KR100361087B1 - Preparation method of catalyst for polymerization and copolymerization of olefin - Google Patents

Abstract

PURPOSE: A method for preparing a heterogeneous catalyst for the polymerization or copolymerization of an olefin is provided, to enable a polymer with a narrow distribution of composition and the wide distribution of molecular weight and to improve the morphology and the processability of a polymer. CONSTITUTION: The method comprises the steps of reacting tetrabromocresol with a Grinard reagent to prepare a liquid magnesium compound; heating the obtained magnesium compound to 40-50 deg.C to prepare a solid magnesium compound; and reacting the obtained magnesium compound with the chelated transition metal compound represented by the formula I, wherein R1 and R2 are an aliphatic or aromatic hydrocarbon group; M is a transition metal of group 4; X is a halogen atom; and A and B are O or other heteroatoms. Also the method comprises the steps of reacting a mixture of tetrabromocresol and a chelate ligand in the ratio of 10:3 to 10: 1.5 in an ether solvent, with a Grinard reagent to prepare a solid chelate ligand-containing magnesium compound; heating and reacting the obtained magnesium compound with the transition metal compound of group 4.

Description

Process for preparing catalyst for olefin polymerization and copolymerization

The present invention is a non-uniform for olefin polymerization and copolymerization in which a transition metal compound chelated by at least one alkoxide ligand is supported on a magnesium compound carrier produced by the reaction of a Grignard reagent with tetrabromo cresol. The present invention relates to a method for preparing a heterogeneous catalyst.

Despite the excellent (co) polymerization of homogeneous catalysts with metallocene compounds, which have been in the spotlight in the 1980s, polymers produced by metallocene catalysts exhibit problems of low molecular weight or cyclopentadienyl groups. Synthesis of cyclopentadienyl groups with special substituents such as Indenyl, Cycloheptadiene and Fluorenyl, which controls the electronic or steric space environment, is required. Synthesis of the metallocene compound has a disadvantage that the production cost is very expensive, and there is a problem that it is difficult to control the particle properties of the polymer, which is a disadvantage of a general homogeneous catalyst. Magnesium-supported catalysts based on traditional titanium tetrachloride (TiCl ₄ ), on the other hand, have excellent polymer particle control properties, but are poorly copolymerizable or have a wide molecular weight distribution and polymer composition distribution. (Anti-blocking), heat sealing (heat sealing), etc. are exposed to the disadvantages that show a poor compared to the metallocene catalyst. Accordingly, efforts have been made to develop catalysts using chelated organometallic compounds including transition metal compounds, such as metallocenes, which are not difficult to synthesize, or are heterogeneous by supporting compounds such as metallocenes on non-uniform carrier components. Efforts have been made to develop catalysts based on metallocenes. For example, titanium compounds or zirconium compounds chelated by an alkoxy group are very easy to synthesize, and demanding organometallic chemical reaction conditions are not actively studied. Japanese Patent Application Laid-Open No. 63-191811 discloses the result of polymerizing ethylene and propylene using a catalyst component in which a halide ligand of a titanium halide compound is substituted with a TBP ligand (6-tert butyl-4-methylphenoxy). It was. Polymerization of ethylene and propylene using MAO as a promoter reported the formation of a high activity, high molecular weight polymer (average molecular weight = 3,600,000 or more). U.S. Patent No. 5,134,104 discloses a catalyst for olefin polymerization using a dioctylaminetitahalide [(C ₈ H ₁₇ ) ₂ NTiCl ₃ ] compound as a catalyst component in which a halide ligand of titanium tetrachloride is replaced with a bulky amine ligand. J. Am. Chem. Soc No. 117 3008, a chelate compound that can limit the steric space of transition metals, contains 1,1'-bi-2,2'-naphthoxy ligands (1,1'-bi) on titanium or zirconium transition metals. -2,2'-naphthol) has been disclosed a catalyst for olefin polymerization using a compound chelate-bonded and derivatives thereof, and Japanese Unexamined Patent Publication Nos. 6-140711 and 0606125A2 have a titanium halide and a zirconium halide compound A catalyst for polymerizing a chelated olefin with a narrow molecular weight distribution while producing a high molecular weight polymer by replacing a halide ligand with a chelated phenoxy group. Catalysts using the chelated transition metal compounds described above are generally expected to have good (co) polymerization as shown in metallocene catalysts. That is, the three-dimensional structure of the chelate ligand bound to titanium or zirconium stericly localizes the pi (π) orbital of the transition metal so that the active site of titanium, zirconium and olefins is coordinated. It provides a wider space for the sigma orbital used to make the copolymer easier to access and shows a tendency to increase copolymerizability. However, while the catalyst using the titanium or zirconium compound chelate-bonded by the alkoxy group reported above has the advantage that the organometallic synthesis is not more difficult than the catalyst using the metallocene compound, it is used as a homogeneous catalyst. It is difficult to control the morphology of the polymer, and there is a disadvantage that it is necessary to change and control the polymerization process and apply expensive methylaluminoxane (MAO) or boron compound as a promoter for direct application to existing commercial processes. .

