KR100491627B1 - Method for polymerization and copolymerization of ethylene using carbodiimide ligand chelated catalyst - Google Patents

Abstract

The present invention relates to a process for ethylene polymerization or copolymerization. In the present invention, a magnesium compound is reacted with a carbodiimide-based ligand and then reacted with a transition metal compound of Group IV of the periodic table, and a catalyst comprising a transition metal compound component chelate-bonded by a carbodiimide-based ligand is used. It is characterized by providing an ethylene polymerization or copolymerization method to be used. According to the present invention, ethylene polymerization and copolymerization are possible using the catalyst prepared by the above method, a magnesium-containing support and a commonly used organometallic compound cocatalyst component, and the prepared (co) polymer has a narrow molecular weight distribution and uniformity. (Co) polymer composition distribution.

Description

Ethylene polymerization and copolymerization method using a catalyst chelate bonded by carbodiimide-based ligand {METHOD FOR POLYMERIZATION AND COPOLYMERIZATION OF ETHYLENE USING CARBODIIMIDE LIGAND CHELATED CATALYST}

The present invention is prepared by reacting a magnesium compound with a carbodiimide-based ligand and then reacting with a transition metal compound of Group IV of the periodic table, using a catalyst consisting of a transition metal compound component chelate-bonded by a carbodiimide-based ligand. It relates to an ethylene polymerization or copolymerization method.

In the olefin polymerization reaction in which the transition metal compound reacts with the olefin, efforts have been made to improve the properties of the polymer produced by changing the reaction environment of the transition metal compound. In particular, efforts to control the environment in which the transition metal compound reacts with the olefin using the metallocene compound obtained by converting the ligand of the transition metal compound into the cyclopentadiene ligand have made significant progress.

In the 80's, homogeneous catalysts using metallocene compounds started to attract attention due to their excellent (co) polymerization properties with alpha olefins, showing excellent properties in impact strength and transparency of the prepared (co) polymers. In particular, by synthesizing a metallocene compound having special substituents such as indenyl, cycloheptadiene, and fluorenyl, which controls the electronic or steric spatial environment of the cyclopentadienyl group Metallocene catalysts that can control the size and molecular weight of polymers have been developed and are expanding their applications.

Recently, the development of a catalyst capable of controlling the particle properties of a polymer while producing an excellent copolymer by preparing a metallocene compound on an inorganic carrier to produce a non-uniform catalyst has been actively developed. For example, US Pat. No. 5,439,995, US Pat. No. 5,455,316, and the like describe the preparation of non-uniform catalysts having excellent particle properties and excellent copolymerization properties by supporting zirconocene and titanocene compounds on magnesium or silica compounds. It is.

However, to date, metallocene catalysts require complex organometallic chemical synthesis, and use expensive methylaluminoxane (MAO) or boron compounds as cocatalysts in the polymerization of olefins. The desire for is continued, and the polymer produced by the metallocene catalyst has a narrow molecular weight distribution (Mw / Mn = 2 to 5), which has disadvantages in terms of processing of the polymer.

Recently, a transition metal compound called a non-metallocene catalyst, a supermetallocene catalyst or an organometallic catalyst is used as a catalyst component. While using tridentated chelate compounds, efforts have been made to develop catalysts that produce polymers of narrow molecular weight distribution without being difficult to synthesize, such as metallocene compounds. Japanese Patent Application Laid-Open No. 63-191811 discloses a result of polymerizing ethylene and propylene using a compound in which a halide ligand of a titanium halide compound is substituted with TBP ligand (6-tert-butyl-4-methylphenoxy) as a catalyst component. . Polymerization of ethylene and propylene using MAO as a promoter reported the formation of a highly active polymer of high molecular weight (average molecular weight = 3,600,000 or more).

