KR100828716B1 - Method for preparing catalyst for polymerizing polyolefin having wide range molecular weight distribution - Google Patents

Abstract

The present invention provides a method for producing a titanium catalyst for polyolefin polymerization having magnesium, titanium, halogen and aluminum as essential components, including magnesium compounds; Alcohols having 6 or more carbon atoms; And a hydrocarbon solvent; preparing a homogeneous solution by stirring; Preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in the step; Contacting the mixture obtained in the step with a titanium halide compound; And a step of contacting the catalyst component obtained in the step with an alkylaluminum compound.

The catalyst preparation method of the present invention is a method of preparing a catalyst by contacting a homogeneous solution of a magnesium compound with titanium halide and again an alkylaluminum compound at a relatively high temperature above room temperature (25 ° C.). Easily controlled, it is possible to prepare polymers with various particle size distribution, high catalyst activity in olefin polymerization process, small amount of undesirable microparticles in final polymer, very uniform particle size distribution of polymer, and molecular weight distribution A wide polymer can be obtained.

Magnesium, Titanium, Alkyl Aluminum Compounds, Olefin Polymerization

Description

Method for preparing catalyst for polymerizing polyolefin having wide range molecular weight distribution}

The present invention relates to a method for producing a titanium catalyst capable of producing a polymer having high activity for olefin polymerization, uniform particle size distribution of the resulting polymer, easy to control average particle size, and wide molecular weight distribution of the polymer, and a catalyst component obtained by the method. will be

The size of the polymer polymerized using the Ziegler type catalyst is generally influenced by the size of the catalyst used. Because of these replication phenomena, the technique of controlling the size and particle size distribution of Ziegler-type catalysts in the preparation of catalysts is an important key for producing polymers having desired particle size.

For this reason, many techniques for controlling the size of catalysts have been published, and these techniques often consist of treating the carriers in various ways, and one of them has been widely described in the literature for dissolving the carrier in a soluble solvent and then recrystallizing it. As such documents, there are mentioned US Patent Nos. 4,330,649, 5,106,807, 5,459,116, 4,315,874, 4,399,054, 4,071,674 and 4,439,540, and Japanese Patent Laid-Open No. 63-54004.

Magnesium chloride, one of the most commonly used carriers, has high solubility in alcohols, aldehydes, amines, and the like, and these solvents are commonly used in recrystallization methods. Among them, when used with hydrocarbon solvents such as alcohols having 6 or more carbon atoms, especially octanol, silver decane, kerosene, hexane, etc., magnesium is completely dissolved at a high temperature of 100 ° C. or higher, and the magnesium compound is present in a homogeneous solution state without reprecipitation at room temperature. do. This type of homogeneous solution can produce a catalyst of a solid component through various treatment methods. Most easily, this homogeneous solution can be contacted with a tetravalent halogen-containing titanium compound such as titanium tetrachloride to obtain a solid titanium compound. This method eliminates the process of recrystallization by lowering the temperature of the solution or adding a non-solvent, and makes it easy to manufacture a catalyst because a solid catalyst can be formed by directly reacting a homogeneous solution of a liquid magnesium compound with a halogen-containing titanium compound. It has the advantage of excellent activity, high specific gravity of polymer and very uniform particle size distribution. The particle size of the catalyst prepared in this way is greatly influenced by the reaction temperature of the homogeneous solution and the titanium chloride compound and the magnesium concentration of the homogeneous solution.

When the reaction temperature of the homogeneous solution and the titanium chloride compound is at a high temperature such as room temperature (25 ° C.), the average particle size of the catalyst formed in the reaction is relatively low such that the reaction temperature of the homogeneous solution and the titanium chloride compound is -20 ° C. It becomes smaller compared to the case where not only the average particle size of the polymer is reduced, but also increases the content of undesirable microparticles. In addition, when the magnesium content of the homogeneous solution is high, the particle size of the polymer of the prepared catalyst is reduced, thereby increasing the content of fine particles.

Various prior arts are known to solve the above problems.

For example, Japanese Patent Application Laid-Open No. Hei 6-220120 includes a magnesium solution formed from a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a hydrocarbon solvent, and an organoaluminum compound to contact magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms, and A catalyst component for ethylene polymerization is disclosed, which is prepared by preparing a solid magnesium-aluminum composite containing alcohol and / or contacting the composite with a tetravalent titanium compound. According to the catalyst component there is an advantage that the production of fine particles of ethylene polymer particles is small.

