KR101710211B1 - Ziegler-Natta catalyst for olefin polymerization and its preparing method - Google Patents

Abstract

The present invention relates to a Ziegler-Natta catalyst for olefin polymerization having a high activity and a broad molecular weight distribution, and a process for producing the Ziegler-Natta catalyst. The present invention relates to a Ziegler-Natta catalyst for olefin polymerization, A precipitating accelerator is added and reacted to prepare a magnesium carrier mixed solution; Secondly, the magnesium mixed carrier solution is added to the transition metal compound to obtain a precipitate; Third, adding a transition metal to react to obtain a compound, and then washing the compound with a hydrocarbon solvent to obtain a solid catalyst; Here, the inner electron donor is an amide, and is necessarily added in at least one of the first stage and the third stage of the catalyst production process.

Description

Ziegler-Natta catalyst for olefin polymerization and a process for producing the same Ziegler-Natta catalyst for olefin polymerization and its preparing method

The present invention relates to a Ziegler-Natta catalyst for olefin polymerization having a high activity and a broad molecular weight distribution, and a process for producing the same.

The catalyst for olefin polymerization, which is generally called a Ziegler-Natta catalyst, is a catalyst system comprising a combination of a main catalyst which is a main component of a transition metal compound, a cocatalyst which is an organometallic compound, and an electron donor and has conventionally been improved in polymerization activity and stereoregularity And the molecular weight distribution of the polymer is broadly studied.

The Ziegler-Natta catalyst directly affects the properties and properties of the polyolefin produced according to its constituent components, structure and preparation method. Therefore, in order to change the properties of the produced polyolefin, it is necessary to change the composition of the catalyst, the structure of the carrier, and the method of preparing the catalyst during the production of the catalyst. The activity of the modified catalyst and the molecular weight and stereoregularity of the polymerized polymer should be studied in parallel.

Conventional Ziegler-Natta catalysts consist of a solid catalyst component, mainly titanium, magnesium and halogen compounds, and an organoaluminum compound system which is a cocatalyst. Although many improvements have been made in improving the catalytic activity and stereoregularity, which are basic elements of this system, diversification of applications of polyolefins is required to further broaden the molecular weight distribution of the resulting polymers.

In order to broaden the molecular weight distribution, WO00 / 63261 proposes a method of improving the stereoregularity and widening the molecular weight distribution by using a succinate derivative instead of phthalate as an internal electron donor in the solid catalyst component. However, there is a problem in that the catalytic activity drops sharply during the polymerization process, failing to satisfy the present requirement level.

Therefore, it is required to develop a new Ziegler-Natta catalyst for olefin polymerization, which is capable of obtaining a polymer having a high polymerization activity and a broad molecular weight distribution while a catalyst preparation method is relatively simple.

In studying Ziegler-Natta catalysts for olefin polymerization having a high activity and a broad molecular weight distribution, the present inventors have found that when anhydrous magnesium dichloride is dissolved in anhydrous alcohol and hydrocarbon solvent, a precipitating accelerator is added thereto, The resulting mixture was added to a transition metal compound to obtain a precipitate, and then a transition metal compound and an internal electron donor were added and reacted to obtain a compound. The compound was washed with a hydrocarbon solvent to prepare a solid catalyst, The catalyst exhibits high activity, and the polyolefin prepared by using the solid catalyst in the olefin polymerization reaction has a wide molecular weight distribution, and the present invention has been completed.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention is characterized in that an amide having the structure of the formula (2) is used as an internal electron donor.

