KR20120006719A - Method of preparation of spherical support and solid catalyst for olefin polymerization, and propylene polymers obtained using the support - Google Patents

Abstract

PURPOSE: A producing method of a sphere carrier for an olefin polymerization catalyst, a solid catalyst using thereof, and a propylene polymer are provided to control the particle size in the wide domain by the reaction condition. CONSTITUTION: A producing method of a sphere carrier for an olefin polymerization catalyst comprises a step of reacting metal magnesium, alcohol, and a reaction initiator by inserting the metal magnesium and the alcohol after dividing the amount more than three parts. The reaction initiator is firstly inserted into a reaction system. The total amount of the metal magnesium and the alcohol has a volume ratio of 1:5-50. The reaction temperature of the metal magnesium and the alcohol is 25-110 deg C.

Description

Process for producing spherical carriers for olefin polymerization catalysts and solid catalysts and propylene polymers using the same

The present invention relates to a method for preparing a spherical carrier for an olefin polymerization catalyst, and a solid catalyst and a propylene polymer prepared by using the carrier. More specifically, the addition of metal magnesium, alcohol and a reaction initiator in the reaction of metal magnesium with alcohol A method for preparing a carrier for producing a dialkoxy magnesium carrier having a uniform particle size in the range of 10 to 100 μm and a spherical particle shape by adjusting the amount, the number of times and the reaction temperature, and a solid catalyst for olefin polymerization prepared by using the same. It relates to a propylene polymer produced using a solid catalyst.

Magnesium chloride-supported Ziegler-Natta catalysts are the most widely used catalysts for olefin polymerization. This magnesium chloride-supported Ziegler-Natta catalyst is generally a solid catalyst component composed of magnesium, titanium, halogens, and electron-donating organic compounds, and when used in alpha-olefin polymerization such as propylene, it is a co-catalyst organoaluminum compound and a steric rule. It may be mixed with the organosilane compound, which is a sex regulator, in an appropriate ratio. Since supported solid catalysts for olefin polymerization are applied in various commercial processes such as slurry polymerization, bulk polymerization, gas phase polymerization, etc., in addition to the high activity and stereoregularity of the catalyst which are basically required, That is, it must satisfy the appropriate particle size and shape, uniformity of particle size distribution, minimization of macro and fine particles, high apparent density, and the like.

In order to achieve the requirements for the particle shape of the catalyst as described above, there is a method for improving the particle shape of the carrier for the olefin polymerization catalyst, and at present, such a method using a recrystallization and reprecipitation method, spray drying method, chemical reaction Methods and the like are known.

Among these known methods, the recrystallization and reprecipitation methods are difficult to arbitrarily size in the preparation of the carrier. However, a method of preparing a catalyst using dialkoxymagnesium obtained by reacting magnesium with alcohol as a carrier, which is a method using a chemical reaction, has a catalyst having a much higher activity and higher stereoregularity than other methods. In addition to providing a resultant polymer having the ability to control the size of the carrier required for the process characteristics and products, there is a recent interest in this. On the other hand, when dialkoxy magnesium is used as a carrier, the particle shape, particle size distribution and apparent density of the dialkoxy magnesium used as the carrier directly affect the particle characteristics of the catalyst and the polymer. In the process, a dialkoxy magnesium carrier having a uniform size, a spherical shape, and a sufficiently high apparent density should be prepared. In addition, when the amount of the macroparticles is large, the flowability of the polymer may be difficult to be applied to the production plant, so the dialkoxy magnesium carrier having a small amount of the macroparticles should be prepared.

Various methods for producing dialkoxy magnesium of uniform shape are disclosed in the prior art documents. In U.S. Pat. I'm suggesting how. Further, Japanese Laid-Open Patent Publication No. 06-87773 discloses a method of spray-drying an alcohol solution of diethoxy magnesium carboxylated with carbon dioxide and decarboxylating it to produce spherical particles. However, these conventional methods not only require a complicated process using many kinds of raw materials, but also do not provide a satisfactory level of particle size and shape of the carrier. On the other hand, Japanese Patent Application Laid-Open Nos. 03-74341, 04-368391 and 08-73388 provide methods for synthesizing spherical or elliptical diethoxy magnesium by reacting metal magnesium with ethanol in the presence of iodine. It is becoming. However, the diethoxy magnesium produced by this method is difficult to properly control the reaction rate because the reaction occurs very rapidly with a large amount of hydrogen generated along with a large amount of heat in the reaction, and the resulting dialkoxymagnesium There is a problem in that the carrier contains a large amount of large particles of heterogeneous particles in which a large amount of fine particles or several particles are aggregated. When the catalyst prepared from the resultant carrier is used for the polymerization of olefins, problems such as excessively large particle size of the polymer or serious disruption of the process due to destruction of the particle shape by the heat of polymerization during the polymerization process are caused. have.

