KR101072750B1 - Method of preparation of spherical support for olefin polymerization catalyst - Google Patents

Abstract

The present invention relates to a method for producing a spherical carrier for an olefin polymerization catalyst, and more particularly, to prepare a MgX (I) (here, X = halogen atom) by first reacting a halogen compound as a reaction initiator with metal magnesium, The present invention relates to a method for producing a spherical carrier for an olefin polymerization catalyst having a smooth spherical dialkoxy magnesium having a uniform particle size distribution by adding a metal magnesium and an alcohol.

Halogen compound, olefin, polymerization, catalyst, carrier, metal magnesium, MgX (I), alcohol, dialkoxymagnesium, spherical

Description

Manufacturing method of spherical carrier for olefin polymerization catalyst {METHOD OF PREPARATION OF SPHERICAL SUPPORT FOR OLEFIN POLYMERIZATION CATALYST}

The present invention relates to a method for producing a spherical carrier for an olefin polymerization catalyst, and more particularly, to prepare a MgX (I) (here, X = halogen atom) by first reacting a halogen compound as a reaction initiator with metal magnesium, The present invention relates to a method for producing a spherical carrier for an olefin polymerization catalyst having a smooth spherical dialkoxy magnesium having a uniform particle size distribution by adding a metal magnesium and an alcohol.

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 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.

As a method for improving the particle shape of the carrier for an olefin polymerization catalyst, recrystallization and reprecipitation methods, spray drying methods, methods using chemical reactions, and the like are known so far, and among these, magnesium, which is one of methods using chemical reactions, is known. The process for preparing a catalyst using dialkoxymagnesium obtained by reacting with an alcohol as a carrier can provide a catalyst having a much higher activity and a resultant polymer having high stereoregularity than other methods. There is a growing interest in this.

However, in general, the process of preparing dialkoxy magnesium by reacting metal magnesium with alcohol is very difficult to control the reaction rate of the initial stage between alcohol and metal magnesium, and the coagulation phenomenon between particles does not form spherical particles. A large quantity of large particle | grains whose is 100 micrometers or more are produced | generated. As a result, when the resulting catalyst is used for the polymerization of olefins, the surface of the polymer is very uneven, the particle size becomes too large, or the breakage of the granular shape due to the heat of polymerization occurs, which lowers the apparent density of the resulting polymer. In particular, a large amount of macroparticles may make the polymer poor in flowability, making it difficult to apply to production plants. As such, 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. During the reaction, dialkoxy magnesium carriers of uniform size, spherical shape and sufficiently high apparent density should be prepared.

Various methods for producing dialkoxy magnesium of uniform shape are disclosed in the prior art documents. In US Pat. Nos. 5,162,277 and 5,955,396, a carrier having a size of 5 to 10 µm is prepared by recrystallizing magnesium ethyl carbonate obtained by carboxylating an amorphous diethoxy magnesium with carbon dioxide using various additives and solvents. I'm suggesting how. In addition, 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, according to Japanese Patent Application Laid-Open Nos. 03-74341, 04-368391 and 08-73388, a method for synthesizing spherical or elliptical diethoxy magnesium by reacting metal magnesium with ethanol in the presence of iodine is provided. 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 with a lot of heat of reaction during the reaction, and the reaction occurs very rapidly, and the resulting diethoxy 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.

When the catalyst prepared from the resultant carrier is used as it is for the polymerization of olefins, problems such as excessively large particle size of the polymer or serious disruption of the process due to the destruction of the particle shape by the heat of polymerization during the polymerization process are caused. have.

The present invention has been made to solve the above problems, the object of the present invention is to carry out the reaction more stably than the conventional method using the reaction initiator directly to reduce the number of large particles, the surface of the uniform size Olefin polymerization catalyst suitable for use in the preparation of a catalyst capable of sufficiently satisfying the particle characteristics required in commercial olefin polymerization processes such as slurry polymerization, bulk polymerization, gas phase polymerization, etc. by preparing a dialkoxy magnesium carrier having a smooth spherical particle shape. It is to provide a method for producing a spherical carrier.

In the method for producing a spherical carrier for an olefin polymerization catalyst according to the present invention, a halogen compound is first reacted with a metal magnesium as a reaction initiator to prepare MgX (I) (here, X = halogen atom), and then in the presence of MgX. Metal magnesium and alcohol are added to the metal magnesium and the alcohol is reacted.