(2)

Wherein R ² , R ³ and R ⁴ may be the same or different and are hydrogen, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, Ar- (CH ₂ ) _n CH _3, Ar-halogen, or _{Ar-OH, Ar-NO 2} , Ar-CF 3 , or aryl substituent is selected from _{Ar-O (CH 2) n} CH 3, alkyl aryl, alkyl containing a hetero atom / RTI >

The process for producing a Ziegler-Natta catalyst for olefin polymerization according to the present invention comprises the steps of: 1) dissolving anhydrous magnesium halide in anhydrous alcohol and a hydrocarbon solvent, adding a precipitating accelerator thereto, and reacting the mixture at 60 to 150 ° C for 1 to 3 hours, 2) lowering the transition metal compound represented by the following formula (1) to -40 to 0 占 폚, slowly dropping the magnesium support mixture thereon for 1 to 5 hours, and then heating the mixture at a temperature of 0.1 to 5 占 폚 / min to a temperature of 70 to 130 ° C for 1 to 6 hours and then reacted for 1 to 4 hours to obtain a precipitate; 3) washing the precipitate with a hydrocarbon solvent; Adding a metal compound and reacting at 70 to 120 ° C for 1 to 5 hours and then washing until no transition metal component is detected with a hydrocarbon solvent to obtain a solid catalyst, Wherein the internal electron donor used in the method for preparing a Ziegler-Natta catalyst for olefin polymerization is an amide having the structure of Formula 2, and the internal electron donor is a compound represented by Formula It is always added.

≪ Formula 1 >
MX _n (OR ¹ ) _4-n

Wherein M is a metal, X is halogen, OR ¹ is C ₁ -C ₁₀ hydrocarbyloxy and n is 0 to 4 oxidation number of metal.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention comprises 1.5 to 6.0% by weight of a transition metal, 10 to 20% by weight of magnesium, 40 to 70% by weight of a halogen and 5 to 25% by weight of an internal electron donor do.

Further, the Ziegler-Natta catalyst for olefin polymerization according to the present invention is characterized by containing the above-mentioned solid catalyst, the organoaluminum compound represented by the formula (3) and the external electron donor represented by the formula (4).

(3)
R ⁴ _n AlX _3-n

Wherein R ⁴ is C ₁ -C ₂₀ alkyl, X is halogen and n is 0-3.

≪ Formula 4 >
R ⁵ _n Si (OR ⁶ ) _4-n

Here, R ⁵ and R ⁶ is C ₁ to C ₂₀ hydrocarbons, and n is 0 to 4.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention exhibits high activity, and the use amount of titanium, which is expensive in the raw material, can be greatly reduced, thereby reducing the catalyst production cost. Further, the polyolefin produced by using the Ziegler-Natta catalyst of the present invention has a broad molecular weight distribution, and thus can be usefully used for molding materials such as plates, films, containers, and fibers.

The present invention provides a Ziegler-Natta catalyst for olefin polymerization characterized in that an amide having the structure of the formula (2) is used as an internal electron donor.

The present invention

1) dissolving anhydrous magnesium dichloride (MgCl ₂ ) in anhydrous alcohol and a hydrocarbon solvent, adding a precipitating accelerator thereto, and reacting at 60 to 150 ° C for 1 to 5 hours to prepare a magnesium carrier mixed solution;

2) Lowering the transition metal compound represented by the formula (1) to -40 to 0 占 폚, adding the magnesium carrier mixture thereto, raising the temperature at 70 to 130 占 폚 for 1 to 6 hours, reacting for 1 to 4 hours Obtaining a precipitate, and

3) adding a transition metal represented by the following formula (1) and an internal electron donor represented by the following formula (2) for 1 to 3 hours to obtain a precipitate, followed by washing with a hydrocarbon solvent to obtain a solid catalyst ,

4) a process for preparing a Ziegler-Natta catalyst for olefin polymerization, wherein the internal electron donor is added during at least one of steps 1) and 3) during the catalyst preparation.

≪ Formula 1 >
MX _n (OR ¹ ) _4-n

Wherein M is a metal, X is halogen, OR ¹ is C ₁ to C ₁₀ hydrocarbyloxy, and n is 0 to 4 oxidation number of metal.

Preferably, in the above formula (1), M is a group IVB of Ti, Zr, Hf, Rf or Rf, a group VB of V, Nb, Ta or Db or a group VIB of Cr, Mo, W or Sg,

X is Cl, Br, I, OR ¹ is when C ₁ ~ C ₄ alkoxy or phenoxy.

