KR100430978B1 - Method for producing supported catalyst for producing ethylene polymer and ethylene/alpha-olefin copolymer - Google Patents

Abstract

The present invention relates to a method for preparing an ethylene polymer and a copolymer of ethylene and an α-olefin and a supported catalyst for preparing a copolymer, more specifically MgPh ₂ .nMgCl ₂ .mR ₂ O (where Ph = phenyl and an organic magnesium compound and an organic chlorine compound having a composition of n = 0.37 to 0.7; m≥1; R ₂ 0 = ether) at a temperature of -20 ° C to 80 ° C with a molar ratio of organochlorine compound to magnesium of 0.5 or more. Reacting; And reacting the magnesium-containing carrier obtained in the reaction with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound and an alkoxysilane compound.

The method of the present invention provides a catalyst capable of producing polyethylene and polyethylene copolymers having a narrow molecular weight distribution.

Description

METHODS FOR PRODUCING SUPPORTED CATALYST FOR PRODUCING ETHYLENE POLYMER AND ETHYLENE / ALPHA-OLEFIN COPOLYMER}

The present invention relates to the production of a supported catalyst for ethylene polymerization and copolymerization of ethylene and α-olefin, and more particularly, a supported catalyst comprising a transition metal on a magnesium-containing carrier having a narrow particle size distribution. A method for producing a supported catalyst for ethylene polymerization and ethylene / α-olefin copolymerization.

By a method of coating a transition metal compound on a carrier, that is, an organic having a composition of MgPh ₂ .nMgCl ₂ .mR ₂ O, wherein n = 0.37 to 0.7; m ≧ ₂ ; R ₂ O = ether; Ph = phenyl A method of preparing a supported catalyst for ethylene polymerization and copolymerization of ethylene and α-olefin by reacting a magnesium compound with an organic halide and then supporting a transition metal compound such as TiCl ₄ , VCl ₄ or VOCl ₃ on the obtained carrier It was developed by some of the inventors of the invention (Japanese Patent No. 330675/1995).

The catalyst prepared by the above known method, in particular, a catalyst prepared by coating TiCl ₄ on a carrier, has a wide molecular weight distribution even though the polymerization process is partially improved by preparing a polymer having a narrow particle size distribution and an increased apparent density. And there is a problem that has a high initial activity.

For polymers with narrow molecular weight distribution, especially linear low density polyethylene products produced by copolymerization of ethylene and α-olefins, narrow molecular weight distribution reduces the content of low molecular weight polymers that can be extracted by hexane in the product. It is known that it can be improved.

For this purpose, there is a need for a catalyst with a homogeneous active site capable of narrowing the molecular weight distribution.

An object of the present invention is to enable the preparation of polymers having a narrow particle size distribution and increased apparent density, and ethylene polymers and ethylene having molecular weight distribution of 4 or less in ethylene polymerization and ethylene / α-olefin copolymerization by slurry and gas phase polymerization It is to provide a method for preparing a useful catalyst that can produce a / α-olefin copolymer.

The invention is as it relates to a process for the preparation of the ethylene polymerization and ethylene with supported catalyst for the copolymerization of the α- olefins, and more particularly, MgPh ₂ .nMgCl ₂ .mR ₂ O (wherein, Ph = phenyl, n = 0.37~0.7; reacting the organic magnesium compound and the organic chlorine compound having a composition of m ≧ 1; R ₂ 0 = ether) with a molar ratio of the organic chlorine compound to magnesium of 0.5 or more at a temperature of -20 ° C to 80 ° C; And reacting the magnesium-containing carrier obtained in the reaction with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound and an alkoxysilane compound.

The invention also MgPh ₂ .nMgCl ₂ .mR ₂ O (wherein, Ph = phenyl, n = 0.37~0.7; m≥1; R 2 0 = ether) an organomagnesium compound with an organic chlorine compound having a composition of -20 Reacting with a molar ratio of the organochlorine compound to magnesium of 0.5 or more at a temperature of from ℃ to 80 ℃; Reacting the magnesium-containing carrier obtained in the reaction with an alkoxysilane compound; And reacting the reactant reacted with a titanium compound, a vanadium compound, or a mixture of a titanium compound and a vanadium compound.

