KR102544797B1 - A solid catalyst for polymerizing olefin comprising novel internal electron donors and a preparation method for the same - Google Patents

Abstract

The present invention relates to a solid catalyst for olefin polymerization containing a novel internal electron donor and a method for preparing the same. An olefin polymer having excellent physical properties such as density can be provided in high yield.

Description

A solid catalyst for olefin polymerization containing a novel internal electron donor and a method for preparing the same

The present invention relates to a novel solid catalyst for olefin polymerization containing an internal electron donor and a method for preparing the same, and more particularly, to a solid catalyst for olefin polymerization that exhibits activity equal to or higher than that of conventional solid catalysts for olefin polymerization and has excellent polymerization efficiency during olefin polymerization. It relates to a solid catalyst for olefin polymerization, a method for preparing the same, and a method for preparing an olefin polymer having excellent physical properties in high yield using the same.

Polyolefins are a class of polymers derived from simple olefins, and are widely used as very useful materials in real life and commercially.

A known process for producing polyolefins involves the use of Ziegler-Natta polymerization catalysts, which polymerize vinyl monomers using transition metal halides to form highly isotactic stereochemical configurations. A polymer having In order to obtain a polymer with desired physical properties, the role of a polymerization catalyst is most important, and in particular, the design of the catalyst system should be accompanied to improve the stereoregularity of the resulting polymer and to satisfy high copolymerizability with alpha olefins. In addition, for economic efficiency in polymer production, the higher the polymerization activity of the catalyst, the more advantageous it is.

In general, a catalyst system used for polymerization of olefins is composed of a Ziegler-Natta catalyst component, aluminum alkyl, and an external electron donor. These catalytic components are known as solid catalysts containing magnesium, titanium, and internal electron donors and halogens as essential components. In particular, internal electron donors have a significant effect on the activity of the catalyst and the stereoregularity of the resulting polymer depending on the molecular structure. It is known.

Korean Patent Registration No. 10-1930165, which uses a phthalate compound as an internal electron donor, in order to lower the cost and improve the physical properties of the polymer such as stereoregularity by improving the catalyst performance through this increase in catalytic activity, Korean Patent No. 10-1930165, aromatic dicarboxylic acid U.S. Patent No. 4,562,173 and the like which use diesters of acids are disclosed.

However, in the case of conventionally used internal electron donors, they are inferior in terms of activity and stereoregularity and require improvement, or even in extremely small amounts, they cause human and ecological problems such as reduced human reproductive function, growth disorder, deformity, and cancer. Because it is an environmental hormone substance that can have a bad effect, there was a disadvantage that caution should be exercised when using it.

On the other hand, the above-mentioned background art is technical information that the inventor possessed for derivation of the present invention or acquired in the process of derivation of the present invention, and cannot necessarily be said to be known art disclosed to the general public prior to filing the present invention. .

Korean Patent Registration No. 10-1930165 US Patent No. 4,562,173

The present invention was devised (described) as a result of research on "development of internal electron donors for polypropylene polymerization catalysts", and an object of the present invention is to provide a solid catalyst for olefin polymerization containing a novel internal electron donor, a method for preparing the same, and using the same It is to provide a method for producing an olefin polymer.

The present invention is to solve the above problems, and an object of the present invention is to provide a solid catalyst for olefin polymerization containing a novel internal electron donor, a method for preparing the same, and a method for preparing an olefin polymer using the same.

The above and other objects and advantages of the present invention will become apparent from the following description of preferred embodiments.

The purpose is

titanium,

magnesium,

halogen, and

It can be solved by a solid catalyst for olefin polymerization comprising an internal electron donor compound represented by the following formula (I).

[Formula I]

In the above formula I,

R ₁ is hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms;

R ₂ is hydrogen, a linear or branched alkyl group of 1 to 8 carbon atoms, or -OR ₄ ;

R ₃ is hydrogen or -OR ₅ ;

R ₄ and R ₅ are each hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms.