More preferably, M is a group IVB wherein M is Ti, Zr, Hf or Rf, X is Cl and OR ¹ is ethoxy, butoxy, chlorotriethoxy, dichlorodiethoxy or trichloroethoxy. Most preferably, M is Ti.

(2)

Wherein R ² , R ³ and R ⁴ may be the same or different and are hydrogen, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, Ar- (CH _{2) n CH 3, Ar-} halogen, Ar-OH, Ar-NO 2, Ar-CF 3 , or _{Ar-O (CH 2) n} CH 3 , or aryl substituent is selected from, or alkylaryl, Ar- (CH ₂ ) _n CH _3, an alkyl aryl of Ar-halogen, Ar-OH, Ar-NO 2, Ar-CF 3 , or _{Ar-O (CH 2) n} CH 3 alkylaryl substituent selected from or contain heteroatoms.

Hereinafter, the present invention will be described in detail.

In the manufacturing method of the present invention, the above step 1) is a step of preparing a mixed solution of a magnesium carrier, wherein 0.1 to 20 moles, preferably 0.1 to 10 moles, of anhydrous alcohol and 0.1 to 20 moles of hydrocarbons After the solution is dissolved in a solvent, 0.001 to 10 moles, preferably 0.001 to 1 mole, of a precipitating accelerator is added thereto and reacted at 60 to 150 ° C for 1 to 5 hours to prepare a magnesium carrier mixed solution.

The hydrocarbon solvent may be an aliphatic hydrocarbon such as butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, dodecane, hexadecane or octadecane, or an aliphatic hydrocarbon such as cyclopentane, methylcyclopentane, cyclohexane or cyclooctane Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene or xylene, preferably aliphatic hydrocarbons, more preferably decane.

The precipitation-promoting agent serves to control the rate of formation of catalyst particles, and may be an anhydrous organic acid such as acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride or succinic anhydride, or an organic acid such as acetic acid, propionic acid, butylic acid, acrylic acid or methacrylic acid , Ketones such as acetone, methyl ethyl ketone or benzophenone, ethers such as dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether or 1,3-diether, aldehydes, succinates, Amides or mixtures thereof, preferably anhydrous organic acids, more preferably phthalic anhydride. The concentration of the precipitating accelerator is suitably 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of anhydrous magnesium dichloride.

The step 2) is a step of obtaining a precipitate of a solid catalyst, wherein 1 to 20 moles of the transition metal compound and the hydrocarbon solvent are cooled to -40 to 10 ° C per 1 mole of magnesium, and then the magnesium carrier mixture is stirred for 1 to 5 hours After gradually dropping, the temperature is raised at a rate of 0.1 to 5 ° C / min to 70 to 130 ° C for 1 to 6 hours, followed by a reaction for 1 to 4 hours to obtain a precipitate. At this time, the temperature condition and the heating rate affect carrier uniformity.

In the step 3), 1 to 20 moles of the transition metal compound and 0.01 to 2 moles of the internal electron donor are added at 50 to 130 ° C per 1 mole of magnesium, and the reaction is carried out for 1 to 5 hours To obtain a compound. The prepared compound is washed with a hydrocarbon solvent until no transition metal component is detected to obtain a solid catalyst.