The metal magnesium used in the preparation method of the carrier of the present invention is not particularly limited in the form of particles. However, the metal magnesium is preferably in the form of a powder having an average particle diameter of 10 to 300 µm and more preferably in the form of a powder of 50 to 200 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 a product becomes too fine. If the average particle size of the metal magnesium exceeds 300 mu m, the average particle size of the carrier is too large. It is not preferable because it becomes difficult to form.

As the halogen compound used as a reaction initiator in the carrier preparation method of the present invention, for example, halogen molecules such as I ₂ , Br ₂ , IBr, CH ₃ I, CH ₃ Br, CH ₃ CH ₂ Br, BrCH ₂ Alkyl halide compounds such as CH ₂ Br and the like, acyl halide compounds such as CH ₃ COCl, PhCOCl (Ph = phenyl), Ph (COCl) ₂ , LiCl, LiBr, LiI, MgCl ₂ , MgBr ₂ , MgI ₂ , CaCl ₂ , CaBr ₂ , alkali or alkaline earth metal halide compounds such as CaI ₂ , TiCl ₄ , TiBr ₄ , TiI ₄ , ZrCl ₄ , ZrBr ₄ , ZrI ₄ , HfCl ₄ , HfBr ₄ , HfI ₄ , CrCl ₃ , MoCl ₃ , WCl ₃ , _{FeCl 2, FeBr 2, NiCl 2} , NiBr 2, NiI 2, PdCl 2, PdBr 2, PdI 2, PtCl 2, PtBr 2, PtI 2, ZnCl 2, AgCl 2, AgBr 2, AgI 2, CuCl 2, CuBr 2 Transition metal halide compounds such as, CuI ₂ , HgCl _2, etc. and LaCl ₃ , LaBr ₃ , LaI ₃ , CeCl ₃ , CeBr ₃ , CeI ₃ , PrCl ₃ , PrBr ₃ , PrI ₃ , NdCl ₃ , NdBr ₃ , NdI ₃ , PmCl ₃ , PmBr ₃ , PmI ₃ , SmCl ₃ , SmI ₃ , SmI ₂ , GaCl ₃ , EuCl ₃ , TbCl ₃ , Metal halide compounds containing lanthanide and actinic metals such as DyCl ₃ , HoCl ₃ , ErCl ₃ , TmCl ₃ , YbCl ₃ , LuCl ₃ , and general formula AlCl _m (OR) _3-m , where R is 1 carbon An aluminum halide compound represented by -10 hydrocarbon group, m is a natural number of 1 to 3, and general formula SiCl _n (OR) _4-n , wherein R is a hydrocarbon group of 1 to 10 carbon atoms, n Is one or two or more selected from the silicon halide compounds represented by 1 to 4), and preferably a magnesium halide compound such as MgCl ₂ , MgBr ₂ , MgI _2, or the like. It is more preferable to use species or two or more kinds alone or in combination.

The amount of the halogen compound should be used as the number of moles in which MgX (I) is formed by reacting with the metal magnesium, otherwise the reaction rate is too slow, or the particle size of the product is too large or a large amount of fine particles are generated. It is not desirable because it can be. For example, when using a halogen molecule such as I ₂ or Br ₂ as a halogen compound, since 2 mol of halogen atoms react per mol of Mg, 0.5 mol of halogen molecules should be reacted per mol of Mg, and MgCl ₂ In the case of using a halogen compound, MgCl ₂ is produced only by reacting 1 mol of MgCl ₂ per mol of Mg. In this case, the metal magnesium and the halogen compound must be reacted in the same mole number. Depending on the type of halogen compound used, the amount (molar number) of the halogen compound for obtaining MgX (I) by reaction with metal magnesium may be easily determined by those skilled in the art.

In the carrier production method of the present invention, the reaction of the halogen compound and the metal magnesium is preferably carried out in the presence of alcohol, the reaction temperature of the reaction of the halogen compound and the metal magnesium is preferably 25 ~ 110 ℃. It is more preferable that the reaction temperature is less than 25 ° C, but the reaction is too slow because the reaction temperature is less than 25 ° C. Agglomeration of particles occurs, which is not preferable because a uniform spherical carrier of a desired size cannot be obtained.