On the other hand, in recent years, research to manufacture a non-uniform catalyst by supporting the metallocene on the inorganic carrier has been very active, showing a lot of progress. This is understood as an effort to directly apply metallocene catalysts to existing commercial processes using non-homogeneous catalysts. For example, U. S. Patent No. 5,439, 995 and U. S. Patent No. 5, 455, 316, etc., disclose 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. . However, to date, expensive methylaluminoxane (MAO) or boron compounds have to be used as cocatalysts as cocatalysts required for the polymerization of metallocene olefins supported on the support component of magnesium compounds. Another characteristic of polymers produced by metallocene catalysts or chelated organometallic compounds is the production of polymers with narrow molecular weight distribution (Mw / Mn = 2-5), which has been disadvantageous in terms of processing of polymers to date. . Recently, metallocenes with constrained geometries that produce polymers with long chain branches have been developed to develop metallocene catalysts with improved processability. It does not reach the outstanding workability which the polymer of the wide molecular weight distribution which has has.

Therefore, the method of the present invention is characterized in that a catalyst component of a chelate-bonded Group 4 transition metal compound (eg, titanium or zirconium compound) is supported on a magnesium compound prepared by a specific method to prepare a non-uniform catalyst. 4th generation catalyst with excellent processability of polymer and expensive methylaluminoxane (MAO) or polymer because of excellent polymer morphology and excellent copolymerization characteristics, narrow composition distribution of polymer and broad molecular weight distribution An object of the present invention is to provide an olefin polymerization and copolymerization method using an organometallic aluminum compound such as a trialkyl aluminum compound as a promoter without using the boron compound as a promoter.

The catalyst for olefin polymerization and copolymerization of the present invention is composed of a main catalyst component composed of a transition metal component and a cocatalyst component composed of an organometallic aluminum compound. The main catalyst component composed of a transition metal component prepares a carrier component of the magnesium halide component by reacting a Grignard compound with an aromatic compound including a specific halide and a hydroxyl group, and a chelated transition represented by the following general formula (I) Prepared by contact reaction of a metal (eg, titanium or zirconium) compound. The promoter component is characterized by the use of organometallic aluminum compounds such as trialkyl aluminum without the use of expensive methylaluminoxanes (MAO).

Here, R ₁ and R ₂ are aliphatic or aromatic hydrocarbons, M is a Group 4 transition metal element, X is a halide element, and A and B each represent an oxygen atom or a hetero atom.

