KR20040067429A - A method for ethylene homo- and copolymerization - Google Patents

Abstract

PURPOSE: A method for polymerization and copolymerization of ethylene is provided to increase the polymerization activity of a catalyst and to improve the flowability of the resultant polymer. CONSTITUTION: The method for polymerization and copolymerization of ethylene is carried out in the presence of both (a) a solid complex titanium catalyst and (b) an organometallic compound of the group II or III in the periodic table. The solid complex titanium catalyst is prepared by the method comprising the steps of: (i) contacting a magnesium halide compound with an alcohol to form a magnesium solution; (ii) reacting the magnesium solution with an ester compound having at least one hydroxyl group and a silicon compound having an alkoxy group; (iii) reacting the reaction mixture of step (ii) with a mixture of a titanium compound and a haloalkane compound to obtain a solid titanium catalyst component; and (iv) treating the solid titanium catalyst component with a mixture of an aluminum compound with a magnesium compound, or a magnesium compound to obtain a solid complex titanium catalyst.

Description

Ethylene polymerization and copolymerization method {A METHOD FOR ETHYLENE HOMO- AND COPOLYMERIZATION}

The present invention relates to an ethylene polymerization and copolymerization method using a solid titanium catalyst obtained by treating a solid titanium catalyst component supported on a support containing magnesium with a mixture of an aluminum compound and a magnesium compound or a magnesium compound.

Catalysts for ethylene polymerization and copolymerization containing magnesium are known to provide polymers with very high catalytic activity, high apparent density, and are also suitable for liquid and gas phase polymerization. Ethylene liquid phase polymerization refers to a polymerization process performed in a medium such as bulk ethylene, isopentane and hexane, and the degree of activity of the catalyst used, the apparent density of the produced polymer, or the low molecular weight content dissolved in the medium is applicable. These are important characteristics of the catalyst to be considered when judging.

Many catalysts for the polymerization of olefins and methods for preparing the catalysts, including magnesium and based on titanium, have been reported. In particular, many methods using magnesium solution are known in order to obtain a catalyst for olefin polymerization which gives the above-mentioned high density polymer. There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as an alcohol, an amine, a cyclic ether, and an organic carboxylic acid in the presence of a hydrocarbon solvent, using alcohols of US Pat. 5,106,807. In addition, a method of preparing a magnesium supported catalyst by reacting the liquid magnesium solution with a halogen compound such as titanium tetrachloride is well known. Such a catalyst provides a high apparent density of the polymer, but there is a need to be improved in terms of the active or hydrogen reactivity of the catalyst. Tetrahydrofuran, a cyclic ether, is used in US Pat. Nos. 4,477,639 and 4,518,706 as solvents of magnesium compounds.

U.S. Patent Nos. 4,847,227, 4,816,433, 4,829,037, 4,970,186 and 5,130,284 react with electron donors such as dialkyl phthalates and phthaloyl chlorides and titanium chloride compounds to provide excellent polymerization activity, and the apparent appearance of the polymer A method for preparing a catalyst for olefin polymerization having an improved density is reported.

U.S. Patent No. 5,459,116 reports a method of preparing a supported titanium solid catalyst by bringing a magnesium solution comprising a ester having at least one hydroxy group as an electron donor into contact with a titanium compound. Using this method, a catalyst having excellent polymerization activity of the catalyst and apparent density of the synthesized polymer can be obtained, but there is room for improvement in terms of molecular weight distribution.

U.S. Patent No. 3,899,477 discloses a catalyst using a titanium halide, vanadium halide and organoaluminum compound together. By treating the catalyst with alkylaluminum sesquiethoxide and trialkylaluminum prior to polymerization, polymers having a broad molecular weight distribution can be prepared. However, the present prior art has a disadvantage in that the control of the polymerization process conditions is difficult due to the complicated process for preparing the catalyst and the different hydrogen reactivity of titanium and vanadium, and the reactivity of monomers and comonomers.

As indicated above, attempts to improve in terms of catalyst performance have continued.

Therefore, the present invention is to propose a new ethylene polymerization and copolymerization method further improved the polymerization activity of the catalyst.

An object of the present invention is to provide an ethylene polymerization and copolymerization method further improving the polymerization activity of the catalyst and excellent in the fluidity of the produced polymer.