In addition, Korean Patent Publication No. 2001-0080857 discloses that a mixture of at least one alcohol added to a homogeneous solution of a magnesium compound is contacted with a halogen-containing titanium to prepare a catalyst of a solid component, thereby reducing the amount of undesirable fine particles. The method has been proposed. This method is easy to control the particle size of the catalyst, the activity of the catalyst is very high and the specific gravity is controlled by controlling the magnesium concentration and the temperature at the first contact with the halogen-containing titanium in the mixture of alcohols having 5 or less carbon atoms in the homogeneous solution of the magnesium mixture. High polymers can be obtained.

Such a reduction in the fine particle content facilitates the primary processing of the produced polymer, but it is difficult to expect an improvement in the processability and physical properties of the final product thereafter. The biggest factor influencing the physical properties and processability of the final product is the molecular weight distribution of the polymer, and for the improvement thereof, there is still a need for a method for preparing a catalyst capable of providing a polymer having a wider molecular weight distribution than the polymer prepared by the above-mentioned prior art. .

In order to solve the problems of the prior art, the first technical problem to be achieved by the present invention is a uniform particle size distribution and easy to control the particle size is easy to control the particle size of the polymer produced using the catalyst and uniform particle size distribution The present invention provides a method for producing a catalyst capable of producing a polymer having a wide molecular weight distribution as well as a small amount of undesirable fine particles.

The second technical problem to be achieved by the present invention is to provide a catalyst prepared by the above production method.

The third technical problem to be achieved by the present invention is to provide a method for producing an olefin polymer having a wide molecular weight distribution using the catalyst.

The present invention to achieve the first technical problem,

As a method for producing a titanium catalyst for polyolefin polymerization having magnesium, titanium, halogen and aluminum as essential components,

a) iii) a magnesium compound;

 Ii) alcohols having 6 or more carbon atoms; And

 Iii) preparing a homogeneous solution by stirring a hydrocarbon solvent;

b) preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in step a);

c) contacting the mixture obtained in step b) with a titanium halide compound; And

d) contacting the catalyst component obtained in step c) with an alkylaluminum compound.

According to one embodiment of the present invention, in the method for preparing a titanium catalyst for polyolefin polymerization, the amount of alcohol having a carbon number of 6 or more of ii) to 6 mol of magnesium compound of a) step iii) is 0.5 to 10 moles, and iii) It is preferable that the input amount of a hydrocarbon solvent is 15 mol or more.

According to another embodiment of the present invention, it is preferable that the magnesium concentration of the homogeneous solution obtained in step a) in the method of preparing a titanium catalyst for polyolefin polymerization is 5 to 10 g / L.

According to another embodiment of the present invention, in the method for preparing a titanium catalyst for polyolefin polymerization, the amount of alcohol having a carbon number of 5 or less in step b) is preferably 0.5 to 6 mol per mol of the magnesium compound.

According to another embodiment of the present invention, it is preferable that the contact temperature of the mixture of step c) and the titanium halide compound is -50 to 100 ° C in the method for preparing a polyolefin polymerization titanium catalyst.

According to another embodiment of the present invention, in the method for producing a titanium catalyst for polyolefin polymerization, the amount of the alkylaluminum compound added in step d) is preferably 0.1 to 100 mol per mol of the catalyst titanium component.

According to another embodiment of the present invention, in the method for preparing a titanium catalyst for polyolefin polymerization, the magnesium compound of step a) i) may be magnesium chloride, magnesium bromide, magnesium fluoride, or magnesium halide of magnesium iodide; Alkoxy activating magnesiums of methoxy magnesium chloride, ethoxy magnesium chloride, isoproxy magnesium chloride, butoxy magnesium chloride, or ocoxy magnesium chloride; Allyloxyhalogenated magnesium of magnesium phenoxychloride; And alkoxymagnesium of ethoxymagnesium, isoproxymagnesium, or butoxymagnesium.

According to another embodiment of the present invention, in the method for preparing a titanium catalyst for polyolefin polymerization, the alcohol having at least 6 carbon atoms of a) step ii) is n-hexanol, n-heptanol, n-octanol, decanol, Aliphatic alcohols such as dodecanol, 2-methylpentanol, 2-ethylbutanol, or 2-ethylhexanol; Arylcyclic alcohols of cyclohexanol or methylcyclohexanol; And an aromatic alcohol of benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, or α-methyl-benzyl alcohol.