On the other hand, U.S. Patent No. 5,134,104 describes a catalyst for olefin polymerization using dioctylaminetitanium halide ((C ₈ H ₁₇ ) ₂ NTiCl ₃ ) compound in which a halide ligand of TiCl ₄ is replaced with a bulky amine ligand. It is. American 'J. Am. Chem. Soc. No. 117, page 3008, is a chelating compound that can limit the steric space of transition metals and is a 1,1'-bi-2,2'-naphthoxy ligand (1,1'-bi-2) (2'-naphthol) and a catalyst for olefin polymerization using chelate-bonded derivatives thereof are described. Japanese Unexamined Patent Publication No. Hei 6-340711 and European Patent EP 0606125 A2 disclose the use of titanium halide and zirconium halide compounds. A catalyst for chelate olefin polymerization has been described in which a halide ligand is substituted with a chelated phenoxy group to produce a polymer of high molecular weight and narrow molecular weight distribution.

Recently, a catalyst for non-metallocene olefin polymerization using an amine-based chelate transition metal compound has been attracting attention. 'Organometallics 1996, 15, 2672' and 'Chem. Commun. 1996, 2623 'introduces an example of synthesizing a titanium compound chelate-bonded with various types of diamide compounds and utilizing them as catalysts for olefin polymerization. Am. Chem. Soc., 1998, 120, 8640 'describes propylene polymerization using titanium compounds and zirconium compounds chelated by diamides. 'Organometallics 1998, 17, 4795' introduce catalysts for polymerization using titanium or zirconium chelated by [(ArylNCH ₂ CH ₂ ) ₂ O] and [(ArylNCH ₂ CH ₂ ) ₂ S], and 'Organometallics 1998 , 17, 4541 'introduce a catalyst for olefin polymerization using titanium, vanadium, and chromium compounds chelated by [N, N-diphenyl-2,4-pentanediimine] ligands. Also, 'J. Am. Chem. Soc., 1996, 118, 10008 'show a titanium compound chelate-bonded by (ArylNCH ₂ CH ₂ CH ₂ NAryl) as a catalyst for olefin polymerization. In addition, U.S. Patent No. 5,502,128 describes an sPS polymerization method using a titanium zirconium compound chelate-bonded with an amidinate ligand. Highly active nonmetallocene catalysts using titanium or zirconium compounds bound by (amide) compounds have been introduced.

However, the non-metallocene-based olefin polymerization catalyst using the chelated titanium and zirconium compounds has been developed as a homogeneous catalyst that uses expensive MAO or boron compounds as cocatalysts, and is activated by an inorganic carrier. As a homogeneous catalyst, there is a problem in that it is difficult to directly apply to most existing polymerization processes, particularly processes requiring a catalyst having excellent particulate properties such as gas phase polymerization. Therefore, there is a demand for the development of a polymerization method using a catalyst which can be easily activated by an inorganic carrier such as MgCl _{2 that} is applied to most existing processes while using a nonmetallocene compound or a metallocene compound as a catalyst component.

The present invention is to solve the above problems, and the catalyst component is a titanium compound chelate-bonded by a carbodiimide-based ligand prepared by a unique method, and an inorganic carrier such as magnesium halide and a general organometallic compound It is an object of the present invention to provide an ethylene polymerization or copolymerization method that produces a polymer or copolymer having a narrow molecular weight distribution and a uniform composition distribution using a new concept of ethylene polymerization and copolymerization catalyst activated by a catalyst.

The ethylene polymerization and copolymerization method provided by the present invention comprises a catalyst (A) consisting of a periodic table Group IV transition metal compound chelate-bonded with a carbodiimide-based ligand prepared by the method described below, and a magnesium-containing carrier (B). And ethylene in the presence of periodic table group II or group III organometallic compound (C) as a promoter.

The catalyst for ethylene polymerization and copolymerization (A) used in the present invention comprises (i) reacting a Grignard compound in the form of dialkyl magnesium with a carbodiimide-based ligand, and then (ii) reacting the reaction product of (i) in the periodic table. It is prepared by reaction with a transition metal compound of Group IV.

In the preparation of the catalyst (A) used in the present invention, the Grignard compound in the dialkyl magnesium form in step (i) is represented by the general formula MgR ₂ (R is an alkyl group having 1 to 30 carbon atoms). Dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium, etc. are preferable.

