KR100828719B1 - Non-metallocene catalyst for ethylene polymerization and polymerizing method of ethylene using the same - Google Patents

Abstract

The present invention relates to a non-metallocene-based ethylene polymerization catalyst and a method for producing the same, more specifically, having an amidate group as a coordinating ligand, preferably a cocatalyst such as alkylaluminoxane, alkylaluminum, weakly coordinating Lewis acid, or the like. It relates to a non-metallocene-based ethylene polymerization catalyst activated by the same and a method for preparing the same.

The production of ethylene polymers or ethylene copolymers using the non-metallocene ethylene polymerization catalysts of the present invention has the effect of producing polymers of much higher average molecular weight than those using conventional polymerization catalysts.

Bimetallocene, coordination ligand, amidinate, ethylene, promoter

Description

Non-metallocene ethylene polymerization catalyst and ethylene polymerization method using the same {Non-metallocene catalyst for ethylene polymerization and polymerizing method of ethylene using the same}

The present invention relates to a nonmetallocene ethylene polymerization catalyst and a method for preparing the same, and more particularly, a nonmetallocene ethylene polymerization capable of preparing an ethylene polymer or an ethylene copolymer having a much higher molecular weight than a conventional catalyst. It relates to a catalyst and a method for producing the same.

Ethylene polymers can be classified into high density polyethylene, low density polyethylene, linear low density polyethylene, and the like depending on the degree of side chains in the polymer backbone. Such polyethylenes have generally been prepared by radical polymerization or polymerization by conventional Ziegler-Natta catalysts. These olefin polymers are processed by various methods such as injection molding and extrusion molding, and are used for packaging materials, household goods, toys, and the like. However, in the case of polyethylene prepared using a conventional heterogeneous Ziegler-Natta catalyst, it is difficult to control in molecular weight distribution, comonomer distribution, molecular weight, and the like. Unlike polyethylene based on conventional Ziegler-Natta catalysts or radicals, polyethylene produced by a single active site homogeneous catalyst has an impact strength and tensile strength due to uniform molecular weight and molecular weight distribution and uniform comonomer distribution. It shows excellent properties in processability as well as physical properties of polymers such as transparency and transparency.

As nonmetallocene catalysts in homogeneous catalysts, U.S. Patent Nos. 6,875,718 and 874,005 disclose nonmetals which are a compound in which a salicylide imine ligand comprising N atoms and O atoms in a Group 4 transition metal is coordinated. A method for producing ethylene polymers in high yield using a Rosene catalyst as a main catalyst and an alkylaluminoxane as a cocatalyst is disclosed. That is, a non-metallocene compound in which the N and O atoms of the salicylide imine ligand are coordinated to the central metal is activated with a methylaluminoxane cocatalyst to prepare a highly active ethylene polymer, wherein the catalyst expressing high activity is One or more salicylide imine ligands are compounds that are coordinated to the central metal via N and O atoms.

US Patent No. 6,340, 730 discloses a method for preparing an ethylene / 1-hexene copolymer by activating a nonmetallocene compound having pyridyl-amine and benzyl as a ligand with alkylaluminoxane.

These previous studies show that suitable ligands containing N and O atoms can be introduced as nonmetallocene catalysts and activated with the compound using alkylaluminoxanes as promoters to be used as ethylene polymerization catalysts.

However, as described above, the average molecular weight of a polymer produced using a conventional catalyst which introduces a ligand containing N atoms and O atoms as a nonmetallocene catalyst is not so high and the molecular weight distribution is not easy to control. There was a disadvantage.

The first technical problem to be achieved by the present invention is to provide a nonmetallocene-based ethylene polymerization catalyst capable of producing a polymer having a high average molecular weight.

The second technical problem to be achieved by the present invention is to provide a method for producing the nonmetallocene-based ethylene polymerization catalyst.

The third technical problem to be achieved by the present invention is to provide another method for producing the non-metallocene ethylene polymerization catalyst.

The fourth technical problem to be achieved by the present invention is to provide a production method for producing an ethylene polymer using the non-metallocene-based ethylene polymerization catalyst.

The present invention provides a non-metallocene ethylene polymerization catalyst of the general formula (1) to achieve the first technical problem.