According to another embodiment of the present invention, in the method for preparing a titanium catalyst for polyolefin polymerization, the hydrocarbon solvent of step a) i) is pentane, hexane, heptane, octane, decane, dodecane, tetradecane, or kerosene. Aliphatic hydrocarbons; Alicyclic hydrocarbons of cyclic pentane, cyclic hexane, halicoctane, methyl cyclic pentane, or methyl cyclic hexane; Aromatic hydrocarbons of benzene, toluene, xylene, ethylbenzene, or cumene; And halogenated hydrocarbons of dichloroethane, dichloropentane, trichloroethane, carbon tetrachloride, or chlorobenzene.

According to another embodiment of the present invention, in the method for preparing a titanium catalyst for polyolefin polymerization, the alcohol having 5 or less carbon atoms of step b) is methanol, ethanol, isopropanol, N-butanol, tert-butanol, and n-pentanol It is preferable to select at least one from the group consisting of.

According to another embodiment of the present invention, the titanium halide compound of step c) is a titanium tetrahalide of TiCl ₄ , TiBr ₄ , or TiI ₄ in the method for preparing a titanium catalyst for polyolefin polymerization; Alkoxy titanium trihalides of Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ or Ti (OC ₂ H ₅ ) Br ₃ ; Alkoxytitanium dihalide of Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ or Ti (OC ₂ H ₅ ) ₂ Br ₂ ; And alkoxytrititanium halide of Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, or Ti (OC ₂ H ₅ ) ₃ Br.

According to another embodiment of the present invention, the alkyl aluminum compound of step d) is Al (CH ₃ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al (C ₃ H) ₇ ) trialkylaluminum of ₃ , Al (C ₄ H ₉ ) ₃ or Al (C ₈ H ₁₇ ) ₃ ; Dialkyl of Al (CH ₃ ) ₂ Cl, Al (C ₂ H ₅ ) ₂ Cl, Al (C ₃ H ₇ ) ₂ Cl, Al (C ₄ H ₉ ) ₂ Cl or Al (C ₈ H ₁₇ ) ₂ Cl Aluminum halides; Al (CH ₃ ) Cl ₂ , Al (C ₂ H ₅ ) Cl ₂ , Al (C ₃ H ₇ ) Cl ₂ , Al (C ₄ H ₉ ) Cl ₂ or Al (C ₈ H ₁₇ ) Cl ₂ Alkyl aluminum dihalides; And alkyltrihalides; it is preferable that one or more selected from the group consisting of.

According to another embodiment of the present invention, in the method for producing a titanium catalyst for polyolefin polymerization,

Adding 2-ethylhexyl alcohol and hexane to magnesium chloride, dissolving and stirring at a temperature of 100 ~ 150 ℃ to prepare a magnesium chloride homogeneous solution;

Preparing a mixture by adding ethanol and methanol to the magnesium chloride homogeneous solution of step a);

Contacting the mixture of step b) with titanium tetrachloride at 10˜50 ° C .; And

Contacting the catalyst component of step c) with an alkylaluminum compound at 0˜100 ° C .;

The present invention to achieve the second technical problem,

It provides a solid titanium catalyst for polyolefin polymerization prepared by the above production method.

The present invention to achieve the third technical problem,

Provided is a method for producing an olefin polymer, wherein the solid titanium catalyst for polyolefin polymerization prepared by the above production method is brought into contact with an olefin monomer.

In the catalyst production method of the present invention, a titanium catalyst supported on a magnesium compound is reacted with a Group 13 organometallic compound to uniform catalyst particle size distribution and to easily control particle size, thereby facilitating particle size control of a polymer produced using the catalyst. Provided is a method for producing a catalyst which can produce a polymer having a wide molecular weight distribution as well as a small amount of undesirable fine particles due to uniform distribution.

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

In the catalyst preparation method of the present invention, a homogeneous solution of a magnesium compound is prepared using a magnesium compound and an alcohol having at least 6 carbon atoms as a hydrocarbon solvent, and then a mixture of at least one alcohol having 1 to 5 carbon atoms is added to a tetravalent liquid form. A method for preparing a catalyst by reacting a solid component formed in contact with a halogenated titanium compound with an alkylaluminum compound, wherein the catalyst prepared by the above method includes magnesium, titanium, halogen and aluminum as essential components.