The invention also MgPh ₂ .nMgCl ₂ .mR ₂ O (wherein, Ph = phenyl, n = 0.37~0.7; m≥1; R 2 0 = ether) an organomagnesium compound with an organic chlorine compound having a composition of -20 Reacting with a molar ratio of the organochlorine compound to magnesium of 0.5 or more at a temperature of ℃ to 80 ℃; Reacting the magnesium-containing carrier obtained in the reaction with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound; It characterized in that it comprises the step of reacting the reactant obtained in the reaction with an alkoxysilane compound.

In preparing the magnesium-containing carrier of the present invention, the organomagnesium compound is prepared by reacting powdered magnesium with chlorobenzene in the presence of at least one electron donor compound. The electron donor may include aliphatic ethers and cyclic ethers. Aliphatic ethers have the structural formula of R ² OR ³ , wherein R ² and R ³ are the same or different alkyl radicals of ^{2 to} 8 carbon atoms, and are preferably aliphatic ethers of 4 to 5 carbon atoms. The cyclic ether is a cyclic ether having 3 to 4 carbon atoms. Most preferred as electron donor is dibutyl ether or diisoamyl ether.

The magnesium-containing carrier is prepared by reacting the organomagnesium compound solution with at least one organochlorine compound, preferably carbon tetrachloride, at a molar ratio of organochlorine compound / Mg ≧ 0.5 at a temperature of −20 ° C. to 80 ° C. The suspension of the carrier powder containing magnesium obtained in this step has a specific particle size and narrow particle size distribution.

In the step of preparing a magnesium-containing carrier in the present invention, the organochlorine compound is preferably CR ' _n Cl _(4-n) wherein R' is an alkyl radical having 1 to 12 carbon atoms, where n is 0 An integer of 3 or less) is used. The size of the carrier and the catalyst particles can be controlled within the range of 5 μm to 150 μm by the composition of the organic magnesium compound and the reaction conditions of the organic magnesium compound and the organic chlorine compound.

In the step of preparing a magnesium-containing carrier in the present invention, the complex of the organomagnesium compound [MgPh ₂ .nMgCl ₂ .mR ₂ O] is chlorobenzene, ether (R ₂ O) or a mixture of chlorobenzene and ether, chlorobenzene Used in the form of solutions dissolved in mixtures of aliphatic or aromatic compounds with predominantly magnesium dichloride (80-90% by weight), ether (7-15% by weight) and hydrocarbon complexes (1-5% by weight). Done.

In the supported catalyst for ethylene polymerization and copolymerization of ethylene and α-olefin of the present invention, the molar ratio (Si / Ti) of alkoxysilane to titanium in the magnesium-containing carrier prepared as described above is a titanium compound and an alkoxysilane compound. Preferably it is 0.5-1.0, and the molar ratio of titanium to magnesium (Ti / Mg) = 0.01-2.0, Preferably it is 0.04-0.5, The temperature is 20 degreeC-100 degreeC in a hydrocarbon solvent, Preferably it is 40 degreeC It is obtained by processing at -80 degreeC.

When the molar ratio of titanium to magnesium (Ti / Mg) exceeds 2.0, it is generally necessary to remove excess titanium compounds which are not immobilized on the support (carrier) in the catalyst washing process, Corrosion is an expensive and difficult process for waste disposal. In addition, if the molar ratio of titanium to magnesium (Ti / Mg) is less than 0.01, there is a problem that the activity is not sufficient.

The titanium compound has _a structural formula of Ti (OR) _a X _4-a . R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR '(wherein R' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms), X is Cl, Br or I, and a is 0, 1, 2 Or three. Preferred titanium compounds are titanium tetrachloride and titanium alkoxychlorides. Examples of these compounds include TiCl ₄ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) Cl ₃ , Ti (OC ₃ H ₇ ) ₃ Cl, Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₃ Cl.

Instead of the titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound may be used. The vanadium compound may include, for example, a compound such as VCl ₄ , VOCl ₃ .