[Formula 1]

L _a MX _b

Wherein L is a bidentate ligand and is an amidinate of Formula 2;

[Formula 2]

R ¹ and R ² are each independently a hydrogen atom, a halogen group, a C1-C20 alkyl group, a C1-C20 cycloalkyl group, a C1-C20 alkenyl group, a C1-C20 alkylsilyl group, or a C1-C20 A 20 haloalkyl group, a C1-C20 alkoxy group, a C1-C20 alkylsiloxy group, an amino group, a C1-C20 alkoxyalkyl group, a C1-C20 thioalkoxyalkyl group, a C1-C20 alkylsiloxyalkyl group , C1-C20 aminoalkyl group, C1-C20 alkylphosphinoalkyl group, C6-C40 aryl group, C6-C40 arylalkyl group, C6-C40 alkylaryl group, C6-C40 aryl Silyl group, arylalkylsilyl group having 6 to 40 carbon atoms, haloaryl group having 6 to 40 carbon atoms, aryloxy group having 6 to 40 carbon atoms, aryloxoalkyl group having 6 to 40 carbon atoms, thioaryloxo having 6 to 40 carbon atoms Alkyl group, C6-C40 aryl oxoaryl group, C6-C40 aryl siloxy group, C6-C40 arylalkyl siloxy group, C6-C40 aryl siloxane alkyl group, C6-C40 aryl siloxane aryl group , An arylamino group having 6 to 40 carbon atoms, an arylaminoalkyl group having 6 to 40 carbon atoms, an arylaminoaryl group having 6 to 40 carbon atoms, or an arylphosphinoalkyl group having 6 to 40 carbon atoms;

M is a transition element of Groups 3 to 10;

a and b are each independently an integer of 1 or more and a + b is an oxidation number of M;

X is a sigma-ligand having a single coordination and is independently a hydrogen atom, a halogen group, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, and a carbon number. Alkenyl group of 1 to 20, alkoxy group of 1 to 20 carbon atoms, alkenyloxy group of 1 to 20 carbon atoms, thioalkoxy group of 1 to 20 carbon atoms, alkylsiloxy group of 1 to 20 carbon atoms, amide group of 1 to 20 carbon atoms, An alkoxy alcohol group having 1 to 20 carbon atoms, a sulfonyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group having 6 to 40 carbon atoms, an arylalkyl group having 6 to 40 carbon atoms, and an arylsilyl group having 6 to 40 carbon atoms A haloaryl group having 6 to 40 carbon atoms, an aryloxy group having 6 to 40 carbon atoms, an arylalkoxy group having 6 to 40 carbon atoms, a thioaryloxy group having 6 to 40 carbon atoms, an arylsiloxy group having 6 to 40 carbon atoms, and having 6 to 40 carbon atoms. 40 Aryl siloxy, an aryl amide group having a carbon number of 6 to 40, an aryl alkyl amide group having 6 to 40 carbon atoms, or an aryl giim oxo-alcohol having 6 to 40 carbon atoms)

The present invention to achieve the second technical problem,

Reacting the coordinating ligand L with an alkali metal or a compound thereof to prepare an alkali metal salt; And

It provides a method for producing a non-metallocene ethylene polymerization catalyst comprising the step of reacting the alkali metal salt with the chlorine salt MCl _y of the metal M.

Where L and M are as defined above and y is the oxidation number of the metal M

The present invention to achieve the third technical problem,

It provides a method for producing a non-metallocene-based ethylene polymerization catalyst comprising the step of reacting the _coordination ligand L with a tetraamide compound M (NMe ₂ ) _y of the metal M.

Where L and M are as defined above and y is the oxidation number of the metal M

The present invention provides a method for producing an ethylene polymer, characterized in that the polymerization of the ethylene monomer using a catalyst system comprising the non-metallocene-based ethylene polymerization catalyst and the promoter in order to achieve the fourth technical problem.

When the ethylene polymer or the ethylene copolymer is prepared using the nonmetallocene ethylene polymerization catalyst of the present invention, there is an effect that a polymer having a much higher average molecular weight can be prepared than using a conventional polymerization catalyst.

Hereinafter, the present invention will be described in more detail.

