KR101087857B1 - Process for preparing ziegler-natta catalyst for olefin polymerization - Google Patents

Abstract

The present invention relates to a method for preparing a Ziegler-Natta catalyst for olefin polymerization having high activity and high stereoregularity. Specifically, anhydrous magnesium dichloride is dissolved in a dioxane compound and a hydrocarbon solvent, and then an organic phosphorus compound. And a precipitate promoter was added and reacted to prepare a magnesium carrier mixed solution. Then, a transition metal compound and an internal electron donor were added to the magnesium carrier mixed solution to react with each other to obtain a precipitate. The precipitate was washed with a hydrocarbon solvent, and again, a hydrocarbon solvent. It relates to a method for producing a Ziegler-Natta catalyst for olefin polymerization comprising the step of adding and reacting with a transition metal compound to obtain a solid catalyst.

Description

Process for preparing ziegler-natta catalyst for olefin polymerization

The present invention relates to a process for preparing a Ziegler-Natta catalyst for olefin polymerization having high activity and high stereoregularity.

The catalyst for olefin polymerization, generally called a Ziegler-Natta catalyst, refers to a catalyst system composed of a combination of a main catalyst composed mainly of a transition metal compound, a cocatalyst of an organometallic compound, and an electron donor, and has conventionally improved polymerization activity and stereoregularity. It has been extensively researched in order to make many related technologies.

The Ziegler-Natta catalyst directly affects the properties, particle distribution, and the like of the polyolefin produced according to its components, structure, and preparation method. Therefore, in order to change the properties of the polyolefin, a change in the composition of the catalyst, a change in the structure of the carrier and a change in the preparation method of the catalyst should be accompanied during the preparation of the catalyst. The activity of the changed catalyst and the particle size, molecular weight and stereoregularity of the polymerized polymer should also be studied.

Conventional Ziegler-Natta catalysts consist of a solid catalyst component centered on titanium, magnesium and halogen compounds and an organoaluminum compound system that is a promoter. Although many improvements have been made to improve the catalytic activity and stereoregularity, which are the basic elements in this system, due to the diversified use of polyolefins, there is a need for improvement due to the lack of uniformity of catalyst activity, stereoregularity, particle size and particle size distribution. There is.

In order to solve the stereoregularity problem, U.S. Patent No. 4,544,717 describes a method of adding an electron donor, and U.S. Patent No. 4,226,741 relates to a high stereoregularity catalyst having a stereoregularity of 94 to 95 or more. It is described. EP 045,977 also describes the technology of solid Ziegler-Natta catalysts which are characterized by high activity, high stereoregularity, and derivatives of certain carboxylic acid ester compounds, preferably phthalate derivatives, are solid catalysts as internal electron donors. Coordination to the compound produces a Ziegler-Natta catalyst with the titanium compound. In addition, these main catalysts have been proposed to improve the polymerization activity and stereoregularity by alpha-olefin polymerization using an aluminum alkyl compound and a silicon compound having at least one silicon-ether bond as an external electron donor. However, in these manufacturing methods, there is a difficulty in controlling the size of the carrier particles, and in many cases, the molecular weight distribution of the polymer is also not good.

Further, in order to make the particle size uniform, U.S. Patent Nos. 4,946,816, 4,866,022, 4,988,656, 5,124,297, and the like, (i) prepare a solution containing magnesium from magnesium carboxylate or magnesium alkylcarbonate. (Ii) precipitating the magnesium solution in the presence of a transition metal halide and an organosilane additive, and (iii) reacting the precipitate with a transition metal component and an electron donor compound to produce a catalyst having a uniform particle size. The method is described. However, these methods have many problems in the production of catalysts, complicated production processes, rapid degradation of the catalyst activity during the polymerization process, and failure to meet current requirements in terms of stereoregularity and particle size.

Therefore, there is a need for the development of a new Ziegler-Natta catalyst for olefin polymerization, which is relatively simple, has a high polymerization activity and stereoregularity, has a narrow particle size distribution, and has a good molecular weight distribution of the polymerized polymer.

