KR20120002790A - A method for preparing a solid catalyst for propylene polymerization - Google Patents

Abstract

PURPOSE: A manufacturing method of a solid catalyst for polypropylene polymerization is provided to obtain polypropylene having high yield, superior tacticity without containing environmental toxic material. CONSTITUTION: A manufacturing method of a solid catalyst comprises: a step of reacting titanium halide and magnesium compound on the presence of an organic solvent; a step of reacting one or more compound selected from the dicarboxylate compound in the chemical formula (II), as an internal electron donor; and a step of reacting the outcome with titanium halide and washing the same. In the chemical formula (II), R is C1-10 linear, branched or cyclic alkyl, and n is the integer of 1-6.

Description

Process for producing solid catalyst for propylene polymerization {A METHOD FOR PREPARING A SOLID CATALYST FOR PROPYLENE POLYMERIZATION}

The present invention relates to a method for preparing a solid catalyst for propylene polymerization, and more particularly, by using a dicarboxylate compound having a chemical formula according to the present invention as an internal electron donor, it does not contain environmentally harmful substances and is environmentally friendly. The present invention relates to a method for producing a solid catalyst for propylene polymerization having excellent catalytic activity and stereoregularity.

Polypropylene is a very industrially useful material and has been widely applied in various applications, especially in materials related to automobiles and electronic products. In order to further expand the application of polypropylene, it is important to improve the rigidity by increasing the crystallinity. For this purpose, the solid catalyst for propylene polymerization should be designed to exhibit high stereoregularity.

In the polymerization of olefins such as propylene, a solid catalyst containing magnesium, titanium, an electron donor and a halogen as essential components is known, and an olefin is obtained by using a catalyst system composed of the solid catalyst, an organoaluminum compound and an organosilicon compound. Many methods have been proposed for polymerizing or copolymerizing the solvents. However, this method is not satisfactory enough to obtain high stereoregular polymers in high yield, and improvements are required in this respect.

In propylene polymerization catalysts, activity is one of the most basic and important properties. If the activity is high, a small amount of the catalyst can be used, thereby reducing the production cost and reducing the residual amount of volatile substances such as metal catalyst residues such as magnesium, titanium, halogen, and hexane used for the catalyst injection.

As described above, in the propylene polymerization, a diester of an aromatic dicarboxylic acid is used as an internal electron donor in order to lower the cost by increasing the catalytic activity and to improve the physical properties of the polymer by improving the catalytic performance such as stereoregularity. Methods are well known and patents have been filed. US Pat. No. 4,562,173, US Pat. No. 4,981,930, and the like can be exemplified, and the above patents use a aromatic dialkyl diester or an aromatic monoalkyl monoester to produce a catalyst that expresses high activity and high stereoregularity. It introduces.

However, diester compounds of aromatic dicarboxylic acids, such as those used in the above patents, may have adverse effects on humans and ecosystems such as infertility in humans, growth disorders, malformations, and cancer, even in very small amounts. It is known as an environmental hormone substance. Therefore, in recent years, the production of polypropylene for use in food packaging containers and the like, there is a demand for using an environmentally friendly material as an internal electron donor. In addition, the method of the above patents is not satisfactory enough to obtain high stereoregular polymers in high yield and requires improvement.

On the other hand, in addition to the alkyl ester as described above as an internal electron donor, a catalyst using a non-aromatic diester material (Korean Patent No. 0491387) and a non-aromatic material having both a ketone and an ether functional group (Korean Patent No. 0572616) Methods are known. However, both methods have room for significant improvement in terms of both activity and stereoregularity.

The present invention has been made to solve the above problems, an object of the present invention is a solid catalyst for propylene polymerization that can produce a polypropylene excellent in stereoregularity with high yield without containing environmentally harmful substances It is to provide a method for producing.

In order to solve the above problems, the present invention provides a method for producing a solid catalyst for propylene polymerization, comprising the following steps:

(1) reacting the magnesium compound with titanium halide in the presence of an organic solvent;

(2) reacting the resultant of step (1) with at least one selected from dicarboxylate compounds represented by the following general formula (II) as an internal electron donor,

‥‥‥ (II)

‥‥‥ (II)

Wherein R is a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms and n is a natural number of 1 to 6; And

(3) reacting the product of step (2) with titanium halide and washing the product.