The present invention provides a non-metallocene ethylene polymerization catalyst of the formula (1).

[Formula 1]

L _a MX _b

Wherein L is a bidentate ligand and is an amidate of formula (2);

[Formula 2]

R ¹ and R ² are each independently a hydrogen atom, a halogen group, a C1-C20 alkyl group, a C1-C20 cycloalkyl group, a C1-C20 alkenyl group, a C1-C20 alkylsilyl group, or a C1-C20 A 20 haloalkyl group, a C1-C20 alkoxy group, a C1-C20 alkylsiloxy group, an amino group, a C1-C20 alkoxyalkyl group, a C1-C20 thioalkoxyalkyl group, a C1-C20 alkylsiloxyalkyl group , C1-C20 aminoalkyl group, C1-C20 alkylphosphinoalkyl group, C6-C40 aryl group, C6-C40 arylalkyl group, C6-C40 alkylaryl group, C6-C40 aryl Silyl group, arylalkylsilyl group having 6 to 40 carbon atoms, haloaryl group having 6 to 40 carbon atoms, aryloxy group having 6 to 40 carbon atoms, aryloxoalkyl group having 6 to 40 carbon atoms, thioaryloxo having 6 to 40 carbon atoms Alkyl group, C6-C40 aryl oxoaryl group, C6-C40 aryl siloxy group, C6-C40 arylalkyl siloxy group, C6-C40 aryl siloxane alkyl group, C6-C40 aryl siloxane aryl group , An arylamino group having 6 to 40 carbon atoms, an arylaminoalkyl group having 6 to 40 carbon atoms, an arylaminoaryl group having 6 to 40 carbon atoms, or an arylphosphinoalkyl group having 6 to 40 carbon atoms;

M is a transition element of Groups 3 to 10;

a and b are each independently an integer of 1 or more and a + b is an oxidation number of M;

X is a sigma-ligand having a single coordination and is independently a hydrogen atom, a halogen group, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, and a carbon number. Alkenyl group of 1 to 20, alkoxy group of 1 to 20 carbon atoms, alkenyloxy group of 1 to 20 carbon atoms, thioalkoxy group of 1 to 20 carbon atoms, alkylsiloxy group of 1 to 20 carbon atoms, amide group of 1 to 20 carbon atoms, An alkoxy alcohol group having 1 to 20 carbon atoms, a sulfonyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group having 6 to 40 carbon atoms, an arylalkyl group having 6 to 40 carbon atoms, and an arylsilyl group having 6 to 40 carbon atoms A haloaryl group having 6 to 40 carbon atoms, an aryloxy group having 6 to 40 carbon atoms, an arylalkoxy group having 6 to 40 carbon atoms, a thioaryloxy group having 6 to 40 carbon atoms, an arylsiloxy group having 6 to 40 carbon atoms, and having 6 to 40 carbon atoms. 40 Aryl siloxy, an aryl amide group having a carbon number of 6 to 40, an aryl alkyl amide group having 6 to 40 carbon atoms, or an aryl giim oxo-alcohol having 6 to 40 carbon atoms)

The non-metallocene ethylene polymerization catalyst of Formula 1 is formed by combining at least one amidine, which is a double ligand and an N-O coordination ligand, with a transition metal of Group 3 to Group 10. In particular, by stabilizing the catalyst by binding one or more sigma-ligands tightly with the central metal through the coordination, the catalyst deactivation due to side reactions is reduced while being activated by the cocatalyst in the preparation of ethylene polymer, resulting in a sustained activation time. Therefore, the nonmetallocene ethylene polymerization catalyst of the present invention may be an amidate catalyst.

It is preferable that M is especially a Group 4 transition metal element, and it is especially preferable that it is titanium (Ti), zirconium (Zr), or hafnium (Hf).

Specific examples of the nonmetallocene-based olefin polymerization catalyst include (tBuNC (Ph) O) ₂ TiCl ₂ , (tBuNC (Ph) O) ₂ ZrCl ₂ or (tBuNC (tBu) O) ₂ TiCl ₂ , (tBuNC ( tBu) O) ₂ ZrCl ₂ .