The inventors of the present invention studied Ziegler-Natta catalysts for olefin polymerization having high activity and high stereoregularity. After dissolving anhydrous magnesium dichloride in a dioxane compound and a hydrocarbon solvent, an organic phosphorus compound and a precipitation accelerator were added thereto. After adding and reacting to prepare a magnesium carrier mixed solution, to which a transition metal compound and an internal electron donor are added and reacted to obtain a precipitate, the precipitate is washed with a hydrocarbon solvent, and then a hydrocarbon solvent and a transition metal compound are added and reacted. A solid catalyst was prepared, and the prepared solid catalyst exhibited high activity and high stereoregularity. In the case of the polyolefin prepared by using the solid catalyst in the olefin polymerization reaction, the polymer particles were large in size, uniform in size, and had a wide molecular weight distribution. It was confirmed that the present invention was completed.

The present invention seeks to provide a process for preparing a Ziegler-Natta catalyst for olefin polymerization having high activity and high stereoregularity.

The present invention

1) Anhydrous magnesium dichloride (MgCl ₂ ) is dissolved in a dioxirane compound represented by the following formula (1) and a hydrocarbon solvent, followed by adding an organophosphorus compound and a precipitation promoter to react for 1 to 3 hours at 50 to 100 ° C. Preparing a magnesium carrier mixed solution,

2) After lowering the temperature of the magnesium carrier mixed solution to -40 ~ 0 ℃, put the transition metal compound represented by the following formula (2) to increase the temperature to 70 ~ 120 ℃, then put the internal electron donor 1 ~ Reacting for 3 hours to obtain a precipitate, and

3) washing the precipitate with a hydrocarbon solvent, and then adding a hydrocarbon solvent and a transition metal compound represented by the following Chemical Formula 2 and reacting at 70 to 120 ° C. for 1 to 5 hours to obtain a solid catalyst. Provided is a method for preparing a Ziegler-Natta catalyst for polymerization.

In Formula 1, R ¹ and R ² are each independently hydrogen or C ₁ ~ C ₂₀ alkyl.

The C ₁ ~ C ₂₀ alkyl includes methyl, ethyl, propyl, butyl, isopropyl, isobutyl and the like.

MR ³ _x

In Formula 2, M is a metal, R ³ is halogen or C ₁ ~ C ₁₀ hydrocarbyloxy, x is the number of oxidation of the metal.

Preferably, in Formula 2, M is a group IVB, such as Ti, Zr, Hf, Rf; VB group, such as V, Nb, Ta, and Db; Or VB group such as Cr, Mo, W, Sg,

R ³ is Cl, Br, C ₁ -C ₄ alkoxy or phenoxy.

More preferably, in Formula 2, M is a group IVB such as Ti, Zr, Hf, Rf, and R ³ is Cl or ethoxy.

Most preferably, in Chemical Formula 2, M is Ti and R ³ is Cl.

Hereinafter, the present invention will be described in detail.

Step 1) in the preparation method of the present invention is to prepare a magnesium carrier mixed solution, 0.1 to 20 mol, preferably 0.1 to 10 mol of the dioxirane compound and 10 to 30 mol of anhydrous magnesium dichloride. After dissolving in a hydrocarbon solvent of 0.01 to 30 mol, preferably 0.01 to 4 mol of an organophosphorus compound and 0.01 to 10 mol, preferably 0.01 to 1 mol of a precipitation accelerator, are added at 50 to 100 ° C. The reaction was carried out for 3 hours to prepare a magnesium carrier mixed solution.

The hydrocarbon solvent may be aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; Aromatic hydrocarbons, such as benzene, toluene, and xylene, may be included, Preferably they are aromatic hydrocarbons, More preferably, toluene.

The dioxirane compound represented by Formula 1 may include dimethyldioxirane, ethylmethyldioxane, methylpropyldioxirane, methylisopropyldioxirane, methylbutyldioxirane or methylisobutyldioxirane. Can be. The concentration of the dioxirane compound is preferably 0.1 to 20 moles, preferably 0.1 to 10 moles per mole of anhydrous magnesium dichloride, and the average particle size of the catalyst and the particles of the polymer depending on the concentration of the dioxane compound. The distribution will be affected. If the concentration of the dioxirane compound is less than 0.1 mole, the magnesium cannot be dissolved to prevent the formation of magnesium particles, resulting in uneven particle formation of the catalyst, lowering of activity, and narrowing of particle distribution of the polymer. On the contrary, when the concentration of the dioxirane compound exceeds 20 mol, dissolution of magnesium becomes easy, but precipitation of the carrier does not occur, resulting in a decrease in the size of the resulting carrier and an uneven distribution of active sites. Accordingly, the appropriate amount of dioxirane compound forms a suitable environment when magnesium dichloride is produced as a carrier to form a carrier having a uniform particle size, and the obtained polymer has a wide particle distribution.