As the organic solvent used in the step (1), there is no particular limitation to the kind, and aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like having 6 to 12 carbon atoms may be used, more preferably saturated aliphatic having 7 to 10 carbon atoms. Or aromatic hydrocarbons or halogenated hydrocarbons, and specific examples thereof may be used alone or in combination of one or more selected from octane, nonane, decane, toluene and xylene, chlorobutane, chlorohexane, chloroheptane and the like. have.

As the magnesium compound used as the carrier in step (1), dialkoxy magnesium, magnesium alkyl carbonates such as magnesium ethyl carbonate, and magnesium chloride in a solid state and a solution state may be used, in particular dialkoxy magnesium is preferably used. . Diaalkoxy magnesium is spherical particles having an average particle diameter of 10 to 200 µm and a smooth surface obtained by reacting metal magnesium with anhydrous alcohol in the presence of a reaction initiator such as magnesium chloride, for example, the spherical particle shape is propylene. It is preferable to maintain it as it is, even if it is superposition | polymerization, but when the said average particle diameter is less than 10 micrometers, it is unpreferable because the fine particle of the manufactured catalyst increases, and when it exceeds 200 micrometers, apparent density tends to become small and it is unpreferable.

In addition, the use ratio of the organic solvent to the magnesium compound is preferably 1: 5 to 50, more preferably 1: 7 to 20, in terms of magnesium compound weight: organic solvent volume. If it is less than 1, the viscosity of the slurry is rapidly increased to make it difficult to uniformly stir, and if it is more than 1:50, the apparent density of the resulting carrier is rapidly decreased or the surface of the particles is rough, which is not preferable.

The titanium halide used in step (1) of the solid catalyst preparation process is preferably represented by the following general formula (I):

Ti (OR) _a X _(4-a) ‥‥‥ (I)

Here, R is an alkyl group of 1 to 10 carbon atoms, X is a halogen element, a is for matching the valence of the general formula (I), and is an integer of 0 to 3. Especially as said titanium halide, it is preferable to use titanium tetrachloride.

The reaction in step (1) of the solid catalyst preparation process is preferably performed by slowly adding titanium halide in a state in which a magnesium compound is suspended in an organic solvent at a temperature range of -20 to 50 ° C.

The amount of the titanium halide used in the step (1) is preferably 0.1 to 10 moles, more preferably 0.3 to 2 moles with respect to 1 mole of the magnesium compound. When the amount is less than 0.1 mole, the reaction of changing the magnesium compound into the magnesium halide is smooth. It is not preferable because it does not proceed, and exceeding 10 moles is not preferable because excessively many titanium components are present in the catalyst.

In the process for producing a solid catalyst for propylene polymerization, a dicarboxylate compound represented by the following general formula (II) may be used as the internal electron donor used in the step (2).

‥‥‥ (II)

‥‥‥ (II)

Here, R is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and n is a natural number of 1 to 6 carbon atoms.

