KR101309457B1 - Method of preparation of spherical support and solid catalyst for olefin polymerization, and method of preparation of propylene polymers using the catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a spherical carrier for an olefin polymerization catalyst and a method for producing a solid catalyst and a propylene polymer prepared using the carrier, and more particularly, alcohol which reacts with magnesium when preparing a dialkoxy magnesium carrier. By using two kinds of mixed alcohols as the preparation of dialkoxy magnesium carrier, the particle size of the catalyst prepared using this carrier can be controlled in the range of 40-80 μm, and when producing the propylene polymer using this catalyst, In addition to the morphology, the present invention relates to a method for producing a spherical carrier for an olefin polymerization catalyst and a method for producing a solid catalyst and a propylene polymer, which can significantly reduce the fine content to less than 0.1 wt%.

Description

METHODS OF PREPARATION OF SPHERICAL SUPPORT AND SOLID CATALYST FOR OLEFIN POLYMERIZATION, AND METHOD OF PREPARATION OF PROPYLENE POLYMERS USING THE CATALYST}

The present invention relates to a method for preparing a spherical carrier for an olefin polymerization catalyst and a method for producing a solid catalyst and a propylene polymer prepared using the carrier, and more particularly, alcohol which reacts with magnesium when preparing a dialkoxy magnesium carrier. To prepare a dialkoxy magnesium carrier using two kinds of mixed alcohols, and to produce a propylene polymer using a catalyst prepared by using the carrier, it is possible to significantly reduce the fine content to 0.1 wt% or less with excellent morphology. And a method for producing a spherical carrier for an olefin polymerization catalyst and a method for producing a solid catalyst and a propylene polymer prepared using the carrier.

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 methods include recrystallization and reprecipitation, spray drying, and chemical reaction. The methods used are known, but among these known methods, recrystallization and reprecipitation methods are difficult to arbitrarily control the size 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.

However, 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 particular, when the amount of large particles is large, the flowability of the polymer may be poor, making it difficult to apply to a production plant.

Various methods for producing dialkoxy magnesium of uniform shape are disclosed in the prior art documents. In U.S. Pat. I'm suggesting how. Japanese Laid-Open Patent Publication No. 06-87773 discloses a method of spray-drying an alcoholic solution of diethoxy magnesium carboxylated by carbon dioxide and decarboxylating it to prepare 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 prepared by this method is difficult to properly control the reaction rate because a large amount of hydrogen is generated along with a lot of heat of reaction during the reaction, and the reaction occurs very rapidly, and the resulting dialkoxy magnesium carrier There is a problem in that a large amount of fine particles or a plurality of particles contain a large amount of agglomerated large particles.

According to Korean Patent Application No. 10-2009-0005298, a method for synthesizing spherical or elliptical diethoxy magnesium having an average particle diameter of 60 to 200 µm is provided. However, this method requires too many or ten consecutive metal intercalations and alcohols during preparation, which may cause problems in commercial applications due to too many reaction times and the number of manipulations.

According to Korean Patent Application No. 10-2010-0135828, in order to prepare dialkoxy magnesium having improved mechanical strength and uniform particle size distribution, it is obtained by reacting a metal magnesium with a mixture of alcohol and iodine. The bulk density of the polymerized resin was 0.32 to 0.38, which is too low for commercial use.

According to European patent EP 1,783,109, when preparing dialkoxy magnesium, metal magnesium is obtained by reacting a mixture of ethanol and methanol in the presence of iodine. The bulk density of the resin prepared by polymerizing the catalyst obtained from the dialkoxy magnesium thus obtained was 0.35 to 0.41, and the activity was 15 to 35 kgPP / gcat, which was not higher than the bulk density of 0.28 to 0.31 and the active 4 to 14 kgPP / gcat when methanol was not used. Only low for commercial use.

The present invention is to solve the problems of the prior art as described above, an object of the present invention, in particular suitable for the production of a catalyst for olefin polymerization capable of sufficiently satisfying the particle characteristics required in the commercial olefin polymerization process such as gas phase polymerization, etc. It is to provide a method for producing a dialkoxy magnesium carrier for an olefin polymerization catalyst having a spherical particle shape excellent in morphology.

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.

It is another object of the present invention to provide a method for producing a propylene polymer using the solid catalyst for olefin polymerization of the present invention, wherein the particles are uniform and contain no microparticles.

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 with an alcohol and a reaction initiator, and is used by mixing ethanol, normal propanol or isopropanol as the alcohol. The metal magnesium and the alcohol are divided and added three times or more, and the reaction initiator is injected at the start of the first reaction, and then divided into three or more times as necessary during the reaction, and further added.