The carbodiimide-based ligand used in step (i) at the time of preparing the catalyst (A) used in the present invention is a compound satisfying the following general formula,

(W, Y, Z is independently alkyl, phenyl, or an alkyl group containing heteroatoms), for example dimethylcarbodiimide, dicyclohexylcarbodiimide, 1,3-bistrimethylsilylcarbodiimide or Derivatives are suitable.

Catalyst (A) used in the present invention is in the form of a liquid chelated transition metal compound by reacting a magnesium compound containing a carbodiimide ligand prepared in step (i) with a transition metal compound of group IV of the periodic table. It is prepared as (step (ii) above). That is, the magnesium compound containing the carbodiimide-based ligand prepared in step (i) is added dropwise to the transition metal compound at room temperature, and then reacted at 65 ° C to 70 ° C for at least 1 hour to chelate the transition metal compound. Manufacture. The molar ratio of the magnesium compound containing the carbodiimide-based ligand and the Group IV transition metal compound of the periodic table is preferably 0.5 to 2.0 moles per 1 mole of magnesium in the magnesium compound.

The transition metal compound of Group IV of the periodic table is a general formula M (OR) _a X _4-a (M is Ti, Zr or Hf, R is a hydrocarbon group, X is a halogen atom _, and a is 0 ≦ a ≦ 2). is a compound that satisfies a natural number), and examples thereof include MCl _4, transition metal _{halide, M (OR) 2 Cl 2} , M (OR) Cl 3, M (OR) 2 Br 2, M (OR) , such as MBr ₄ Transition metal compounds containing at least two or more halide groups, such as Br ₃ , are suitable, and titanium halide compounds are particularly preferred. In addition, it is preferable to use a transition metal halide compound in the form of an adduct such as MX ₄ (THF) ₂ by reacting a transition metal compound with an ether solvent such as tetrahydrofuran (THF) for a smooth reaction. Do.

In the preparation of the chelated transition metal compound in step (ii), a magnesium halide compound is produced as a reaction by-product, which is easily dissolved because it is not dissolved in a hydrocarbon solvent. Chelated transition metal compounds dissolved in non-polar solvents such as heptane and hexane are very stable and can be used directly in a hydrocarbon solvent without a separate separation process. The chelated transition metal compound catalyst (A) thus prepared is used for ethylene polymerization or copolymerization together with the promoter component in the form of a liquid dissolved in a nonpolar solvent such as hexane and heptane.

Catalyst (A) used in the present invention is suitable for ethylene homopolymerization and copolymerization with alpha olefins, wherein alpha olefins having 3 to 10 carbon atoms are suitable as alpha olefins. For example, copolymerization of ethylene with alpha olefins of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene is possible. The catalyst is suitable for slurry or gas phase polymerization, and aliphatic and aromatic hydrocarbons are preferable as solvents in slurry polymerization. In the slurry polymerization, hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used as a solvent, and the polymerization temperature is preferably 50 ° C to 120 ° C. In the slurry polymerization, the amount of the catalyst according to the present invention may vary, and it is preferable to use about 0.005 to 1 mmol of the catalyst in 1 L of the hydrocarbon solvent, and more preferably 0.01 to 0.1 mmol in 1 L of the hydrocarbon solvent. In the case of ethylene polymerization, the pressure of ethylene is preferably 2 to 50 kg / cm 2 .G. Control of the molecular weight size can be achieved through control of temperature and ethylene pressure, control of hydrogen pressure, and the like.

Magnesium is used in ethylene polymerization or copolymerization process of the invention contain carrier (B) is MgPh ₂ .nMgCl ₂ .mR ₂ O (wherein, Ph = phenyl, n = 0.37~0.7; m≥1; R 2 0- ether It is prepared by reacting an organic magnesium compound having a composition of) with an organic chlorine compound at a temperature of -20 ℃ ~ 80 ℃.