On the other hand, many methods are known for catalyst compositions and electron donors for producing polypropylene polymers having high stereoregularity. In U.S. Patent No. 4,952,649, a magnesium chloride solution dissolved in 2-ethylhexyl alcohol is reacted with titanium tetrachloride and dialkyl phthalate at -20 to 130 ° C to form recrystallized solid catalyst particles, which is triethylaluminum as a cocatalyst. The present invention provides a method for producing a high stereoregular polypropylene having an isotactic index (% by weight of xylene insolubles) of 96 to 98% by mixing with alkoxysilanes, which are external electron donors, for use in bulk polymerization of propylene. . In addition, according to US Patent No. 5,028,671, a spherical solid catalyst component obtained by reacting a spherical ethanol-containing magnesium chloride carrier prepared by the spray drying method with titanium tetrachloride and dialkyl phthalate as a cocatalyst triethylaluminum, an external electron donor The present invention provides a method for producing a high-stereoregular polypropylene having an isotactic index of 97 to 98% by mixing with phosphorus dialkyldimethoxysilane.

However, the polypropylene provided by the above methods may be considered to be somewhat satisfactory in stereoregularity. However, in the production of polypropylene with reduced catalyst residues as an environmentally friendly material, which has recently emerged, the activity is 30 kg-. PP / g-cat or less is not enough.

The present invention is to solve the problems of the prior art as described above, the object of the present invention, it is easy to control the particle size of a large area according to the reaction conditions, commercial olefin polymerization process such as slurry polymerization, bulk polymerization, gas phase polymerization It is to provide a method for producing a dialkoxy magnesium carrier for an olefin polymerization catalyst having a more spherical particle shape that is uniform and smooth on the surface, which is suitable for producing a catalyst capable of sufficiently satisfying the particle characteristics required by the present invention.

Another object of the present invention is to provide a solid catalyst for olefin polymerization using a spherical carrier for olefin polymerization catalyst prepared by the carrier production method of the present invention and a method for producing the same.

Another object of the present invention is to provide a propylene polymer prepared using the solid catalyst for olefin polymerization of the present invention.

In order to achieve the above object, a method for preparing a carrier for an olefin polymerization catalyst according to the present invention includes reacting a metal magnesium, an alcohol, and a reaction initiator, and the metal magnesium weight is 1: 5 to 50 in an alcohol volume. The amount of the metal magnesium and alcohol is divided into three or more times, and the reaction initiator is injected into the reaction system at the beginning of the first reaction, and then divided into two or more times as necessary during the reaction.

The form of the metal magnesium particles used in the carrier production method of the present invention is not particularly limited, but the size thereof is preferably in the form of a powder having an average particle diameter of 10 to 500 µm and more preferably in the form of a powder of 50 to 300 µm. . If the average particle diameter of the metal magnesium is less than 10 mu m, the average particle size of the carrier which is the product becomes too fine. If the average particle size of the metal magnesium exceeds 500 mu m, the average particle size of the carrier becomes too large, and the shape of the carrier becomes difficult to form a uniform spherical shape. Since it is difficult to have a uniform particle shape in the production of the catalyst.

Examples of the alcohol used in the carrier production method of the present invention include methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, normal pentanol, isopentanol, neopentanol, cyclopentanol and cyclo It is preferable to use one or two or more kinds of alcohols selected from aromatic alcohols such as aliphatic alcohols or phenols represented by the general formula ROH (here, R is an alkyl group having 1 to 6 carbon atoms) such as hexanol, and the like. More preferably, one or two or more alcohols selected from methanol, ethanol, propanol or butanol are used alone or in combination, most preferably ethanol.

In the carrier production method of the present invention, the use ratio of the alcohol to the metal magnesium is preferably 1: 5 to 1:50, more preferably 1: 7 to 1:30, in terms of metal magnesium weight: alcohol volume. Do. If the use ratio is less than 1: 5, the viscosity of the slurry is rapidly increased, making it difficult to uniformly stir. If the ratio is greater than 1:50, the apparent density of the resulting carrier is rapidly decreased or the surface of the particles is roughened.

Nitrogen halide compounds or magnesium halides may be used as the reaction initiator used in the reaction of the metal magnesium with alcohol.

Nitrogen halides that can be used as the reaction initiator are not particularly limited, but one or more compounds selected from the group consisting of the following formulas (1) to (4) may be used:

(1) N-halide succinimide-based compound

　

X is halogen, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or C 1 -C 12 alkyl or C 6 -C 20 aryl;

(2) Trihalo isocyanuric acid compound

　

X is halogen;

(3) N-halophthalimide compound

　

X is halogen, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or C 1 -C 12 alkyl or C 6 -C 20 aryl;

(4) hydantoin compound

　

X is halogen, R ₁ and R ₂ are hydrogen or C ₁ -C 12 alkyl or C 6 -C 20 aryl.

Magnesium halides that can be used as the reaction initiator are not particularly limited, but mention may be made of magnesium chloride (MgCl ₂ ), magnesium bromide (MgBr ₂ ), and magnesium iodide (MgI ₂ ).

The amount of the reaction initiator is preferably used in an amount of 0.001 to 0.2 parts by weight based on 1 part by weight of the total amount of metal magnesium used. If the amount of the reaction initiator is less than 0.001 parts by weight, the reaction rate is too slow. If it exceeds 0.2 parts by weight, the particle size of the product may be too large or a large amount of fine particles may be generated.

In the carrier production method of the present invention, in the reaction of the metal magnesium and alcohol, the metal magnesium and alcohol may be added at least three times, preferably 3 to 4 times, the reaction initiator is injected after the initial reaction start It is preferable to add further dividing | segmenting into 2 or more times preferably 2 to 3 during reaction. If the total number of divided additions of the metal magnesium and alcohol is less than three times, and the number of additional divided additions of the reaction initiator is less than two times, there is a limit in controlling the particle size and it is not only difficult to form spherical particles but also the apparent appearance of the carrier. The disadvantage is that the density can be reduced.