The alkoxysilane compound has _a structural formula of Si (OR) _a R ' _4-a . R is an aliphatic, vinyl, cycloaliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR '' (wherein R '' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms) and R 'is an aliphatic or aromatic hydrocarbon group And a is 0, 1, 2, 3, or 4. Examples of preferred alkoxysilane compounds include dicyclopentyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, diisopropyldimethoxysilane, disecondarybutyldimethoxysilane, dicyclohexyldimeth Oxysilane, isobutyl isopropyldimethoxysilane, isobutyl secondary butyldimethoxysilane, isobutylcyclopentyldimethoxysilane, isopropylsecondarybutyldimethoxysilane, isopropylcyclopentyldimethoxysilane, isopropylcyclohexyldimethoxy Silane, isobutylcyclohexyldimethoxysilane, secondary butylcyclopentyldimethoxysilane, secondary butylcyclohexylsilane, dimethyldiethoxysilane, dimethyldiisopropeneoxysilane, diphenyldimethoxysilane, diphenylsilane, dodecyl tree Ethoxysilane, isobutyltrimethoxysilane, methylcyclopentyldimethoxysilane, dicyclopentyldimethoxysil Column, methyldimethoxysilane, methyldodecyldiethoxysilane, methylphenyldiethoxysilane, methyloctyldimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methyltri-n-propoxysilane, phenyltriethoxy Silane, phenyltrimethoxysilane, vinyltrimethoxysilane, n-propyltrimethoxysilane, triethylsilane, trimethylethoxysilane, trimethylmethoxysilane and the like.

As described above, when the alkoxysilane compound and the titanium compound are reacted with the magnesium-containing carrier, there may be various methods in addition to the method of reacting with the mixture of the alkoxysilane compound and the titanium compound. These methods also go through almost the same steps except for the reaction procedure described above with the mixture of the alkoxysilane compound and the titanium compound described above.

The alkoxysilane compound and titanium compound may be reacted with a magnesium-containing carrier in the following manner.

(1) A method in which an alkoxysilane compound and a titanium compound are mixed and then the mixture is reacted with a magnesium-containing carrier.

(2) The alkoxysilane compound is first reacted with a magnesium-containing carrier and then the titanium compound is reacted.

(3) A method in which a titanium compound is first reacted with a magnesium-containing carrier and then an alkoxysilane compound is reacted.

(4) Method in which the alkoxysilane compound and the titanium compound are directly injected into the prepolymerization step or the polymerization step.

In addition, in the process for preparing the supported catalyst for ethylene polymerization and copolymerization of ethylene and α-olefin, the organoaluminum compound may be reacted with titanium before the titanium compound is reacted or, if necessary, after the catalyst is prepared, before washing. The molar ratio (Al / Ti) of aluminum can be made 0.1 to 2 to react. Preferably, the molar ratio (Al / Ti) of aluminum to titanium is 0.5 to 1.5, and the reaction is carried out at a temperature of 30 ° C to 80 ° C. If an excess amount of the organoaluminum compound is used, there is a disadvantage in that the carrier is destroyed to generate fine particles. As the organoaluminum compound used herein, an organoalkylaluminum aluminum or organoaluminum halogen compound having a structure of AlR ' _n X _(3-n) is used. Here, R 'means an alkyl group containing 1 to 16, preferably 2 to 12 carbon atoms, X represents a halogen compound such as chlorine and bromine, n is an integer or fraction in the range of 0 to 3 . Such organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, ethylaluminum chloride, methylaluminum chloride, ethylaluminum sesquibromide, isobutylaluminum sesquichloride, dimethylaluminum chloride , Diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dinormalpropylaluminum chloride, dinomalbutylaluminum chloride, diisobutylaluminum chloride, dinomaloctylaluminum iodide, methylaluminum dichloride, ethyl Aluminum dichloride, isobutyl aluminum dichloride, normal butyl aluminum dichloride, and the like. The organoaluminum compound is preferably selected from dialkylaluminum chlorides or ethylaluminum sesquichlorides.

The catalyst prepared by the process of the present invention is used for ethylene polymerization or copolymerization of ethylene and an α-olefin and may be used together with one or more organoaluminum compounds, preferably trialkylaluminum as cocatalyst.

The organoaluminum compounds which can be used have a structure of AlR _n X _3-n . Wherein R is an alkyl radical having 1 to 12 carbon atoms, X is a hydrogen atom or a halogen atom such as chlorine or fluorine or an alkoxy radical having 1 to 12 carbon atoms, and n is an integer or fraction of 1 to 3; For example, tri-isobutylaluminum, triethylaluminum, trimethylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, ethylaluminum sesquichloride or diethylaluminum chloride can be used.