Ethylene polymerization and copolymerization method of the present invention,

(a) a solid complex titanium catalyst prepared by a manufacturing method comprising the following steps;

(i) contacting a magnesium halide compound with an alcohol to prepare a magnesium solution;

(ii) reacting therewith an ester compound comprising at least one hydroxy group and a silicon compound having an alkoxy group;

(iii) reacting the mixture of the titanium compound and the haloalkane compound to obtain a solid titanium catalyst component;

(iv) treating the solid titanium catalyst component with a mixture of aluminum compounds and magnesium compounds or magnesium compounds to obtain a solid complex titanium catalyst; And

(b) Periodic table characterized by polymerizing or copolymerizing ethylene in the presence of Group II or Group III organometallic compound.

The solid complex titanium catalyst (a) used in the ethylene polymerization and copolymerization process of the present invention is a step of reacting the solid titanium catalyst component obtained in step (iii) with the titanium compound at least once before the treatment in step (iii). It may further comprise.

Types of magnesium halide compounds used in the present invention include, firstly, dihalogenated magnesiums such as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide; Alkylmagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, amylmagnesium halide; Alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagnesium halide, isopropoxymagnesium halide, butoxymagnesium halide and octoxymagnesium halide; Aryloxymagnesium halides such as phenoxymagnesium halide and methylphenoxymagnesium halide. Two or more of the magnesium compounds may be used in a mixture. Magnesium compounds are also effective when used in the form of complexes with other metals.

The compounds listed above may be represented by simple chemical formulas, but in some cases, they may not be represented by simple formulas depending on the method of preparing magnesium compounds. In this case, it can be regarded as a mixture of magnesium compounds listed generally. For example, a compound obtained by reacting a magnesium compound with a polysiloxane compound, a halogen-containing silane compound, an ester or an alcohol, or the like; Compounds obtained by reacting magnesium metal with alcohol, phenol or ether in the presence of halo silane, phosphorus pentachloride or thionyl chloride can also be used in the present invention. Preferred magnesium compounds are magnesium halides, in particular magnesium chloride, alkyl magnesium chloride, preferably having C ₁ to C ₁₀ alkyl groups, alkoxy magnesium chlorides, preferably having C ₁ to C ₁₀ alkoxy groups, and aryloxy magnesium chloride It is preferable to have a C ₆ to C ₂₀ aryloxy group.

The magnesium solution used in the present invention can be prepared as the solution of the above-described magnesium compound using an alcohol solvent in the presence or absence of a hydrocarbon solvent. Examples of the hydrocarbon solvent used herein include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and cymene; Halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride and chlorobenzene.

In converting the magnesium compound into a magnesium compound solution, alcohol is preferably used in the presence of the aforementioned hydrocarbons. Examples of the alcohol include 1-20, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol and cumyl alcohol. Alcohols containing 3 carbon atoms are included, and preferred alcohols are alcohols containing 1 to 12 carbon atoms. The desired catalyst average size and particle distribution vary depending on the type of alcohol, the total amount, the type of magnesium compound or the ratio of magnesium to alcohol, but in order to obtain a magnesium solution the total amount of alcohol is at least 0.5 mole per mole of magnesium compound, preferably About 1.0 to 20 moles, more preferably about 2.0 to 10 moles are preferred.

The reaction of the magnesium compound with the alcohol in the preparation of the magnesium compound solution is preferably carried out in a hydrocarbon medium, the reaction temperature varies depending on the type and amount of alcohol, but at least about -25 ℃, preferably -10 to 200 ℃, more Preferably it is carried out at about 0 to 150 ℃ for about 15 minutes to 5 hours, preferably about 30 minutes to 4 hours.