The magnesium-containing carrier (B) used in the present invention can be produced by, for example, a method known by Korean Patent Application No. 10-2000-0085050. The magnesium compound according to the known method is a hydrocarbon solvent using an organomagnesium compound complex [MgPh ₂ .nMgCl ₂ .mR ₂ O] prepared by reacting magnesium with an aryl halide or alkyl halide in the presence of an electron donor. It is prepared by chlorination with organochlorine compound at molar ratio of organochlorine compound and magnesium at 0.5 to -20 ° C to 80 ° C. The magnesium compound thus prepared is suitable for preparing a polymer having excellent particle properties by activating a chelated transition metal compound, which is a catalyst according to the present invention, because the particle shape is spherical, the particle size is large, and the particle size distribution is uniform.

The magnesium-containing carrier may be used after further reacting with an alkylaluminum represented by the general formula of AlR ₃ (R represents an alkyl group having 1 to 20 carbon atoms).

The cocatalyst component (C) used in the ethylene polymerization or copolymerization method of the present invention is MR _n (where M is a periodic table group II or IIIA metal component such as magnesium, calcium, zinc, boron, aluminum, gallium, and R is Or an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl and decyl, and n represents the valence of the metal component. More preferred organometallic compounds include trialkylaluminums having 1 to 8 carbon atoms, such as triethylaluminum, triisobutylaluminum and trioctylaluminum, and mixtures thereof. In some cases, organoaluminum compounds having one or more halogen or hydride groups may also be used, such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride or diisobutylaluminum hydride.

The catalyst system as described above may be used by sequentially injecting each component into a polymerization process without undergoing a separate reaction, or may be previously mixed and injected simultaneously in the form of a liquid phase.

The ethylene / alpha olefin copolymers prepared according to the present invention have a narrow compositional distribution, a narrow molecular weight distribution, and thus have very high impact strength, and do not contain sticky low molecular weight polymers, so they have a super hexene grade. Suitable for high impact linear low density polyethylene (LLDPE).

Hereinafter, the present invention will be described in detail through examples. However, the following examples do not limit the content of the present invention.

Example

The hydrocarbon solvent used for preparing the catalyst was removed by distillation in the presence of sodium, and the halogenated hydrocarbon was distilled in the presence of calcium hydride to remove the water. All reactions for catalyst preparation were carried out in a nitrogen atmosphere.

Example 1

Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand

400 mL of dibutylmagnesium 1.0 M heptane solution was injected and 82.4 g of dicyclohexylcarbodiimide (400 mmol) was injected, followed by stirring at room temperature for 1 hour. The compound prepared as described above was reacted with 0.684 g of TiCl ₄ (THF) ₂ 400 mmol at room temperature for 6 hours. By reaction, the TiCl ₄ (THF) ₂ solid, which was initially light yellow, gradually turned red, producing a white magnesium halide solid. After stirring for 6 hours at room temperature, after stopping the stirring and waiting for 20 minutes, the white solid at the bottom settles down. -1) was used.

Preparation of Magnesium-Containing Carrier (B)

In a 1 L glass reactor equipped with a stirrer and a temperature controller, 1.2 mol of 29.2 g of magnesium powder and 436 mL of 307 ml of dibutyl ether and 0.29 g of iodine dissolved in 4 ml butyl chloride as an activator were added. 4.3 mol of chlorobenzene was reacted. The reaction proceeded with stirring for 10 hours under an inert gas atmosphere at a temperature of 80 to 100 ℃. The reaction mixture was then left for 12 hours without stirring to separate the liquid phase from the precipitate. Liquid phase MgPh ₂ .0.5MgCl a ₂ .2 (C ₄ H ₉₎ the solution is dissolved in chlorobenzene and an organic magnesium compound having a composition of ₂ O (the concentration of Mg is 0.92mol per 1L). 120 ml (0.11 mol Mg) of the obtained solution was added to a reactor equipped with a stirrer, and 10.6 ml CCl ₄ (0.11 mol CCl ₄ ) dissolved in 42 ml of N-hexane was reacted at a temperature of 50 ° C. over 1 hour. Added on board. The reaction mixture was stirred at the same temperature for 60 minutes, then the solvent was removed and the precipitate was washed four times at 60 ° C. with 100 ml of n-hexane. As a result, 11.8 g of powdered organomagnesium carrier was obtained in a state suspended in n-hexane.

