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical.

The present invention also comprises the steps of: a) contacting the transition metal compound of Formula 1 with a compound represented by Formula 2 or Formula 3 to obtain a mixture; And b) adding the compound of Formula 4 to the mixture obtained in step a).

The present invention also provides a method for preparing a catalyst composition comprising the step of contacting the transition metal compound of Formula 1 with the compound represented by Formula 2 to obtain a mixture.

In addition, the present invention provides a method for preparing a catalyst composition comprising the step of obtaining a mixture by contacting the transition metal compound of Formula 1 and the compound represented by Formula 4.

The present invention also provides a method for producing a polyolefin, comprising contacting the catalyst composition with an olefin monomer.

The present invention can produce a high molecular weight polyolefin by using a catalyst composition having a high activity and high copolymerizability including a Group 4 transition metal compound of a novel structure.

Hereinafter, the present invention will be described in detail.

The transition metal compound of the present invention represented by Chemical Formula 1 may be used as a catalyst for polyolefin polymerization as a novel compound.

The transition metal compound may be prepared by adding a transition metal to a reaction solution containing a tetrasol-containing compound and a strong base compound such as butyllithium ( n- BuLi) as shown in Scheme 1 below.

As the strong base compound, at least one selected from alkyl-lithium compounds, NaH, and KH may be used.

In the reaction solution and the transition metal for preparing the transition metal compound, the molar ratio of the compound containing a tetrazole: a strong base compound: a transition metal may be 1: 1 to 3: 0.5 to 2, preferably 1: 2 May be: 1.

[Reaction Scheme 1]

Wherein R ₀ , R ₁ , R ₂ , R ₃ , A, M, and X are as defined in Formula 1, in MX ₄ (L) n, L represents an electron donor ligand, n is from 0 to 10 Is an integer.

Although it does not specifically limit as said electron donor ligand, tetrahydrofuran (THF) is preferable.

The catalyst composition according to the invention is present in an activated state in the reaction between the transition metal compound and the promoter and can be used for olefin homopolymerization or copolymerization.

The present invention provides a method for preparing the catalyst composition, comprising the steps of: a) contacting a transition metal compound of Formula 1 with a compound represented by Formula 2 or Formula 3 to obtain a mixture; And b) adding the compound of Formula 4 to the mixture obtained in step a).

In another aspect, the present invention provides a method for preparing a catalyst composition comprising the step of contacting a transition metal compound of Formula 1 with a compound represented by Formula 2 to obtain a mixture.

In another aspect, the present invention provides a method for preparing a catalyst composition comprising the step of contacting a transition metal compound of Formula 1 with a compound represented by Formula 4 to obtain a mixture.

In the first method of preparing the catalyst composition, the molar ratio of the compound represented by Formula 2 or Formula 3 to the transition metal compound of Formula 1 is preferably 1: 1 to 1: 10,000, more preferably 1 : 10 to 1: 5,000, most preferably 1:20 to 1: 1,000. When the molar ratio is in the above range, the amount of the alkylating agent is sufficient to allow the alkylation of the metal compound to proceed fully, and the side reaction between the remaining excess alkylating agent and the activator of Formula 4 can be minimized to fully activate the alkylated metal compound. have.

Next, the molar ratio of the compound represented by Formula 4 to the transition metal compound of Formula 1 is preferably 1: 1 to 1:50, more preferably 1: 1 to 1:25, most preferably 1 : 2 to 1:10. When the molar ratio is in the above range, since the amount of the activator is sufficient to activate the transition metal compound completely, the activity of the resulting catalyst composition does not decrease, and the amount of the remaining activator is minimized, resulting in economical cost of the catalyst composition. It does not degrade the purity of the polymer produced.

The catalyst composition may be prepared by first alkylating X of the transition metal compound with an activator of formula (2) or (3) and forming a complex with boron and the like with the activator of formula (4).