Although the form of the metal magnesium particles used in the carrier production method of the present invention is not particularly limited, the size of the metal magnesium particles is preferably in the form of a powder having an average particle diameter of 10 to 500 µm, 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.

As the mixed alcohol used in the carrier production method of the present invention, normal propanol or isopropanol is mixed with ethanol as a second alcohol component. In the mixed alcohol, the volume ratio of ethanol to normal propanol (or isopropanol) is preferably 2: 1 to 40: 1, and too much or too little propanol outside the above range is preferable because the breakdown strength of the resulting magnesium alkoxide is lowered. Not.

The use ratio of the mixed alcohol with respect to the metal magnesium is preferably 1: 5 to 50, and more preferably 1: 7 to 30 as the ratio of the metal magnesium weight: mixed alcohol volume. When the use ratio is less than 1: 5, the viscosity of the slurry is rapidly increased to make 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 rough. Occurs and is not preferred.

In the carrier production method of the present invention, a nitrogen halide compound or magnesium halide may be used as the reaction initiator used in the reaction of the metal magnesium with the alcohol.

Nitrogen halide compounds 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.

The amount of the reaction initiator is preferably used 0.001 ~ 0.2 parts by weight based on 1 part by weight of metal magnesium. If the amount is less than 0.001 parts by weight, the reaction rate is too slow. If the amount is more than 0.2 parts by weight, the particle size of the product may be too large or a large amount of fine particles may be produced.

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 in three or more times, the reaction initiator is injected at the start of the initial reaction three or more times as necessary during the reaction It is preferable to divide and add further. Thus, by injecting the injection number of the metal magnesium and mixed alcohol three or more times, the slurry viscosity is adjusted to make the surface of the particles smoother, and the formation of fine particles can be suppressed. When the number of divided additions of the metal magnesium and alcohol and the number of additional additions of the reaction initiator are two or less, there is a limit in controlling the particle size, and it is difficult to form spherical particles and also reduces the apparent density of the carrier. have.

In the carrier production method of the present invention, the reaction of the metal magnesium and the mixed alcohol in the presence of the reaction initiator is preferably performed at a temperature of 25 ~ 110 ℃, more preferably at a temperature of 50 ~ 100 ℃. After the aging treatment, the reaction of the metal magnesium and alcohol is preferably made at a temperature of 60 ~ 110 ℃. Moreover, it can also make it react, refluxing at the boiling point temperature of 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 temperature exceeds 110 ° C., since the reaction occurs very rapidly, fine particles may be generated and agglomeration between particles may occur. Not.

In the presence of the reaction initiator, the stirring speed of the reaction of the metal magnesium and the mixed alcohol is preferably 50 to 300 rpm, more preferably 70 to 250 rpm. If the stirring speed is too slow or too fast, there is a disadvantage that the particles are not uniform.

The dialkoxy magnesium carrier prepared by the above production method has a uniform spherical particle shape, a particle size of 40 to 80 μm, a breaking strength of 3.0 MPa or more, and olefin polymerization using a catalyst using the carrier of the present invention. In addition, it is possible to produce polymers with a good morphology, together with a significantly reduced fine content of less than 0.1% by weight.

In the catalyst for olefin polymerization according to the present invention, the dialkoxy magnesium carrier in the form of a uniform spherical particle prepared by the method of the present invention is first reacted with titanium halide in the presence of an organic solvent to replace an alkoxy group of dialkoxy magnesium with a halogen group. Next, it can be prepared by reacting the titanium halide and the internal electron donor in the range of 0 ~ 130 ℃ in the presence of an organic solvent, thereby obtaining a porous solid titanium halide 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, more preferably a saturated aliphatic or aromatic hydrocarbon having 7 to 10 carbon atoms may be used, Specific examples thereof may include octane, nonane, decane or toluene, xylene and the like.

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, diisooctylphthalate, di (3-ethylhexyl) phthalate, dinohexyl phthalate, dinomalheptyl phthalate, diisoheptyl phthalate, dinoheptyl Selected from compounds represented by the following general formulas, such as talate, diomal 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 dialkoxymagnesium, and the injection rate of titanium halide is gradually added over 30 minutes to 3 hours. Preferably, 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 with respect to 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. At this time, the temperature and the number of times of the internal electron donor are not particularly limited, but the total amount of the internal electron donor is used. It is preferable to use 0.1-1.0 weight part with respect to 1 weight part of magnesium. When the amount of the internal electron donor is out of this 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 may optionally be subjected to tertiary contact with titanium halide, washing with an organic solvent, and drying to obtain a resultant solid catalyst for propylene polymerization.