Wherein the internal electron donor is represented by Formula 2, R ² , R ³ , and R ⁴ may be the same or different and are hydrogen, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, or aryl, Ar- (CH _{2) n} CH _3, Ar-halogen, Ar-OH, Ar-NO _2, CF ₃ or _{Ar-Ar-O (CH 2) n} CH 3 , or aryl substituents selected from, alkyl aryl, Ar An alkylaryl substituent selected from - (CH ₂ ) _n CH ₃ , Ar-halogen, Ar-OH, Ar-NO ₂ , Ar-CF ₃ or Ar-O (CH ₂ ) _n CH ₃ , compound and, specifically, N- benzoyl -N- methyl-benzamide (N -Benzoyl- N -methylbenzamide), N- ethyl -N- benzoyl benzamide (N -Benzoyl- N -ethylbenzamide), N- benzoyl -N- propyl benzamide (N -Benzoyl- N -propylbenzamide), N- benzoyl -N- isopropyl-benzamide (N -Benzoyl- N -isopropylbenzamide), N- benzoyl -N- butyl benzamide (N -Benzoyl- N -butylbenzamide) , N-benzoyl- N- hexylbenzamide ( N -Benzoyl- N- hex ylbenzamide), N- benzoyl -N- cyclopentyl-benzamide (N -Benzoyl- N -cyclopenthylbenzamide), N- benzoyl -N- cyclohexyl-benzamide (N -Benzoyl- N -cyclohexylbenzamide), N- benzoyl -N- phenyl benzamide (N -Benzoyl- N -phenylbenzamide), N- propionyl -N- methyl-benzamide (N -Propionyl- N -methylbenzamide), N- propionyl -N- ethyl-benzamide (N -Propionyl- N -ethylbenzamide ), N- propionyl -N- propyl benzamide (N -Propionyl- N -propylbenzamide), N- propionyl -N- isopropyl-benzamide (N -Propionyl- N -isopropylbenzamide), N- propionyl -N- butyl benzamide (N -Propionyl- N -butylbenzamide), N- propionyl -N- cyclohexyl benzamide (N -Propionyl- N -hexylbenzamide), N- propionyl -N- cycloalkyl petil benzamide (N -Propionyl- N -cyclopenthylbenzamide), N- propionyl -N- cyclohexyl-benzamide (N -Propionyl- N -cyclohexylbenzamide), N- propionyl -N- methyl-benzamide (N -Butyryl- N -methylbenzamide), N- butyryl- N-ethylbenzamide (N -Butyryl- N -ethylbenzamide), N- butyryl -N- propyl benzamide (N -Butyryl- N -propylbenzamide), N- butyryl -N- isopropyl-benzamide (N -Butyryl- N -isopropylbenzamide) , N- butyryl -N- butyl-benzamide (N -Butyryl- N -butylbenzamide), N- butyryl -N- cyclohexyl benzamide (N -Butyryl- N -hexylbenzamide), N- butyryl -N- cyclopentyl N -cyclopentylbenzamide, N- Butyryl- N -cyclopentylbenzamide and N- Butyryl- N- cyclohexylbenzamide.

Although the inner electron donor has been described above as being added to step 3), the inner electron donor may be added to at least one of step 1) or step 3).

The constituent components of the solid catalyst prepared by the above method include 0.5 to 6.0 wt% of transition metal, 10 to 20 wt% of magnesium, 40 to 70 wt% of halogen, and 5 to 30 wt% of internal electron donor based on the total weight of the catalyst. In addition, the prepared solid catalyst exhibits a high activity and a broad molecular weight distribution, and it is preferable that the solid catalyst is prepared in a form that the transition metal compound is supported on the carrier in order to improve catalytic activity.

When the prepared solid catalyst is applied to the olefin polymerization, the prepared catalyst is used as the main catalyst and the organoaluminum compound represented by the following formula (3) is used as the co-catalyst, and the external electron donor represented by the following formula .

(3)
R ⁴ _n AlX _3-n

In Formula 3, R ⁴ is C ₁ -C ₂₀ alkyl, X is halogen, and n is 0 to 3.

≪ Formula 4 >
R ⁵ _n Si (OR ⁶ ) _4-n

In Formula 4, R ⁵ is C ₁ to C ₂₀ hydrocarbons, preferably C ₁ to C ₁₀ alkyl, C ₅ to C ₁₂ cycloalkyl, C ₆ to C ₂₀ aryl _, C ₁ to C ₁₀ alkenyl, C ₁ to C ₁₀ haloalkyl Or C ₁ -C ₁₀ aminoalkyl or chlorine and is R ⁶ C ₁ -C ₂₀ hydrocarbons and is preferably C ₁ -C ₁₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₂₀ aryl or C ₁ to a C ₁₀ alkenyl group.