Examples of the internal electron donor represented by the general formula (II) include dimethyl-1,1-cyclopropane dicarboxylate, diethyl-1,1-cyclopropane dicarboxylate, dipropyl-1,1- Cyclopropane dicarboxylate, diisopropyl-1,1-cyclopropane dicarboxylate, dibutyl-1,1-cyclopropane dicarboxylate, diisobutyl-1,1-cyclopropane dicarboxylate , Dibutyl-1,1-cyclopropane dicarboxylate, dioctyl-1,1-cyclopropane dicarboxylate, dimethyl-1,1-cyclobutane dicarboxylate, diethyl-1,1- Cyclobutane dicarboxylate, dipropyl-1,1-cyclobutane dicarboxylate, diisopropyl-1,1-cyclobutane dicarboxylate, dibutyl-1,1-cyclobutane dicarboxylate, Diisobutyl-1,1-cyclobutane dicarboxylate, dietary butyl-1,1-cyclobutane dicarboxylate, di Tyl-1,1-cyclobutane dicarboxylate, dimethyl-1,1-cyclopentane dicarboxylate, diethyl-1,1-cyclopentane dicarboxylate, dipropyl-1,1-cyclopentane dicaca Leboxylate, Diisopropyl-1,1-cyclopentane dicarboxylate, Dibutyl-1,1-cyclopentane dicarboxylate, Diisobutyl-1,1-cyclopentane dicarboxylate, dietary Butyl-1,1-cyclopentane dicarboxylate, dioctyl-1,1-cyclopentane dicarboxylate, dimethyl-1,1-cyclohexane dicarboxylate, diethyl-1,1-cyclohexane dicarboxylic acid Carboxylate, dipropyl-1,1-cyclohexane dicarboxylate, diisopropyl-1,1-cyclohexane dicarboxylate, dibutyl-1,1-cyclohexane dicarboxylate, diisobutyl -1,1-cyclohexane dicarboxylate, dietary butyl-1,1-cyclohexane dicarboxylate, dioctyl-1,1-cyclohexane dicarboxylate, Dimethyl-1,1-cycloheptane dicarboxylate, diethyl-1,1-cycloheptane dicarboxylate, dipropyl-1,1-cycloheptane dicarboxylate, diisopropyl-1,1-cyclo Heptane dicarboxylate, dibutyl-1,1-cycloheptane dicarboxylate, diisobutyl-1,1-cycloheptane dicarboxylate, dietarybutyl-1,1-cycloheptane dicarboxylate, Dioctyl-1,1-cycloheptane dicarboxylate, dimethyl-1,1-cyclooctane dicarboxylate, diethyl-1,1-cyclooctane dicarboxylate, dipropyl-1,1-cyclooctane Dicarboxylate, diisopropyl-1,1-cyclooctane dicarboxylate, dibutyl-1,1-cyclooctane dicarboxylate, diisobutyl-1,1-cyclooctane dicarboxylate, dieter Sherylbutyl-1,1-cyclooctane dicarboxylate, dioctyl-1,1-cyclooctane dicarboxylate, and the like. Can be used in combination.

The step (2) is preferably carried out by reacting for 1 to 3 hours by adding an internal electron donor during the temperature increase process while gradually increasing the temperature of the resultant of step (1) to 80 ~ 130 ℃, the temperature is If the reaction time is less than 80 ° C. or less than 1 hour, the reaction is difficult to complete. If the temperature exceeds 130 ° C. or the reaction time is more than 3 hours, the polymerization reaction of the resulting catalyst or the stereoregularity of the polymer may be lowered by side reactions. Can be.

As long as the internal electron donor is introduced during the temperature raising process, the temperature and the number of times of the internal electron donor are not particularly limited, and the total amount of the internal electron donor is 0.01 to 1.0 mol based on 1 mol of the magnesium compound used. It is preferable that the polymerization activity of the resulting catalyst or the stereoregularity of the polymer be lowered outside the above range, which is undesirable.

Step (3) of the process for preparing a solid catalyst for propylene polymerization is a step of secondary reaction between the product of step (2) and titanium halide, it is preferably carried out at a temperature of 80 ~ 130 ℃. The titanium halide of the general formula (I) may be used as the titanium halide to be used.

In the process for producing a solid catalyst for propylene polymerization of the present invention, the reaction in each step is preferably carried out in a reactor equipped with a stirrer in which water and the like are sufficiently removed in a nitrogen gas atmosphere.

The solid catalyst prepared by the above steps is made of magnesium, titanium, halogen and internal electron donor, considering the catalytic activity, 5 to 40% by weight magnesium, 0.5 to 10% by weight titanium , 50 to 85% by weight of halogen and 0.1 to 30% by weight of the internal electron donor is preferable.

The solid catalyst prepared by the catalyst preparation method of the present invention may be suitably used in the propylene polymerization or copolymerization method, and the propylene polymerization or copolymerization method using the solid catalyst prepared according to the present invention may be used for the solid catalyst, the promoter and the external Polymerizing propylene in the presence of a donor or copolymerizing propylene with other alphaolefins.

The solid catalyst may be prepolymerized with ethylene or alpha olefin before being used as a component of the polymerization reaction.

The prepolymerization reaction can be carried out in the presence of a hydrocarbon solvent (eg hexane), the catalyst component and an organoaluminum compound (eg triethylaluminum) at sufficiently low temperatures and ethylene or alphaolefin pressure conditions. Prepolymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape. The weight ratio of polymer / catalyst after prepolymerization is preferably about 0.1 to 20: 1.