In particular, the non-metallocene-based olefin polymerization catalyst is (tBuNC (Ph) O) ₂ ZrCl ₂ shown in the formula (5a), (tBuNC (tBu) O) ₂ ZrCl ₂ shown in the formula (5b) (PhN (Ph) CO) ₂ ZrCl ₂ or (p- (2,6-diisopropylphenyl) NC (Ph) O) ₂ ZrCl ₂ shown in the following formula (5d) is preferred.

[Formula 5a]

[Formula 5b]

[Formula 5c]

[Formula 5d]

Hereinafter, a manufacturing method of the nonmetallocene-based ethylene polymerization catalyst will be described.

The present invention comprises the steps of reacting the coordination ligand L with an alkali metal or a compound thereof to prepare an alkali metal salt; And

It provides a method for producing a non-metallocene ethylene polymerization catalyst comprising the step of reacting the alkali metal salt with the chlorine salt MCl _y of the metal M.

Where L and M are as defined above and y is the oxidation number of the metal M

In particular, the metal M is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Further, preferably, the alkali metal may be lithium, sodium, or potassium, and the compound thereof may be normal butyl lithium, secondary butyl lithium, tertiary butyl lithium, methyl lithium, lithium bistrimethylsilamide, sodium methoxide, sodium Ethoxide, potassium tert-butoxide, potassium hydroxide, methylmagnesium chloride, ethylmagnesium bromide, or dimethyl magnesium.

The present invention also provides a method for producing a nonmetallocene ethylene polymerization catalyst comprising reacting a _coordinating ligand L with a tetraamide compound M (NMe ₂ ) _y of metal M.

Where L and M are as defined above and y is the oxidation number of the metal M

In particular, the metal M is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Hereinafter, the method of polymerizing an ethylene monomer using the nonmetallocene ethylene polymerization catalyst of this invention is demonstrated.

The present invention is based on the non-metallocene ethylene polymerization catalyst of the formula (1) as a main catalyst by homopolymerization of ethylene with the cocatalyst or copolymerization with other olefin monomers such as 1-butene, 1-hexene or 1-octene Ethylene polymers or ethylene copolymers of various physical properties can be obtained. That is, the present invention provides a method for producing an ethylene polymer in which an ethylene monomer is polymerized under a catalyst system including the nonmetallocene ethylene polymerization catalyst and a promoter.

The ethylene polymer may copolymerize ethylene monomers such as ethylene, propylene, 1-butene, 1-hexene, 1-octene alone or copolymerize.

The concentration of the main catalyst is preferably 1.0 × 10 ^-8 M to 1.0 M. If the concentration of the main catalyst is less than 1.0 × 10 ^-8 M, the concentration is too low, the overall reaction rate is not sufficient, and if the concentration of the main catalyst exceeds 1.0 M there is a disadvantage that the physical properties of the resulting polymer is poor.

The promoter is preferably alkylaluminoxane, alkylaluminum, weakly coordinated Lewis acid or mixtures thereof. Hereinafter, these promoters will be described in detail.

The alkylaluminoxane may be a compound of Formula 3 below.

[Formula 3]

In Formula 3, R ³ is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and an alkyl having 6 to 40 carbon atoms. It is an aryl group or a C6-C40 arylalkyl group, n is an integer of 1-100.

In the usage-amount of the said alkylaluminoxane, it is preferable that the equivalence ratio of the said nonmetallocene type ethylene polymerization catalyst and the alkylaluminoxane is 1: 1-1: 106. If the amount of the alkylaluminoxane used is too small out of the range, the activation of the catalyst is insufficient, so that the activity is insufficient. On the contrary, the amount of the alkylaluminoxane used is out of the range.

The alkyl aluminum may be a compound of Formula 4 below.

[Formula 4]

In Formula 4, R ⁴ , R ⁵ , and R ⁶ are each independently or simultaneously a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cyclo group having 3 to 20 carbon atoms An alkyl group, an aryl group having 6 to 40 carbon atoms, an alkylaryl group, or an arylalkyl group, and at least one of R ⁴ , R ⁵ , and R ⁶ includes an alkyl group.