In addition, the stirring speed during the reaction is preferably 50 ~ 300rpm, more preferably 70 ~ 250rpm. If the stirring speed is too slow or too fast, the particles are not uniform. In addition, the reaction between the metal magnesium and the alcohol is preferably performed at a temperature of 25 to 110 ° C, and more preferably at a temperature of 50 to 100 ° C in the presence of the reaction initiator. After the aging treatment is preferably made at a temperature of 60 ~ 110 ℃. The reaction may be effected while refluxing at the boiling point of the alcohol. When the reaction temperature and the aging treatment temperature is less than the above range, the reaction rate is very slow, and when the reaction temperature exceeds the above range, the reaction occurs very rapidly, and thus, fine particles may be generated and agglomeration between particles may be undesirable.

In the solid catalyst for olefin polymerization according to the present invention, the dialkoxy magnesium carrier in the form of a homogeneous spherical particle prepared by the reaction of metal magnesium and alcohol is first reacted with titanium halide in the presence of an organic solvent to dialkoxy magnesium Substituted alkoxy group of halogen group, and then can be prepared by reacting the titanium halide and the internal electron donor in the presence of an organic solvent, thereby obtaining a porous solid catalyst particles.

As the organic solvent used in the preparation of the solid catalyst of the present invention, an aliphatic hydrocarbon or aromatic hydrocarbon having 6 to 12 carbon atoms may be used, and more preferably, a saturated aliphatic or aromatic hydrocarbon having 7 to 10 carbon atoms may be used. As a specific example, octane, nonane, decane or toluene, xylene and the like can be used.

As the titanium halide used in the preparation of the solid catalyst of the present invention, any titanium halide may be used, and for example, titanium tetrachloride may be used.

Moreover, as said internal electron donor used for manufacture of the said solid catalyst, diesters, especially aromatic diesters, More specifically, phthalic acid diesters are preferable. Suitable examples of the phthalic acid diesters include dimethyl phthalate, diethyl phthalate, dinormal propyl phthalate, diisopropyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, dinormal pentyl phthalate, di (2-methylbutyl) phthalate, Di (3-methylbutyl) phthalate, dinopentylphthalate, dinomalhexylphthalate, di (2-methylpentyl) phthalate, di (3-methylpentyl) phthalate, diisohexylphthalate, dinohexylphthalate, di (2 , 3-dimethylbutyl) phthalate, dinormalheptyl phthalate, di (2-methylhexyl) phthalate, di (2-ethylpentyl) phthalate, diisoheptyl phthalate, dinoheptyl phthalate, dinomal octyl phthalate, di (2- Methylheptyl) phthalate, diisooctyl phthalate, di (3-ethylhexyl) phthalate, dinohexyl phthalate, dinomalheptyl phthalate, diisoheptyl phthalate, dinoheptyl Selected from compounds represented by the following general formulas, such as phthalate, dinomal octyl phthalate, diisooctyl phthalate, dinooctyl phthalate, dinomal nonyl phthalate, diisononyl phthalate, dinomaldecyl phthalate, diisodecyl phthalate, and the like. It can be used 1 type or in mixture of 2 or more types.

(Wherein R is an alkyl group having 1 to 10 carbon atoms)

In the production of the solid catalyst of the present invention, the contact and reaction of the above components are carried out in a reactor equipped with a stirrer in which water and the like are sufficiently removed in an inert gas atmosphere.

In the preparation of the solid catalyst, the primary reaction of dialkoxy magnesium and titanium halides, such as titanium tetrachloride, is in the range of 0 to 50 ° C., more specifically 10 to 40 ° C. in suspension in an aliphatic or aromatic organic solvent. If the temperature is out of the temperature range, the shape of the carrier particles may be destroyed, thereby generating a problem in which a large amount of fine particles are generated. At this time, the amount of titanium halide to be used is preferably 0.1 to 10 moles, more specifically 0.3 to 2 moles per 1 mole of dialkoxy magnesium, and the injection rate of titanium halide is preferably added slowly over 30 minutes to 3 hours. , After the addition is completed, the temperature is gradually raised to 40 ~ 80 ℃ to complete the reaction.

After the reaction is completed, the mixture in the slurry state is washed one or more times with an organic solvent such as toluene, and then aged by adding a titanium halide again to 90-130 ° C. At this time, the amount of titanium halide to be used is 0.5 to 10 moles per 1 mole of dialkoxymagnesium used initially, more preferably 1 to 5 moles.

In addition, the temperature increase rate is not very important, but the internal electron donor should be introduced during the temperature increase process, but the temperature and the number of times of the electron donor are not particularly limited, but the total amount of the electron donor used is the dialkoxy magnesium 1 used. It is preferable to use 0.1-1.0 weight part with respect to a weight part. When the amount of the internal electron donor is out of the above range, the polymerization activity of the resulting catalyst or the stereoregularity of the polymer may be lowered.

After the completion of the reaction, the mixed slurry is optionally subjected to a third contact with titanium halide, washing with an organic solvent, and drying to obtain a resultant solid catalyst for olefin polymerization.