In the second method of preparing the catalyst composition, the molar ratio of the compound represented by Formula 2 to the transition metal compound of Formula 1 is preferably 1:10 to 1: 10,000, more preferably 1: 100 to 1: 5,000, most preferably 1: 500 to 1: 2,000. When the molar ratio is in the above range, since the amount of the activator is sufficient to activate the metal compound completely, the activity of the resulting catalyst composition does not drop, and the amount of the remaining activator is minimized, resulting in economical cost of the catalyst composition. The purity of the resulting polymer does not fall.

In addition, in the third method of preparing the catalyst composition, the molar ratio of the compound represented by the following Chemical Formula 4 to the transition metal compound of Chemical Formula 1 is preferably 1: 1 to 1:50, more preferably 1: 1 to 1:25, most preferably 1: 2 to 1:10. When the molar ratio is in the above range, since the amount of the activator is sufficient to activate the transition metal compound completely, the activity of the resulting catalyst composition does not decrease, and the amount of the remaining activator is minimized, resulting in economical cost of the catalyst composition. It does not degrade the purity of the polymer produced.

Hydrocarbon solvents such as pentane, hexane, heptane and the like or aromatic solvents such as benzene and toluene may be used as the reaction solvent in the preparation of the catalyst composition, but the solvent is not necessarily limited thereto and any solvents available in the art may be used. Can be.

In addition, the transition metal compound and the cocatalyst of the formula (1) may be used in a form supported on silica or alumina, the supporting method may be prepared by a method known in the art.

The compound represented by Chemical Formula 2 is not particularly limited as long as it is an alkyl aluminoxane, but preferable examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and particularly preferred compound is methyl aluminoxane.

The alkyl metal compound represented by Chemical Formula 3 is not particularly limited, but preferred examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, and 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, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like are particularly preferred. The compound is selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 4 include triethylammonium tetra (phenyl) boron, tributylammonium tetra (phenyl) boron, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethyl Ammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl ) Boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylamidium tetra (phenyl) boron, N, N- diethylanilidedium tetra (phenyl) boron, N, N- Diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, trimethyl phosphonium tetra (phenyl) boron, tripropyl ammonium Tetra (p-tolyl) boron, triethylam Niumtetra (o, p-dimethylphenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra Pentafluorophenyl) boron, trityltetra (pentafluorophenyl) boron, triethylammonium tetra (phenyl) aluminum, tributylammonium tetra (phenyl) aluminum, trimethylammonium tetra (phenyl) aluminum, tripropylammonium Umtetra (phenyl) aluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethyl phenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (pentafluorophenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (penta fluorophenyl) aluminum, diethylammonium tetra (pentafluorophenyl) aluminum, triphenylphosphonium Tetra (phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammonium tetra (phenyl) aluminum, tributylammonium tetra (phenyl) aluminum, and the like.

The present invention also provides a method for producing a polyolefin using the catalyst composition. Specifically, the present invention provides a method for producing polyolefin, comprising contacting the catalyst composition with at least one olefin monomer.

In the polyolefin production method according to the invention, the most preferred polymerization process using the catalyst composition is a solution process. In addition, when the catalyst composition is used together with an inorganic carrier such as silica, it is applicable to a slurry or a gas phase process.

In the method for producing a polyolefin according to the present invention, the catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene, benzene; It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with chlorine atoms such as dichloromethane and chlorobenzene. The solvent used herein is preferably used by removing a small amount of water, air or the like acting as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

Examples of the olefin monomer that can be polymerized by using the transition metal compounds and the cocatalyst include ethylene, alpha-olefin and cyclic olefin, and include diene olefin monomers or triene olefin monomers having two or more double bonds. And the like can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. In the present invention, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- It is preferably at least one monomer selected from the group consisting of dodecene, 1-tetradecene, 1-hexadecene and 1-aitocene.

Polyolefins prepared according to the process of the invention can be either homopolymers or copolymers. When the polyolefin is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer consist of ethylene, 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.