The compound represented by Chemical Formula 4 is preferably an organosilicon compound. Specific examples thereof include triethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxy Silane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane, and preferably diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane or dicyclopentyldiethoxysilane.

External electron donors are used in conjunction with co-catalysts in polymerization and can be used as needed. The concentration of the external electron donor is 0.001 to 50 mol%, preferably 0.01 to 20 mol%, more preferably 0.02 to 10 mol%, per mole of the co-catalyst. If the concentration of the external electron donor is less than 0.001 mol%, there is a problem that the stereoregularity can not be improved. When the concentration of the external electron donor is more than 50 mol%, the stereoregularity is not affected any more.

When the solid catalyst according to the present invention is applied to the olefin polymerization, a polyolefin having a high activity and a wide molecular weight distribution can be produced.

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

The polymerization reaction can be carried out in a gas phase, a liquid phase, or a solution phase. When the polymerization reaction is carried out in a liquid phase, a hydrocarbon solvent may be used, and the olefin itself may be used as a solvent. The polymerization temperature is usually in the range of -50 to 350 占 폚, preferably 0 to 200 占 폚. If the polymerization temperature is less than -50 ° C, the activity of the catalyst is not good. If the polymerization temperature exceeds 350 ° C, the stereoregularity is deteriorated. The polymerization pressure is usually from atmospheric pressure to 250 kg / cm 2, preferably from 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 higher than 250 kg / cm < 2 >, this is not preferable from the industrial and economical point of view.

A heat stabilizer, a light stabilizer, a flame retardant, carbon black, a pigment, an antioxidant and the like which are conventionally added may be added to the polyolefin produced using the solid catalyst according to the present invention. The polyolefin may be mixed with low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, polybutene, EP (ethylene / propylene) rubber or the like.

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.

Example  1 to 15 and Comparative Example  1 to 2: Ziegler - Appear  Preparation of Catalyst

Example  One :

(0.05 mol) of anhydrous magnesium dichloride (MgCl ₂ ), 25 mL (0.16 mol) of 2-ethyl-1-hexanol and 23 mL (0.12 mol) of decane were placed in a double jacketed reactor equipped with a stirrer under a high- , The temperature was raised to 130 ° C and stirred until a clear solution was formed. 1.4 g (0.01 mol) of phthalic anhydride was added thereto, and the mixture was stirred for 1 hour to prepare a magnesium carrier mixed solution. 28 ml (0.2 mol) of titanium tetrachloride (TiCl ₄ ) and 100 ml (0.94 mol) of toluene were dropped to -20 ° C. and then the magnesium carrier mixture solution was slowly added dropwise. The temperature was then decreased to 110 ° C. at a rate of 0.5 ° C./min The temperature was maintained for 2 hours to obtain a compound. After the compound was washed twice with toluene and titanium tetrachloride (TiCl ₄₎ 25㎖ (0.23mol) and toluene into a 100ml (0.94mol), and then the temperature was raised to 110 ℃ N- benzoyl -N- methyl-benzamide (N - (0.01 mol) of benzoyl- N- methylbenzamide was added thereto, followed by reaction for 2 hours to obtain a precipitate. Thereafter, the solid component was filtered and washed with toluene and hexane to obtain a solid catalyst.

Example  2 :

Example 1 N- benzoyl -N- methyl-benzamide instead of N- benzoyl -N- ethyl benzamide from (N -Benzoyl- N -ethylbenzamide) 2.5g ( 0.01mol) , except that used in Example 1, In the same manner, a solid catalyst was prepared.

Example  3:

Example 1 N- benzoyl -N- methyl-benzamide instead of N- benzoyl -N- propyl benzamide from (N -Benzoyl- N -propylbenzamide), except for using 2.7g (0.01mol) in Example 1, and In the same manner, a solid catalyst was prepared.