The polymerization is carried out by slurry polymerization at a temperature of 50 ° C.-100 ° C. in a hydrocarbon solvent (eg hexane, heptane), or in the gas phase at a temperature of 60-120 ° C. and a pressure of 2-40 atmospheres in the absence of a hydrocarbon solvent. It is carried out by the polymerization method. Hydrogen (5-90% by volume) is used as the molecular weight regulator of the polymer. Propylene, butene-1, hexene-1, 4-methylpentene-1 and other α-olefins are useful for the copolymerization of ethylene with α-olefins.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are for illustrative purposes only, and the present invention is not limited to these examples.

Example

Comparative Example 1

[A] Preparation of Organomagnesium Compound

In a 1 L glass reactor equipped with a stirrer and a temperature controller, 29.2 g of magnesium powder (1.2 mol) in the presence of 410 ml of dibutyl ether (2.4 mol) and 0.29 g of iodine dissolved in 4 ml butyl chloride as an activator And 330 ml of chlorobenzene (3.2 mol) were reacted. The reaction proceeded with stirring for 10 hours under an inert gas atmosphere (nitrogen, argon) at a temperature of 80 to 100 ℃. The reaction mixture was then left for 12 hours without stirring and the liquid phase was separated from the precipitate. Liquid phase MgPh ₂ .0.49MgCl a ₂ .2 (C ₄ H ₉₎ the solution is dissolved in the organic magnesium compound having a composition of ₂ O chlorobenzene (the concentration of Mg was 1.1mol per 1ℓ).

[B] Synthesis of Magnesium-Containing Carrier

100 ml (0.11 mol Mg) of the solution obtained in [A] was added to a reactor equipped with a stirrer, and 10.6 ml CCl ₄ (0.11 mol CCl ₄ ) dissolved in 42 ml heptane was added at a temperature of 20 ° C. for 1 hour. Over into the reactor. 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 suspended state in n-hexane.

[C] Preparation of Catalyst

The molar ratio of titanium to magnesium is obtained by mixing titanium propoxychloride prepared by mixing 1.5 mL of TiCl ₄ with 3.8 mL of titanium propoxide (Ti (OC ₃ H ₅ ) ₄ ) in an n-hexane suspension of the obtained organic magnesium-containing carrier. (Ti / Mg) = 0.25 was added and the reaction mixture was heated to 60 ° C. and then stirred for 2 hours to wash the solid precipitate obtained at 60 ° C. four times with 100 ml n-hexane. The average particle size of the catalyst was 55 μm.

[D] polymerization

The polymerization of ethylene was carried out in a 2 L steel reactor equipped with a stirrer and a temperature controlled jacket. N-hexane (1000 mL) was used as a hydrocarbon solvent and 1.5 mmol of Al (Ot) ₃ was used as a promoter. The polymerization was carried out at a temperature of 80 ° C. after putting 1200 cc of hydrogen (0 ° C., 1 atm) and 120 cc of 1-hexene into the reactor, filling the ethylene pressure such that the reactor pressure was 7.8 atm. As the ethylene was consumed during the reaction, ethylene was continuously supplied to the reactor to maintain 7.8 atmospheres (atm).

0.5 g of catalyst was taken for the experiment and the catalytic activity was 550 g PE per g of catalyst, per unit time. The polyethylene melt index (MI) was 0.89 g / 10min at a load of 2.16 kg and a temperature of 190 ° C., and the melt index fraction (MFRR) of 21.6 kg and 2.16 kg was 29.6. The ethylene polymerization results are shown in Table 1.

Example 1

A mixture prepared by mixing 1.5 ml of TiCl ₄ and 3.0 ml of methylcyclopentyldimethoxysilane in an n-hexane suspension of the organic magnesium-containing carrier obtained in Comparative Example 1 was prepared. The molar ratio of titanium to magnesium (Ti / Mg A catalyst was prepared in the same manner as in Comparative Example 1, except that the ratio was 0.125 and the molar ratio of the alkoxysilane to magnesium (Si / Mg) = 0.125. Ethylene polymerization was carried out in the same manner as in Comparative Example 1 except that 200 cc of 1-hexene was used. The ethylene polymerization results are shown in Table 1.

Example 2

Using the catalyst obtained in Comparative Example 1, methylcyclopentyldimethoxysilane was further added to the polymerization reactor such that the molar ratio (Si / Ti) of the alkoxysilane to the titanium (Ti) contained in the catalyst was 3 and Al (octyl) was added. The polymerization was carried out in the same manner as in Example 1, except that trimethylaluminium was used instead of) 3. The ethylene polymerization results are shown in Table 1.