The solid catalyst for olefin polymerization of the present invention prepared by the above method contains magnesium, titanium, an electron donating compound and a halogen atom, and the content of each component is not particularly defined, but preferably 20 to 30% by weight of magnesium , 1 to 10% by weight of titanium, 5 to 20% by weight of electron donating compound, and 40 to 70% by weight of halogen atom.

The resulting solid catalyst of the present invention (hereinafter referred to as component A) is mixed with an alkylaluminum promoter (hereinafter referred to as component B) and an external electron donor (hereinafter referred to as component C) in bulk polymerization method and slurry. It is used for olefin polymerization by polymerization or gas phase polymerization, in particular for propylene polymerization.

The component B is a compound represented by general formula AlR ¹ ₃ (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms), and specific examples thereof include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, Triisobutyl aluminum etc. are mentioned.

The component C is represented by the general formula _{^{R 2 m Si (OR 3)}} 4-m ( wherein, R ² represents an alkyl group or a cycloalkyl group or an aryl group of carbon number 1 ~ 10, R ³ is an alkyl group having a carbon number of 1 ~ 3, m Is 1 or 2, and when m = 2, two R ² groups may be the same or different), and specific examples thereof include nC ₃ H ₇ Si (OCH ₃ ) ₃ and (nC ₃ H ₇ ) ₂ Si (OCH ₃ ) ₂ , iC ₃ H ₇ Si (OCH ₃ ) ₃ , (iC ₃ H ₇ ) ₂ Si (OCH ₃ ) ₂ , nC ₄ H ₉ Si (OCH ₃ ) ₃ , (nC ₄ H ₉ ) ₂ Si (OCH ₃ ) ₂ , iC ₄ H ₉ Si (OCH ₃ ) ₃ , (iC ₄ H ₉ ) ₂ Si (OCH ₃ ) ₂ , tC ₄ H ₉ Si (OCH ₃ ) ₃ , (tC ₄ H ₉ ) ₂ Si (OCH ₃ ) ₂ , nC ₅ H ₁₁ Si (OCH ₃ ) ₃ , (nC ₅ H ₁₁ ) ₂ Si (OCH ₃ ) ₂ , (cyclopentyl) Si (OCH ₃ ) ₃ , (cyclopentyl) ₂ Si (OCH ₃ ) ₂ , (cyclopentyl) (CH ₃ ) Si (OCH ₃ ) ₂ , (cyclopentyl) (C ₂ H ₅ ) Si (OCH ₃ ) ₂ , (cyclopentyl) (C ₃ H ₇ ) Si ( OCH ₃ ) ₂ , (cyclohexyl) Si (OCH ₃ ) ₃ , (cyclohexyl) ₂ Si (OCH ₃ ) ₂ , (cyclohexyl) (CH ₃ ) Si (OCH ₃ ) ₂ , (cyclohexyl) (C ₂ H ₅ ) Si ( OCH ₃ ) ₂ , (cyclohexyl) (C ₃ H ₇ ) Si (OCH ₃ ) ₂ , (cycloheptyl) Si (OCH ₃ ) ₃ , (cycloheptyl) ₂ Si (OCH ₃ ) ₂ , (cycloheptyl) ( CH ₃ ) Si (OCH ₃ ) ₂ , (cycloheptyl) (C ₂ H ₅ ) Si (OCH ₃ ) ₂ , (cycloheptyl) (C ₃ H ₇ ) Si (OCH ₃ ) ₂ , PhSi (OCH ₃ ) ₃ (Ph is a phenyl group), Ph ₂ Si (OCH ₃ ) ₂ , nC ₃ H ₇ Si (OC ₂ H ₅ ) ₃ , (nC ₃ H ₇ ) ₂ Si (OC ₂ H ₅ ) ₂ , iC ₃ H ₇ Si ( OC ₂ H ₅ ) ₃ , (iC ₃ H ₇ ) ₂ Si (OC ₂ H ₅ ) ₂ , nC ₄ H ₉ Si (OC ₂ H ₅ ) ₃ , (nC ₄ H ₉ ) ₂ Si (OC ₂ H ₅ ) ₂ , iC ₄ H ₉ Si (OC ₂ H ₅ ) ₃ , (iC ₄ H ₉ ) ₂ Si (OC ₂ H ₅ ) ₂ , tC ₄ H ₉ Si (OC ₂ H ₅ ) ₃ , (tC ₄ H ₉ ) ₂ Si (OC ₂ H ₅ ) ₂ , nC ₅ H ₁₁ Si (OC ₂ H ₅ ) ₃ , (nC ₅ H ₁₁ ) ₂ Si (OC ₂ H ₅ ) ₂ , (cyclopentyl) Si (OC ₂ H ₅ ) ₃ , (cyclopentyl) ₂ Si (OC ₂ H ₅ ) ₂ , (cyclopentyl) (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , (cyclopentyl) (C ₂ H ₅ ) Si (OC ₂ H ₅ ) ₂ , (cyclopentyl) (C ₃ H ₇ ) Si (OC ₂ H ₅ ) ₂ , (cyclohexyl) Si (OC ₂ H ₅ ) ₃ , (cyclohexyl) ₂ Si (OC ₂ H ₅ ) ₂ , (cyclo Hexyl) (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , (cyclohexyl) (C ₂ H ₅ ) Si (OC ₂ H ₅ ) ₂ , (cyclohexyl) (C ₃ H ₇ ) Si (OC ₂ H ₅ ) ₂ , (cycloheptyl) Si (OC ₂ H ₅ ) ₃ , (cycloheptyl) ₂ Si (OC ₂ H ₅ ) ₂ , (cycloheptyl) (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , (cycloheptyl) (C ₂ H ₅ ) Si (OC ₂ H ₅ ) ₂ , (cycloheptyl) (C ₃ H ₇ ) Si (OC ₂ H ₅ ) ₂ , PhSi (OC ₂ H ₅ ) ₃ , Ph ₂ Si (OC ₂ H ₅ ) _2, and the like.