Example  4 :

Example 1 N- benzoyl -N- methyl-benzamide instead of N- benzoyl -N- phenyl-benzamide from (N -Benzoyl- N -phenylbenzamide) 3.0g ( 0.01mol) , except that used in Example 1, In the same manner, a solid catalyst was prepared.

Comparative Example  One :

A solid catalyst was prepared in the same manner as in Example 1 except that 2.2 g (0.01 mol) of diethyl phthalate was used instead of N-benzoyl-N-methylbenzamide in Example 1.

Comparative Example  2 :

A solid catalyst was prepared in the same manner as in Example 1 except that 2.8 g (0.01 mol) of diisobutylphthalate was used instead of N-benzoyl-N-methylbenzamide 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 conducted.

Polymerization of propylene was carried out using a polymerization reactor having a size of 2 liters. The inside of the reactor was depressurized to a vacuum of 3 torr or less and filled with nitrogen of high purity was repeated 5 times. 500 g of propylene and 750 cc of hydrogen were charged into the reactor at room temperature and then 3 mmol of triethylaluminum, 0.18 mmol of dicyclopentyldimethoxysilane, 0.0044 mmol of the catalyst prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were added , The reactor temperature was raised to 70 캜 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% by weight of HCl-methanol for 24 hours, washed again with clean methanol for 24 hours, filtered through filter paper, and vacuum dried at about 80 ° C for 12 hours or longer to obtain a final polymerized product.

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

The stereochemistry of polypropylene (I.I. isotacticity index) was stereoregular, which was insoluble in boiling heptane. The polymer was previously treated with a heat stabilizer to prevent degradation during the analysis. A certain amount of completely dried polymer was quantified in a timble filter and extracted with heptane in a Soxhlet type extraction apparatus. The extraction time was fixed to 5 hours. After the extraction, the remaining polymer was collected, vacuum-dried at 80 ° C, and weighed and weighed. The weight of the remaining polymer and the weight ratio of the original polymer were measured. Respectively.

Table 1 shows the polymerization activity of the catalyst, the stereoregularity and properties of the polymerization product.

Ti content
(weight%) activation
(kg / g cat) Stereoregularity
(%) Volume Density (BD) Molecular weight distribution
(MWD) Example 1 1.0 28.0 98.0 0.40 4.9 Example 2 1.4 32.0 97.9 0.42 5.2 Example 3 1.2 33.0 98.1 0.41 5.3 Example 4 1.3 35.0 98.3 0.40 5.6 Comparative Example 1 2.5 20.0 97.7 0.39 4.4 Comparative Example 2 0.8 25.0 97.5 0.38 4.8

As shown in Table 1, it was confirmed that the Ziegler-Natta catalyst for olefin polymerization according to the present invention had a high activity and a broad molecular weight distribution.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention exhibits high activity, and the use amount of titanium, which is expensive in the raw material, can be greatly reduced, thereby reducing the catalyst production cost. Further, the polyolefin produced by using the Ziegler-Natta catalyst of the present invention has a broad molecular weight distribution, and thus can be usefully used for molding materials such as plates, films, containers, and fibers.

Claims (11)

A Ziegler-Natta catalyst for olefin polymerization characterized in that an amide having the structure of formula (2) is used as an internal electron donor.
(2)