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

According to the present invention, in the preparation of the main catalyst component consisting of transition metal components, the carrier component of the magnesium compound has a special structure such as Grignard reagent such as butylmagnesium chloride and tetrabromocresol, as shown in the following reaction formula (1). It is prepared by reaction with a halide component having

Scheme (1)

2RMgCl + Br ₄ (Me) C ₆ (OH) → [Br ₄ (Me) C ₆ OMgCl] n [RMgCl] m (R ₂ O) P (clear solution)

Tetrabromocresol generates a liquid magnesium compound that dissolves well in an ether solvent while hydrogen of a hydroxy group is substituted with a magnesium component when reacting with a Grignard reagent at room temperature. The liquid solution containing the transparent liquid magnesium compound thus produced is gradually heated to produce a solid magnesium compound by a reaction in which the remaining Grignard reagent substitutes bromide bonded to the aromatic carbon, wherein the reaction temperature is controlled. It is possible to adjust the particle properties of the magnesium compound produced by. As is generally known, the production of a transparent liquid phase magnesium compound is very important for the production of a magnesium compound having excellent particle properties, but in general, the magnesium halide component having an alkoxy group or an aryloxy group is not present in the liquid phase in an ether solvent. It is known to be difficult. However, according to the present invention, when the molar ratio of the Grignard reagent to be reacted is twice as large as the equivalent number of the hydroxy group to be reacted, a uniform liquid transparent solution can be obtained in an ether solvent. In addition, after obtaining a clear solution, the carrier component of the magnesium halide having excellent particle properties by producing a magnesium compound in a solid state through a further reaction is characterized in that the manufacturing. This is expected to be due to the interaction of the hydroxyl group and four bromide groups of tetrabromocresol. Specifically, when a Grignard reagent such as butylmagnesium halide or dibutylmagnesium and tetrabromocresol are reacted at an temperature of 10 ° C. to 20 ° C. under an ether solvent in an equivalent ratio of 2 to 3: 1, a white solid is obtained at the beginning of the reaction. Magnesium compounds are produced and soon converted into clear liquid magnesium compound solutions. When the magnesium compound solution, which is turned into a transparent liquid solution, is slowly reacted at a lukewarm temperature of 40 to 50 ° C., an unreacted Grignard reagent and an aryl bromide react to produce a solid magnesium carrier component. After the Grignard reagent was mixed with an ether solvent, a tetrabromocresol solution was slowly added dropwise to the Grignard reagent at 40 to 50 ° C. at a lukewarm temperature to prepare a carrier component of a magnesium compound having excellent particle properties. As the ether solvent that can be used for this reaction, dibutyl ether or diisoamyl ether having a breaking point of 60 ° C. or higher is suitable, and the reaction temperature is preferably 40 to 50 ° C. as described above. It is made to fully react at 90 degreeC for 1 hour or more. The magnesium compound thus prepared is oval in shape and has a distribution of 20 to 60 µm in size. The thus prepared support is removed by washing with a hydrocarbon solvent. Of particular note are other types of aromatic organic compounds (e.g., 2,4,6-tribromophenol, 2,3-dibromopropanol, carbon tetrachloride, chlorobenzene, etc.) containing hydroxyl or halide groups Under various reaction conditions, it cannot react with Grignard reagent to form liquid magnesium compound. Since they form a solid magnesium compound upon reaction with the Grignard reagent, it is not easy to control the particle properties. Therefore, the particle properties of the carrier must be controlled by other methods. However, the unique characteristic that can make the liquid magnesium compound of tetrabromocresol comes from the structural characteristics of tetrabromocresol.

The preparation of chelated transition metal compounds is by conventional organometallic chemical synthesis methods. Specifically, as shown in the following scheme (II), a chelate ligand having a linking group capable of bonding with a transition metal halide compound, such as a hydroxyl group or an amino group, may be substituted with an alkyl halide solvent such as dichloromethane or titanium halide or zirconia. A chelated transition metal compound is synthesized by reacting with a transition metal halide component such as umhalide. In the case of using a titanium compound as a transition metal compound, even if a solid compound of the TiCl ₄ (THF) ₂ type is used, the reaction is performed well, and an alkyl halide solvent such as chloroform or dichloromethane is used as a reaction solvent rather than using a hydrocarbon such as toluene. The separation of the reaction product is easy using.