In the polymerization of olefins, in particular propylene, using the catalyst for olefin polymerization of the present invention, an appropriate ratio of component B to component A varies slightly depending on the polymerization method, but aluminum atoms in component B relative to titanium atoms in component A. The molar ratio may be in the range of 1 to 1000, and more preferably in the range of 10 to 300. If the ratio of component B to component A deviates from the above ratio, there is a problem that the polymerization activity is rapidly lowered.

In the polymerization of olefins, in particular propylene, using the catalyst for olefin polymerization of the present invention, an appropriate ratio of component C to component A is 1 to 200 as the molar ratio of silicon atoms in component C to titanium atoms in component A. It is a range, More preferably, the range of 10-100 is suitable. If the molar ratio is less than 1, the stereoregularity of the resulting polymer is significantly lowered, and if it exceeds 200, there is a problem that the polymerization activity of the catalyst is significantly lowered.

The dialkoxymagnesium carrier prepared by adjusting the injection amount and the number of injections of the metal magnesium, alcohol and the reaction initiator and the reaction temperature according to the present invention is easy to control the particle size in a wide range of 10 ~ 100㎛ according to the reaction conditions, more It has a spherical particle shape.

The solid catalyst prepared using the dialkoxy magnesium carrier as described above has a high catalytic activity of 52 kg-PP / g-cat or more, and has an apparent density of 0.43 g / cc or more, which greatly affects high stereoregularity and especially commercial productivity. As a result, it is possible to provide a high polymer, which can be suitably used for commercial application of various processes.

1 is an electron micrograph of the carrier prepared in Example 1 according to the present invention,
2 is an electron micrograph of the carrier prepared in Comparative Example 3.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but these Examples are for illustrative purposes only, and the present invention is not limited thereto.

Example  One

[rectangle Carrier  Produce]

After fully ventilating a 5L sized reactor equipped with a stirrer, an oil heater and a cooling reflux with nitrogen, 4 g of N-bromosuccinimide, 40 g of metal magnesium (powder product having an average particle diameter of 100 μm), and 400 ml of anhydrous ethanol were added thereto. The reactor was kept at 60 ° C. while stirring at 250 rpm. After about 10 minutes, the reaction starts and hydrogen is generated, so that the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. At the end of hydrogen evolution, the reactor temperature was maintained at 60 ° C. for 1 hour. After 1 hour, 20 g of metal magnesium (powder product having an average particle diameter of 100 µm), 300 ml of anhydrous ethanol, and 20 g of N-bromosuccinimide were injected into the reactor and maintained for 1 hour, and finally, metal magnesium (average particle diameter of 100 µm) Phosphorus powder product) 10 g, 200 ml of anhydrous ethanol, and 1 g of N-bromosuccinimide were injected and aged for 3 hours until the reaction was completed. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 263 g (yield 93.2%) of diethoxy magnesium carrier as a solid, white powdery product.

The particle size of the dried product was measured with a laser particle analyzer (Mastersizer X: manufactured by Malvern Instruments) by light transmission, and the average particle size was 25.2 µm. Particle size distribution (P) (P = (D ₉₀ -D ₁₀ ) / D ₅₀ , where D ₉₀ is the particle size equivalent to 90% cumulative weight and D ₅₀ is the particle size equivalent to 50% cumulative weight And D ₁₀ is the size of the particle corresponding to 10% of the cumulative weight) of 0.71, and the apparent density measured by ASTM D1895 was 0.32 g / cc.

[Production of Solid Catalyst Component]

150 ml of toluene and 25 g of spherical diethoxy magnesium # 25 were prepared in a glass reactor equipped with a 1 liter stirrer sufficiently substituted with nitrogen, and maintained at 10 ° C. After diluting 25 ml of titanium tetrachloride in 50 ml of toluene and injecting it over 1 hour, the temperature of the reactor was raised to 60 ° C. at a rate of 0.5 ° C. per minute. The reaction mixture was kept at 60 ° C. for 1 hour, then the stirring was stopped to wait for a solid product to precipitate, the supernatant was removed, stirred for 15 minutes using 200 ml of fresh toluene and washed once in the same manner.