In the method for preparing a carrier of the present invention, MgX (I) (herein, X = halogen atom) is generated by the reaction of the halogen compound with the metal magnesium, and then the metal magnesium and the alcohol are added again to present the MgX (I). Under the reaction of the metal magnesium and alcohol, the MgX (I) acts as a catalyst in the reaction between the metal magnesium and the alcohol, for example, methanol, ethanol, General formula -ROH, wherein R is an alkyl group having 1 to 6 carbon atoms, such as normal propanol, isopropanol, normal butanol, isobutanol, normal pentanol, isopentanol, neopentanol, cyclopentanol, and cyclohexanol. It is preferable to use a mixture of one or more alcohols selected from aliphatic alcohols represented by the above and aromatic alcohols such as phenol, and may be selected from methanol, ethanol, propanol and butanol. 1 is more preferable to use a mixture of more thereof, and is most preferable to use ethanol, and there is no particular limitation on the mixing ratio of the two or more kinds of alcohol.

In the preparation method of the carrier of the present invention, the use ratio of the alcohol to the metal magnesium used in the reaction of the metal magnesium with the alcohol is preferably 1: 5 to 1:50 in the metal magnesium weight: alcohol volume. , 1: 7 to 1:20, more preferably, the use ratio is less than 1: 5, the viscosity of the slurry is rapidly increased to uniform stirring is difficult, it is not preferable, if the ratio exceeds 1:50 the apparent of the resulting carrier This is undesirable because of the sharp decrease in density or roughness of the particle surface.

It is preferable that the reaction temperature of the said metal magnesium and alcohol is 60-110 degreeC, It is more preferable that it is 70-90 degreeC, In addition, it can also make it react, refluxing at the boiling point temperature of alcohol.

The preparation method of the carrier of the present invention has a spherical particle shape with a uniform particle size distribution, and greatly reduces the number of microparticles of 5 μm or less and large particles of 100 μm or more, thereby enabling commercial application of the resulting carrier.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1

Ventilate the 5 L sized reactor (reactor A) equipped with a stirrer, oil heater and cooling reflux with nitrogen sufficiently, and then use magnesium chloride 3.0 g (32 mmol) and metal magnesium (powder product with an average particle diameter of 100 μm) as a reaction initiator. g (32 mmol) and 100 ml of anhydrous ethanol were added thereto, and the temperature of the reactor was raised to 78 ° C. while maintaining the stirring speed at 200 rpm. After about 5 minutes, MgCl (I) was generated, and 20 g of metal magnesium (powder product having an average particle diameter of 100 µm) and 200 ml of ethanol were added and reacted for 20 minutes. Since the hydrogen is generated as the reaction starts, the outlet of the reactor is left open so that the generated hydrogen is released, thereby maintaining the pressure in the reactor at atmospheric pressure. After the generation of hydrogen, 20 g of metal magnesium (powder product having an average particle diameter of 100 µm) was suspended in 500 mL of anhydrous ethanol, and added to Reactor A, which was divided into three times every 30 minutes while stirring to make the concentration uniform. After about 5 minutes of injecting the mixture of metal magnesium and ethanol into the reactor A, the reaction starts and hydrogen is generated. Therefore, the outlet of the reactor was left open so that the generated hydrogen was released, and the pressure was maintained at atmospheric pressure. . After the injection of both metal magnesium and ethanol, the temperature and stirring speed of reactor A were maintained at reflux for 2 hours (aging treatment). 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 278 g (yield 98.4%) of a solid white powdery product.

The particle shape of the dried product was observed by electron microscope and the apparent density was measured. In addition, the particle size of the dried product suspended in normal hexane was measured by a light transmission method using a laser particle analyzer (Mastersizer X: manufactured by Malvern Instruments) to obtain a cumulative distribution of particle size, from which the average particle diameter , The particle size distribution index and the content of the macroparticles were determined as follows.

① Average particle size (D ₅₀ ): Size of particles corresponding to 50% cumulative weight

② Particle size distribution index (P): P = (D ₉₀ -D ₁₀ ) / D ₅₀

(Wherein D ₉₀ is the particle size equivalent to 90% cumulative weight and D ₁₀ is the size particle equivalent to 10% cumulative weight)

③ Large Particle Content: Cumulative weight percentage (%) of particles with a particle size of 100㎛ or more

The above observed, measured and determined results are shown in Table 1.

Example 2

4 g (16 mmol) of iodine (I ₂ ) was added to Reactor A together with 0.766 g (32 mmol) of metal magnesium and 100 ml of anhydrous ethanol as the reaction initiator, in the same manner as in Example 1, 274 g (yield 97.0%) of solid product having a very good flowability in white powdery form were obtained, and the results observed, measured and determined in the same manner as in Example 1 are shown in Table 1.