Wherein R ² , R ³ and R ⁴ may be the same or different and are hydrogen, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, Ar- (CH ₂ ) _{n CH 3, Ar-halogen,} Ar-OH, Ar-NO 2, Ar-CF 3 , or _{Ar-O (CH 2) n} CH 3 , or aryl substituents selected from, alkyl, aryl, alkyl containing heteroatom aryl to be. 1) dissolving anhydrous magnesium halide in anhydrous alcohol and hydrocarbon solvent, adding a precipitating accelerator thereto, and reacting at 60 to 150 ° C for 1 to 3 hours to prepare a magnesium carrier mixed solution,
2) The transition metal compound represented by the following formula (1) is lowered to -40 to 0 占 폚, the magnesium carrier mixture is gradually added dropwise thereto for 1 to 5 hours, Heating the mixture at 130 ° C for 1 to 6 hours, reacting the mixture for 1 to 4 hours to obtain a precipitate,
3) The precipitate is washed with a hydrocarbon solvent, and then a transition metal compound represented by the following formula (1) is added and reacted at 70 to 120 ° C for 1 to 5 hours, until the transition metal component is not detected in the hydrocarbon solvent To obtain a solid catalyst, the method comprising the steps of: preparing a Ziegler-Natta catalyst for olefin polymerization,
The internal electron donor used in the method for preparing the Ziegler-Natta catalyst for olefin polymerization is an amide having the structure of Formula 2, and the internal electron donor is necessarily added in any one of the 1) or 3) steps To obtain a Ziegler-Natta catalyst for olefin polymerization.
≪ Formula 1 >
MX _n (OR ¹ ) _4-n
Wherein M is a metal, X is halogen, OR ¹ is C ₁ -C ₁₀ hydrocarbyloxy and n is 0 to 4 oxidation number of metal.
(2)

Wherein R ² , R ³ and R ⁴ may be the same or different and are hydrogen or C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl or aryl, or Ar- (CH ₂ ) _n CH ₃ , Ar-halogen, Ar-OH, Ar-NO ₂ , Ar-CF ₃ or Ar-O (CH ₂ ) _n CH ₃ , alkylaryl or alkylaryl containing a heteroatom. The process for preparing a Ziegler-Natta catalyst for olefin polymerization according to claim 2, wherein the precipitation accelerator in step 1) is an anhydrous organic acid, an organic acid, an ether, an aldehyde, a ketone, a succinate, a diacylsulfide or an amide. 4. The method according to claim 3, wherein the anhydrous organic acid is acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride or succinic anhydride and the organic acid is acetic acid, propionic acid, butyric acid, acrylic acid or methacrylic acid, Or a benzophenone, and the ether is dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether or 1,3-diether. The compound according to claim 2, wherein M is a Group IVB compound of Ti, Zr, Hf or Rf, a Group VB compound of V, Nb, Ta or Db or a Group VIB compound of Cr, Mo, W or Sg , X is Cl, Br or I, and OR ¹ is ethoxy, butoxy, chlorotriethoxy, dichlorodiethoxy or trichloroethoxy. 3. The process for producing a Ziegler-Natta catalyst for olefin polymerization according to claim 2, wherein M in the formula (1) is Ti and X is Cl. The process for producing a Ziegler-Natta catalyst for olefin polymerization according to claim 2, wherein in step 1), the anhydrous magnesium halide is magnesium dichloride. The process of claim 2 wherein said hydrocarbon solvent is selected from the group consisting of butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, dodecane, hexadecane, octadecane, cyclopentane, methylcyclopentane, cyclohexane, , Toluene, or xylene. The method for producing a Ziegler-Natta catalyst for olefin polymerization according to claim 1, delete The composition of the solid catalyst produced by the process of any one of claims 2 to 8 comprises 1.5 to 6.0% by weight of transition metal, 10 to 20% by weight of magnesium, 40 to 70% by weight of halogen, And 5 to 25% by weight of an electron donor, based on the total weight of the Ziegler-Natta catalyst. A solid catalyst produced by any one of claims 2 to 8;
An organoaluminum compound represented by the formula (3); And
A Ziegler-Natta catalyst for olefin polymerization, which comprises an external electron donor represented by the general formula (4).
(3)
R ⁴ _n AlX _3-n
Wherein R ⁴ is C ₁ -C ₂₀ alkyl, X is halogen and n is 0-3.
≪ Formula 4 >
R ⁵ _n Si (OR ⁶ ) _4-n
Here, R ⁵ and R ⁶ is C ₁ to C ₂₀ hydrocarbons, and n is 0 to 4.