In particular, in the method for producing the olefin polymer according to the present invention, the catalyst composition is not only at the reaction temperature conventionally used, but also at a high reaction temperature of 90 ° C. or higher, even at a reaction temperature of 140 ° C. or higher, such as ethylene and 1-octene. Copolymerization of highly troublesome monomers is also possible, and by introducing various substituents into substituents having heteroatoms such as amine groups and imine groups, the electronic and three-dimensional environment around the metal can be easily controlled and ultimately the structure and physical properties of the resulting polyolefin. The back can be adjusted.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are provided only to assist in understanding the present invention, and the scope of the present invention is not limited to the Examples.

Example

Organic reagents and solvents were purchased from Aldrich and Merck and used by standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. 400 MHz nuclear magnetic resonance (NMR) was used to demonstrate the structure of the compound.

The melting point (Tm) of the polymer was obtained using a DSC (Differential Scanning Calorimeter) 2920 manufactured by TA. That is, the temperature was increased to 200 ° C., maintained at that temperature for 5 minutes, then lowered to 30 ° C., and the temperature was increased again to make the top of the DSC curve a melting point. At this time, the rate of temperature rise and fall is 10 ° C./min, and a melting point is obtained while the second temperature rises.

Example 1: Synthesis of 2- (octylamino) benzonitrile (I)

[Reaction Scheme 2]

2- (octylamino) benzonitrile was prepared as in Scheme 2 below.

30.0 g (0.254 mol) of 2-aminobenzonitrile and 300 ml of acetonitrile were added and stirred in a two-neck round bottom flask. At room temperature, 47.0 mL (35.1 g, 0.272 mol, 1.07 eq) of N-Ethyldiisopropylamine and 43.9 mL (19.0 g, 0.254 mol, 1.00 eq) of 1-bromooctane were added. Put and stirred for 4 hours. After raising the temperature to 110 ℃ reflux for 2 days. Washed twice with water and the organic layers were combined to give a Crude product. Then column chromatography gave 20.4 g (88.6 mmol, Yield: 34.9%) of 2- (octylamino) benzonitrile.

NMR ¹ H: 7.38 (m, 2H), 6.62 (m, 2H), 4.51 (s, 1H), 3.20 (m, 2H), 1.63 (m, 2H), 1.40 (m, 2H), 1.3 (m, 8H), 0.90 (t, 3H)

Example 2: Synthesis of N-octyl-2- (1H-tetrazol-5-yl) benzeneamine (II)

[Reaction Scheme 3]

N-octyl-2- (1H-tetrazol-5-yl) benzeneamine was prepared in the following manner.

After vacuum drying, 4.81 g (20.9 mmol) of 2- (octylamino) benzonitrile (I) synthesized in Preparation Example 1 and 50 mL of DMF were added to a three-necked flask filled with argon (Argon), followed by stirring. 1.40 g (21.5 mmol, 1.03 eq) of sodium azaid was added thereto, and the mixture was refluxed at 160 ° C. for 16 hours. After completion of the reaction, the temperature was lowered, poured into 100 mL of 0.1 N NaOH aqueous solution, and the unreacted organic material was recovered and removed with hexane. Gather the water layers, drop the acetic acid in small amounts, and adjust the pH to around 5 to form a white solid. The filtered white solid was washed with 10 mL of hexane (Hexane) and dried in vacuo to give a white solid. Thereafter, the resultant was dissolved in MC to remove impurities, and the solvent was removed to obtain 0.51 g (1.9 mmol, Yield: 9.1%) of clean N-octyl-2- (1H-tetrazol-5-yl) benzeneamine.

NMR ¹ H: 7,65 (d, 1H), 7.37 (t, 1H), 6.81 (d, 1H), 6.70 (t, 1H), 3.25 (t, 2H), 1.74 (m, 2H), 1.42 ( m, 2H), 1.3 (m, 8H), 0.85 (t, 3H)

NMR ¹³ C: 156, 147, 133, 128, 116, 112, 105, 44, 32, 29, 29, 28, 22, 14

Example 3: Preparation of N-octyl-2- (tetrazol-5-yl) benzeneiminylzirconium dichloride

[Reaction Scheme 4]

N-octyl-2- (tetrazol-5-) benzeneiminylziroconium dichloride was prepared in the following manner.