In the usage-amount of the said alkyl aluminum, it is preferable that the equivalence ratio of the said nonmetallocene type ethylene polymerization catalyst and alkyl aluminum is 1: 1-1: 104. If the amount of the alkylaluminum is too small out of the range, the activation of the catalyst is insufficient and the activity is insufficient.

The weakly coordinated Lewis acid is trimethylammonium tetrafetyl borate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium Tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (Pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, tris (pentafluorophenyl) borane, tris (2,3,4,5-tetraflu Rophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, and tris (2,4,6-trifluorophenyl) borane But it is not limited to this.

Although the weakly coordinated Lewis acid may be used alone, it is more preferable to use in combination with alkylaluminum in terms of stability of the catalyst.

Although the amount of the coordinating Lewis acid is not particularly limited, the equivalent ratio of the nonmetallocene-based ethylene polymerization catalyst, the alkylaluminum aluminum and the coordinating Lewis acid when used with the alkylaluminum is 1: 1: 0.1 to 1: 3000: It is preferable that it is 50.

When the equivalence ratio of the nonmetallocene ethylene polymerization catalyst, alkylaluminum, and weakly coordinated Lewis acid is in the above range, the catalyst is smoothly activated and preferable.

The process of polymerizing the ethylene monomer using the main catalyst or the main catalyst and the cocatalyst may be by a method such as slurry polymerization, liquid phase polymerization, gas phase polymerization or bulk polymerization, and is not particularly limited.

When the polymerization is carried out in a liquid phase such as slurry polymerization or liquid phase polymerization, a solvent may be used as a medium for polymerization, butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclo Alkanes or cycloalkane solvents having 4 to 20 carbon atoms such as hexane; Aromatic arylene solvents having 6 to 20 carbon atoms such as benzene, toluene, xylene, mesitylene, and the like; Dichloromethane, chloromethane, chloroform, carbon tetrachloride, chloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichloro Halogen alkanes or halogen arenes having 1 to 20 carbon atoms such as benzene; Or mixtures thereof.

The polymerization is injected into the reactor in the order of a solvent, an olefinic comonomer, a cocatalyst and a nonmetallocene ethylene polymerization catalyst, and an ethylene monomer, or the nonmetallocene ethylene polymerization catalyst is activated by contacting with a promoter to activate an olefinic copolymer. It can be carried out by injection into the reactor filled with monomer, and finally by injection of ethylene monomer.

As described above, when the main catalyst is contacted with the promoter to activate the polymerization reaction, the activation time is preferably performed for 0.1 to 60 minutes. If the activation time is less than 0.1 minutes, the activation of the catalyst is insufficient and the activity is not maximized. If the activation time is longer than 60 minutes, the effect of activation is saturated and not economical. In addition, the activation reaction is preferably carried out at a temperature of 0 ℃ to 150 ℃.

The polymerization reaction may be carried out at a temperature of -80 ℃ to 200 ℃, it is more preferably carried out at a temperature of 0 ℃ to 150 ℃. If the polymerization reaction is carried out at a temperature lower than -80 ℃ reaction rate is too slow, if the polymerization reaction is carried out at a temperature higher than 200 ℃ has the disadvantage that the active time of the active catalyst is shortened.

The polymerization reaction may be carried out at a pressure of 0.01 to 1000 atm, more preferably at a pressure of 0.5 to 20 atm. If the polymerization reaction is carried out at a pressure lower than 0.01 atm, the activity of the catalyst is not well expressed, it is uneconomical to perform the polymerization reaction at a pressure higher than 1000 atm.

Hereinafter, the structure and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

Example 1 Preparation of (tBuN (Ph) CO) ₂ ZrCl ₂ Catalyst of Formula 5a

To a solution of 1.4 g (10 mmol) of benzoyl chloride in 50 mL THF solution was slowly added 2 equivalents of tertiary butylamine (tBuNH ₂ ) at -78 ° C. The reaction temperature was slowly raised to room temperature, followed by stirring for 12 hours. After the reaction, all of the solvent was removed under vacuum, and then diethyl ether was added to remove the amine salt through a filter to obtain a colorless solution. The solvent was removed in vacuo to yield a white crystalline solid.