When treated with alkylaluminum, the molecular weight distribution of the polyolefin polymer to be polymerized by changing the active site of the catalyst can be obtained. There is a method of treating alkylaluminum to the catalyst itself and a method of adding alkylaluminum at the time of polymerization, but in the former case, the properties of the catalyst can be controlled by precisely controlling the conditions such as temperature, time and equivalent to which alkylaluminum reacts In the latter case, since the reaction time and temperature of the aluminum alkyl and the catalyst are determined, it is difficult to obtain the desired catalytic properties, so the former method is preferable.

The magnesium compound used in the present invention is not reducible, and examples thereof include magnesium halides such as magnesium chloride, magnesium bromide, magnesium fluoride, and magnesium iodide; Magnesium alkoxy halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isoproxy magnesium chloride, magnesium butoxy chloride, octoxy chloride, etc .; Allyloxy magnesium halide such as phenoxy magnesium chloride and the like; Alkoxy magnesium, such as ethoxy magnesium, isoproxy magnesium, butoxy magnesium, etc. These magnesium compounds can be used in mixture of 2 or more. Double halogen-containing magnesium is useful, and magnesium chloride is particularly preferred.

 The alcohol having 6 or more carbon atoms used in the present invention is n-hexanol, n-heptanol, n-octanol, decanol, dodecanol, 2-methylpentanol, 2-ethylbutanol, 2-ethylhexanol, and the like. Aliphatic alcohols; Arylcyclic alcohols such as cyclohexanol, methylcyclohexanol and the like; Aromatic alcohols such as benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, -methyl benzyl alcohol, and the like, which can be used by mixing two or more thereof. Preferably, aliphatic alcohol is useful, and 2-ethylhexyl alcohol is particularly preferable. .

The homogeneous solution of the magnesium compound can be obtained by contacting the above-mentioned magnesium compound with an alcohol having a carbon number of 6 or more together with a hydrocarbon, and the hydrocarbons usable here include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, kerosene, etc. Aliphatic hydrocarbons such as; Alicyclic hydrocarbons such as cyclic pentane, cyclic hexane, cyclic octane, methyl cyclic pentane, methyl cyclic hexane and the like; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; Halogenated hydrocarbons such as dichloroethane, dichloropentane, trichloroethane, carbon tetrachloride, chlorobenzene and the like, and preferably aliphatic hydrocarbons are used, among which hexane, heptane and decane are particularly useful. Alcohols of 5 or less carbon atoms may be used instead, but only about 15 times the molar ratio of magnesium compounds is completely dissolved. If less than this, alcohol precipitates of magnesium compounds may be formed at room temperature.

Homogeneous solutions of magnesium compounds can be formed by simply mixing and stirring magnesium compounds, alcohols having 6 or more carbon atoms, and saturated hydrocarbons, but applying heat is very helpful for dissolving magnesium compounds. Dissolution temperature is preferably used 100 ~ 150 ℃. At this time, the alcohol used is 0.5 to 10 mol per mol of the magnesium compound, preferably 1.5 to 5 mol is useful. Here, the hydrocarbon solvent is preferably 15 mol or more per mol of the magnesium compound. The dissolution of the magnesium compound depends on the magnesium compound used and the type and molar ratio of the alcohol and hydrocarbon, but in general, the higher the molar ratio of the alcohol, the higher the dissolution temperature, the easier dissolution, and when the magnesium compound is not completely dissolved, more alcohol is added. Or higher temperatures may help dissolve the magnesium compound.

Next, one or more alcohols having 5 or less carbon atoms are added to the homogeneous solution of the magnesium compound to form a mixture. Examples of the alcohol having 5 or less carbon atoms include methanol, ethanol, isopropanol, n-butanol, tert-butanol, n-pentanol, and the like. If the molar ratio of methanol and ethanol is high, precipitation of a magnesium compound may be formed. The molar ratio of the alcohol having 5 or less carbon atoms to the magnesium compound is 0.5 to 6 moles, preferably 0.5 to 3 moles. Among the above examples, the alcohol having 5 or less carbon atoms is preferably ethanol, and more preferably, ethanol and methanol are used together.

Next, a tetravalent titanium halide compound represented by the formula (1) is brought into contact with the compound to form a catalyst.

<Formula 1>

Ti (OR) _n X _4-n

In the above formula,

R is a hydrocarbon, n is an integer having a range of 0 ≦ n <4, and X is halogen.