Examples of the ester compound containing at least one hydroxy group among the electron donors used in the present invention include 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate and 2-hydroxy propyl meth. Unsaturated fatty acid esters comprising at least one hydroxy group such as acrylate, 4-hydroxy butyl acrylate and pentaerythritol triacrylate; 2-hydroxy ethyl acetate, methyl 3-hydroxy butyrate, ethyl 3-hydroxy butyrate, methyl 2-hydroxy isobutylate, ethyl 2-hydroxy isobutylate, methyl 3-hydroxy-2-methyl Propionate, 2,2-dimethyl-3-hydroxy propionate, ethyl 6-hydroxy hexanoate, t-butyl-2-hydroxy isobutylate, diethyl-3-hydroxy glutarate, Ethyl lactate, isopropyl lactate, butyl isobutyl lactate, isobutyl lactate, ethyl mandelate, dimethyl ethyl tartrate, ethyl tartrate, dibutyl tartrate, diethyl citrate, triethyl citrate, ethyl 2 Aliphatic monoesters or polyesters comprising at least one hydroxy group such as hydroxy caproate, diethyl bis- (hydroxy methyl) malonate; 2-hydroxy ethyl benzoate, 2-hydroxy ethyl salicylate, methyl 4- (hydroxy methyl) benzoate, methyl 4-hydroxy benzoate, ethyl 3-hydroxy benzoate, 4-methyl salicylate Such as ethyl salicylate, phenyl salicylate, propyl 4-hydroxy benzoate, phenyl 3-hydroxy naphtanoate, monoethylene glycol monobenzoate, diethylene glycol monobenzoate, triethylene glycol monobenzoate Aromatic esters comprising at least one hydroxy group; Or alicyclic esters including at least one hydroxy group such as hydroxy butyl lactone. The amount of the ester compound including at least one hydroxy group is from 0.001 to 5 mol per mol of magnesium, preferably 0.01 to 2 mol per mol.

As another electron donor used in the present invention, a silicon compound having an alkoxy group is represented by the general formula of R _n Si (OR) _4-n (where R is a hydrocarbon group having 1 to 12 carbon atoms and n is a natural number of 1 to 3). Preference is given to compounds having Specifically, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, phenyl Trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate And at least one compound such as butyl silicate and methyltriaryloxysilane can be used. The amount thereof is preferably 0.05 to 3 mol, more preferably 0.1 to 2 mol per mol of magnesium.

The contact reaction temperature of the liquid magnesium compound solution, the ester compound containing at least one hydroxy group, and the alkoxy silicon compound is preferably 0 to 100 ° C, more preferably 10 to 70 ° C.

A mixture of a titanium compound and a haloalkane compound in the liquid state represented by the general formula Ti (OR) _a X _4-a (R is a hydrocarbon group, X is a halogen atom and a is a natural number of 0 ≦ a ≦ 4) And the catalyst particles are recrystallized. In general formula, R preferably represents an alkyl group having 1 to 10 carbon atoms. Examples of the titanium compound satisfying the general formula include titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ; Trihalogenated alkoxytitanium such as Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (O (iC ₄ H ₉ )) Br ₃ ; Dihalogenated alkoxytitanium such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O (iC ₄ H ₉ )) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ ; Tetraalkoxytitaniums such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (OC ₄ H ₉ ) ₄ . In addition, mixtures of the above titanium compounds can also be used in the present invention. Preferred titanium compounds are halogen-containing titanium compounds, and more preferred titanium compounds are titanium tetrachloride.

Haloalkane compounds are compounds having from 1 to 20 carbon atoms comprising at least one halogen, and mixtures thereof may also be used. Examples are monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, monochloroethane, 1,2-dichloroethane, monochloropropane, monochlorobutane, monochloro-secondary butane, monochloro-tertibutane, mono Chlorocyclohexane, chlorobenzene, monobromomethane, monobromopropane, monobromobutane and monoiodomethane and the like. Preferred haloalkane compounds are chloroalkane compounds.

The amount of the mixture of the titanium compound and the haloalkane compound used to recrystallize the magnesium compound solution is suitably 0.1 to 200 moles per mole of the magnesium compound, preferably 0.1 to 100 moles, and more preferably 0.2 to 80 moles. . The mixing ratio of the haloalkane compound to the titanium compound is preferably 0.05 to 0.95, more preferably 0.1 to 0.8 in molar ratio. When reacting a magnesium compound solution with a mixture of a titanium compound and a haloalkane compound, the shape and size of the solid component recrystallized in accordance with the reaction conditions vary greatly. Therefore, the reaction of the magnesium compound solution with the mixture of the titanium compound and the haloalkane compound is preferably performed at a sufficiently low temperature to produce a solid component. Preferably, the contact reaction is preferably performed at -70 ° C to 70 ° C, and more preferably at -50 ° C to 50 ° C. After the contact reaction, the reaction temperature was gradually raised to fully react for 0.5 hours to 5 hours at 50 ° C to 150 ° C.