150 ml of toluene was added to the solid product treated with titanium tetrachloride, and 50 ml of titanium tetrachloride was added at a constant rate over 1 hour while stirring at 250 rpm while maintaining the temperature at 30 ° C. When the addition of titanium tetrachloride was completed, 2.5 ml of diisobutyl phthalate was added, and the temperature of the reactor was raised to 110 ° C. at a constant rate over 80 minutes (temperature rising at a rate of 1 ° C. per minute). When the temperature of the reactor reached 40 ° C. and 60 ° C. during the temperature increase, 2.5 ml of diisobutyl phthalate was further added. The mixture was kept at 110 ° C. for 1 hour and then the temperature was lowered to 90 ° C. to stop stirring, the supernatant was removed, and further washed once with 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 each time, and washed 5 times with 200 ml each time with normal hexane at 40 ° C. to obtain a light yellow solid catalyst component. Titanium content in the solid catalyst component obtained by drying under flowing nitrogen for 18 hours was 2.32% by weight, and the solid catalyst suspended in normal hexane was measured by a laser particle analyzer (Mastersizer X: manufactured by Malvern Instruments) by light transmission. , Average particle size was 25.2 μm.

[Propylene polymerization]

After mounting a small glass tube filled with 5 mg of the catalyst prepared as described above in a 2-liter high-pressure stainless steel reactor, the reactor was sufficiently replaced with nitrogen. 3 mmol of triethylaluminum and 0.15 mmol of cyclohexyl-methyldimethoxysilane were added together as an external electron donor. Subsequently, 1000 ml of hydrogen and 1.2 L of propylene in a liquid state were sequentially added thereto, and then the temperature was raised to 70 ° C., and a stirrer was operated to break the glass tube mounted therein to start polymerization. One hour after the start of the polymerization, the temperature of the reactor was lowered to room temperature (25 ° C.), and the valve was opened to completely degas the propylene inside the reactor.

The physical properties of the obtained polypropylene polymer were measured, and the results are shown in Table 1.

In Table 1, catalytic activity, stereoregularity, melt flow index, and apparent density (BD) were determined by the following method.

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

② Stereoregularity (X.I.): Weight% of insoluble component precipitated by crystallization in mixed xylene

④ apparent density (BD) = value measured by ASTM D1895

Example  2

[rectangle Carrier  Produce]

After fully ventilating a 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux with nitrogen, 3 g of N-bromosuccinimide, 10 g of metal magnesium (powder product having an average particle diameter of 120 µm), and 250 ml of anhydrous ethanol were added thereto. The reactor temperature was maintained at 70 ° C. under ethanol reflux while operating at 250 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the end of hydrogen generation, 1 g of N-bromosuccinimide, 20 g of metalloid magnesium (powder product having an average particle diameter of 120 µm) and 150 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is finished, 3 g of N-bromosuccinimide, 450 g of magnesium metal (powder product having an average particle diameter of 120 µm) and 560 ml of ethanol are third After the addition, the reactor temperature and stirring rate were maintained at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 336 g (yield 95.2%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dried carrier suspended in normal hexane was 32.1 µm, the particle size distribution index was 0.89, and the apparent density was 0.32 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.27 wt%, and the average particle size was 32.1. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Example  3

[rectangle Carrier  Produce]

After fully ventilating a 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux with nitrogen, 2 g of N-bromosuccinimide, 10 g of metal magnesium (powder product having an average particle diameter of 120 µm), and 150 ml of anhydrous ethanol were added thereto. The temperature of the reactor was maintained at 80 ° C. under ethanol reflux while operating the stirring speed at 200 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 3 g of N-bromosuccinimide, 30 g of metallobetic magnesium (powder product having an average particle diameter of 120 µm) and 450 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is finished, 1 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm) and 250 ml of ethanol are sequentially After the addition, the reactor temperature and stirring rate were maintained at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 271 g (yield 95.8%) of a diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 38.2 µm, the particle size distribution index was 0.62, and the apparent density was 0.34 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.33 wt%, and the average particle size was 48.2. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Example  4

[rectangle Carrier  Produce]

After sufficiently ventilating a 5L sized reactor equipped with a stirrer, an oil heater, and a cooling reflux with nitrogen, 3.5 g of N-chlorosuccinimide, 15 g of metal magnesium (powder product having an average particle diameter of 150 µm), and 300 ml of anhydrous ethanol were added thereto. And, while operating the stirring speed at 150rpm to raise the reactor temperature to 85 ℃ to maintain a state of reflux of ethanol. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 2.0 g of N-chlorosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 150 µm), and 300 ml of anhydrous ethanol were further added. When the hydrogen was generated by the reaction of the metal magnesium and ethanol by the second additional addition, 0.5 g of N-chlorosuccinimide, 27 g of metal magnesium (powder product having an average particle diameter of 150 µm) and 375 ml of anhydrous ethanol were added to the third. After the addition, the reactor temperature and the stirring rate were maintained at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 285 g (yield 97.6%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 61.4 µm, the particle size distribution index was 0.83, and the apparent density was 0.29 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.24 wt%, and the average particle size was 61.4. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Example  5

[rectangle Carrier  Produce]

A 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux was sufficiently ventilated with nitrogen, and then 7g of N-bromosuccinimide, 20g of metal magnesium (powder product having an average particle diameter of 150㎛), and 400ml of anhydrous ethanol were added thereto. The temperature of the reactor was maintained at 95 ° C. under reflux of ethanol while operating the stirring speed at 200 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen was completed, 3 g of N-bromosuccinimide, 40 g of metallometallic magnesium (powder product having an average particle diameter of 150 µm) and 600 ml of ethanol were added thereto. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is completed, 4 g of N-bromosuccinimide, 80 g of metallo-metal magnesium (powder product having an average particle diameter of 150 µm) and 1100 ml of ethanol are 3rd After the addition, the reactor temperature and stirring rate were maintained at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 629 g (yield 95.5%) of a diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 94.7 µm, the particle size distribution index was 0.94, and the apparent density was 0.29 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.18 wt%, and the average particle size was 60.6. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Example  6