In addition, the above object can be solved by a method for producing an olefin polymer, characterized in that olefin polymerization is carried out using the solid catalyst for olefin polymerization.

In addition, the above object can be solved by a method for preparing a solid catalyst for olefin polymerization comprising the following steps.

(1) stirring at a speed of 100 rpm to 200 rpm after adding diethoxy magnesium to an organic solvent;

(2) adding titanium tetrachloride (TiCl ₄ ) to the solution of step (1) at a temperature of 0° C. to 10° C.;

(3) A compound represented by the following formula (I) was added to the product of step (2) heated to 80℃ to 100℃ in a molar ratio of the compound of formula (I):magnesium = 0.1 to 1:1, and the temperature was increased to 100℃ to 120℃. Stirring for 1 hour to 3 hours in

[Formula I]

(Description of Formula I is as described above); and

(4) Obtaining a solid catalyst for olefin polymerization by reacting the product of step (3) with titanium tetrachloride (TiCl ₄ ) at a temperature of 80 ° C to 100 ° C and washing it with an organic solvent.

According to the present invention, a solid catalyst for olefin polymerization containing a novel internal electron donor and a method for preparing the same are provided, which has an effect of having excellent activity equal to or higher than that of conventional solid catalysts.

According to the present invention, it has an effect of providing an olefin polymer having excellent physical properties such as stereoregularity and bulk density in high yield.

According to the present invention, it has an effect of providing an environmentally friendly solid catalyst for olefin polymerization including an internal electron donor.

However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

1 is a ¹ H-NMR analysis result for the compound of Preparation Example 1.
Figure 2 is a ¹ H-NMR analysis result for the compound of Preparation Example 2.
3 is a ¹ H-NMR analysis result for the compound of Preparation Example 3.
4 is a result of ¹ H-NMR analysis of the compound of Preparation Example 4.
5 is a result of ¹ H-NMR analysis of the compound of Preparation Example 5.
6 is a ¹ H-NMR analysis result for the compound of Preparation Example 6.
7 is a ¹ H-NMR analysis result for the compound of Preparation Example 7.
8 is a ¹ H-NMR analysis result for the compound of Preparation Example 8.
9 is a result of ¹ H-NMR analysis of the compound of Preparation Example 9.

Hereinafter, the present invention will be described in detail with reference to examples of the present invention. These examples are only presented as examples to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

In addition, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art to which this invention belongs, and in case of conflict, this specification including definitions of will take precedence.

When a certain component is said to "include", this means that it may further include other components, not excluding other components unless otherwise stated.

In order to clearly explain the proposed invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification. And, when a certain component is said to "include", this means that it may further include other components without excluding other components unless otherwise stated. Also, a “unit” described in the specification means one unit or block that performs a specific function.

In each step, the identification code (first, second, etc.) is used for convenience of description, and the identification code does not describe the order of each step, and each step does not clearly describe a specific order in context. It may be performed differently from the order specified above. That is, each step may be performed in the same order as specified, may be performed substantially simultaneously, or may be performed in the reverse order.

As used herein, the term "about" will be understood by those skilled in the art, and in cases where the use of the term is not apparent to those skilled in the art, given the context in which it is used, "about" is the maximum ± That would mean 10%.

As used herein, the term "alkyl group" includes straight-chain and branched alkyl groups, and may include both substituted or unsubstituted alkyl groups. An alkyl group may be substituted one or more times. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, tert-butyl, neopentyl, and isopentyl groups, and the like. Representative substituted alkyl groups may be substituted one or more times with, for example, amino, thio, hydroxy, cyano, alkoxy, and/or halo groups such as F, Cl, Br, and I groups.

A solid catalyst for olefin polymerization according to an embodiment of the present invention may include titanium, magnesium, halogen, and an internal electron donor compound represented by Formula I below.

[Formula I]

In the above formula I,

R ₁ is hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms;

R ₂ is hydrogen, a linear or branched alkyl group of 1 to 8 carbon atoms, or -OR ₄ ;

R ₃ is hydrogen or -OR ₅ ;

R ₄ and R ₅ are each hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms.