The solid catalyst component obtained above can be further reacted with the titanium compound. The titanium compound used at this time is preferably a halogenated alkoxy titanium having 1 to 20 carbon atoms of the titanium halide and the alkoxy functional group. In some cases, mixtures thereof may also be used. Among them, titanium halides and alkoxy halide titanium having 1 to 8 carbon atoms of alkoxy functional groups are preferable, and titanium tetrahalide is more preferable.

The solid titanium catalyst component prepared through the above process is treated with a mixture of aluminum compound and magnesium compound or magnesium compound to obtain a final solid titanium catalyst.

The aluminum compound used in the present invention is a compound having a general formula of R _n AlX _3-n (wherein R is an alkyl group having 1 to 20 carbon atoms, X is halogen or hydride, n is 1, 2 or 3). desirable. Specifically, trialkyl aluminum having an alkyl group having 1 to 20 carbon atoms such as triethyl aluminum and triisobutyl aluminum, and ethyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride, diisobutyl aluminum hydride As such, organoaluminum compounds having one or more halogen or hydride groups and mixtures thereof may be used.

In addition, the magnesium compound used in the present invention is a general formula MgR ¹ R ² (wherein R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, R ² is a hydrocarbon group or halogen having 1 to 30 carbon atoms). The compound which has is preferable. Examples include dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium, butyl magnesium chloride, phenyl magnesium chloride and the like.

The aluminum compound is preferably used in an amount of 0.05 mol to 500.0 mol per mol of the titanium compound in the solid titanium catalyst component obtained in step (iii), more preferably at a ratio of 0.1 mol to 100.0 mol per mol of the titanium compound. It is desirable to. The reaction temperature is preferably carried out at -50 ° C to 50 ° C, more preferably at -20 ° C to 30 ° C.

The ethylene polymerization and copolymerization process of the present invention is carried out using a catalyst system composed of (a) a solid complex titanium catalyst and (b) a Group II or Group III organometallic compound prepared as described above. In particular, the catalyst (a) is useful for the homopolymerization of ethylene and the copolymerization of ethylene with at least 3 carbon atoms α-olefins such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 1-hexene Used.

The organometallic compound (b) which is advantageous in the present invention may be represented by the general formula of MR _n , wherein M is a periodic table group II or group IIIA metal component such as magnesium, calcium, zinc, boron, aluminum and gallium, and R Represents 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 are advantageously trialkylaluminums having 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and mixtures thereof. In some cases organoaluminum compounds containing one or more halogen or hydride groups may be used, such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride and diisobutylaluminum hydride.

The polymerization reaction can be performed by gas phase or bulk polymerization in the absence of an organic solvent or by liquid phase slurry polymerization in the presence of an organic solvent. These polymerization methods are carried out in the absence of oxygen, water and other compounds that can act as catalyst poisons. The preferred concentration of the solid complex titanium catalyst (a) in the case of liquid phase slurry polymerization is about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, based on the titanium atom of the catalyst with respect to 1 liter of solvent. Solvents include alkanes or cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane and methylcyclohexane; Alkylaromatics such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene and diethylbenzene; Halogenated aromatics such as chlorobenzene, chloronaphthalene and ortho-dichlorobenzene; And mixtures thereof. In the case of gas phase polymerization, the amount of the solid complex titanium catalyst (a) is about 0.001 to 5 mmol, preferably about 0.001 to 1.0 mmol, more preferably about 0.01 to 0.5 mmol, based on the titanium atom of the catalyst per 1 liter of polymerization capacity. It is good to do. The preferred concentration of the organometallic compound (b) is about 1 to 2,000 moles per mole of titanium atoms in the catalyst (a) calculated from organometallic atoms, more preferably about 5 to 500 moles.

In order to obtain a high polymerization rate, the polymerization reaction is carried out at a sufficiently high temperature regardless of the polymerization process. Generally, about 20 to 200 ° C is suitable, and more preferably 20 to 95 ° C. As for the pressure of the monomer at the time of superposition | polymerization, atmospheric pressure-100 atmospheres are suitable, More preferably, the pressure of 2-50 atmospheres is suitable.