Example 3

The polymerization was carried out in the same manner as in Example 2, except that dicyclopentyldimethoxysilane was used instead of methylcyclopentyldimethoxysilane in Example 2. The polymerization results are shown in Table 1.

Example 4

The polymerization was carried out in the same manner as in Example 2, except that vinyltrimethoxysilane was used instead of methylcyclopentyldimethoxysilane in Example 2. The polymerization results are shown in Table 1.

Example 5

Polymerization was carried out in the same manner as in Example 2, except that diisopropyldimethoxysilane was used instead of methylcyclopentyldimethoxysilane in Example 2. The polymerization results are shown in Table 1.

Comparative Example 2

The polymerization was carried out in the same manner as in Comparative Example 1 using a Ziegler-Natta catalyst composed of 7.3 wt% titanium (Ti), 13.6 wt% magnesium (Mg), 43.6 wt% chlorine (Cl), and 35.5% other organic materials. Was performed. The polymerization results are shown in Table 1.

Example 6

The polymerization was carried out in the same manner as in Example 2 except that the catalyst of Comparative Example 2 was used instead of the catalyst of Comparative Example 1 in Example 2 and the molar ratio (Si / Ti) of the alkoxysilane to titanium was 0.4. It became. The polymerization results are shown in Table 1.

Example 7

The polymerization was carried out in the same manner as in Example 3 except that the catalyst of Comparative Example 2 was used instead of the catalyst of Comparative Example 1 in Example 3, and the molar ratio (Si / Ti) of the alkoxysilane to titanium was 0.4. Was performed. The polymerization results are shown in Table 1.

Example 8

The polymerization was carried out in the same manner as in Example 6, except that 7 mmol of trimethylaluminum was further used as a promoter in Example 7, and the molar ratio (Si / Ti) of the alkoxysilane to titanium was 2.0. The polymerization results are shown in Table 1.

Table 1. Polymerization result

Alkoxysilane Compound activation MI MFRR density Comparative Example 1 - 550 0.89 29.60 0.9201 Example 1 A 570 0.32 21.90 0.9285 Example 2 A 860 0.64 26.80 0.9249 Example 3 B 570 0.38 21.70 0.9275 Example 4 C 910 0.35 24.20 0.9242 Example 5 D 430 0.26 24.60 0.9273 Comparative Example 2 - 1.22 33.00 0.9199 Example 6 A 600 1.1 28.00 0.9265 Example 7 B 600 0.91 26.70 0.9250 Example 8 B 300 1.68 28.50 0.9248

Activity: g-PE / g-cat / hr, MFRR = MI 21.6Kg / MI 2.16Kg, Density: g / cc

Alkoxysilane Compound A:

Methylcyclopentyldimethoxysilane

Alkoxysilane Compound B: dicyclpentyldimethoxysilane

Alkoxysilane Compound C: vinyltrimethoxysilane

Alkoxysilane Compound D: diisopropyldimethoxysilane

The process of the present invention provides for the preparation of highly active catalysts having a narrow particle size distribution and various average particle sizes, which can be used for a variety of applications.

As in the present invention, when a mixture of an alkoxysilane compound and a titanium compound is used as the active ingredient of the catalyst, polyethylene having a relatively narrow molecular weight distribution is obtained than using only the titanium compound to which the alkoxysilane compound is not added. The narrow molecular weight distribution (MWD) is characterized by a molecular weight distribution <6 measured by gel permeation chromatography, and the titanium supported catalyst mixed with the alkoxysilane compound according to the present invention has a polyethylene content of 2.5 <MWD <4 or less. And polyethylene copolymers.

Claims (15)