The organophosphorus compound may include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and the like, preferably tributyl phosphate or tripentyl phosphate. . The concentration of the organophosphorus compound is preferably 0.01 to 30 moles, preferably 0.01 to 4 moles per one mole of anhydrous magnesium dichloride, and the size distribution of the particles is significantly affected by the concentration of the organophosphorus compound. . If the concentration of the organophosphorus compound is less than 0.01 mole, almost no complex is formed with the carrier, so the carrier reacts at an excessively high rate by the transition metal compound added later, so that the size of the resulting carrier is small and the pores are almost There is no distribution of active points. On the contrary, when the concentration of the organophosphorus compound exceeds 30 moles, after forming a complex with a carrier, the remaining organophosphorus compound remains as it is, and reacts with the transition metal to decrease the activity of the catalyst and cause the polymer particles to be uneven.

The precipitation promoter serves to control the rate of production, phthalic anhydride is preferred. The concentration of the precipitation accelerator is preferably 0.01 to 10 mol, preferably 0.01 to 1 mol per mol of anhydrous magnesium dichloride.

Step 2) is a step of obtaining a precipitate of a solid catalyst, the magnesium carrier mixed solution prepared in step 1) is cooled to between -40 ~ 0 ℃, and then 1 ~ 5 ~ 20 mol of transition metal compound per mol of magnesium After slowly dropping for 3 hours, the temperature was raised to 70-120 ° C. at a rate of 0.5-5 ° C./min. Temperature conditions then affect carrier uniformity. Here, 0.05-2 mol of internal electron donor is added per 1 mol of magnesium and reacted at 70-120 ° C. for 1-3 hours to obtain a precipitate.

The internal electron donor is added during the preparation of the catalyst, and may include a phthalate compound, a carboxylic acid ester compound or a diether compound. Specifically, the phthalate compound is monomethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dipentyl phthalate, dioctyl phthalate or mixtures thereof. It may include; Carboxylic acid ester compounds include methyl acetate, ethyl acetate, phenyl acetate, ethyl propane, ethyl butyrate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate and diethyl malo. Nates or mixtures thereof; Ether compounds are 2,2-dimethyl-1,3-dimethoxypropane in the form of 1,3-diether, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2,2-diphenyl-1,3 -Dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 1,3-diisobutoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane or these It may include a mixture of.

Step 3) is a step of obtaining a Ziegler-Natta solid catalyst, washing the precipitate prepared in step 2) with a hydrocarbon solvent, and then adding a hydrocarbon solvent and a transition metal compound and at 1 ~ 5 at 70 ~ 120 ℃ After reacting for a time, the solid component is filtered off and washed with a hydrocarbon solvent until no titanium component is detected to obtain a solid catalyst.

Components of the solid catalyst prepared by the above method include 1.5 to 6.0% by weight of titanium, 10 to 20% by weight of magnesium, 50 to 70% by weight of halogen and 5 to 25% by weight of internal electron donor based on the total weight of the catalyst. In addition, the prepared solid catalyst exhibits high activity and high solid regularity, and is preferably prepared in a form in which a transition metal compound is supported on a carrier for improving catalytic activity. The carrier is a chemically inert solid component that does not cause chemical reaction with the transition metal compound.

When the prepared solid catalyst is applied to olefin polymerization, the prepared catalyst is used as the main catalyst, the organoaluminum compound represented by the following Chemical Formula 3 is used as a promoter, and the external electron donor represented by the following Chemical Formula 4 is a subcatalyst. Used as

R ⁴ _n AlY _3-n

In Formula 3, R ⁴ is C ₁ ~ C ₂₀ Alkyl, Y is halogen, 0≤n≤3.

상기 화학식 4에서, R⁵는 C₁~C₄ 알콕시이며,
R⁶는 C₁~C₄ 알킬 또는 C₁~C₄ 알콕시이고,
R⁷는 C₁~C₄ 알킬, C₁~C₄ 알콕시, C₃~C₁₀ 시클로알킬 또는 C₆~C₂₀ 아릴이며,
R⁸는 C₁~C₄ 알킬, C₃~C₁₀ 시클로알킬, C₆~C₂₀ 아릴 또는 비닐기이고,
X는 탄소 또는 실리콘이다.
바람직하게는, 상기 화학식 4에서, R⁵는 메톡시 또는 에톡시이며,
R⁶는 메틸, 에틸, 메톡시 또는 에톡시이고,
R⁷는 메틸, 에틸, 이소프로필, 메톡시, 에톡시, 시클로펜틸, 시클로헥실 또는 페닐이며,
R⁸는 메틸, 에틸, 이소프로필, 시클로펜틸, 시클로헥실, 페닐 또는 비닐기이고,
X는 실리콘이다.