Molecular weight in the present invention is represented by the melt index (MI, 2.16Kg) (ASTM D 1238) commonly known in the art. In general, the melt index is higher when the molecular weight is lower. In addition, the molecular weight distribution of the polymer is expressed as MFRR (MI, 21.6Kg / 2.16Kg), and its measuring method and meaning are generally well known in the art.

The product obtained by the polymerization method of the present invention is a solid ethylene homopolymer or a copolymer of ethylene and an α-olefin, and the yield of the polymer is also high enough so that the removal of the catalyst residue is not necessary and has excellent fluidity.

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

Example 1

Catalyst manufacturing

The solid complex titanium catalyst component was prepared through the following three steps.

(Iii) step: preparation of magnesium solution

19.0 g of MgCl ₂ and 400 ml of heptane were added to a 1.0 l reactor equipped with a mechanical stirrer, which was replaced with a nitrogen atmosphere, and stirred at 700 rpm. Then, 120 ml of 2-ethylhexanol was added thereto, and the temperature was raised to 120 ° C. for 3 hours. Reacted. The homogeneous solution obtained after the reaction was cooled to room temperature (25 ° C).

(Ii) step: catalytic reaction of magnesium solution with ester containing hydroxy group and alkoxy silane compound

2.4 ml of 2-hydroxyethyl methacrylate and 10.0 ml of ethyl silicate were added to the magnesium solution cooled to room temperature and reacted for 1 hour.

(Iii) step: treatment of the mixture of titanium compound and haloalkane compound and reaction of titanium compound

The solution was adjusted to 10 DEG C and a mixed solution of 50 ml of tetrachlorotitanium and 50 ml of trichloromethane was added dropwise for 30 minutes. When the addition was completed, the reactor was heated to 80 ° C. over 1 hour, and then 150 ml of tetrachlorotitanium was injected and maintained at this temperature for 2 hours. After the reaction, the reactor was cooled to room temperature, and then washed by pouring 400 ml of hexane until unreacted free tetrachlorotitanium was removed. The titanium content of the prepared solid catalyst component was 5.1%.

(Iii) step: treatment of a mixture of aluminum and magnesium compounds

The prepared solid titanium catalyst component was subdivided into 200 ml of hexane slurry at a concentration of 6 mmol / l based on titanium atoms. The temperature of the solid titanium catalyst hexane slurry solution was lowered to 0 ° C., and 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were slowly injected while stirring. After the injection was complete the solution temperature was raised to 20 ° C. and stirred for 5 hours to treat the solid titanium catalyst component. After 5 hours, stirring was terminated and stored at -10 ° C.

polymerization

The high-pressure reactor with a capacity of 2 liters was dried in an oven and assembled in a hot state, and then nitrogen and vacuum were operated three times in alternation to make the reactor into a nitrogen atmosphere. After injection of 1,000 ml of n-hexane into the reactor, 3 mmol of triisobutylaluminum and 0.03 mmol of a solid catalyst were injected on a titanium atom, and 1,000 ml of hydrogen was injected. The temperature of the reactor was raised to 80 ° C. and the ethylene pressure was adjusted to 80 psi while stirring the stirrer at 700 rpm, followed by polymerization for one hour. After the polymerization was completed, the temperature of the reactor was lowered to room temperature, and excess ethanol solution was added to the polymerization contents. The resulting polymer was collected separately and dried in a vacuum oven at 50 ° C. for at least 6 hours to obtain a white powder of polyethylene.

Polymerization activity (kg polyethylene / g catalyst) was calculated as the weight (kg) ratio of the resulting polymer per gram of catalyst used. The polymerization results are shown in Table 1 together with the melt index (g / 10 min) and molecular weight distribution (MFRR) of the polymer.