0.10 g (0.37 mmol) of N-octyl-2- (1H-tetrazol-5-yl) benzeneamine (II) prepared in Preparation Example 2 was added to a vacuum dried Shrink flask. THF 50mL was added. After cooling to −78 ° C., 0.30 mL (0.75 mmol, 2.0 eq) of n-BuLi solution at 2.5 M concentration was slowly added thereto. After stirring for 4 hours at room temperature to completely send the reaction was cooled again. In a small flask, 0.14 g (0.37 mmol, 1.00 eq) of ZrCl ₄ (THF) ₂ solid was dissolved in 20 mL of THF and added as a slurry. After stirring for 16 hours at room temperature, the solvent was completely removed by vacuum, dried methylene chloride (Methylenechloride) was filtered to remove salt, and then the solvent was removed again to obtain 0.16 g (0.37 mmol) of a white solid catalyst. .

NMR ¹ H: 7.77 (t, 1H), 7.47 (t, 1H), 7.40 (d, 1H), 6.91 (d, 1H), 3.21 (t, 2H), 1.5-1.2 (m, 12H), 0.85, (t, 3H)

Example 4: Synthesis of 5-tert-butyl-2- (octylamino) benzonitrile (IV)

[Reaction Scheme 5]

5-tert-butyl-2- (octylamino) benzonitrile was prepared as in Scheme 5 below.

45.0 g (0.258 mol) of 5-tert-butyl-2-Aminobenzonitrile and 500 mL of acetonitrile were added to a 1 L round bottom flask and stirred. At room temperature, 65.0 mL (48.5 g, 0.391 mol, 1.51 eq) of N-Ethyldiisopropylamine and 49.1 mL (14.8 bromooctane) of 1-bromooctane (54.8 g, 0.284 mol, 1.10 eq) Put and stirred for 4 hours. After raising the temperature to 110 ℃ was refluxed for 48 hours. Washed twice with water and the organic layers were combined to give a Crude product. Then column chromatography gave 24.5 g (85.5 mmol, Yield: 33.2%) of 5-tert-butyl-2- (octylamino) benzonitrile.

NMR ¹ H: 7.30 (d, 1H), 6.6 (m, 2H), 4.51 (s, 1H), 3.20 (m, 2H), 1.63 (m, 2H), 1.40 (m, 2H), 1.3 (m, 8H), 1.29 (s, 9H), 0.90 (t, 3H)

Example 5: Synthesis of 4-tert-butyl-N-octyl-2- (1H-tetrazol-5-yl) benzeneamine (V)

[Reaction Scheme 6]

4-tert-butyl-N-octyl-2- (1H-tetrazol-5-yl) benzeneamine was prepared in the following manner.

After vacuum drying, 7.00 g (24.4 mmol) of 5-tert-butyl-2- (octylamino) benzonitrile (IV) synthesized in Preparation Example 4 and 100 mL of DMF were added to a three-necked flask filled with argon. Stirred. 1.63 g (25.1 mmol, 1.03 eq) of sodium azaid was added thereto, and the mixture was refluxed at 160 ° C. for 20 hours. After the reaction was completed, the temperature was lowered, poured into 200 mL of 0.1 N NaOH aqueous solution, and the unreacted organic material was recovered and removed with hexane. Gather the water layers, drop the acetic acid in small amounts, and adjust the pH to around 5 to form a white solid. The filtered white solid was washed with 10 mL of hexane (Hexane) and dried in vacuo to give a white solid. It was then dissolved in MC to remove impurities and the solvent was removed to obtain 0.89 g (2.7 mmol, Yield: 11.0%) of clean 4-tert-butyl-N-octyl-2- (1H-tetrazol-5-yl) benzeneamine. .

NMR ¹ H: 7.37 (t, 1H), 6.81 (d, 1H), 6.70 (t, 1H), 3.25 (t, 2H), 1.74 (m, 2H), 1.42 (m, 2H), 1.3 (m, 8H), 1.29 (s, 9H), 0.85 (t, 3H)

Example 6: Preparation of 4-tert-butyl-N-octyl-2- (tetrazol-5-yl) benzeneiminylzirconium dichloride

[Reaction Scheme 7]

4-tert-butyl-N-octyl-2- (tetrazol-5-yl) benzeneiminylzirconium dichloride was prepared in the following manner.