In one embodiment of the present invention,

R ₁ may be, but is not limited to, a methyl group.

R ₂ is a methyl group or -OR ₄ , and R ₄ may be, but is not limited to, a methyl, ethyl, propyl or butyl group.

R ₃ may be hydrogen or an -OCH ₃ group, but is not limited thereto.

In one embodiment of the present invention,

R ₁ is a methyl group, R ₂ is a methyl group or -OR ₄ , R ₄ is a methyl, ethyl, propyl or butyl group, R ₃ may be hydrogen or an -OCH ₃ group, but is not limited thereto.

In one embodiment of the present invention,

The compound of Formula I may be one or more selected from the group consisting of the following compounds, but is not limited thereto.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

및

and

[Formula 9]

A method for preparing a solid catalyst for olefin polymerization according to an embodiment of the present invention may include the following steps.

(1) stirring at a speed of 100 rpm to 200 rpm after adding diethoxy magnesium to an organic solvent;

(2) adding titanium tetrachloride (TiCl ₄ ) to the solution of step (1) at a temperature of 0° C. to 10° C.;

(3) A compound represented by the following formula (I) was added to the product of step (2) heated to 80℃ to 100℃ in a molar ratio of the compound of formula (I):magnesium = 0.1 to 1:1, and the temperature was increased to 100℃ to 120℃. Stirring for 1 hour to 3 hours in

[Formula I]

In the above formula I,

R ₁ is hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms;

R ₂ is hydrogen, a linear or branched alkyl group of 1 to 8 carbon atoms, or -OR ₄ ;

R ₃ is hydrogen or -OR ₅ ;

R ₄ and R ₅ are each hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms; and

(4) Obtaining a solid catalyst for olefin polymerization by reacting the product of step (3) with titanium tetrachloride (TiCl ₄ ) at a temperature of 80 ° C to 100 ° C and washing it with an organic solvent.

In the method for preparing the solid catalyst specified above, diethoxymagnesium used in step (1) is spherical particles having an average particle diameter of 10 to 200 μm and a smooth surface obtained by reacting metallic magnesium with anhydrous alcohol in the presence of magnesium chloride. As, the spherical particle shape is preferably maintained even during the polymerization of propylene. If the average particle diameter is less than 10 μm, the fine particles of the prepared catalyst are undesirably increased, and if it exceeds 200 μm, the apparent density is small It is difficult to have a uniform particle shape when preparing a high-catalyst, which is not preferable.

As the organic solvent used in the step (1), there is no particular limitation on its type, and aliphatic hydrocarbons having 6 to 12 carbon atoms, aromatic hydrocarbons, halogenated hydrocarbons, etc. may be used, and more preferably saturated aliphatic hydrocarbons having 7 to 10 carbon atoms. Hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons may be used, and specific examples thereof may be a mixture of at least one selected from heptane, octane, nonane, decane, toluene, xylene, chlorohexane, and chloroheptane. More preferably, it may be toluene, but is not limited thereto.

In addition, the use ratio of the organic solvent to the diethoxymagnesium is preferably 1:3 to 1:30, preferably 1:10 to 1:20, in terms of diethoxymagnesium weight (g): organic solvent volume (mL) More preferably, if the ratio is less than 1:3, it is difficult to uniformly stir, and if it exceeds 1:30, the surface of the particles produced is not smooth.

In step (1), the stirring speed may be 100 rpm to 200 rpm, more preferably 150 rpm to 200 rpm. When the stirring speed is 100 rpm or less, sufficient stirring is not achieved, and when the stirring speed exceeds 200 rpm, target particles are caused by excessive stirring. It is undesirable because the size cannot be obtained.

In step (2), titanium tetrachloride (TiCl ₄ ) should be slowly added to the solution in step (1), which is preferably carried out at a temperature of 0 ° C to 10 ° C, and carried out at a temperature of 0 ° C to 5 ° C. it is more preferable

In the step (3), the compound represented by the following formula (I) is added to the product of step (2), preferably heated to 80 ° C. to 100 ° C., the compound of formula I: magnesium = 0.1 to 1: 1, preferably 0.1 to 0.5: It may be added in a molar ratio of 1 and stirred for 1 hour to 3 hours at 100 ℃ to 120 ℃.