Example 2

In the catalyst preparation step of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyl ethyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 3

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride and 1.8 ml of 1 M butyl ethyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 4

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride and 3.0 ml of 1 M butyl ethyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 5

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride and 6.0 ml of 1 M butyl ethyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 6

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride and 1.8 ml of 1 M butyl octyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 7

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride and 3.0 ml of 1 M butyl octyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 8

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride and 6.0 ml of 1 M butyl octyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 9

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 1.8 ml of 1 M butyl octyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 10

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M butyl octyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 11

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 6.0 ml of 1 M butyl octyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 12

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M butyl ethyl magnesium. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 1

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 3.0 ml of 1 M ethyl aluminum sesquichloride. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 2

In the catalyst preparation step (iii) of Example 1, 3.0 ml of 1 M diethyl aluminum chloride and 3.0 ml of 1 M butyloctyl magnesium were replaced with 6.0 ml of hexane. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

According to the present invention, it is possible to provide a method of ethylene polymerization and copolymerization which is further improved in catalytic activity by a simple and easy process and excellent in fluidity of the produced polymer.

Claims (9)

Ethylene polymerization or copolymerization method characterized by polymerizing or copolymerizing ethylene in the presence of the following (a) and (b): (a) a solid complex titanium catalyst prepared by a manufacturing method comprising the following steps; (i) contacting a magnesium halide compound with an alcohol to prepare a magnesium solution; (ii) reacting therewith an ester compound comprising at least one hydroxy group and a silicon compound having an alkoxy group; (iii) reacting the mixture of the titanium compound and the haloalkane compound to obtain a solid titanium catalyst component; (iv) treating the solid titanium catalyst component with a mixture of aluminum compounds and magnesium compounds or magnesium compounds to obtain a solid complex titanium catalyst; And (b) Group II or III organometallic compounds of the periodic table. The method of claim 1, wherein the solid complex titanium catalyst is characterized in that it is prepared by a manufacturing method further comprising the step of reacting the solid titanium catalyst component obtained in step (iii) with the titanium compound at least one or more times. Ethylene Polymerization or Copolymerization Method. 3. The ester compound according to claim 1 or 2, wherein the ester compound comprising at least one hydroxy group is an unsaturated fatty acid ester comprising at least one hydroxy group, an aliphatic monoester or polyester comprising at least one hydroxy group, at least one Aromatic esters containing a hydroxy group or alicyclic esters containing at least one hydroxy group, wherein the silicon compound having an alkoxy group is R _n Si (OR) _4-n , wherein R is a hydrocarbon having 1 to 12 carbon atoms N is a compound having a general formula of 1 to 3 natural number), ethylene polymerization or copolymerization method. 4. The silicone compound according to claim 3, wherein the silicone compound having an alkoxy group is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane and vinyltrimethoxy. Silane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane And vinyltributoxysilane, ethyl silicate, butyl silicate or methyltriaryloxysilane. The titanium compound according to claim 1 or 2, wherein the titanium compound satisfies the general formula Ti (OR) _a X _4-a (R silver hydrocarbon group, X is a halogen atom, a is a natural number of 0 ≦ a ≦ 4). , The haloalkane compound is a compound having 1 to 20 carbon atoms or a mixture thereof comprising at least one halogen. The method of claim 5, wherein the titanium compound is TiCl ₄ , TiBr ₄ , TiI _4, Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O (iC ₄ H ₉ )) Br ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O (iC ₄ H ₉ )) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ or Ti (OC ₄ H ₉ ) ₄ , wherein the haloalkane compound is monochloromethane, dichloromethane, trichloromethane, tetrachloromethane , Monochloroethane, 1,2-dichloroethane, monochloropropane, monochlorobutane, monochloro-secondary butane, monochloro-butarybutane, monochlorocyclohexane, chlorobenzene, monobromethane, monobromopropane Ethylene polymerization or copolymerization method, characterized in that monobromobutane or monoiodomethane. The method of claim 1 or 2, wherein the aluminum compound is a general of R _n AlX _3-n , wherein R is alkyl having 1 to 20 carbon atoms, X is halogen or hydride, n is 1, 2 or 3 Ethylene polymerization or copolymerization method characterized in that the compound or a mixture thereof satisfying the formula. According to claim 1 or 2, wherein the magnesium compound of step (iii) is a general formula MgR ¹ R ² (wherein, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, R ² is 1 to 30 carbon atoms A hydrocarbon group or a halogen) compound. The ethylene polymerization or copolymerization method according to claim 1 or 2, wherein the periodic table group II or group III organometallic compound has the following general formula: MR _n [Wherein M is magnesium, calcium, zinc, boron, aluminum or gallium, R is an alkyl group having 1 to 20 carbon atoms and n is the valence of the metal component].