0.20 g (0.61 mmol) of 4-tert-butyl-N-octyl-2- (1H-tetrazol-5-yl) benzeneamine (V) prepared in Preparation Example 5 in a vacuum dried Shrink flask. ) Was added, and 100 mL of dried THF was added thereto. After cooling to -78 degrees, 0.49 mL (1.22 mmol, 2.0 eq) of n-BuLi solution at a concentration of 2.5M was slowly added thereto. After slowly raising the temperature and stirring at room temperature for 4 hours, the reaction was completely sent and cooled again. In a small flask, 0.23 g (0.61 mmol, 1.00 eq) of ZrCl ₄ (THF) ₂ solid was dissolved in 50 mL of THF and added as a slurry. After stirring for 16 hours at room temperature, the solvent was completely removed by vacuum, and 100 mL of dried Methylene chloride was added to remove salt, and then the solvent was removed to remove 0.27 g (0.55 mmol) of a white solid catalyst. Got.

NMR ¹ H: 7.77 (t, 1H), 7.40 (d, 1H), 6.91 (d, 1H), 3.21 (t, 2H), 1.5-1.2 (m, 12H), 1.3 (s, 9H), 0.85 ( t, 3H)

Example 7: Ethylene Homopolymerization Using Prepared Catalyst

250 mL of purified toluene and 2.93 mL of a 4.6 wt% methylaluminoxane toluene solution (manufactured by Albemarle) as a promoter were injected into a pressure reactor under a high purity argon atmosphere, and the temperature was raised to 60 ° C. 5 mL (5 mmol Zr) of a toluene solution in which N-octyl-2- (tetrazol-5-) benzeneiminyljiroconium dichloride (III) nonmetallocene-based transition metal compound prepared in Example 3 was dissolved was added thereto. Stirred. Thereafter, polymerization was started at 60 ° C. while adding 50 psig of ethylene to the reactor. After stirring for 30 minutes, stirring was stopped and depressurized. 10 wt% hydrochloric acid-ethanol solution was added to the polymerizer to terminate the polymerization, and filtered to obtain a white solid precipitate. The precipitate was washed with ethanol and dried in a vacuum oven at 60 ° C. for 24 hours to produce the final ethylene polymer. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Example 8: Ethylene Homopolymerization Using Prepared Catalyst

An ethylene polymer was prepared in the same manner as in Example 7, except that the polymerization was performed at a polymerization temperature of 80 ° C. Reaction conditions and physical properties of the prepared polymer were summarized as in Table 1 below.

Example 9: Ethylene Homopolymerization Using Prepared Catalyst

The polymerization was carried out using the 4-tert-butyl-N-octyl-2- (tetrazol-5-yl) benzeneiminylzirconium dichloride (IV) nonmetallocene-based transition metal compound prepared in Example 6. Except for the ethylene polymer was prepared in the same manner as in Example 7. Reaction conditions and physical properties of the prepared polymer were summarized as in Table 1 below.

Example 10: Ethylene Homopolymerization Using Prepared Catalyst

Ethylene polymer was prepared in the same manner as in Example 9, except that polymerization was performed at a polymerization temperature of 80 ° C. Reaction conditions and physical properties of the prepared polymer were summarized as in Table 1 below.

[Table 1]

Polymerization Catalyst Polymerization temperature
(° C) Number average molecular weight
(Mn (× 103)) Molecular weight distribution
(Mw / Mn) Melting point
(Tm) Yield Example 7 (III) 60 250 2.1 129.3 3.1 g Example 8 (III) 80 293 2.4 129.8 4.2 g Example 9 (VI) 60 234 2.2 129.4 3.2 g Example 10 (VI) 80 302 2.3 129.9 4.5 g

Polymerization conditions: ethylene pressure 50 psig, polymerization time 30 min, promoter MAO (Al / Zr = 1000), toluene 250 mL

Number average molecular weight: measured using gel permeation chromatography (GPC)