Scheme (II)

(Wherein R ₁ and R ₂ are aliphatic or aromatic hydrocarbons, A and B represent an oxygen atom or a hetero atom).

Examples of chelating ligands having alkoxides or aminoxy groups that can be used in the reaction include ethylene glycol, propylene glycol, pentaerythritol, 2,2-biphenol and derivatives thereof, catholic, tetrabromocatholic, tetra Chlorocatechol, 2,3-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 1,10-dihydroxyphenanthrine, 2,3-dihydroxypyridine, 2,3-dihydroxyquinoxa Lean, 2,2'-hydroxybiphenyl ether and derivatives thereof, 1,8-dihydroxyanthraquinone, 2-acetylpyrrole, 2-benzoylpyrrole, 8-hydroxyquinone, methylacetylacetone, methylacetylacetonate Etc. can be mentioned. More preferred chelate ligands include a catiyl which reacts with a Group 4 transition metal to form a 5-membered ring, tetrabromocatechol, tetrachlorocatechol, 2,3-dihydroxynaphthalene, 4-t. Butyl cationic, 2,3-dihydroxypyridine, 8-hydroxyquinone and the like.

The preparation of the catalyst is completed by reacting the chelate compound thus prepared with the carrier component of the magnesium compound prepared above in a hydrocarbon solvent. That is, the carrier component of the magnesium compound prepared above and the transition metal halide compound such as titanium halide or zirconium halide with a reaction molar ratio of Ti / Mg or Zr / Mg of 0.6 to 0.2 are used at a reaction temperature of 70 to 90 ° C. The catalyst is prepared by the catalytic reaction at. If the molar ratio of Ti / Mg or Zr / Mg is 0.6 or more, the distribution of transition metal components on the magnesium surface becomes dense, resulting in a poor grain morphology of the resulting polymer. A more convenient production method is to proceed the reaction described in Scheme (n) in the presence of the carrier component of the magnesium compound prepared previously. According to this method, the process of preparing a chelated transition metal compound and then reacting additionally with the carrier component of the magnesium compound can be omitted, thereby simplifying the reaction process. That is, the chelating ligand capable of chelation with the transition metal halide compound, such as a hydroxy group or an amino group, is sufficiently stirred with the carrier component of the magnesium compound in a hydrocarbon solvent, and then dropwise added the transition metal halide compound is represented by the reaction formula (II). Reaction can occur at the contact surface of the magnesium halide compound to prepare a catalyst in which the chelated transition metal compound is directly supported on the support component of the magnesium compound. That is, after suspending the carrier component of the magnesium compound prepared above in a hydrocarbon solvent, the chelating ligand is mixed in a ratio of 0.6 to 0.2 with the magnesium component, and then the titanium is equivalent to the number of equivalents of the titanium that can react with the chelating ligand. The catalyst can be conveniently prepared by reacting a chloride or zirconium halide compound.

In another method, tetrabromocresol is mixed with a chelating ligand in an ether solvent, and then reacted with a Grignard reagent, as shown in Scheme (III), to mix the carrier component of the magnesium compound with the chelate compound bound to magnesium. There is a method of preparing a non-uniform catalyst in which a chelate compound is supported on a carrier component of a magnesium compound by preparing a solid, and reacting the thus prepared solid with a Group 4 transition metal compound such as titanium halide.