Ethylene polymerization

1000 ml of hexane as a polymerization solvent was added to a 2 L autoclave, which was sufficiently substituted with nitrogen at room temperature, and then nitrogen in the autoclave was replaced with ethylene. 3 mmol of trioctyl aluminum was injected at room temperature, 0.05 mmol of the chelated titanium compound (A-1) prepared above and 0.2 g of a magnesium-containing carrier component (B) in the solid phase were injected. Hydrogen was added at 1.5 Kg / cm 2 at 60 ° C., the temperature was raised to 80 ° C., and then pressurized with ethylene to maintain a total pressure of 6 Kg / cm 2. The polymerization proceeded for 1 hour. The polymerized polymer was separated from hexane and dried. The polymerization results are shown in Table 1 together with the other analysis results.

Ethylene / 1-hexene Copolymerization Reaction

A vacuum pump was connected to an internal 2 L autoclave to remove oxygen and moisture and filled with ethylene gas. The vacuum pump connection and ethylene gas purge were repeated three more times to purge the reactor interior with ethylene gas. 900 ml of hexane as a polymerization solvent was injected, and 90 ml of 1-hexene was added thereto, followed by stirring for 10 minutes. Again, 3 mmol of trioctyl aluminum was injected at room temperature, and 0.05 mmol of the chelated titanium compound (A-1) prepared above and 0.1 g of a magnesium-containing carrier component (B) were injected. Hydrogen was added at 1.5 Kg / cm 2 at 60 ° C., and the temperature was raised to 80 ° C., and then pressurized with ethylene to maintain the total pressure at 6 Kg / cm 2. The polymerization proceeded for 20 minutes. After the polymerization, the reaction was stopped by adding an ethanol solution, and the acidic alcohol solution was added to separate the polymer. The polymerization results are shown in Table 1 together with the other analytical results.

The low MFRR values in Table 1 indicate that the molecular weight distribution of the polymer produced is narrow, and that a uniform copolymer composition distribution was obtained from the Tm analysis results obtained through DSC analysis of polymers containing the same amount of copolymer. I could confirm it.

Example 2

Preparation of Titanium Compound (A-2) Chelated with Dimethylcarbodiimide Ligand

Chelated titanium compound (A-2) was prepared and used in the same manner as in Example 1 except for using dimethylcarbodiimide ligand instead of dicyclohexylcarbodiimide.

Preparation of Magnesium-Containing Carrier (B)

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

Ethylene Polymerization and Copolymerization Reaction

The polymerization and copolymerization reaction were carried out in the same manner as in Example 1, except that the titanium compound (A-2) was used instead of the titanium compound (A-1). The polymerization results are shown in Table 1.

Example 3

Preparation of Titanium Compound (A-3) Chelated by 1,3-Bistrimethylsilylcarbodiimide

Chelated titanium compound (A-3) was prepared and used in the same manner as in Example 1, except that 1,3-bistrimethylsilylcarbodiimide was used instead of dicyclohexylcarbodiimide.

Preparation of Magnesium-Containing Carrier (B)

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

Ethylene Polymerization and Copolymerization Reaction

The polymerization and copolymerization reaction were carried out in the same manner as in Example 1, except that the titanium compound (A-3) was used instead of the titanium compound (A-1). The polymerization results are shown in Table 1.

Example 4

Preparation of Titanium Compound (A-4) Chelated by Dicyclohexylcarbodiimide

A chelated titanium compound (A-4) was prepared and used in the same manner as in Example 1 except that Ti (O-iPr) ₂ Cl ₂ (400 mmol) was used instead of TiCl ₄ (THF) ₂ .

Preparation of Magnesium-Containing Carrier (B)

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

Ethylene Polymerization and Copolymerization Reaction

The polymerization and copolymerization reaction were carried out in the same manner as in Example 1, except that the titanium compound (A-4) was used instead of the titanium compound (A-1). The polymerization results are shown in Table 1.