Melting Point: Measured using Differential Heat Syringe (DSC)

Claims (19)

A transition metal compound represented by Formula 1 below: [Chemical Formula 1]

In Formula 1, R ₀ is a hydrogen atom; or alkyl having 1 to 20 carbon atoms, R ₁ to R ₃ each independently represent a hydrogen atom; Or alkyl having 1 to 20 carbon atoms, A represents an electron donor group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, Each X may be the same or different and is a halogen group, M is selected from Group 4 transition metals selected from the group consisting of titanium, zirconium and hafnium. delete delete delete Method for producing a transition metal compound according to claim 1, characterized in that prepared by adding a transition metal to the reaction solution containing a tetrasol compound and a strong base compound: [Reaction Scheme 1]

Wherein R _0, R ₁ , R ₂ , R ₃ , A, M, and X are as defined in Formula 1, in MX ₄ (L) n, L represents an electron donor ligand, n is from 0 to 10 Is an integer. The method of claim 5, wherein the electron donor ligand (L) is tetrahydrofuran (THF). The method of claim 5, wherein the strong base compound comprises at least one selected from an alkyl-lithium compound, NaH, and KH. A catalyst composition for olefin polymerization comprising a) a transition metal compound according to claim 1 and b) at least one cocatalyst compound selected from the group consisting of compounds represented by the following formulas (2) to (4): (2) ^{- [Al (R 4) -O} ] a - Wherein R ⁴ is each independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more; (3) J (R ⁵ ) ₃ Wherein J is aluminum or boron; Each R ⁵ is independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; [Chemical Formula 4] ^{[LH] + [Z (R} 6) 4] - or ^{[L] + [Z (R} 6) 4] - Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; Each R ⁶ is independently one or more hydrogen atoms is halogen; Hydrocarbyl having 1 to 20 carbon atoms; Or an aryl or alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical. The catalyst composition for olefin polymerization according to claim 8, wherein the compound of Chemical Formula 2 is selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobuty aluminoxane and butyl aluminoxane. The method of claim 8, wherein the compound of Formula 3 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, 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, Catalyst composition for olefin polymerization, characterized in that selected from the group consisting of trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron. The method of claim 8, wherein the compound of Formula 4 is triethyl ammonium tetra (phenyl) boron, tributyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron, Trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoro Methylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethyl amyldium tetra (phenyl) boron, N, N-diethylanilidedium tetra (phenyl) boron, N, N -Diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, trimethyl phosphonium tetra (phenyl) boron, tripropyl ammonium Umtetra (p-tolyl) boron, triethyl Monium tetra (o, p-dimethylphenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (Pentafluorophenyl) boron, trityl tetra (pentafluorophenyl) boron, triethyl ammonium tetra (phenyl) aluminum, tributyl ammonium tetra (phenyl) aluminum, trimethyl ammonium tetra (phenyl) aluminum, tripropyl Ammonium tetra (phenyl) aluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethyl phenyl) aluminum, tributylammonium Tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (pentafluorophenyl) aluminum, N, N-diethyl anilinium tetra (phenyl Aluminium , N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (penta fluorophenyl) aluminum, diethylammonium tetra (pentafluorophenyl) aluminum, triphenylforce Catalyst composition for olefin polymerization, which is selected from the group consisting of phosphonate tetra (phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammonium tetra (phenyl) aluminum and tributylammonium tetra (phenyl) aluminum . delete delete Method for preparing a catalyst composition comprising the step of contacting the transition metal compound of claim 1 with a compound represented by the formula (2): (2) ^{- [Al (R 4) -O} ] a - Wherein R ⁴ is each independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more. The method of claim 14, wherein a molar ratio of the compound represented by Formula 2 to the transition metal compound is 1:10 to 1: 10,000. delete delete A method for producing a polyolefin, comprising contacting the catalyst composition according to claim 8 with an olefin monomer. The method of claim 18, wherein the olefin monomer is 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-itocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethyl styrene comprising one or two or more selected from the group consisting of Manufacturing method.