Scheme (III)

That is, as shown in the reaction formula (III), tetrabromocresol and chelate ligand were mixed in a ratio of 10: 3 to 10: 1.5, dissolved in an ether solvent, and then equivalent to 2 to 3 times larger than the tetrabromocresol equivalent number. By slowly dropwise addition to a number of Grignard reagents at 40 to 50 ° C., a compound in which the magnesium carrier component of the solid phase and the chelate ligand is bound to magnesium is prepared. At this time, after completion of the dropwise addition to complete the reaction, it is preferable to react at 70 to 80 ℃ for 1 hour or more. After the reaction, to remove the unreacted compound, the solid component is separated and washed with a hydrocarbon solvent to separate the pure solid component. By reacting the compound in which the chelate ligand is bound to magnesium again with the titanium halide compound, a catalyst in the solid state in which the chelate titanium compound is supported on the carrier component of the magnesium compound is prepared.

In the present invention, the promoter used in the polymerization reaction is a general organometallic aluminum compound represented by R _n Cl _3-n Al (n = 1,2,3). When methylaluminoxane (MAO) is used as a promoter, the polymerization activity tends to be narrow in molecular weight distribution, which is not similar to that of a general organometallic aluminum compound, but methylaluminoxane (MAO) has a disadvantage of being expensive. In the case of using a general organometallic aluminum compound represented by R _n Cl _3-n Al (n = 1,2,3) as a promoter of the polymerization reaction, the ratio of Al / Ti is appropriately 50 to 150 and the polymerization temperature is 40 degreeC-90 degreeC is suitable.

In addition, the catalyst for olefin polymerization prepared according to the present invention is capable of ethylene homopolymerization and copolymerization with alpha (α) olefins, and alpha olefins having 3 to 10 carbon atoms are suitable as alpha olefins copolymerizable with ethylene. . For example, alpha olefins of propylene, 1-butene, 1-pentene, 1-hexyne, 4-methyl-1-pentene, and 1-octene can be copolymerized with ethylene and have a weight ratio of ethylene of at least 70% or more. It is preferable. The catalyst for olefin polymerization according to the present invention is suitable for slurry or gas phase polymerization, and aliphatic and aromatic hydrocarbons are preferable as a solvent in slurry polymerization. In the slurry polymerization, hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used as the solvent, and the polymerization temperature is preferably 50 ° C to 120 ° C. In slurry polymerization, the dosage of the catalyst according to the present invention can be varied, and it is preferable to use about 0.005 mmol to 1 mmol of catalyst for 1 liter of hydrocarbon solvent, and more preferably 0.01 to 0.1 mmol for 1 liter of solvent. Do. In the ethylene polymerization, the pressure of ethylene is preferably 2 to 50 kg / cm ³ · G. Control of molecular weight size can be achieved through control of temperature and olefin pressure, control of hydrogen pressure, and the like. In the polymerization catalyst according to the present invention, a polymer having a density of 0.900 to 0.960 g / cm ³ can be obtained by ethylene and alpha (α) olefin copolymerization during slurry polymerization.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Example 1

Hydrocarbon solvents used in the preparation of the catalyst were removed by distillation in the presence of sodium and halogenated hydrocarbons were distilled in the presence of calcium hydride to remove the water.

<Production of Catalyst>

(A) Preparation of Titanium Compound Chelated by Tetrabromocatechol

To a solution of 5 ml of titanium tetrachloride (TiCl ₄ ) in 200 ml of dichloromethane (CH ₂ Cl ₂ ), a solution of 10.6 g of tetrabromocatechol in 200 ml of dichloromethane was slowly added dropwise at room temperature. After the mixed solution was stirred at room temperature for 30 minutes, 500 ml of hexane was slowly added to precipitate a solid. After washing three times with 800 ml of hexane again, the solid was dissolved in 150 ml of dichloromethane. 300 ml of hexane was slowly added dropwise along the flask wall to precipitate reddish brown crystals. The solution was again poured out and the residual solvent was removed by vacuum at 40 ° C./5 mmHg to separate 13.5 g of chelate titanium compound [molecular formula = (Br ₄ C ₆ O ₂ ) TiCl ₂ ]. Elemental analysis results are as follows. C: 13.11%, H: 0.05%, Ti: 8.73%,