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

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. can be used.

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, 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 is 2, two R ² groups may be the same or different.), And specific examples of these compounds include nC ₃ H ₇ Si (OCH ₃ ) ₃ , (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 H7) 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 ₂ Si (OCH ₃ ) ₂ (Ph is a phenyl group), 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 , (cyclohexyl ) (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 , (phenyl) Si (OC ₂ H ₅ ) ₃ , (phenyl) 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, a suitable ratio of component C to component A is in the range of 1 to 200 as the molar ratio of silicon atoms in component C to titanium atoms in component A. 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, the polymerization activity of the catalyst is significantly lowered.

According to the present invention by controlling the use of the mixed alcohol of a specific composition, the injection amount and the number of injection of the metal magnesium, alcohol and the reaction initiator, having a particle size of 40 ~ 80㎛ depending on the reaction conditions, the breaking strength is improved The dialkoxy magnesium carrier which has the spherical particle shape which is excellent in the morphology of the surface is manufactured. In addition, the use of certain mixed alcohols can significantly reduce the total amount of microparticles in the resulting polymer to less than 0.1% by weight.

The solid catalyst prepared using the dialkoxy magnesium carrier prepared according to the present invention has a high catalytic activity of 55 kg-PP / g-cat or more, and has an apparent density of 0.42 g, which greatly affects high stereoregularity and especially commercial productivity. It is possible to provide polymers of higher than / cc, which makes it particularly suitable for commercial applications of gas phase polymerization processes.

1 is an electron micrograph of the polymer prepared in Example 1.
2 is an electron micrograph of the polymer prepared in Comparative Example 1.

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 1

[Preparation of Spherical Carrier]

A 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux was sufficiently ventilated with nitrogen, followed by 2 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm), and mixed alcohol (ethanol 200 ml). 100 ml of normal propanol) was added thereto, and the temperature of the reactor was maintained at 78 ° 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. After the end of hydrogen evolution, the reactor temperature was maintained at 78 ° C. for 1 hour. After 1 hour, 20 g of metal magnesium (powder product having an average particle diameter of 120 µm), 300 ml of mixed alcohol (200 ml of ethanol + 100 ml of normal propanol), and 2 g of N-bromosuccinimide were introduced into the reactor and maintained for 1 hour. Finally, 20 g of metal magnesium (powder product with an average particle diameter of 120 μm), 600 ml of mixed alcohol (400 ml of ethanol + 200 ml of normal propanol) and 2 g of N-bromosuccinimide were injected, followed by 3 hours until the reaction was completed. Was aged. 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 259 g (yield 91.7%) 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 48.3 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 0.75, and the apparent density measured by ASTM D1895 was 0.32 g / cc.

Fracture strength was 3.7 MPa as measured by the Micro Compression Testing Machine. The amount of alkoxy in dialkoxy magnesium is shown in Table 1 by hydrolysis with acid and gas chromatography.

[Production of Solid Catalyst Component]

150 ml of toluene and 25 g of spherical diethoxy magnesium 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 held at 60 占 폚 for 1 hour, then the stirring was stopped and the solid product was allowed to settle, the supernatant liquid was removed, stirred with 200 ml of fresh toluene for 15 minutes 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. The titanium content in the solid catalyst component obtained by drying under flowing nitrogen for 18 hours was 2.10% 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 49.4 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 2.

In Table 1, catalytic activity, stereoregularity, apparent density (BD) and fine particle content (% by weight) were determined by the following method.

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

(2) Stereoregularity (XI): Weight% of insoluble matter crystallized and crystallized in mixed xylene

③ apparent density (BD) = value measured by ASTM D1895

④ Fine particle content (% by weight) = weight% of particles with a particle size of 250 μm or less based on the total polymer

Example 2

[Preparation of Spherical Carrier]

A 5L sized reactor equipped with a stirrer, oil heater and cooling reflux was sufficiently ventilated with nitrogen, followed by 2 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 200 µm), and mixed alcohol (200 ml of ethanol). 300 ml of isopropanol) was added thereto, and the temperature of the reactor was maintained at 78 ° C. while the stirring speed was maintained 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. After the end of hydrogen evolution, the reactor temperature was maintained at 78 ° C. for 1 hour. After 1 hour, 2 g of N-bromosuccinimide was injected into the reactor together with 20 g of metal magnesium (200 탆 powder) and 300 ml of mixed alcohol (200 ml of ethanol + 100 ml of isopropanol). Finally, 20 g of metal magnesium (powder product with an average particle diameter of 200 µm), 600 ml of mixed alcohol (400 ml of ethanol + 200 ml of isopropanol), and 3 g of N-bromosuccinimide were injected for 3 hours until the reaction was completed. Aged. 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 running nitrogen for 24 hours to obtain 263 g (yield 93.6%) of a 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 71.5 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 0.76, and the apparent density measured by ASTM D1895 was 0.31 g / cc. Fracture strength was 3.2 MPa as measured by the Micro Compression Testing Machine. The amount of alkoxy in dialkoxy magnesium is shown in Table 1 as measured by gas chromatography by hydrolysis with acid.