Specific examples of such a titanium halide compound include titanium tetrahalide such as TiCl ₄ , TiBr ₄ , TiI ₄ ; Alcohol cititantrihalides such as Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br _3, and the like; Alkoxy titanium dihalides such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br _2, and the like; Alkoxy tritide halides such as Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, and the like, among which titanium tetrahalide is preferable, and titanium tetrachloride is particularly desirable.

When the mixture formed by adding alcohols having 5 or less carbon atoms to the homogeneous solution of the magnesium compound is brought into contact with the halogen-containing titanium compound, the catalyst is brought into contact with the halogen-containing titanium compound without adding alcohols having 5 or less carbon atoms to the homogeneous solution of the magnesium compound. Average particle size increases greatly. In other words, the addition of alcohols of 5 or less carbon atoms before the reaction of the homogeneous solution and the titanium compound has the effect of increasing the average particle size of the final catalyst, especially when used in combination with ethanol and methanol, the average particle size is greatly increased and less than 100㎛ The fine particles of are also significantly reduced.

The reaction temperature of the homogeneous solution or mixture of the magnesium compound and the titanium compound is -50 ~ 100 ℃, preferably -20 ~ 80 ℃, especially 10 ~ 50 ℃ is useful. This is the reaction temperature of the first homogeneous solution or mixture with the titanium compound.The reaction proceeds by stirring the homogeneous solution or mixture in the reactor and adding a certain amount of titanium compound little by little for a certain time. Post-treatment may be performed by addition or addition of another type of titanium compound.

The magnesium concentration of the homogeneous solution or mixture, together with the reaction temperature with the titanium halide compound, affects the average size of the catalyst. The magnesium concentration is from 5 to 100 g / L, preferably from 10 to 50 g / L. The catalyst concentration can be controlled by the amount of hydrocarbon solvent when the magnesium compound is dissolved in the soluble solvent, and the average particle size of the catalyst tends to decrease as the concentration of the magnesium compound in the homogeneous solution or mixture is increased.

The catalyst of the present invention is formed by contacting one or two or more alkyl aluminum compounds represented by the following formula (2) with a solid complex titanium catalyst formed as described above.

<Formula 2>

AlR _m X _(3-m)

In the above formula,

R is a hydrocarbon having 1 to 12 carbon atoms, m is an integer having a range of 0≤m <3, and X is halogen

Specific examples of such alkyl aluminum compounds include triethyl aluminum, trimethyl aluminum, triisopropyl aluminum, trioctyl aluminum, diethyl aluminum chloride, diethyl aluminium bromide, diethyl aluminum iodide, diethyl aluminum fluoride, ethyl Aluminum dichloride, dimethylaluminum chloride, methylaluminum dichloride, ethylaluminum sesquichloride. It is preferable to use 0.01-100 mol per 1 mol of titanium in a catalyst, and, as for the preferable use amount of an alkyl aluminum compound, 0.1-50 mol is especially preferable. The reaction temperature is preferably -50 to 150 ° C, particularly preferably 0 to 100 ° C. It is preferable to increase the reaction temperature after the contact reaction and react for 0.5 to 10 hours at -50 to 150 ° C.

If the amount of the alkylaluminum compound is less than 0.01 mole per mole of titanium in the catalyst, there is a problem that MFRR does not increase. The contact with the alkyl aluminum compound increases the activity of the catalyst and serves to widen the melt flow rate ratio (MFRR). It is possible to prepare an olefin polymer having a broad molecular weight distribution by contacting the catalyst prepared by the above method with an olefin monomer. The olefin monomer used for the polymerization may be used without particular limitation so long as it is an olefin applicable in the art such as ethylene, propylene, butylene, and the like. In the case of an olefin polymer having a wide molecular weight distribution, it is excellent in processability and other physical properties, and is suitable for use in films, pipes, and the like.

Hereinafter, the present invention will be described in more detail, but the following examples and comparative examples are provided to aid the understanding of the present invention, and the present invention is not limited to these ranges.

Example

Comparative Example 1

[Catalytic preparation]

12.5 g of anhydrous magnesium dichloride, 64.5 ml of 2-ethylhexyl alcohol and 300 ml of hexane were placed in a pressure-resistant glass reactor substituted with a sufficient amount of nitrogen and stirred at 120 ° C. for 3 hours. Subsequently, when the magnesium compound was completely dissolved to form a homogeneous solution, the temperature was lowered to room temperature and hexane was added so that the total volume was 500 ml. The solution was stirred for 10 minutes, 7.8 ml of ethanol and 5.3 ml of methanol were added and stirred for about 1 hour.