MgPh ₂ .nMgCl ₂ .mR ₂ O (herein, Ph = phenyl, n = 0.37 to 0.7; m ≧ ₁ ; R ₂ 0 = ether) is used to prepare an organic magnesium compound and an organic chlorine compound at -20 ° C to 80 ° C. Reacting at a temperature such that the molar ratio ≧ 0.5 of the organochlorine compound to magnesium; Reacting the magnesium-containing carrier obtained in the reaction with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound and an alkoxysilane compound, wherein the alkoxysilane compound is Si (OR) _a R ' _4-a (Wherein R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR '' (wherein R '' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms), R 'is an aliphatic or aromatic hydrocarbon group, a is 1, 2, or 3), and a process for producing a supported catalyst for ethylene polymerization or copolymerization of ethylene with an α-olefin. MgPh ₂ .nMgCl ₂ .mR ₂ O (herein, Ph = phenyl, n = 0.37 to 0.7; m ≧ ₁ ; R ₂ 0 = ether) is used to prepare an organic magnesium compound and an organic chlorine compound at -20 ° C to 80 ° C. Reacting at a temperature such that the molar ratio ≧ 0.5 of the organochlorine compound to magnesium; Reacting the magnesium-containing carrier obtained in the reaction with an alkoxysilane compound; Reacting the reactant reacted with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound, wherein the alkoxysilane compound is Si (OR) _a R ′ _4-a , wherein R is carbon number An aliphatic or aromatic hydrocarbon group or COR '' (wherein R '' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms), R 'is an aliphatic or aromatic hydrocarbon group, a is 1, 2, Or 3). A process for producing a supported catalyst for ethylene polymerization or copolymerization of ethylene and an α-olefin. MgPh ₂ .nMgCl ₂ .mR ₂ O (herein, Ph = phenyl, n = 0.37 to 0.7; m ≧ ₁ ; R ₂ 0 = ether) is used to prepare an organic magnesium compound and an organic chlorine compound at -20 ° C to 80 ° C. Reacting at a temperature such that the molar ratio ≧ 0.5 of the organochlorine compound to magnesium; Reacting the magnesium-containing carrier obtained in the reaction with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound; And reacting the reactant obtained in the reaction with an alkoxysilane compound, wherein the alkoxysilane compound is Si (OR) _a R ' _4-a , wherein R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms. Or COR '' (wherein R '' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, R 'is an aliphatic or aromatic hydrocarbon group, and a is 1, 2, or 3). A method for producing a supported catalyst for ethylene polymerization or copolymerization of ethylene and α-olefin. The ethylene polymerization or ethylene according to any one of claims 1 to 3, wherein the organomagnesium compound is prepared by reaction of metal magnesium with chlorobenzene in the presence of dibutyl ether or diisoamyl ether. A method for producing a supported catalyst for copolymerization with α-olefins. The method for producing a supported catalyst for ethylene polymerization or copolymerization of ethylene and α-olefin according to any one of claims 1 to 3, wherein the organochlorine compound is carbon tetrachloride. 4. The titanium compound of claim 1, wherein the titanium compound is selected from Ti (OR) _a X _4- a, wherein R is an aliphatic or aromatic hydrocarbon group having from 1 to 14 carbon atoms or COR ′ (wherein R is Is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, X is Cl, Br or I, and a is 0, 1, 2, 3 or 4). A method for producing a supported catalyst for copolymerization with α-olefins. delete 7. The method of claim 6, wherein the titanium compound is titanium alkoxychloride, or a supported catalyst for copolymerization of ethylene and α-olefin. The ethylene polymerization or copolymerization of ethylene and α-olefin according to any one of claims 1 to 3, wherein the content of the titanium compound is 0.01 to 2.0 in a molar ratio of titanium to magnesium (Ti / Mg). Method for preparing a supported catalyst for solvents. 4. The ethylene polymerization or ethylene and α-olefin according to any one of claims 1 to 3, wherein the content of the alkoxysilane compound is 0.1 to 2.0 in terms of the molar ratio (Si / Ti) of the alkoxysilane to titanium. Method for producing a supported catalyst for copolymerization of. The method of claim 3, wherein the reaction between the reactant and the alkoxysilane compound is carried out during the prepolymerization step or the polymerization step. The method according to any one of claims 1 to 3, wherein before the magnesium-containing carrier obtained by the reaction of the organomagnesium compound and the organochlorine compound is reacted with a titanium compound, a vanadium compound or a mixture of a titanium compound and a vanadium compound, or preparation of a catalyst A method for producing a supported catalyst for ethylene polymerization or copolymerization of ethylene and α-olefin, wherein the organoaluminum compound is further reacted with a molar ratio (Al / Ti) of aluminum to titanium of 0.1 to 2. The method of claim 12, wherein the organoaluminum compound is AlR ' _n X _(3-n) , wherein R' is an alkyl group having 1 to 16 carbon atoms, X is Cl or Br, n is an integer or fraction of 0 to 3 A process for producing a supported catalyst for ethylene polymerization or copolymerization of ethylene and α-olefin, which has a structure. delete delete