[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 2.08 wt%, and the average particle size was 72.3. [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 2.

Example 3

[Preparation of Spherical Carrier]

A 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux was sufficiently ventilated with nitrogen, followed by 2 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 200 µm), and mixed alcohol (ethanol 300 ml). 400 ml of normal propanol) was added thereto, and the temperature of the reactor was maintained at 78 ° 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. After the end of hydrogen evolution, the reactor temperature was maintained at 78 ° C. for 1 hour. After 1 hour, 2 g of N-bromosuccinimide was injected into the reactor together with 20 g of metal magnesium (powder product having an average particle diameter of 200 µm) and 400 ml of mixed alcohol (300 ml of ethanol + 100 ml of normal propanol) into the reactor and maintained for 1 hour. Finally, 20 g of metal magnesium (powder product with an average particle diameter of 200 µm), 800 ml of mixed alcohol (600 ml of ethanol + 200 ml of normal propanol), and 3 g of N-bromosuccinimide were injected until the reaction was completed. Aged for 3 hours. 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 256 g (yield 90.7%) 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 66.3 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 0.75, and the apparent density measured by ASTM D1895 was 0.31 g / cc. Fracture strength was 3.4 MPa as measured by the Micro Compression Testing Machine. The amount of alkoxy in dialkoxy magnesium is shown in Table 1 by hydrolysis with acid and gas chromatography.

[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 2.15 wt%, and the average particle size was 67.5. [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 2.

Example 4

[Preparation of Spherical Carrier]

A 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux was sufficiently ventilated with nitrogen, followed by 2 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 200 µm), and mixed alcohol (ethanol 300 ml). 400 ml of isopropanol) was added thereto, and the temperature of the reactor was maintained at 78 ° C. while operating the stirring speed 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. After the end of hydrogen evolution, the reactor temperature was maintained at 78 ° C. for 1 hour. After 1 hour, 20 g of metal magnesium (powder product having an average particle diameter of 200 µm) was mixed with 400 ml of mixed alcohol (300 ml of ethanol + 100 ml of isopropanol) and 2 g of N-bromosuccinimide was injected into the reactor and maintained for 1 hour. Finally, 20 g of metal magnesium (powder product with an average particle diameter of 200 µm), 800 ml of mixed alcohol (600 ml of ethanol + 200 ml of isopropanol), and 3 g of N-bromosuccinimide were injected, and then 3 hours until the reaction was completed. Were aged. 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 256 g (yield 90.7%) 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 69.1 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 0.78, and the apparent density measured by ASTM D1895 was 0.32 g / cc. Fracture strength was 3.1 MPa as measured by the Micro Compression Testing Machine. The amount of alkoxy in dialkoxy magnesium is shown in Table 1 as measured by gas chromatography by hydrolysis with acid.

[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. As a result, the titanium content in the resultant solid catalyst was 2.24 wt%, and the average particle size was 70.7. [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 2.

Example 5

[Preparation of Spherical Carrier]

A 5L sized reactor equipped with a stirrer, oil heater, and cooling reflux was sufficiently ventilated with nitrogen, followed by 1 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 200 µm), and mixed alcohol (ethanol 300 ml). 360 ml of normal propanol) was added thereto, and the temperature of the reactor was maintained at 78 ° C. while operating the stirring speed 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. After the end of hydrogen evolution, the reactor temperature was maintained at 78 ° C. for 1 hour. After 1 hour, 2 g of N-bromosuccinimide was injected into the reactor together with 20 g of metal magnesium (powder product having an average particle diameter of 200 µm) and 360 ml of mixed alcohol (300 ml of ethanol + 60 ml of normal propanol) into the reactor and maintained for 1 hour. Finally, 20 g of metal magnesium (powder product with an average particle diameter of 200 µm), 600 ml of mixed alcohol (500 ml of ethanol + 100 ml of normal propanol), and 3 g of N-bromosuccinimide were injected. Aged for hours. 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 266 g (yield 94.1%) 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 65.6 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 0.77, and the apparent density measured by ASTM D1895 was 0.30 g / cc. Fracture strength was 3.5 MPa as measured by the Micro Compression Testing Machine. The amount of alkoxy in dialkoxy magnesium is shown in Table 1 as measured by gas chromatography by hydrolysis with acid.