Example 5

Preparation of Titanium Compound (A-5) Chelated by Dicyclohexylcarbodiimide

Chelated titanium compound (A-5) was prepared and used in the same manner as in Example 1 except that TiCl ₄ (400 mmol) was used instead of TiCl ₄ (THF) ₂ .

Preparation of Magnesium-Containing Carrier (B)

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

Ethylene Polymerization and Copolymerization Reaction

The polymerization and copolymerization reaction were carried out in the same manner as in Example 1, except that the titanium compound (A-5) was used instead of the titanium compound (A-1). The polymerization results are shown in Table 1.

Comparative Example 1

Preparation of the catalyst

19.2 g of magnesium metal was added to a 1 L flask, and 20 ml of dibutyl ether was injected. After raising the temperature to 80 ° C., 5 ml of a solution of 2 g of iodine and 50 ml of chlorobutane was taken and injected to activate the magnesium surface. 20 ml of chlorobenzene was further injected with 200 ml of dibutyl ether, and 400 ml of chlorobenzene was added dropwise at 90 DEG C to maintain the reaction. The reaction at 90 ° C. was continued for at least 5 hours to complete the preparation of Grignard reagent. Liquid Grignard reagent was isolated from the solid component. 120 ml (100 mmol Mg content) of the separated supernatant was added to a 1 L flask, and 20 ml of carbon tetrachloride was slowly added dropwise at 40 ° C. to prepare a spherical magnesium halide. After the dropwise addition, the temperature was raised to 80 ° C. and reacted for 1 hour or more to complete the preparation of the magnesium halide component. The supernatant was again decanted and washed three times with hexane to separate the magnesium halide carrier component in the solid state. After injecting 300 ml of hexane to the carrier thus prepared, 30 ml of TiCl ₄ was injected and heated at 60 ° C. for 1 hour. After the reaction was completed, the supernatant solution was decanted at 60 ° C. and washed three times with hexane to complete the preparation of the catalyst. The titanium loading rate was 3.5%.

Ethylene Polymerization and Copolymerization

Polymerization and copolymerization reaction were carried out in the same manner as in Example 1, except that the catalyst prepared above was used instead of the titanium compound (A-1). The polymerization results are shown in Table 1.

Comparative Example 2

Preparation of Ti Component

After dissolving 82.4 g of dicyclohexylcarbodiimide in 400 mL of toluene solution, 40 mL (400 mmol) of TiCl ₄ was injected and reacted at 90 ° C. for 4 hours. As the reaction progressed, the colorless solution became dark brown. After the reaction, toluene was removed with a vacuum pump, and the remaining solid was sufficiently washed with hexane to remove the unreacted carbodiimide compound and TiCl ₄ to obtain a brown catalyst Ti catalyst component.

Preparation of Magnesium-Containing Carrier (B)

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

Preparation of Catalyst (C)

After dissolving the Ti catalyst component in 400 ml of toluene, 20 g of the magnesium-containing carrier (B) was poured into 100 ml of the suspended slurry, followed by stirring at 60 ° C. for 1 hour. After stirring was stopped, 20 ml of hexane was injected and washed three times to obtain a catalyst (C) in which a powdery solid was suspended in n-hexane.

Ethylene Polymerization and Copolymerization Reaction

The polymerization and copolymerization reaction were carried out in the same manner as in Example 1, except that the catalyst (C) prepared above was used instead of the titanium compound (A-1) and the magnesium-containing support. The polymerization results are shown in Table 1.

Comparative Example 3

Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand

Chelated titanium compound (A-1) was prepared and used in the same manner as in Example 1.

Preparation of Magnesium-Containing Carrier (B)

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

Ethylene Polymerization and Copolymerization Reaction

The copolymerization reaction of ethylene polymerization and ethylene / 1-hexene was carried out in the same manner as in Example 1, except that 3 mmol of PMAO was used instead of 3 mmol of trioctyl aluminum in Example 1 as a cocatalyst. And the polymerization results are shown in Table 1.