In the propylene polymerization or copolymerization method, an organometallic compound of Group II or Group III of the periodic table may be used as the cocatalyst component. As an example, preferably, an alkylaluminum compound is used. The alkylaluminum compound is represented by general formula (III):

AlR ₃ ‥‥‥ (III)

Here, R is a C1-C8 alkyl group.

Specific examples of the alkyl aluminum compound include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, trioctyl aluminum and the like.

The ratio of the promoter component to the solid catalyst component is somewhat different depending on the polymerization method, but the molar ratio of aluminum atoms in the promoter component to titanium atoms in the solid catalyst component is preferably in the range of 1 to 1000, More preferably, it is good that it is the range of 10-300. If the molar ratio of aluminum atoms in the cocatalyst component to titanium atoms in the solid catalyst component is outside the range of 1 to 1000, there is a problem that the polymerization activity is greatly reduced.

In the propylene polymerization or copolymerization method, at least one of the alkoxysilane compounds represented by the following general formula (IV) may be used as the external electron donor:

R ¹ _m R ² _n Si (OR ³ ) _(4-mn) ‥‥‥ (IV)

Here, R ¹ , R ² may be the same or different, a linear or branched or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group, R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms, m and n are 0 or 1, respectively, and m + n is 1 or 2, respectively.

Specific examples of the external electron donor include normal propyl trimethoxy silane, dinormal propyl dimethoxy silane, isopropyl trimethoxy silane, diisopropyl dimethoxy silane, normal butyl trimethoxy silane and di normal butyl dimethoxy Silane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, tertiarybutyltrimethoxysilane, dietarybutyldimethoxysilane, normalpentyltrimethoxysilane, dinormalpentyldimethoxysilane, cyclopentyltrimethoxy Silane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane , Cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane, cycloheptyl Methyldimethoxysilane, cycloheptylethyldimethoxysilane, cycloheptylpropyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, normal Propyltriethoxysilane, dinormalyl diethoxysilane, isopropyltriethoxysilane, diisopropyl diethoxysilane, normal butyl triethoxysilane, dinormal butyl diethoxysilane, isobutyl triethoxysilane, diisobutyl Diethoxysilane, tertiary butyl triethoxysilane, dietary butyl diethoxy silane, normal pentyl triethoxy silane, dinomal pentyl diethoxy silane, cyclopentyl triethoxy silane, dicyclopentyl diethoxy silane, cyclopentyl methyl Diethoxysilane, cyclopentylethyl diethoxysilane, cyclopentylpropyl diethoxysilane, cyclohexyl triethoxysilane, dicyclohexyl diethoxysilane , Cyclohexyl methyl diethoxy silane, cyclohexyl ethyl diethoxy silane, cyclohexyl propyl diethoxy silane, cycloheptyl triethoxy silane, dicycloheptyl diethoxy silane, cycloheptyl methyl diethoxy silane, cycloheptyl ethyl diethoxy silane, Cycloheptylpropyl diethoxysilane, phenyltriethoxysilane, diphenyl diethoxysilane, phenylmethyl diethoxysilane, phenylethyl diethoxysilane, and phenylpropyl diethoxysilane, and the like. Can be.

The amount of the external electron donor to the solid catalyst varies slightly depending on the polymerization method, but the molar ratio of the silicon atom in the external electron donor to the titanium atom in the catalyst component is preferably in the range of 0.1 to 500, 1 to 100 It is more preferable that it is the range of. If the molar ratio of silicon atoms in the external electron donor to the titanium atoms in the solid catalyst component is less than 0.1, the stereoregularity of the resulting propylene polymer is significantly lowered, and if it exceeds 500, the polymerization activity of the catalyst is significantly lowered. There is this.

In the above propylene polymerization or copolymerization method, it is preferable that the temperature of the polymerization reaction is 20 to 120 ° C. It is not preferable because the deterioration is severe and adversely affects the polymer physical properties.

By using the solid catalyst for propylene polymerization prepared by the method of the present invention, it is possible to polymerize polypropylene having excellent stereoregularity with high yield without containing environmentally harmful substances.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these examples are for illustrative purposes only, and the present invention is not limited to these examples.