In one embodiment of the present invention,

R ₁ may be, but is not limited to, a methyl group.

R ₂ is a methyl group or -OR ₄ , and R ₄ may be, but is not limited to, a methyl, ethyl, propyl or butyl group.

R ₃ may be hydrogen or an -OCH ₃ group, but is not limited thereto.

In one embodiment of the present invention,

R ₁ is a methyl group, R ₂ is a methyl group or -OR ₄ , R ₄ is a methyl, ethyl, propyl or butyl group, R ₃ may be hydrogen or an -OCH ₃ group, but is not limited thereto.

In one embodiment of the present invention,

The compound of Formula I may be one or more selected from the group consisting of compounds represented by Formulas 1 to 9, but is not limited thereto.

In step (4), a solid catalyst for olefin polymerization can be obtained by reacting the product of step (3) with titanium tetrachloride (TiCl ₄ ) at a temperature of 80 ° C to 100 ° C and washing it with an organic solvent.

When the temperature is less than 80 ° C, the reaction is difficult to complete, and when the temperature exceeds 100 ° C, a side reaction occurs and the yield of the obtained catalyst may be lowered.

As the organic solvent, the type is not particularly limited, and aliphatic hydrocarbons and aromatic hydrocarbons having 6 to 12 carbon atoms, halogenated hydrocarbons, etc. may be used, and more preferably saturated aliphatic hydrocarbons or aromatic hydrocarbons having 6 to 10 carbon atoms, halogenated hydrocarbons, etc. May be used, and specific examples thereof may be a mixture of one or more selected from hexane, heptane, octane, nonane, decane, toluene, xylene, chlorohexane, chloroheptane, and the like. More preferably, it may be hexane, but is not limited thereto.

In the method for producing a solid catalyst, the reaction in each step is preferably carried out in a nitrogen atmosphere in a reactor equipped with an agitator from which moisture is sufficiently removed.

The solid catalyst prepared according to the present invention can be used for olefin polymerization, and the method for preparing an olefin polymer according to an embodiment of the present invention is to polymerize olefins using the solid catalyst for olefin polymerization prepared according to the present invention. may include Polymerization of olefins may include being performed in the presence of the solid catalyst and, if necessary, a cocatalyst and an external electron donor.

In one embodiment of the present invention,

The olefin may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene, and is preferably at least one selected from the group consisting of ethylene and propylene, It is more preferably propylene, but is not limited thereto.

In one embodiment of the present invention, the cocatalyst may be an organometallic compound of Group II or Group III of the periodic table, and for example, an alkylaluminum compound may be preferably used.

In one embodiment of the present invention, the external electron donor includes normal propyltrimethoxysilane, dinormalpropyldimethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, and normalbutyltrimethoxysilane. , dinormalbutyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, tertiarybutyltrimethoxysilane, ditertiarybutyldimethoxysilane, normalpentyltrimethoxysilane, dinormalpentyldimethoxysilane , Cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, Cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane, cycloheptylmethyldimethoxysilane, cycloheptylethyldimethoxysilane, cyclo Heptylpropyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, normalpropyltriethoxysilane, dinormalpropyldiethoxysilane, Isopropyltriethoxysilane, diisopropyldiethoxysilane, normalbutyltriethoxysilane, dinormalbutyldiethoxysilane, isobutyltriethoxysilane, diisobutyldiethoxysilane, tertiarybutyltriethoxysilane, diter Shiributyldiethoxysilane, normalpentyltriethoxysilane, dinormalpentyldiethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl Propyldiethoxysilane, cyclohexyltriethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylpropyldiethoxysilane, cycloheptyltriethoxysilane, dicycloheptyl diethoxysilane, cycloheptylmethyldiethoxysilane, cycloheptylethyldiethoxysilane, cycloheptylpropyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, phenylethyldiethoxysilane and phenyl propyl diethoxysilane and the like, and one or more of these may be used alone or in combination.