¹ H NMR (300.13 MHz, CDCl ₃ ) δ = 8.03 (d, 2H) 7.50 (t, 1H) 7.41 (t, 2H) 4.13 (br, 3H) 2.04 (s, 15H)

4 mmol (1.07 g) of Zr (NMe ₂ ) ₄ was added to 8 mmol (1.42 g) of the ligand thus synthesized, and 50 mL of toluene was slowly added thereto at -78 ° C, followed by stirring. The reaction vessel was stirred for 12 hours while slowly raising the temperature to room temperature. After the reaction, all solvent was removed under vacuum, and then 50 mL of toluene was added again. After lowering the temperature of the reactor to -78 ℃, 8 mmol of trimethylsilyl chloride was slowly added. The temperature of the reaction vessel was slowly raised to room temperature, followed by stirring for another 12 hours. After the reaction, the solvent was removed using a vacuum to obtain a white solid.

¹ H NMR (300.13 MHz, CDCl ₃ ) δ = 7.45 (m, 4H) 7.41 (m, 6H) 1.31 (s, 18H)

Example 2 Preparation of (tBuN (tBu) CO) ₂ ZrCl ₂ Catalyst of Formula 5b

White solid was obtained in the same manner as in Example 1, except that 1.20 g (10 mmol) of trimethylacetyl chloride (C ₄ H ₉ COCl) was used instead of benzoyl chloride.

¹ H NMR (300.13 MHz, CDCl ₃ ) δ = 1.35 (m, 18H) 1.31 (m, 18H)

Example 3 Preparation of (PhN (Ph) CO) ₂ ZrCl ₂ Catalyst of Formula 5c

White solid was obtained in the same manner as in Example 1, except that 1.20 g (10 mmol) of aniline (PhNH ₂ ) was used instead of tertiary butylamine.

¹ H NMR (300.13 MHz, CDCl ₃ ) δ = 7.45 (m, 8H) 7.41 (m, 12H)

Example 4 Preparation of (p- (2,6-diisopropylphenyl) N (Ph) CO) ₂ ZrCl ₂ Catalyst of Formula 5d

White solid was obtained in the same manner as in Example 1, except that 1.77 g (10 mmol) of diisopropyl aniline (2,6-diisopropylaniline) was used instead of the tertiary butylamine.

¹ H NMR (300.13 MHz, CDCl ₃ ) δ = 7.95 (m, 4H) 7.51 (m, 2H) 6.9 (m, 10H), 3.3 (q, 4H), 1.31 (d, 12H)

Example 5 Preparation of Ethylene Polymer Using Catalyst of Formula 5a

250 mL of purified toluene was added to a polymerization reactor in a high-purity nitrogen atmosphere, and 3.85 mL of a 10% by weight solution of methylaluminoxane (Albemarle) dissolved in toluene solvent was injected and then heated to a temperature of 60 ° C. . 5 mL (5 μmol of Zr) in a toluene solution in which the nonmetallocene ethylene polymerization catalyst obtained in Example 1 was dissolved was added. Then, polymerization was initiated by stirring with adding 2 bar of ethylene to the reactor. After the reaction was stirred for 60 minutes, the reaction was stopped by addition of a 10% by weight hydrochloric acid-ethanol solution, which was filtered to yield 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 6 Preparation of Ethylene Polymer Using Catalyst of Formula 5b

An ethylene polymer was prepared in the same manner as in Example 5, except that the nonmetallocene ethylene polymerization catalyst obtained in Example 2 was used instead of the nonmetallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Example 7 Preparation of Ethylene Polymer Using Catalyst of Formula 5c

An ethylene polymer was prepared in the same manner as in Example 5, except that the nonmetallocene ethylene polymerization catalyst obtained in Example 3 was used instead of the nonmetallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Example 8 Preparation of Ethylene Polymer Using Catalyst of Formula 5d

An ethylene polymer was prepared in the same manner as in Example 5, except that the nonmetallocene ethylene polymerization catalyst obtained in Example 4 was used instead of the nonmetallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Comparative Example 1

An ethylene polymer was prepared in the same manner as in Example 5, except that the Cp ₂ ZrCl ₂ catalyst was used instead of the non-metallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Example 9 Preparation of Ethylene / Hexene-1 Copolymer Using Catalyst of Formula 5a