[rectangle Carrier  Produce]

After sufficiently ventilating a 5L sized reactor equipped with a stirrer, an oil heater and a cooling reflux with nitrogen, 7 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 120 μm) and 400 ml of anhydrous ethanol were added thereto. The temperature of the reactor was maintained at 85 ° C. under ethanol reflux while operating the stirring speed at 200 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 0.5 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm) and 150 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the second additional type is completed, 0.5 g of N-bromosuccinimide, 40 g of metal magnesium (powder product having an average particle diameter of 120 µm) and 300 ml of ethanol After the addition of tea, the reactor temperature was lowered to 80 ° C. and maintained at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 357 g (yield 94.8%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 40.2 µm, the particle size distribution index was 0.73, and the apparent density was 0.33 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.33 wt%, and the average particle size was 40.2. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Example  7

[rectangle Carrier  Produce]

After fully ventilating a 5L sized reactor equipped with a stirrer, an oil heater, and a cooling reflux with nitrogen, 9 g of N-chlorosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 160 µm), and 300 ml of anhydrous ethanol were added thereto. The temperature of the reactor was maintained at 78 ° C. under reflux of ethanol while operating the stirring speed at 200 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 1 g of N-bromosuccinimide, 50 g of metal magnesium (powder product having an average particle diameter of 160 µm) and 1240 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is finished, 1 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 160 µm) and 300 ml of ethanol in 3rd order After further addition, the temperature of the reactor was increased to 95 ° C. and kept at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 310 g (yield 94.2%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dried carrier suspended in normal hexane was 56.8 µm, the particle size distribution index was 0.67, and the apparent density was 0.29 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.37 wt%, and the average particle size was 56.8. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Comparative example  One

[ Carrier  Produce]

After sufficiently ventilating a 5L sized super reactor equipped with a stirrer, oil heater, and cooling reflux with nitrogen, add 5 g of MgCl ₂ , ₂₀ g of metal magnesium (powder product having an average particle diameter of 150 μm), and 300 ml of anhydrous ethanol. The temperature of the reactor was maintained at 78 ° C. under ethanol reflux while operating at 180 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 20 g of metal magnesium (powder product having an average particle diameter of 150 µm) and 350 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is finished, 20 g of metal magnesium (powder product having an average particle diameter of 150 μm) and 350 ml of ethanol are further added in a third step, and the reactor temperature and stirring speed It was matured by maintaining at reflux for 2 hours. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 267 g (yield 94.5%) of a diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dried carrier suspended in normal hexane was 51.3 µm, the particle size distribution index was 1.93, and the apparent density was 0.26 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.30 wt%, and the average particle size was 51.3. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Comparative example  2

[ Carrier  Produce]

After sufficiently ventilating a 5L sized reactor equipped with a stirrer, an oil heater, and a cooling reflux with nitrogen, 7 g of N-bromosuccinimide, 10 g of metal magnesium (powder product having an average particle diameter of 120 µm), and 250 ml of anhydrous ethanol were added thereto. The reactor temperature was maintained at 70 ° C. under ethanol reflux while operating at 250 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm) and 150 ml of ethanol were further added. After the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary, 450 g of metal magnesium (powder product having an average particle diameter of 120 μm) and 560 ml of ethanol were further added in a third step, and the reactor temperature and stirring speed were added. It was matured by maintaining at reflux for 2 hours. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 328 g (yield 92.8%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 27.6 µm, the particle size distribution index was 1.37, and the apparent density was 0.27 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.13 wt%, and the average particle size was 27.6. [Mu] m.

 [Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Comparative example  3

[ Carrier  Produce]

After adequately ventilating a 5L sized reactor equipped with a stirrer, an oil heater, and a cooling reflux with nitrogen, 5 g of iodine (I ₂ ), 30 g of metal magnesium (powder product having an average particle diameter of 120 μm), and 500 ml of anhydrous ethanol were added thereto. While maintaining the stirring speed at 250 rpm, the temperature of the reactor was maintained at 70 ° C. under ethanol reflux. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 50 g of metal magnesium (powder product having an average particle diameter of 120 µm) and 500 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is finished, the reactor temperature and stirring rate were maintained at reflux for 2 hours to mature. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 264 g (yield 93.6%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 40.2 µm, the particle size distribution index was 1.57, and the apparent density was 0.26 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.23 wt%, and the average particle size was 40.2. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Comparative example  4

[ Carrier  Produce]

After fully ventilating a 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux with nitrogen, 2 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm), and 400 ml of anhydrous ethanol were added thereto. The temperature of the reactor was maintained at 75 ° C. under reflux of ethanol while operating the stirring speed at 200 rpm. After about 5 minutes, the reaction starts and hydrogen is generated, so the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure of the reactor at atmospheric pressure. After the generation of hydrogen, 2 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm) and 350 ml of ethanol were further added. When the hydrogen generation by the reaction of the metal magnesium and ethanol by the additional addition of the secondary is completed, 20 g of metal magnesium (powder product having an average particle diameter of 120 μm) and 350 ml of ethanol are further added in a third step, and the reactor temperature and stirring speed It was matured by maintaining at reflux for 2 hours. After the aging treatment was completed, the resultant was washed three times using 2,000 ml of normal hexane per wash at 50 ° C. The washed resultant was dried under flowing nitrogen for 24 hours to obtain 264 g (yield 92.8%) of diethoxy magnesium carrier as a solid white powdery product.