In the olefin polymerization, the temperature of the polymerization reaction is preferably 30 ° C to 150 ° C, and preferably 50 ° C to 90 ° C. , If the temperature exceeds 150 ° C., the activity is severely lowered, and it is not preferable because it adversely affects the physical properties of the polymer.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through specific examples. However, these examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

(Example)

Preparation Examples 1 to 3. Preparation of Internal Electron Donor

Under a nitrogen atmosphere, 20 mmol of 2-methoxybenzoic acid was dissolved using 60 mL of tetrahydrofuran anhydride (THF anhydrous). After adding 50 mmol of triethylamine (TEA) thereto, the mixture was cooled to 0 °C. After adding 50 mmol of methyl chloroformate, ethyl chloroformate or isobutylchloroformate, the mixture was stirred at room temperature for 3 hours. The resulting salt (NH (Et) ₂ Cl salt form of the compounds of Formulas 1 to 3) was filtered under reduced pressure, and the solvent was removed using a rotary evaporator. The crude product obtained through the above process (crude) product) was sufficiently washed with distilled water to obtain the compounds of Preparation Examples 1 to 3 (represented by Formulas 1 to 3, respectively) (Yield: Compound of Formula 1 - 92%; Compound of Formula 2 - 95%; Formula Compound of 3 - 91%)

Preparation Examples 4 to 9. Preparation of Internal Electron Donor

A step. Preparation of internal electron donor of Preparation Example 4

Under a nitrogen atmosphere, 20 mmol of 2,6-dimethoxybenzoic acid was dissolved in 60 mL of tetrahydrofuran (THF). It was cooled to -10 °C and 50 mmol of triethylamine (TEA) was added. After adding 25 mmol of acetyl chloride thereto, the mixture was stirred at room temperature for 6 hours. The resulting salt (NH(Et) ₂ Cl salt form of the compound of Formula 4) was filtered under reduced pressure, and the solvent was removed using a rotary vacuum concentrator to obtain the compound of Preparation Example 4 (represented by Formula 4) . (approximately 80% yield)

B step. Preparation of internal electron donors of Preparation Examples 5 to 8

Under a nitrogen atmosphere, 20 mmol of 2,6-dimethoxybenzoic acid was dissolved in 60 mL of tetrahydrofuran (THF). It was cooled to 0 °C, and 50 mmol of triethylamine (TEA) was added. After adding 25 mmol of methyl chloroformate, ethyl chloroformate, isopropylchloroformate or isobutylchloroformate, the mixture was stirred at room temperature for 3 hours. The resulting salt was filtered under reduced pressure, the solvent was removed using a rotary vacuum concentrator, and then purified using column chromatography (silica and ethyl acetate: hexane = 1: 4 solution used) to obtain the compounds of Preparation Examples 5 to 8 ( Represented by Formulas 5 to 8, respectively) were obtained . (Yield: compound of formula 5 - 90%; compound of formula 6 - 88%; compound of formula 7 - 91%; compound of formula 8 - 89%)

C step. Preparation of internal electron donor of Preparation Example 9

Under a nitrogen atmosphere, 20 mmol of 2,6-dimethoxybenzoic acid and 10 mol% (2 mmol) of 4-dimethylaminopyridine (DMAP) were dissolved in 60 mL of tetrahydrofuran (THF). After adding 25 mmol of di-tertbutyl dicarbonate thereto, the mixture was stirred at room temperature for 3 hours, the solvent was removed using a rotary vacuum evaporator, and extraction was performed with ethyl acetate. After washing with distilled water three times, the water was removed with magnesium sulfate. After removing magnesium sulfate by filtration under reduced pressure, the solvent was removed using a rotary vacuum evaporator, and then purified by column chromatography (silica and ethyl acetate: hexane = 1: 4 solution was used) to obtain the compound of Preparation Example 9 (represented by Formula 9) got it (Approximately 91% yield)