250 mL of purified toluene was added to a polymerization reactor in a high-purity nitrogen atmosphere, and 3.85 mL of a 10% by weight solution of methylaluminoxane (Albemarle) dissolved in toluene solvent was injected and then heated to a temperature of 60 ° C. . 5 mL (5 μmol of Zr) and 10 mL of 1-hexene in which the non-metallocene ethylene polymerization catalyst obtained in Example 1 was dissolved were added. Then, polymerization was initiated by stirring with adding 2 bar of ethylene to the reactor. After the reaction was stirred for 60 minutes, the reaction was stopped by addition of a 10% by weight hydrochloric acid-ethanol solution, which was filtered to yield 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 10 Preparation of Ethylene / Hexene-1 Copolymer Using Catalyst of Formula 5b

An ethylene polymer was prepared in the same manner as in Example 9, except that the nonmetallocene ethylene polymerization catalyst obtained in Example 2 was used instead of the nonmetallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Example 11 Preparation of Ethylene / Hexene-1 Copolymer Using Catalyst of Formula 5c

An ethylene polymer was prepared in the same manner as in Example 9, except that the nonmetallocene ethylene polymerization catalyst obtained in Example 3 was used instead of the nonmetallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Example 12 Preparation of Ethylene / Hexene-1 Copolymer Using Catalyst of Formula 5d

An ethylene polymer was prepared in the same manner as in Example 9, except that the nonmetallocene ethylene polymerization catalyst obtained in Example 4 was used instead of the nonmetallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

Comparative Example 2

An ethylene polymer was prepared in the same manner as in Example 9, except that the Cp ₂ ZrCl ₂ catalyst was used instead of the non-metallocene ethylene polymerization catalyst obtained in Example 1. Reaction conditions and physical properties of the prepared polymer are summarized as shown in Table 1 below.

TABLE 1

Used catalyst Al / Zr 1-hexene (ml) Mn ^a (× 10 ^-3 ) Mw / Mn ^a Tm ^b (℃) Example 5 Formula 5a 1000 - 120 2.5 132 Example 6 Formula 5b 1000 - 135 2.7 130 Example 7 Formula 5c 1000 - 130 2.7 130 Example 8 Chemical Formula 5d 1000 - 125 2.6 129 Comparative Example 1 Cp ₂ ZrCl ₂ 1000 - 90 2.2 127 Example 9 Formula 5a 1000 10 110 3.1 124 Example 10 Formula 5b 1000 10 130 3.2 125 Example 11 Formula 5c 1000 10 125 3.5 125 Example 12 Chemical Formula 5d 1000 10 115 3.1 126 Comparative Example 2 Cp ₂ ZrCl ₂ 1000 10 65 2.6 124

^a : Measured by gel permeation chromatography (GPC)

^b : Measured by differential scanning

As can be seen in Table 1, the liquid-polymerized polyethylene using the non-metallocene-based ethylene polymerization catalyst prepared in Examples 1 to 4 compared to the polyethylene produced by the metallocene catalyst of Comparative Example 1 It can be seen that it has an extremely high molecular weight (Examples 5 to 8 and Comparative Example 1).

In addition, the liquid-polymerized ethylene / 1-hexene copolymer using the non-metallocene-based ethylene polymerization catalyst prepared in Examples 1 to 4 is ethylene / 1-hexene prepared by the metallocene catalyst of Comparative Example 1 It turns out that it has a molecular weight outstandingly high compared with a copolymer (Examples 9-12, Comparative Example 2).

Although described in detail with respect to preferred embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not depart from the technology of the present invention.

The production of ethylene polymers or ethylene copolymers using the non-metallocene ethylene polymerization catalysts of the present invention has the effect of producing polymers of much higher average molecular weight than those using conventional polymerization catalysts.