In Chemical Formula 4, R ⁵ is C ₁ ~ C ₄ alkoxy,
R ⁶ is C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy,
R ⁷ is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₁₀ cycloalkyl or C ₆ -C ₂₀ aryl,
R ⁸ is C ₁ -C ₄ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₂₀ aryl or vinyl group,
X is carbon or silicon.
Preferably, in Formula 4, R ⁵ is methoxy or ethoxy,
R ⁶ is methyl, ethyl, methoxy or ethoxy,
R ⁷ is methyl, ethyl, isopropyl, methoxy, ethoxy, cyclopentyl, cyclohexyl or phenyl,
R ⁸ is a methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, phenyl or vinyl group,
X is silicon.

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The compound represented by the formula (4) is preferably an organic silicon compound, specifically triethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxy Silane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyl diethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, preferably diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclopentyldiethoxysilane.

The external electron donor is used together with the promoter in the polymerization, and may be used if necessary. The concentration of the external electron donor includes 0.001 to 50 mol%, preferably 0.01 to 20 mol%, more preferably 0.02 to 10 mol% per mole of promoter. If the concentration of the external electron donor is less than 0.001 mol%, there is a problem that the improvement of stereoregularity does not occur.

Application of the solid catalyst according to the present invention to olefin polymerization enables the production of polyolefins having a large and uniform particle size and a wide molecular weight distribution of the polymer.

In the present invention, 'polymerization' includes not only homopolymerization but also copolymerization.

The polymerization reaction can be carried out in gas phase, liquid phase, or solution phase. When performing a polymerization reaction in a liquid phase, a hydrocarbon solvent may be used and olefin itself can also be used as a solvent. The polymerization temperature is usually -50 to 350 ° C, preferably 0 to 200 ° C. If the polymerization temperature is less than -50 ° C, the activity of the catalyst is not good, and if it exceeds 350 ° C, the stereoregularity is poor, which is not good. The polymerization pressure is usually at normal pressure to 250 kg / cm 2, preferably at atmospheric pressure to 200 kg / cm 2, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. When the polymerization pressure is 250 kg / cm 2 or more, it is not preferable from an industrial and economic point of view.

To the polyolefin prepared using the solid catalyst according to the present invention, a heat stabilizer, a light stabilizer, a flame retardant, carbon black, a pigment, an antioxidant, and the like, which are commonly added, may be added. In addition, the prepared polyolefin may be used in combination with low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, polybutene, EP (ethylene / propylene) rubber and the like.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention exhibits high activity and high solidity regularity, and can significantly reduce the amount of expensive titanium in the raw material, thereby reducing the catalyst manufacturing cost. In addition, the polyolefin prepared by using the Ziegler-Natta catalyst of the present invention can be usefully used for molding materials such as plates, films, containers, and fibers, because the particle size is large, uniform, and shows a wide molecular weight distribution.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Examples 1-4 and Comparative Examples 1-2  : Preparation of Ziegler-Natta Catalyst

Example 1  :

Under high purity nitrogen atmosphere, 4.8 g (0.05 mol) of anhydrous magnesium dichloride (MgCl ₂ ), 4.5 g (0.05 mol) of dimethyldioxirane, 95 ml (0.89 mol) of toluene, tributylphosphate in a double jacketed glass reactor with a stirrer 12.5 mL (0.046 mol) was added, the temperature was raised to 80 ° C. and stirred until a clear solution was produced. 1.4 g (0.009 mol) of phthalic anhydride was added thereto and stirred for 2 hours to prepare a magnesium carrier mixed solution. After the temperature of the mixed solution was lowered to -20 ° C, 20 ml (0.1 mol) of titanium tetrachloride (TiCl ₄ ) was slowly added dropwise, and then the temperature was constantly raised to 110 ° C at a rate of 0.5 ° C / min. 3.68 ml (0.014 mol) of diisobutyl phthalate was added at 110 ° C. and reacted for 2 hours to obtain a precipitate. The precipitate was washed with toluene, and then 60 ml (0.56 mol) of toluene and 40 ml (0.2 mol) of titanium tetrachloride were added and reacted at 110 ° C. for 2 hours. After filtering the solid component was washed with toluene and hexane to obtain a solid catalyst.