[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 2.35 wt%, and the average particle size was 67.1. [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 2.

Comparative Example 1

[Preparation of Spherical Carrier]

After adequately ventilating a 5L sized reactor equipped with a stirrer, an oil heater and a cooling reflux with nitrogen, 1 g of N-bromosuccinimide, 20 g of metal magnesium (powder product having an average particle diameter of 200 μm), and 350 ml of ethanol were added thereto. The temperature of the reactor was maintained at 78 ° C. while operating the stirring speed 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. After the end of hydrogen evolution, the reactor temperature was maintained at 78 ° C. for 1 hour. After 1 hour, 20 g of metal magnesium (powder product with an average particle diameter of 200 µm), 350 ml of ethanol, and 2 g of N-bromosuccinimide were injected into the reactor and maintained for 1 hour, and finally, the metal magnesium (average particle diameter was 20 g of a 200 µm powder product), 600 ml of ethanol, and 3 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 260 g (yield 92.0%) 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 68.5 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 0.72, and the apparent density measured by ASTM D1895 was 0.30 g / cc. Fracture strength was 2.3 MPa as measured by the Micro Compression Testing Machine.

[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 69.3. [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 2.

Average particle diameter (mm) Ethoxy content
(weight%) Normal Propoxy
Content (% by weight) Isopropoxy content (% by weight) Breaking strength
(MPa) Example 1 48.3 84.5 15.5 0 3.7 Example 2 71.5 82.3 0 17.7 3.2 Example 3 66.3 90.7 9.3 0 3.4 Example 4 69.1 88.6 0 11.4 3.1 Example 5 65.6 93.8 7.2 0 3.5 Comparative Example 1 68.5 100.0 0 0 2.3

Catalyst size
(탆) activation
(kg-PP / g-cat) Stereoregularity (X.I.) Apparent Density (BD) Fine particle content
(weight%) Example 1 49.4 58.6 98.3 0.43 0.07 Example 2 72.3 57.2 98.5 0.42 0.05 Example 3 67.5 65.2 98.4 0.43 0.04 Example 4 70.7 60.5 98.5 0.42 0.02 Example 5 67.1 65.8 98.2 0.43 0.06 Comparative Example 1 69.3 53.2 98.1 0.39 1.7

As shown in Table 1, the dialkoxy magnesium carrier prepared according to the method of the present invention has a higher breaking strength than that prepared by the conventional method, and as shown in FIG. As a result of analyzing the polymer polymerized using the catalyst using the carrier, the stereoregularity was equal to or higher than the conventional catalyst, and the catalytic activity was higher than 55 kg-PP / g-cat. In the case of using the solid catalyst thus prepared, especially in the gas phase process, a polypropylene polymer having an excellent morphology having an apparent density of 0.42 g / cc or more and a fine particle content of less than 0.1% by weight has a great influence on commercial productivity. can do.

Claims (6)

In the method for producing a dialkoxy magnesium carrier for an olefin polymerization catalyst comprising reacting a metal magnesium with an alcohol in the presence of a reaction initiator, the reaction initiator is a nitrogen halide compound or magnesium halide, and ethanol and A mixed alcohol obtained by mixing normal propanol or isopropanol is used, and the metal magnesium and mixed alcohol are added by dividing three or more times, and the reaction initiator is added at the start of the first reaction, and then added by dividing three or more times during the reaction. A method for producing a spherical carrier for an olefin polymerization catalyst, characterized in that. The method for producing a spherical carrier for an olefin polymerization catalyst according to claim 1, wherein the amount of the metal magnesium and the mixed alcohol is 1: 5 to 50 in the ratio of the weight of the metal magnesium to the volume of the mixed alcohol. The method of claim 1, wherein the reaction temperature of the metal magnesium and the mixed alcohol is 25 ~ 110 ℃. The method of claim 1, wherein the reaction initiator is a nitrogen halide compound 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 carrier prepared according to the method for preparing a spherical carrier for an olefin polymerization catalyst according to any one of claims 1 to 4 is reacted with a titanium halide and diester internal electron donor in the presence of an aliphatic hydrocarbon or an aromatic hydrocarbon having 6 to 12 carbon atoms. The catalyst for olefin polymerization, which is prepared by A process for producing a propylene polymer, comprising polymerizing propylene using a catalyst according to claim 5 and an alkoxysilane compound as alkyl aluminum and an external electron donor as cocatalyst.

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