Subsequently, while maintaining the temperature of the mixed solution to which the ethanol and methanol were added at 35 ° C., 75 ml of TiCl ₄ was slowly added in small portions over 3 hours. After complete addition of TiCl ₄ , the mixture was stirred for 1 hour and the solid component formed was precipitated. Then, the solution of the upper layer was removed and hexane was added to 600 ml to adjust the molar ratio of the titanium component in the precipitate solid to 1: 1.5 of the titanium component in the solution. The mixture was then stirred at 80 ° C. for 2 hours, after which the solid components were filtered and washed several times with a large amount of hexane until no titanium tetrachloride was detected. The catalyst obtained by drying the solid phase thus obtained had a content of 3.1 wt% titanium, 57.6 wt% chlorine, and 16.9 wt% magnesium.

 [polymerization]

1 L of purified hexane was added to a 2 L stainless autoclave sufficiently substituted with nitrogen, the temperature was adjusted to 80 ° C., 4 mmol of triethylaluminum was added, and 0.05 mmol of the solid catalyst component prepared above was added based on titanium atoms. . Then, hydrogen was added so that the pressure in the reactor was 60 psi, the pressure in the reactor was maintained at 128 psi, and ethylene was added for 1 hour to perform polymerization. After the polymerization, the polymer in the form of a slurry was filtered to obtain 112 g of a polymer in a powder form. The melt index of the polymer was 0.71 (2.16 kg / 10 min), the bulk density was 0.24, and the average particle size was 129 µm.

Example 1

[Catalytic preparation]

100 mL of the catalyst (31.4 mM) prepared in Comparative Example 1 was placed in a 250 mL flask, and 10.3 mL of a 610 mM triethylaluminum hexane solution was added at room temperature for 10 minutes. Then it was stirred for 2 hours at room temperature. The catalyst obtained by drying the slurry thus obtained had a content of 2.8 wt% titanium, 50.5 wt% chlorine, and 15.8 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1, and the polymerization results are shown in Table 1 below.

Example 2

[Catalytic preparation]

100 mL of the catalyst (31.4 mM) prepared in Comparative Example 1 was placed in a 250 mL flask, and 3.1 mL of 2M trimethylaluminum hexane solution was added at room temperature for 10 minutes. Then stirred at room temperature for 2 hours. The catalyst thus well dried was 3.0 wt% titanium, 53.2 wt% chlorine, and 16.0 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1 and the polymerization results are shown in Table 1 below.

Example 3

[Catalytic preparation]

100 mL of the catalyst (31.4 mM) prepared in Comparative Example 1 was placed in a 250 mL flask, and 6.3 mL of 1M diethylaluminum chloride hexane solution was added at room temperature for 10 minutes. Then stirred at room temperature for 2 hours. The catalyst thus well dried was 2.9 wt% titanium, 53.1 wt% chlorine, and 15.0 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1 and the polymerization results are shown in Table 1 below.

Example 4

[Catalytic preparation]

100 mL of the catalyst (31.4 mM) prepared in Comparative Example 1 was placed in a 250 mL flask, and 6.3 mL of 1 M ethyl aluminum dichloride hexane solution was added at room temperature for 10 minutes. Then stirred at room temperature for 2 hours. The catalyst obtained by drying the slurry thus obtained had a content of 2.7% by weight of titanium, 61.4% by weight of chlorine, and 14.7% by weight of magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1 and the polymerization results are shown in Table 1 below.

Example 5

[Catalytic preparation]

Except that 51.5 mL of triethylaluminum was used in Example 1, the same process as in Example 1 was followed. The catalyst obtained by drying the slurry thus obtained had a content of 2.0 wt% titanium, 33.0 wt% chlorine, and 9.5 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1 and the polymerization results are shown in Table 1 below.

Example 6

[Catalytic preparation]

Except that 1.6 mL of diethyl aluminum chloride in Example 3 was prepared in the same manner as in Example 3. The catalyst obtained by drying the slurry thus obtained had a content of 3.1 wt% titanium, 54.7 wt% chlorine, and 17.1 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1, and the polymerization results are shown in Table 1 below.

Example 7

[Catalytic preparation]

Except that 31.5 mL of diethylaluminum chloride in Example 3 was prepared in the same manner as in Example 3. The catalyst obtained by drying the slurry thus obtained had a content of 1.9% by weight titanium, 45.2% by weight chlorine, and 9.1% by weight magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1, and the polymerization results are shown in Table 1 below.