Example 2  :

A solid catalyst was prepared in the same manner as in Example 1, except that 4.4 g (0.05 mol) of ethylmethyldioxane was used instead of 4.5 g (0.05 mol) of dimethyldioxane in Example 1.

Example 3  :

A solid catalyst was prepared in the same manner as in Example 1, except that 5.1g (0.05mol) of methylpropyldioxane was used instead of 4.5g (0.05mol) of dimethyldioxane in Example 1.

Example 4  :

A solid catalyst was prepared in the same manner as in Example 1, except that 5.8 g (0.05 mol) of methylbutyl dioxirane was used instead of 4.5 g (0.05 mol) of dimethyldioxane in Example 1.

Comparative Example 1  :

A solid catalyst was prepared in the same manner as in Example 1, except that 4.6 g (0.05 mol) of epoxy chloropropane was used instead of 4.5 g (0.05 mol) of dimethyldioxane in Example 1.

Comparative Example 2  :

A solid catalyst was prepared in the same manner as in Example 1, except that 6.5 g (0.05 mol) of 2-ethylhexanol was used instead of 4.5 g (0.05 mol) of dimethyldioxane in Example 1.

Experimental Example 1  : Catalyst Performance Evaluation Experiment

In order to evaluate the performance of the Ziegler-Natta catalyst for olefin polymerization according to the present invention, the following experiment was performed.

The polymerization of propylene was carried out using a 2 L polymerization reactor. The reactor was decompressed to a vacuum of 3 torr or less and charged with nitrogen of high purity five times. After filling 500 g of propylene and 750 cc of hydrogen in the reactor at room temperature, 3 mmol of triethyl aluminum, 0.18 mmol of dicyclopentyldimethoxysilane, and 0.0044 mmol of the catalyst prepared in Examples 1 to 4 and Comparative Examples 1 to 2 were added thereto. The reactor temperature was raised to 70 ° C. and reacted for 1 hour. A small amount of methanol was added to the polymer to terminate the polymerization. The reaction product was stirred in about 5 wt% HCl-methanol for 24 hours, washed again in clean methanol for 24 hours, filtered over filter paper, and vacuum dried at about 80 ° C. for at least 12 hours to obtain a final polymerization product.

The activity of the catalyst was determined in units of g-polymer / g-catalyst from the weight of the final polymerization product.

The stereoregularity (I.I .: isotacticity index) of polypropylene was performed with stereoregularity, an amount insoluble in boiling heptane. The polymer was previously treated with a heat stabilizer to prevent degradation during analysis. A certain amount of the completely dried polymer was quantitatively placed in a timing filter and extracted with heptane in a Soxhlet type extraction apparatus. The extraction time was fixed at 5 hours. After extraction, the remaining polymer was collected and dried in vacuo at 80 ° C., and then quantitatively weighed. It was.

The polymerization activity of the catalyst, the stereoregularity and the properties of the polymerization product are shown in Table 1.

Ti content
(weight%) activation
(Kg / g cat) Stereoregularity Average particle diameter (㎛) Polymer Undistributed
(<250 μm) Volume density (BD) Molecular Weight Distribution (MWD) Example 1 2.3 25.9 97.6 800 1.8 0.40 5.7 Example 2 1.9 24.2 96.9 850 1.3 0.42 5.9 Example 3 2.1 27.3 97.3 880 2.0 0.41 6.1 Example 4 2.6 30.1 98.1 860 0.9 0.44 5.7 Comparative Example 1 2.2 23.8 97.9 630 1.8 0.42 4.8 Comparative Example 2 2.4 25.1 97.5 780 2.1 0.36 4.1

As shown in Table 1, the Ziegler-Natta catalyst for olefin polymerization according to the present invention showed high activity and high stereoregularity. In addition, it was confirmed that the polypropylene polymerized using the catalyst had a large and uniform particle size and a wide molecular weight distribution.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention exhibits high activity and high solidity regularity, and can significantly reduce the amount of expensive titanium in the raw material, thereby reducing the catalyst manufacturing cost. In addition, the polyolefin produced using the Ziegler-Natta catalyst of the present invention can be usefully used for molding materials such as plates, films, containers, and fibers, because the particle size is large and uniform, and the molecular weight distribution is wide.