(B) Preparation of Titanium Compounds Chelated with Tetrabromocatechol

A solution of 50 mmol of BuMgCl dissolved in 200 ml of Bu ₂ O was heated to 40 ° C., and then 10.55 g of tetrabromocresol was slowly added dropwise to the mixed solution of 100 ml Bu ₂ O and 100 ml of heptane over 1 hour. The dropwise addition produces a white solid, but soon becomes a clear solution. During the dropping, the white solid is generated after the formation of the white solid, and then the white solid is generated at the end of the dropping. Again, the reaction was completed by raising the temperature of the solution to 80 ° C and reacting for 1 hour. The resulting white solid was separated and washed with 500 ml of hexane.

To a magnesium compound prepared above, a solution in which 13.5 g of (Br ₄ C ₆ O ₂ ) TiCl ₂ compound chelated with tetrabromocatechol was dissolved in 200 ml of toluene was injected. After injection, the reaction was carried out at 80 ° C. for 1 hour to complete the preparation of the catalyst. After the preparation of the catalyst was completed, the supernatant was poured out, washed with toluene, and then washed with hexane to complete the preparation of the catalyst.

(Ethylene polymerization)

1000 ml of hexane as a polymerization solvent was added to a 2 liter autoclave, which was sufficiently nitrogen-substituted at room temperature, and then nitrogen in the autoclave was replaced with ethylene. After adding ₂ mmol of AlEt ₃ at room temperature, the catalyst prepared above was injected to a titanium concentration of 0.02 mmol / l. Hydrogen was added at ¹ Kg / cm ² at 60 ° C. and pressurized with ethylene to maintain a total pressure of 6 Kg / cm ² and the temperature was raised to 70 ° C., and polymerization was carried out for 1 hour after the addition of the catalyst. The polymerized polymer was separated from hexane and dried. 180 g of polyma was recovered as a result of the polymerization. As a result of the polymerization, polyethylene having a MFR (g / 10 min) of 0.05 / 2.16 kg and an apparent density of 0.35 was obtained.

Examples 2-6

Ethylene / l-butene copolymerization reaction was carried out using the catalyst prepared in Example 1. After 1000 ml of hexane as a polymerization solvent was added to a 2 liter autoclave, which was sufficiently nitrogen-substituted at room temperature, nitrogen in the autoclave was replaced with ethylene. After adding 8 mmol of AlEt ₃ at room temperature, the catalyst prepared above was injected with a titanium concentration of 0.08 mmol / l. The temperature was maintained at 40 ° C. and 50 ml of hydrogen were injected through a mass flow controller, then pressurized with ethylene to maintain a total pressure of 20 psi. 1-butene with ethylene was polymerized for 1 hour while injecting over an hour in the amounts shown in Table 1 below. The polymerized polymer was separated from hexane and dried, and the polymerization results are shown in Table 1 below.

Example 7

(A) Preparation of Titanium Compound Chelated by Tetrabromocatechol

To a solution of 5 ml of titanium tetrachloride (TiCl ₄ ) in 200 ml of dichloromethane (CH ₂ Cl ₂ ), a solution of 10.6 g of tetrabromocatechol in 200 ml of CH ₂ Cl ₂ was slowly added dropwise at room temperature. After the mixed solution was stirred at room temperature for 30 minutes, 500 ml of hexane was slowly added to precipitate a solid. After washing three times with 800 ml of hexane again, the solid was dissolved in 150 ml of CH ₂ Cl ₂ . 300 ml of hexane was slowly added dropwise along the flask wall to precipitate reddish brown crystals. The solution was again poured out and the remaining solvent was removed by vacuum at 40 ° C./5 mmHg to separate 13.5 g of chelate titanium compound ((Br ₄ C ₆ O ₂ ) TiCl ₂ ). Elemental analysis results are as follows. C: 13.11%, H: 0.05%, Ti: 8.73%.