Example 8

[Catalytic preparation]

200 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 1 L pressurized reactor, and 6..3 mL of a 1M diethylaluminum chloride hexane solution was added at room temperature for 10 minutes. Then, the temperature was slowly raised, stirred at 80 ° C. for 2 hours, and then lowered to room temperature. The catalyst obtained by drying the slurry thus obtained had a content of 2.9% by weight of titanium, 54.6% by weight of chlorine, and 15.2% by weight of magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1, and the polymerization results are shown in Table 1 below.

Example 9

[Catalytic preparation]

100 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 250 mL flask, and 3.2 mL of 1M diethylaluminum chloride hexane solution was added at room temperature for 10 minutes. To this was added 5.2 mL of 610 mM triethylaluminum chloride hexane solution again for 10 minutes. This was followed by stirring at room temperature for 2 hours. The catalyst obtained by drying the slurry thus obtained had a content of 2.7% by weight of titanium, 51.7% by weight of chlorine, and 15.0% by weight of magnesium.

[polymerization]

The polymerization was carried out in the same manner as in Comparative Example 1, and the polymerization results are shown in Table 1 below.

division Amount [g] Melt Index (MFR, 2.16kg) [g / 10min] MFRR [21.6Kg / 2.16Kg] Apparent density (BD) [g / cm3] Active [Kg-PE / mmole Ti] Average particle size [㎛] Comparative Example 1 112 0.71 35.8 0.24 2.24 129 Example 1 120 0.26 36.9 0.21 2.40 142 Example 2 116 0.86 36.3 0.19 2.32 108 Example 3 140 1.71 37.3 0.24 2.80 138 Example 4 180 6.60 39.4 0.28 3.60 124 Example 5 150 1.27 36.8 0.23 3.00 117 Example 6 180 2.51 37.3 0.24 3.60 107 Example 7 220 4.21 37.5 0.28 4.40 130 Example 8 83 0.32 37.1 0.19 1.66 146 Example 9 150 1.45 36.4 0.22 3.00 121

As shown in Table 1, the polymers polymerized using the catalysts of Examples 1 to 9 showed improved MFRR values and catalytic activity as compared to the case of Comparative Example 1. As such, since the improved MFRR value exhibits a wider range of molecular weight distribution, it provides improved processability and physical properties and further improves catalyst activity, and thus is advantageous in preventing quality deterioration due to the presence of catalyst residues.

The catalyst preparation method of the present invention is a method for preparing a catalyst by contacting a homogeneous solution of a magnesium compound with titanium halide and again with an alkylaluminum compound at a relatively high temperature of room temperature (25 ° C.) or higher. Easy to control the size, it is possible to prepare a polymer having various particle size distribution, high catalyst activity in the olefin polymerization process, small amount of undesirable microparticles in the final polymer, very uniform particle size distribution of the polymer, molecular weight A wide distribution polymer can be obtained.

Claims (15)