[ Example ]

Example  One

[Production of Solid Catalyst]

Into a glass reactor equipped with a 1 liter stirrer sufficiently substituted with nitrogen, 150 ml of toluene and 20 g of diethoxy magnesium (a sphere having an average particle diameter of 20 µm, having a particle size distribution index of 0.86 and an apparent density of 0.35 g / cc) were charged. And maintained at 10 ° C. After diluting 40 ml of titanium tetrachloride in 60 ml of toluene 투입 and injecting it over 1 hour, 4.5 g of diethyl-1,1-cyclobutane dicarboxylate was injected while raising the temperature of the reactor to 110 ° C. After holding at 110 ° C. for 2 hours, the temperature was lowered to 90 ° C. to stop stirring, the supernatant was removed, and further washed once with 200 ml of toluene.

150 ml of toluene and 50 ml of titanium tetrachloride were added thereto, and the temperature was raised to 110 ° C. and maintained for 2 hours. After completion of the aging process, the slurry mixture was washed twice with 200 ml of toluene per second, and washed five times with 200 ml each time with normal hexane at 40 ° C. to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by drying for 18 hours in flowing nitrogen was 3.0% by weight.

[Polypropylene Polymerization]

10 mg of the solid catalyst, 6.6 mmol of triethylaluminum, and 0.66 mmol of cyclohexylmethyldimethoxysilane were charged into a 4 liter high-pressure stainless steel reactor. Subsequently, 1000 ml of hydrogen and 2.4 L of propylene in a liquid state were added sequentially, followed by polymerization at a temperature of up to 70 ° C. After 2 hours from the start of the polymerization, the valve was opened while lowering the temperature of the reactor to room temperature to completely degas the propylene inside the reactor.

Catalytic activity and stereoregularity were analyzed for the obtained propylene polymer, and the results are shown in Table 1.

Here, polymerization activity and stereoregularity were determined by the following method.

① polymerization activity (kg-PP / g-catalyst) = amount of polymer produced per hour (kg) ÷ catalyst (g)

② Stereoregularity (XI) (% by weight): In 100% of the polymer, the weight% of the insoluble component that is crystallized and precipitated in the mixed xylene

Example 2

In the preparation of the solid catalyst of Example 1, 3.1 g of diethyl-1,1-cyclopropane dicarboxylate was used instead of 4.5 g of diethyl-1,1-cyclobutane dicarboxylate. Then, a solid catalyst was prepared in the same manner as in Example 1. The titanium content in the solid catalyst component was 3.3% by weight.

Thereafter, polypropylene polymerization was carried out in the same manner as in Example 1, and the polymerization activity and stereoregularity of the obtained propylene polymer were analyzed, and the results are shown in Table 1.

Example 3

In the preparation of the solid catalyst of Example 1, except that 4.5 g of diethyl-1,1-cyclohexane dicarboxylate was used instead of 4.5 g of diethyl-1,1-cyclobutane dicarboxylate. Then, a solid catalyst was prepared in the same manner as in Example 1. The titanium content in the solid catalyst component was 2.6% by weight.

Thereafter, polypropylene polymerization was carried out in the same manner as in Example 1, and the polymerization activity and stereoregularity of the obtained propylene polymer were analyzed, and the results are shown in Table 1.

Example 4

In the preparation of the solid catalyst of Example 1, except that 4.8 g of dibutyl-1,1-cyclohexane dicarboxylate was used instead of 4.5 g of diethyl-1,1-cyclobutane dicarboxylate. Then, a solid catalyst was prepared in the same manner as in Example 1. The titanium content in the solid catalyst component was 3.1% by weight.

Thereafter, polypropylene polymerization was carried out in the same manner as in Example 1, and the polymerization activity and stereoregularity of the obtained propylene polymer were analyzed, and the results are shown in Table 1.

Example 5

In the [polypropylene polymerization] step of Example 1, a propylene polymer was prepared in the same manner as in Example 1, except that dicyclopentyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. The obtained propylene polymer was analyzed for polymerization activity and stereoregularity, and the results are shown in Table 1.

Comparative Example 1

[Production of Solid Catalyst]

150 ml of toluene, 12 ml of tetrahydrofuran, 20 ml of butanol, and 21 g of magnesium chloride were added to a glass reactor equipped with a 1 liter stirrer sufficiently substituted with nitrogen, heated to 110 ° C., and maintained for 1 hour to obtain a homogeneous solution. The temperature of the solution was cooled to 15 ° C., titanium tetrachloride 25 ml was added, and the temperature of the reactor was raised at 60 ° C. over 1 hour. After aging for 10 minutes, the mixture was left for 15 minutes to settle the carrier, and the upper solution was removed. It was. 200 ml of toluene was added to the slurry remaining in the reactor and washed twice by stirring, standing, and removing the supernatant.