Example 3

As a reaction initiator, 8.0 g (32 mmol) of magnesium bromide (MgBr ₂ ) was added to Reactor A together with 0.766 g (32 mmol) of metal magnesium and 100 ml of anhydrous ethanol. Thus, 270 g (yield 95.6%) of solid product having a very good flowability in white powdery form was obtained, and the results observed, measured and determined in the same manner as in Example 1 are shown in Table 1.

Example 4

In the same manner as in Example 1, except that 2.5 g (16 mmol) of bromine (Br ₂ ) was added to Reactor A together with 0.766 g (32 mmol) of metal magnesium and 100 ml of anhydrous ethanol as a reaction initiator. 272 g (yield 96.3%) of solid powder having a very good flowability was obtained, and the results observed, measured and determined in the same manner as in Example 1 are shown in Table 1.

Example 5

In the same manner as in Example 1, except that 4.56 g (32 mmol) of methane iodide (CH ₃ I) was added to the reactor A together with 0.766 g (32 mmol) of metal magnesium and 100 ml of anhydrous ethanol as a reaction initiator. It was carried out to obtain 280 g (yield 99.1%) of a white powdery solid product having very good flowability, and the results observed, measured, and determined in the same manner as in Example 1 are shown in Table 1.

Comparative example

After fully ventilating a 5L sized reactor equipped with a stirrer, an oil heater and a cooling reflux with nitrogen, add 3 g of iodine (3 g) and 1800 ml of anhydrous ethanol, and operate the stirrer at 200 rpm to raise the temperature of the reactor to 78 ° C. to reflux the ethanol. Was maintained. Next, 120 g of metal magnesium (powdery product having an average particle diameter of 100 µm) was added to the reactor in which ethanol was refluxed, divided into six portions of 20 g at 20 minute intervals. After all 120 g of the metal magnesium was added, the same stirring speed was maintained for 2 hours under the condition of reflux of ethanol (aging treatment). After the aging treatment was completed, the resultant was washed three times using 2000 ml of normal hexane per wash at 40 ° C. The washed product was dried under flowing nitrogen for 24 hours to obtain 565 g (99% yield) of a white powdery solid product, and the same results as in Example 1 were shown in Table 1 for the observed, measured, and determined results.

TABLE 1

Particle shape Apparent density
(g / cc) Average particle diameter
(D ₅₀ , μm) Particle size distribution index Large particle amount (% by weight)
(size> 75㎛) Example 1 rectangle 0.28 42 0.75 7.7 Example 2 rectangle 0.30 35 0.69 8.3 Example 3 rectangle 0.31 27 0.88 5.7 Example 4 rectangle 0.30 22 0.82 6.9 Example 5 rectangle 0.27 30 0.96 10.3 Comparative example Rough sphere 0.30 32 1.45 25.4

As shown in Table 1, Examples 1 to 5 have a smooth spherical particle shape, uniform particle size distribution, and have a large particle content of about 5 to 10 wt%, which is more noticeable than a comparative example having a large particle content of 25.0 wt% or more. It can be seen that less.

Claims (4)

In the method for producing a spherical carrier for an olefin polymerization catalyst comprising reacting a metal magnesium with an alcohol, a MgX (I) (here, X = halogen atom) is prepared by first reacting a halogen compound with a metal magnesium as a reaction initiator. After that, the method of producing a spherical carrier for an olefin polymerization catalyst, characterized in that the reaction with a metal magnesium and alcohol in the presence of the MgX (I). The metal halide compound of claim 1, wherein the halogen compound comprises a halogen molecule, an alkyl halide compound, an acyl halide compound, an alkali metal or alkaline earth metal halide compound, a transition metal halide compound, a lanthanide and an actin group metal. And at least one selected from a silicon halide compound. The spherical carrier for an olefin polymerization catalyst according to claim 1, wherein the alcohol is at least one selected from aliphatic alcohols and aromatic alcohols represented by general formula ROH (wherein R is an alkyl group having 1 to 6 carbon atoms). Manufacturing method. The method for producing a spherical carrier for an olefin polymerization catalyst according to claim 1, wherein the use ratio of the alcohol to the metal magnesium is 1: 5 to 1:50 by weight: alcohol volume of the metal magnesium.