Claims (15)

1) Anhydrous magnesium dichloride (MgCl ₂ ) is dissolved in a dioxirane compound represented by the following formula (1) and a hydrocarbon solvent, followed by adding an organophosphorus compound and a precipitation promoter to react for 1 to 3 hours at 50 to 100 ° C. Preparing a magnesium carrier mixed solution, 2) After lowering the temperature of the magnesium carrier mixed solution to -40 ~ 0 ℃, put the transition metal compound represented by the following formula (2) to increase the temperature to 70 ~ 120 ℃, then put the internal electron donor 1 ~ Reacting for 3 hours to obtain a precipitate, and 3) washing the precipitate with a hydrocarbon solvent, and then adding a hydrocarbon solvent and a transition metal compound represented by the following Formula 2 and reacting at 70 to 120 ° C. for 1 to 5 hours to obtain a solid catalyst. The hydrocarbon solvent consists of butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, dodecane, hexadecane, octadecane, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, benzene, toluene and xylene Including at least one selected from the group, The organophosphorus compound includes one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite and tributyl phosphite, The precipitation promoter is phthalic anhydride, The internal electron donor is monomethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dipentyl phthalate, dioctyl phthalate, methyl acetate, ethyl Acetate, Phenyl Acetate, Ethyl Propane, Ethyl Butyrate, Methyl Acrylate, Ethyl Acrylate, Methyl Methacrylate, Ethyl Benzoate, Butyl Benzoate, Methyl Toluate, Diethyl Malonate, 2,2-Dimethyl-1 , 3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3 Diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimeth Oxypropane, 1,3-diisobutoxypropane, and 2-isopropyl-2-i A method for preparing a Ziegler-Natta catalyst for olefin polymerization, characterized in that at least one member selected from the group consisting of sorbent-1,3-dimethoxypropane: <Formula 1>

In Formula 1, R ¹ and R ² are each independently hydrogen or C ₁ ~ C ₂₀ alkyl. <Formula 2> MR ³ _x In Formula 2, M is a metal, R ³ is halogen or C ₁ ~ C ₁₀ hydrocarbyloxy, x is the number of oxidation of the metal. The method of claim 1, wherein in Formula 2, M is a group IVB of Ti, Zr, Hf, Rf; Group VB of V, Nb, Ta, and Db; Or VB group of Cr, Mo, W, Sg, R ³ is Cl, Br, C ₁ ~ C ₄ alkoxy or phenoxy, the method of producing a Ziegler-Natta catalyst for olefin polymerization. The method of claim 1, wherein in Formula 2, M is a group IVB of Ti, Zr, Hf, and Rf, and R ³ is Cl or ethoxy. The method of claim 1, wherein in Chemical Formula 2, M is Ti, and R ³ is Cl. delete According to claim 1, wherein the dioxirane compound represented by Formula 1 is dimethyldioxirane, ethylmethyldioxirane, methylpropyldioxirane, methylisopropyldioxirane, methylbutyldioxirane and methylisobutyl Method for producing a Ziegler-Natta catalyst for olefin polymerization, characterized in that one selected from the group consisting of deoxirane. The method of claim 1, wherein the concentration of the dioxirane compound in step 1) is 0.1-20 mol per mol of anhydrous magnesium dichloride. delete The method for preparing a Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the concentration of the organophosphorus compound in step 1) is 0.01 to 30 moles per mole of anhydrous magnesium dichloride. delete The method of claim 1, wherein the concentration of the precipitation promoter in step 1) is 0.01 to 10 mol per mol of anhydrous magnesium dichloride, the method for producing a Ziegler-Natta catalyst for olefin polymerization. The method according to claim 1, wherein the concentration of the transition metal compound in step 2) is 5 to 20 mol per mol of magnesium. The method according to claim 1, wherein the concentration of the internal electron donor in step 2) is 0.05-2 mol per mol of magnesium. delete The components of the solid catalyst prepared by the method of any one of claims 1 to 4, 6, 7, 9, and 11 to 13 are selected from titanium 1.5 based on the total weight of the catalyst. Ziegler-Natta catalyst for olefin polymerization, comprising -6.0 wt%, magnesium 10-20 wt%, halogen 50-70 wt%, and internal electron donor 5-25 wt%.