As a result of measurement in the same manner as in Example 1, the average particle size of the dry carrier suspended in normal hexane was 24.3 µm, the particle size distribution index was 0.98, and the apparent density was 0.27 g / cc.

[Production of Solid Catalyst Component]

Using the spherical carrier prepared as described above, a solid catalyst was prepared in the same manner as in Example 1, and measured in the same manner, the titanium content in the resultant solid catalyst was 2.24 wt%, and the average particle size was 24.8. [Mu] m.

[Propylene polymerization]

Propylene was polymerized in the same manner as in Example 1 using the solid catalyst component prepared as described above. The physical properties of the obtained polypropylene polymer were analyzed and the results are shown in Table 1.

Catalyst size (μm) Active (kg-PP / g-catalyst) Stereoregularity (X.I.) Apparent Density (BD) Example 1 25.2 61.2 98.5 0.44 Example 2 32.1 55.2 98.2 0.44 Example 3 48.2 54.5 98.3 0.43 Example 4 61.4 56.4 98.5 0.43 Example 5 60.6 53.2 98.2 0.45 Example 6 40.2 57.1 98.7 0.43 Example 7 56.8 53.9 98.2 0.43 Comparative Example 1 51.3 48.2 98.0 0.38 Comparative Example 2 27.6 42.8 97.5 0.37 Comparative Example 3 40.2 40.2 97.7 0.35 Comparative Example 4 24.8 43.3 97.8 0.41

As shown in Table 1, by using a carrier that is easy to control the particle size in a wide range of 10 ~ 100㎛ prepared according to the method of the present invention can be applied to various processes, the stereoregularity compared to conventional catalysts A catalyst having an equivalent level and higher than 52 kg-PP / g-catalyst having high catalytic activity is prepared, and when the solid catalyst thus prepared is mixed with alkylaluminum and an external electron donor to be used for the polymerization of propylene, it is greatly increased in commercial productivity. It is possible to produce high yield polypropylene polymers with an apparent apparent density of 0.43 g / cc or more.

On the other hand, also in the form of the carrier electron microscope picture of the carrier (Example 1) of the carrier (Example 1) prepared according to the carrier production method of the present invention, and the electron microscope of the carrier (Comparative Example 3) prepared according to the conventional carrier production method Referring to FIG. 2, which is a photograph, it can be seen that the shape of the carrier according to the invention has a much more spherical smooth surface.

The carrier of the present invention as described above can be suitably used for the production of catalysts of various sizes that can sufficiently satisfy the properties required in commercial olefin polymerization processes such as slurry polymerization, bulk polymerization, gas phase polymerization.

Claims (8)

In the method for producing a dialkoxy magnesium carrier for an olefin polymerization catalyst comprising reacting a metal magnesium with an alcohol and a reaction initiator, the metal magnesium and the alcohol are divided and added three times or more, and the reaction initiator is initially reacted into the reaction system. A method for producing a spherical carrier for an olefin polymerization catalyst, characterized in that it is added at least two times during the reaction after injection at the start.
The method for producing a spherical carrier for an olefin polymerization catalyst according to claim 1, wherein the total amount of metal magnesium and alcohol is in an amount of 1: 5 to 50 by weight of metal magnesium weight: alcohol.
The method of claim 1, wherein the reaction temperature of the metal magnesium and alcohol is 25 ~ 110 ℃.
The method for producing a spherical carrier for olefin polymerization according to claim 1, wherein a nitrogen halide compound or magnesium halide is used as the reaction initiator.
The method for preparing a spherical carrier for an olefin polymerization catalyst according to claim 4, wherein the nitrogen halide compound is selected from the group consisting of the following formulas (1) to (4):
(1) N-halide succinimide-based compound

X is halogen, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or C 1 -C 12 alkyl or C 6 -C 20 aryl;
(2) Trihalo isocyanuric acid compound

X is halogen;
(3) N-halophthalimide compound

X is halogen, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or C 1 -C 12 alkyl or C 6 -C 20 aryl;
(4) hydantoin compound

X is halogen, R ₁ and R ₂ are hydrogen or C ₁ -C 12 alkyl or C 6 -C 20 aryl.
The method for producing a spherical carrier for an olefin polymerization catalyst according to claim 4, wherein the magnesium halide is magnesium chloride (MgCl ₂ ), magnesium bromide (MgBr ₂ ) or magnesium iodide (MgI ₂ ).
An olefin prepared by reacting a carrier prepared according to the spherical carrier production method for an olefin polymerization catalyst according to any one of claims 1 to 6 with an internal electron donor of titanium halides and diesters in the presence of an organic solvent. Catalyst for polymerization.
A propylene polymer produced by polymerizing propylene using a catalyst according to claim 7 and an alkylaluminum as cocatalyst and an alkoxysilane compound as external electron donor.

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