(B) Preparation of Titanium Compounds Chelated with Tetrabromocatechol

The solution was dissolved in 50mmol BuMgCl of Bu ₂ O was slowly added dropwise to 200ml of tetrabromo-cresol at room temperature to a solution of 10.55g was dissolved in 100ml of Bu ₂ O. The white solid is produced by dropping, but soon becomes a transparent solution. The temperature of the carrier component solution of the liquid magnesium compound thus prepared was raised to 40 ° C. for 1 hour to prepare a white solid, and then heated to 60 ° C. for 1 hour to complete the production of a white solid. The resulting white solid was separated and washed with 500 ml hexane to prepare a carrier component of the magnesium compound.

To a magnesium compound prepared above, 13.5 g of (Br ₄ C ₆ O ₂ ) TiCl ₂ compound chelated with tetrabromocatechol was dissolved in 200 ml of toluene. After injection, the reaction was carried out at 80 ° C. for 1 hour to complete the preparation of the catalyst. After the preparation of the catalyst was completed, the supernatant was poured out, washed with toluene and again with hexane to complete the preparation of the catalyst.

(Ethylene polymerization reaction)

Ethylene polymerization was carried out in the same manner as in Example 1 using the catalyst prepared above. The polymerization resulted in 175 g of polyethylene with an MFR (g / 10 min) of 0.07 / 2.16 kg and an apparent density of 0.34.

Examples 8-12

Ethylene / 1-butene copolymerization was carried out in the same manner as in Example 1 using the catalyst prepared above. The polymerization results are shown in Table 1 below.

Example 13

(Production of Catalyst)

1.33 g of tetrachlorocatechol monohydrate was mixed with 10.5 g of tetrabromocresol and then dissolved in 250 ml of Bu ₂ O. The dissolved solution was slowly added dropwise at 40 ° C. over 1 hour to a solution of 50 mmol of BuMgCl diluted in 250 ml of Bu ₂ O. After the dropwise addition, the temperature was raised and reacted at 70 ° C. for 1 hour to complete the reaction. After the reaction, the supernatant was decanted and washed with decane to separate the solid components. 250 ml of decane was injected into the separated solid, followed by stirring for 10 minutes, followed by 5 ml of titanium tetrachloride. After injection, the reaction was completed at 90 ° C. for 1 hour to complete the reaction. After the reaction was completed, the solid component was separated and washed with hexane to separate the solid component to complete the preparation of the catalyst.

(Ethylene polymerization)

Ethylene polymerization was carried out in the same manner as in Example 1. As a result of the polymerization, 190 g of the polymer was recovered. As a result of the polymerization, polyethylene having a MFR (g / 10 min) of 0.03 / 2.16 kg and an apparent density of 0.35 was obtained.

Examples 14-18

Ethylene / 1-butene copolymerization was carried out in the same manner as in Example 1 using the catalyst prepared in Example 13. The polymerization results are shown in Table 1 below.

Example 19

(Production of Chelate Catalyst)

The solution was dissolved in 50mmol BuMgCl of Bu ₂ O was slowly added dropwise to 200ml of tetrabromo-cresol at room temperature to a solution of 10.55g was dissolved in 100ml of Bu ₂ O. A white solid is produced by dropping, but soon becomes a transparent solution. The temperature of the carrier component solution of the liquid magnesium compound thus prepared was increased to 40 ° C. for 1 hour to prepare a white solid, and then heated to 60 ° C. for 1 hour to complete the production of a white solid. The resulting white solid was separated and washed with 500 ml of hexane to prepare a carrier component of the magnesium compound. 6.6 g of Cl ₄ C ₆ (OH) ₂ .H ₂ O was suspended in 200 ml toluene, and then 25 mmol of Et ₃ Al was injected at room temperature to prepare a liquid transparent solution containing tetrachlorocaticol. The transparent solution thus prepared was injected into the carrier component of the magnesium compound prepared above, followed by stirring for 30 minutes. After 5 ml of TiCl ₄ was injected into the solution, the reaction was completed at room temperature for 1 hour, and the reaction was completed by raising the temperature to 80 ° C for 1 hour. The resulting brown solid was separated, washed once with 300 ml of toluene and again with 500 ml of hexane to complete the preparation of the catalyst.