After injecting 150 ml of toluene into the slurry thus obtained, 25 ml of titanium tetrachloride was diluted in 50 ml of toluene at 15 ° C, and charged over 1 hour, and then the reactor temperature was raised to 30 ° C at a rate of 0.5 ° C per minute. The reaction mixture was kept at 30 ° C. for 1 hour, after which 7.5 ml of diisobutyl phthalate was injected, and the temperature was further raised to 110 ° C. at a rate of 0.5 ° C. per minute.

After maintaining at 110 ° C. for 1 hour, the temperature was lowered to 90 ° C. to stop stirring, the supernatant was removed, and further washed once using the same method using 200 ml of toluene. 150 ml of toluene and 50 ml of titanium tetrachloride were added thereto, the temperature was raised to 110 ° C., and maintained for 1 hour. After the aging process, the slurry mixture was washed twice with 200 ml of toluene per second, and washed 5 times with 200 ml each time with hexane at 40 ° C. to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by drying for 18 hours in flowing nitrogen was 3.3% by weight.

[Polypropylene Polymerization]

Except for using 10 mg of the solid catalyst prepared as described above, propylene polymerization was carried out in the same manner as in Example 1, and the polymerization activity and stereoregularity of the obtained propylene polymer were analyzed, and the results are shown in Table 1. It was.

Comparative Example 2

In the preparation of the solid catalyst of Example 1, 2.7 g of diethyl malonate was used instead of 4.5 g of diethyl-1,1-cyclobutane dicarboxylate in the same manner as in Example 1. Catalyst was prepared. The titanium content in the obtained solid catalyst component was 3.9 weight%.

Thereafter, polypropylene polymerization was carried out in the same manner as in Example 1, and the polymerization activity and stereoregularity of the obtained propylene polymer were analyzed, and the results are shown in Table 1.

Polymerization activity (kg-PP / g-catalyst) Stereoregularity (X.I., wt%) Example 1 42.0 96.0 Example 2 46.5 95.6 Example 3 28.8 97.1 Example 4 34.7 96.8 Example 5 47.2 97.6 Comparative Example 1 26.0 97.3 Comparative Example 2 11.0 89.0

As shown in Table 1, Examples 1 to 4 using the internal electron donor of the general formula II according to the present invention, while environmentally friendly, excellent in both stereoregularity and polymerization activity, the existing dialkyl ester internal electron donor Comparative Example 1 using is not environmentally friendly, very poor in activity, non-aromatic and environmentally friendly, but Comparative Example 2 using an internal electron donor that does not correspond to the general formula II of the present invention, both activity and stereoregularity greatly It can be seen that it is inferior.

Claims (5)

A process for preparing a solid catalyst for propylene polymerization, comprising the following steps:
(1) reacting the magnesium compound with titanium halide in the presence of an organic solvent;
(2) reacting the resultant of step (1) with at least one selected from dicarboxylate compounds represented by the following general formula (II) as an internal electron donor,

‥‥‥ (II)
Wherein R is a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms and n is a natural number of 1 to 6; And
(3) reacting the product of step (2) with titanium halide and washing the product.
The method for producing a solid catalyst for propylene polymerization according to claim 1, wherein the magnesium compound is dialkoxy magnesium.
According to claim 1, wherein the reaction of step (1) is carried out at -20 ~ 50 ℃, the step (2) is carried out while increasing the temperature to 80 ~ 130 ℃, the reaction of step (3) is 80 Process for producing a solid catalyst for propylene polymerization, characterized in that carried out at a temperature of ~ 130 ℃.
The method for preparing a solid catalyst for propylene polymerization according to claim 1, wherein 0.01 to 1.0 mole of the internal electron donor is used per 1 mole of the magnesium compound.
According to claim 1, wherein the solid catalyst is 5 to 40% by weight of magnesium, 0.5 to 10% by weight of titanium, 50 to 85% by weight of halogen and 0.1 to 30% by weight of the internal electron donor solid for propylene polymerization Method for preparing a catalyst.