Example 1. Preparation of a catalyst for olefin polymerization

10 g of Mg(OEt) ₂ (Catylen® S300, manufactured by Evonik) and 140 mL of toluene were put into a 300 mL three-necked flask and stirred at 180 rpm under a nitrogen atmosphere. 20 mL of TiCl ₄ was slowly added at a temperature of 0 to 5 °C. After raising the temperature to 90 ° C., the internal electron donor prepared in Preparation Example 1 was added at a mole ratio of internal electron donor / Mg = 0.3, and then stirred at 110 ° C. for 2 hours. After washing twice with toluene at 90 °C, 20 mL of TiCl ₄ was added thereto and stirred for 2 hours. The reactant was washed 7 times with n-hexane to obtain a product catalyst.

Examples 2 to 9. Preparation of catalysts for olefin polymerization

Examples 2 to 9 were prepared in the same manner as in Example 1, except that catalysts for olefin polymerization were prepared using the internal electron donors prepared in Preparation Examples 2 to 9 instead of the internal electron donors prepared in Preparation Example 1. The catalyst of Example 9 was obtained.

Polymerization Example 1. Preparation of Polypropylene

5 mg of the solid catalyst according to Example 1, 1.3 mmol of triethylaluminum, and 0.1 mmol of dicyclopentyldimethoxysilane were put into a 2-liter high-pressure stainless reactor. Subsequently, 750 ml of hydrogen and 500 g of propylene were sequentially added thereto, and polymerization was performed by raising the temperature to 70°C. When 1 hour elapsed after the start of the polymerization, the temperature of the reactor was lowered to room temperature and the valve was opened to completely remove the propylene inside the reactor. The analysis results of the obtained polypropylene are shown in Table 1.

Polymerization Examples 2 to 9. Preparation of Polypropylene

Polypropylene was prepared in the same manner as in Polymerization Example 1, except that the solid catalysts according to Examples 2 to 9 were used instead of the solid catalysts according to Example 1.

Test Example 1. Solid Catalyst Performance and Polypropylene Characteristics Test

The test was performed on the solid catalyst produced according to the example and the polypropylene of the polymerization example polymerized using the same. Specifically, the titanium content in the catalyst, catalytic activity, bulk density of polypropylene, stereoregularity (X.S) and melting point were measured by the following methods.

(1) Titanium content in catalyst (μmol/g-cat) = number of moles of titanium / amount of catalyst (g)

(2) Catalyst activity (g-PP/g-catalyst) = amount of polypropylene produced (g)÷ amount of catalyst injected (g)

(3) Bulk Density (BD): The weight (g) of polypropylene corresponding to a volume of 100 mL divided by the volume

(4) Melt index (MI): Measured under the condition of 230 ℃, 10 minutes according to ASTM-D 1238

(5) Stereoregularity (X.S): Stereoregularity is measured by xylene solubility as follows, and is the weight percent of components dissolved in mixed xylenes in 100 g of the polymer.

(6) Tm (melting point): measured using differential scanning calorimetry (DSC)

compound name Titanium content in the catalyst ¹ Catalytic activity ² BD ³ MI ⁴ XS ⁵ Tm ⁶ Preparation Example 1
(Polymerization example 1) (methylcarbonic) 2-methoxybenzoic anhydride 1007.5 20 0.28 15 4 160.3 Production Example 2 (Polymerization Example 2) (Ethylcarbonic) 2-methoxybenzoic anhydride 627.4 28 0.31 15 7 160.9 Production Example 3 (Polymerization Example 3) (Isobutylcarbonic) 2-methoxybenzoic anhydride 878.6 37 0.35 13 3 161.1 Production Example 4 (Polymerization Example 4) Acetic 2,6-dimethoxybenzoic anhydride 3382.9 28 0.34 11 5.1 162.3 Production Example 5 (Polymerization Example 5) 2,6-dimethoxybenzoic (methylcarbonic) anhydride 497.4 32 0.32 6.5 1.5 163.8 Production Example 6 (Polymerization Example 6) 2,6-dimethoxybenzoic (ethylcarbonic) anhydride 739.3 35 0.34 6.5 1.9 163.3 Production Example 7 (Polymerization Example 7) 2,6-dimethoxybenzoic (isopropylcarbonic) anhydride 1919.1 36 0.31 11 3.6 161 Production Example 8 (Polymerization Example 8) 2,6-dimethoxybenzoic acid
(isobutylcarbonic) anhydride 1046.1 22 0.39 8.8 2.9 161.2 Production Example 9 (Polymerization Example 9) 2,6-dimethoxybenzoic acid
(tert-butylcarbonic) anhydride 2127.1 36 0.36 9.3 5.5 160.4 ¹ µmol/g-cat, ² kg-PP/g-cat, ³ g/mL, ⁴ 230 °C, 10 min, ⁵ wt%, ⁶ °C