(Ethylene polymerization)

Ethylene polymerization was carried out in the same manner as in Example 1. As a result of the polymerization, 200 g of the polymer was recovered. As a result of the polymerization, polyethylene having a MFR (g / 10 min) of 0.1 / 2.16 g and an apparent density of 0.35 was obtained.

Examples 20-24

Ethylene / 1-butene copolymerization was carried out in the same manner as in Example 1. The polymerization results are shown in Table 1 below.

Comparative Example 1

(Production of Catalyst)

50 ml of decane purified under nitrogen atmosphere was suspended in 4.76 g (0.05 mol) of anhydrous magnesium chloride, and 31 ml (0.2 mol) of 2-ethylhexyl alcohol was added thereto, heated slowly, and reacted at 110 ° C. for 2 hours to completely remove solid particles. A clear homogeneous solution was prepared. This solution was present as a colorless transparent state without depositing even when the temperature was lowered to room temperature. The temperature was lowered to room temperature again, and 33 ml (0.3 mol) of titanium tetrachloride was added dropwise and reacted at 80 ° C. for 2 hours to prepare a solid catalyst. The solid catalyst was washed three more times with hexane. In the solid catalyst, the content of the titanium component was 4.7% (weight).

(Ethylene polymerization)

Ethylene polymerization was carried out in the same manner as in Example 1. As a result of the polymerization, 180 g of the polymer was recovered. As a result of the polymerization, polyethylene having a MFR (g / 10 min) of 0.1 / 2.16 kg and an apparent density of 0.28 was obtained.

(Ethylene / 1-butene copolymerization reaction)

The copolymerization reaction was carried out in the same manner as in Example 1. The polymerization results are shown in Table 1 below (Comparative Examples 1 to 4).

Claims (4)

As a method for producing a catalyst for olefin polymerization and copolymerization in which a chelated transition metal compound represented by the following general formula (I) is supported on a magnesium compound carrier, After preparing a liquid magnesium compound by the reaction of Grignard reagent and tetrabromocresol, the compound was heated to 40-50 ° C. to react to prepare a solid magnesium compound, which was obtained by the following general formula (I) Reacting with a chelated Group 4 transition metal compound.

(Wherein R ₁ and R ₂ are aliphatic or aromatic hydrocarbons, M is a Group 4 transition metal element, X is a halide element, A and B represent an oxygen atom or a hetero atom). As a method for producing a catalyst for olefin polymerization and copolymerization in which a chelated transition metal compound represented by the following general formula (I) is supported on a magnesium compound carrier, A magnesium chelate ligand-containing magnesium compound carrier was prepared by reacting a solution of tetrabromocresol and a chelated ligand in an ether solvent at a ratio of 10: 3 to 10: 1.5 with a Grignard reagent, and then preparing the compound. A method comprising reacting with a Group 4 transition metal compound.

(Wherein R ₁ and R ₂ are aliphatic or aromatic hydrocarbons, M is a Group 4 transition metal element, X is a halide element, A and B represent an oxygen atom or a hetero atom). The method according to claim 1 or 2, The equivalent ratio of Grignard reagent and tetrabromocresol is 2 to 3: 1. The method according to claim 1 or 2, Chelating ligands are tetrabromocatiform, tetrachlorocaticol, 2,3-dihydroxynaphthalene, 4-t-butylcati, 2,3-dihydroxypyridine or 8-hydroxy quinone Characterized in that the method.