As a method for producing a titanium catalyst for polyolefin polymerization having magnesium, titanium, halogen and aluminum as essential components, a) magnesium compound;  Ii) alcohols having 6 or more carbon atoms; And  Iii) preparing a homogeneous solution by stirring the hydrocarbon solvent; b) preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in step a); c) contacting the mixture obtained in step b) with a titanium halide compound; And and d) contacting the catalyst component obtained in step c) with an alkylaluminum compound. The method of claim 1, The amount of the alcohol having a carbon number of 6 or more in ii) is 0.5 to 10 moles, and the amount of the hydrocarbon solvent in iii) to 1 mole of the magnesium compound of step iv) is 15 moles or more. Manufacturing method. The method of claim 1, Method for producing a titanium catalyst for polyolefin polymerization, characterized in that the magnesium concentration of the homogeneous solution obtained in step a) is 5 to 10 g / L. The method of claim 1, Method of producing a titanium catalyst for polyolefin polymerization, characterized in that the addition amount of the alcohol having a carbon number of 5 or less in step b) is 0.5 to 6 mol per mol of the magnesium compound. The method of claim 1, Method for producing a titanium catalyst for polyolefin polymerization, characterized in that the contact temperature of the mixture of step c) and the titanium halide compound is -50 to 100 ℃. The method of claim 1 Method for producing a titanium catalyst for polyolefin polymerization, characterized in that the addition amount of the alkyl aluminum compound of step d) is 0.1 to 100 mol per mol of the catalyst titanium component. The method of claim 1, A) the magnesium compound of step iii) is magnesium halide, magnesium bromide, magnesium fluoride, or magnesium iodide; Alkoxy activating magnesiums of methoxy magnesium chloride, ethoxy magnesium chloride, isoproxy magnesium chloride, butoxy magnesium chloride, or ocoxy magnesium chloride; Allyloxyhalogenated magnesium of magnesium phenoxychloride; And an alkoxymagnesium of ethoxymagnesium, isoproxymagnesium, or butoxymagnesium; and at least one selected from the group consisting of titanium oxide for polyolefin polymerization. The method of claim 1, The alcohol having at least 6 carbon atoms of a) step ii) is n-hexanol, n-heptanol, n-octanol, decanol, dodecanol, 2-methylpentanol, 2-ethylbutanol, or 2-ethylhexanol Aliphatic alcohols; Arylcyclic alcohols of cyclohexanol or methylcyclohexanol; And an aromatic alcohol of benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, or α-methyl-benzyl alcohol; and a method for producing a titanium catalyst for polyolefin polymerization, characterized in that the above-mentioned. The method of claim 1, The hydrocarbon solvent of step a) iii) is an aliphatic hydrocarbon of pentane, hexane, heptane, octane, decane, dodecane, tetradecane, or kerosene; Alicyclic hydrocarbons of cyclic pentane, cyclic hexane, halicoctane, methyl cyclic pentane, or methyl cyclic hexane; Aromatic hydrocarbons of benzene, toluene, xylene, ethylbenzene, or cumene; And halogenated hydrocarbons of dichloroethane, dichloropentane, trichloroethane, carbon tetrachloride, or chlorobenzene; and a method for producing a titanium catalyst for polyolefin polymerization, characterized in that the above-mentioned. The method of claim 1, Preparation of a titanium catalyst for polyolefin polymerization, characterized in that the alcohol having a carbon number of 5 or less in step b) is selected from the group consisting of methanol, ethanol, isopropanol, N-butanol, tert-butanol, and n-pentanol Way. The method of claim 1, The titanium halide compound of step c) is titanium tetrahalide of TiCl ₄ , TiBr ₄ , or TiI ₄ ; Alkoxy titanium trihalides of Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ or Ti (OC ₂ H ₅ ) Br ₃ ; Alkoxytitanium dihalide of Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ or Ti (OC ₂ H ₅ ) ₂ Br ₂ ; And alkoxytrititanium halides of Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, or Ti (OC ₂ H ₅ ) ₃ Br; titanium catalyst for polyolefin polymerization, characterized in that Manufacturing method. The method of claim 1, Al (CH ₃ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al (C ₃ H ₇ ) ₃ , Al (C ₄ H ₉ ) ₃ or Al (C ₈ H ₁₇ ) _{Trialkylaluminum} of ₃ ; Dialkyl of Al (CH ₃ ) ₂ Cl, Al (C ₂ H ₅ ) ₂ Cl, Al (C ₃ H ₇ ) ₂ Cl, Al (C ₄ H ₉ ) ₂ Cl or Al (C ₈ H ₁₇ ) ₂ Cl Aluminum halides; Al (CH ₃ ) Cl ₂ , Al (C ₂ H ₅ ) Cl ₂ , Al (C ₃ H ₇ ) Cl ₂ , Al (C ₄ H ₉ ) Cl ₂ or Al (C ₈ H ₁₇ ) Cl ₂ Alkyl aluminum dihalides; And alkyltrihalides; a method for producing a titanium catalyst for polyolefin polymerization, characterized in that at least one selected from the group consisting of. The method of claim 1 Adding 2-ethylhexyl alcohol and hexane to magnesium chloride, dissolving and stirring at a temperature of 100 ~ 150 ℃ to prepare a magnesium chloride homogeneous solution; Preparing a mixture by adding ethanol and methanol to the magnesium chloride homogeneous solution of step a); Contacting the mixture of step b) with titanium tetrachloride at 10˜50 ° C .; And Contacting the catalyst component of step c) with an alkylaluminum compound at 0˜100 ° C .; a method for producing a titanium catalyst for polyolefin polymerization, comprising: a. A solid titanium catalyst for polyolefin polymerization prepared by the process according to any one of claims 1 to 13. A process for producing an olefin polymer, comprising contacting an olefin monomer with a solid titanium catalyst for polyolefin polymerization produced by the process according to any one of claims 1 to 13.