Claims (20)

Non-metallocene ethylene polymerization catalyst of the formula (1). [Formula 1] L _a MX _b Wherein L is a bidentate ligand and is an amidinate of Formula 2; [Formula 2]

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an arylalkyl group having 6 to 40 carbon atoms, or an alkylaryl group having 6 to 40 carbon atoms; M is titanium (Ti), zirconium (Zr) or hafnium (Hf); X is a hydrogen atom or a halogen group) delete delete According to claim 1, wherein the non-metallocene ethylene polymerization catalyst is (tBuNC (Ph) O) ₂ TiCl ₂ , (tBuNC (Ph) O) ₂ ZrCl ₂ , (tBuNC (tBu) O) ₂ TiCl ₂ , (tBuNC (tBu) O) ₂ ZrCl ethylene polymerization catalyst to the non-metallocene metal, characterized in that at least one member selected from the group consisting of _2. Reacting the coordinating ligand L with an alkali metal or a compound thereof to prepare an alkali metal salt; And Method for producing a non-metallocene-based ethylene polymerization catalyst comprising the step of reacting the alkali metal salt with chlorine salt MCl _y of the metal M. Where L and M are as defined in claim 1 and y is the oxidation number of said metal M) delete 6. The method of claim 5, wherein the alkali metal is lithium, sodium, or potassium, and the compound thereof is normal butyl lithium, secondary butyl lithium, tertiary butyl lithium, methyl lithium, lithium bistrimethylsilamide, sodium methoxide, sodium ethoxide And potassium tert-butoxide, potassium hydroxide, methylmagnesium chloride, ethylmagnesium bromide, or dimethyl magnesium. Reacting the coordinating ligand L with a tetraamide compound M (NMe ₂ ) _y of metal M; Wherein the step of reacting the non-metallocene-based ethylene polymerization catalyst comprising the step of mixing the L and the M (NMe ₂ ) _y and reacting while raising the temperature from -78 ℃ to room temperature. Where L and M are as defined in claim 1 and y is the oxidation number of said metal M) delete A method for producing an ethylene polymer, wherein the ethylene monomer is polymerized using a catalyst system comprising a nonmetallocene-based ethylene polymerization catalyst and a promoter according to any one of claims 1 to 4. The method of claim 10, wherein the promoter is alkylaluminoxane, alkylaluminum, weakly coordinating Lewis acid, or a mixture thereof. 12. The method of claim 11, wherein the alkyl aluminoxane is a compound of formula (3). [Formula 3]

(Wherein R ³ is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group having 6 to 40 carbon atoms) Or an arylalkyl group having 6 to 40 carbon atoms, n is an integer of 1 to 100) The method for producing an ethylene polymer according to claim 12, wherein an equivalent ratio of the nonmetallocene ethylene polymerization catalyst and the alkyl aluminoxane is 1: 1 to 1: 106. The method of claim 11, wherein the alkyl aluminum is a compound of formula (4). [Formula 4]

Wherein R ⁴ , R ⁵ , and R ⁶ are each independently or simultaneously a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, An aryl group, an alkylaryl group, or an arylalkyl group having 6 to 40 carbon atoms, and at least one of R ⁴ , R ⁵ , and R ⁶ includes an alkyl group) The method of claim 14, wherein the equivalent ratio of the non-metallocene catalyst and the alkyl aluminum is 1: 1 to 1: 104. 12. The method of claim 11, wherein the coordinating Lewis acid is trimethylammonium tetrapetylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, N , N-dimethylanilinium tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl ) Borate, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate Sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tris (pentafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, and tris (2,4,6-trifluorophenyl) bore Method for producing an ethylene polymer, characterized in that at least one member selected from the group consisting of phosphorus. The catalyst system of claim 11, wherein the catalyst system comprises both the alkylaluminum and the weakly coordinating Lewis acid as a cocatalyst, and the equivalent ratio of the nonmetallocene catalyst, the alkylaluminum, and the coordinating Lewis acid is 1: 1: 0.1 to 1: 1. 3000: A method for producing an ethylene polymer, characterized in that 50. The method for producing an ethylene polymer according to claim 10, wherein the concentration of the nonmetallocene ethylene polymerization catalyst is 1.0 × 10 ^-8 M to 1.0 M. The method for producing an ethylene polymer according to claim 10, wherein the polymerization is performed by slurry polymerization, liquid phase polymerization, gas phase polymerization, or bulk polymerization. The method for producing an ethylene polymer according to claim 10, wherein the polymerization is carried out under a pressure of 0.01 atm to 1000 atm.