Comparative Example 4

Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand

Chelated titanium compound (A-1) was prepared and used in the same manner as in Example 1.

Ethylene Polymerization and Copolymerization Reaction

Instead of injecting 3 mmol of the trioctyl aluminum in Example 1 as a cocatalyst, PMAO 3 mmol was used, and ethylene polymerization was carried out in the same manner as in Example 1 except that the magnesium-containing carrier component (B) was not used. And copolymerization of ethylene / 1 hexene was carried out, the polymerization results are shown in Table 1.

Table 1 Ethylene Polymerization and Ethylene / 1-Hexene Copolymerization Results

Example Ethylene polymerization Ethylene / 1-hexene Copolymerization Reaction Activation (g PE / g Catalyst) M.I. (g / 10min) MFRR B / D (g / ml) M.I. (g / 10min) MFRR ΔH (J / g) Tm (℃) Example (1) 5400 0.9 25.7 0.41 1.3 23.9 104.8 122.2 Example (2) 5700 1.2 29.1 0.41 1.7 25.2 103.8 122.1 Example (3) 4600 1.2 27.3 0.41 1.8 25.4 108.5 122.8 Example (4) 4900 1.3 27.5 0.40 1.8 24.9 103.2 121.7 Example (5) 5300 1.5 25.6 0.41 1.3 25.4 102.3 123.2 Comparative Example (1) 3500 0.6 30.7 0.36 1.2 30.1 105.6 125.2 Comparative Example (2) 2500 0.2 30.7 0.36 0.7 30.4 125.3 125.4 Comparative Example (3) 5200 1.2 24.7 0.31 1.5 26.5 102.4 122.6 Comparative Example (4) 5400 1.5 23.7 - 1.8 24.1 103.1 122.3

As described above, according to the ethylene polymerization or copolymerization method according to the present invention, polymers and copolymers of ethylene and ethylene / alpha-olefins having a high apparent density and having a narrow molecular weight distribution and a uniform copolymer composition distribution are possible. Do.

Claims (7)

A magnesium compound containing a carbodiimide ligand is prepared by reacting a Grignard compound in a dialkyl magnesium form with a ligand of a carbodiimide series, and a chelated transition metal compound prepared by reacting with a Group IV transition metal compound of the periodic table. Ethylene polymerization or copolymerization method, characterized in that the ethylene is polymerized or copolymerized in the presence of the catalyst (A), the magnesium-containing support (B) and the cocatalyst in the presence of a Group II or Group III organometallic compound (C). According to claim 1, wherein the carbodiimide-based ligand is a compound satisfying the following formula, , Here, W, Y, Z is an ethylene polymerization or copolymerization method, characterized in that independently alkyl, phenyl, or an alkyl group containing a hetero atom. The method of claim 2, wherein the carbodiimide-based ligand is dimethyl carbodiimide, dicyclohexylcarbodiimide, 1,3-bistrimethylsilylcarbodiimide or derivatives thereof. The compound of claim 1, wherein the Group IV transition metal compound of the periodic table is M (OR) _a X _4-a (M is Ti, Zr or Hf, R is a hydrocarbon group, X is a halogen atom _, and a is 0). Ethylene polymerization or copolymerization method characterized by the above-mentioned. 5. The method of claim 4, wherein the Group IV transition metal compound of the periodic table is titanium halide. The method of claim 1, wherein the magnesium containing carrier (B) is MgPh ₂ .nMgCl ₂ .mR ₂ O having a composition of (wherein, Ph is phenyl, n = 0.37~0.7; R ₂ 0 is ether; m≥1) Ethylene polymerization or copolymerization method characterized in that the produced by reacting the organic magnesium compound and the organic chlorine compound with a molar ratio of organic chlorine compound and magnesium of 0.5 or more. The method of claim 1, The promoter (C) is an organometallic compound represented by the general formula of MR _n (M is a group II or IIIA metal atom of the periodic table, R is an alkyl group having 1 to 20 carbon atoms, n is a valence of a metal component) Ethylene polymerization or copolymerization method.