As a result of the test, it was confirmed that the solid catalysts according to the examples had excellent activity and stereoregularity equivalent to or better than those of the conventional solid catalysts.

In addition, it was confirmed that the polypropylene according to Synthesis Example exhibits excellent physical properties such as exhibiting excellent bulk density.

In this specification, only a few examples of various embodiments performed by the present inventors are described, but the technical spirit of the present invention is not limited or limited thereto, and can be modified and implemented in various ways by those skilled in the art, of course.

Claims (6)

titanium,
magnesium,
halogen, and
A solid catalyst for olefin polymerization comprising an internal electron donor compound represented by Formula I:
[Formula I]

In the above formula I,
R ₁ is hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms;
R ₂ is hydrogen, a linear or branched alkyl group of 1 to 8 carbon atoms, or -OR ₄ ;
R ₃ is hydrogen or -OR ₅ ;
R ₄ and R ₅ are each hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms. The method of claim 1,
The olefin is a solid catalyst for olefin polymerization, characterized in that at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene. The method of claim 1,
A solid catalyst for olefin polymerization, characterized in that the compound of Formula I is at least one selected from the group consisting of the following compounds:
[Formula 1]

;
[Formula 2]

;
[Formula 3]

;
[Formula 4]

;
[Formula 5]

;
[Formula 6]

;
[Formula 7]

;
[Formula 8]

; and
[Formula 9]

. A method for producing an olefin polymer, characterized in that olefin polymerization is carried out using the solid catalyst for olefin polymerization according to any one of claims 1 to 3. A method for preparing a solid catalyst for olefin polymerization comprising the following steps:
(1) stirring at a speed of 100 rpm to 200 rpm after adding diethoxy magnesium to an organic solvent;
(2) adding titanium tetrachloride (TiCl ₄ ) to the solution of step (1) at a temperature of 0° C. to 10° C.;
(3) A compound represented by Formula I is added to the product of step (2) after the temperature has been raised to 80° C. to 100° C. in a molar ratio of the compound of Formula I: magnesium = 0.1 to 1: 1, and the temperature is 100° C. to 120° C. Stirring for 1 hour to 3 hours in
[Formula I]

In the above formula I,
R ₁ is hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms;
R ₂ is hydrogen, a linear or branched alkyl group of 1 to 8 carbon atoms, or -OR ₄ ;
R ₃ is hydrogen or -OR ₅ ;
R ₄ and R ₅ are each hydrogen or a linear or branched alkyl group of 1 to 8 carbon atoms; and
(4) Obtaining a solid catalyst for olefin polymerization by reacting the product of step (3) with titanium tetrachloride (TiCl ₄ ) at a temperature of 80 ° C to 100 ° C and washing it with an organic solvent. The method of claim 5,
Method for producing a solid catalyst for olefin polymerization, characterized in that the compound of Formula I is at least one selected from the group consisting of the following compounds:
[Formula 1]

;
[Formula 2]

;
[Formula 3]

;
[Formula 4]

;
[Formula 5]

;
[Formula 6]

;
[Formula 7]

;
[Formula 8]

; and
[Formula 9]

.

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