JPWO2019151483A1 - Alkoxy Magnesium Manufacturing Method and Alkoxy Magnesium - Google Patents

Abstract

In the reaction system, metallic magnesium is intermittently added to alcohol a plurality of times to produce alkoxymagnesium, and all of the second and subsequent additions of metallic magnesium to the reaction system are added to the reaction system. In the addition of 5% by mass or more of metallic magnesium, the generation rate S (liter / min) of hydrogen produced by reacting with the alcohol by the addition of the immediately preceding metallic magnesium increased to the maximum value at least once. After that, it is a method for producing alkoxymagnesium after reducing it to 45% or less of the maximum value, and it is possible to effectively prepare alkoxymagnesium having a high bulk density, a reduced proportion of fine particles, and a narrow particle size distribution. It is a manufacturing method.

Description

The present invention relates to a method for producing alkoxymagnesium and a method for producing alkoxymagnesium.

The main production method of the solid catalyst component for polymerization of highly active olefins known as the Ziegler-Natta catalyst is the surface of a magnesium chloride carrier activated by mechanical pulverization of a vibrating ball mill or the like or dissolution and reprecipitation using alcohol or the like. A method of obtaining a solid catalyst component by supporting a titanium compound, a method of halogenating alkoxymagnesium with a chloride such as titanium tetrachloride, and then supporting a titanium compound to obtain a solid catalyst component for olefin polymerization are known. There is.

However, when the olefins are polymerized using the solid catalyst component for olefin polymerization obtained by the above method, the obtained olefin polymer contains a large amount of fine powder or coarse powder polymer. The particle size distribution also tended to be broadened. When the amount of the fine powder polymer or the crude powder polymer produced in the produced polymer is large, it hinders the continuation of the uniform polymerization reaction and causes process troubles such as blockage of the piping during the polymer transfer, and is obtained. If the particle size distribution of the olefin polymer is widened, the result is an unfavorable effect on the molding process of the polymer.

Further, in recent years, improvement of productivity and transportation efficiency has been required in the production of olefin polymers, and improvement of bulk density of olefin polymers has become one of the important issues.

As a technique for producing dialkoxymagnesium used as a carrier for a solid catalyst component for olefin polymerization, for example, Patent Document 1 (Japanese Unexamined Patent Publication No. 58-41832) describes a reaction consisting of metallic magnesium, alcohol and saturated hydrocarbon. A method for producing particulate dialkoxymagnesium with high purity by gradually adding an activator dissolved in saturated hydrocarbon to the system and reacting the system is disclosed.

Further, in Patent Document 2 (Japanese Patent Laid-Open No. 2006-306949), in the presence of metal alkoxide compound carrier particles such as dialkoxymagnesium having a high bulk density, metallic magnesium is reacted with alcohol, and alkoxy is applied on the surface of the carrier. A method for producing dialkoxymagnesium having a morphology suitable for propylene-ethylene block copolymerization, which forms a layer made of magnesium, is disclosed.

JP-A-58-41832 JP-A-2006-306949

However, in the above-mentioned prior art, it is not always a sufficient method for producing alkoxymagnesium having a high bulk density and a narrow particle size distribution, which is necessary for obtaining an olefin polymer having a high bulk density and a narrow particle size distribution. It was hard to say, and there was room for further improvement.

Therefore, an object of the present invention is to provide an alkoxymagnesium having a high bulk density and a narrow particle size distribution, and a method for producing an alkoxymagnesium capable of effectively preparing such an alkoxymagnesium, and an alkoxymagnesium.

As a result of diligent studies by the present inventors in order to solve the above technical problems, it is a method for producing alkoxymagnesium by intermittently adding metallic magnesium to alcohol a plurality of times in the reaction system, to the reaction system. Of the second and subsequent additions of metallic magnesium, in addition of 5% by mass or more of the total metallic magnesium added to the reaction system, one or more of the additions are produced by reacting with the alcohol by the addition of the immediately preceding metallic magnesium. It was found that the above technical problem can be solved by a method for producing alkoxymagnesium, which is carried out after the generation rate S (liter / min) of the generated hydrogen is increased to the maximum value and then reduced to 45% or less of the maximum value. , The present invention has been completed based on this finding.

That is, the present invention
(1) A method for producing alkoxymagnesium by intermittently adding metallic magnesium to alcohol a plurality of times in a reaction system.
Of the second and subsequent additions of metallic magnesium to the reaction system, in the addition of 5% by mass or more of the total metallic magnesium added to the reaction system, one or more of them are added.
The feature is that the hydrogen generation rate S (liters / minute) generated by reacting with the alcohol is increased to the maximum value by the addition of the metal magnesium immediately before, and then reduced to 45% or less of the maximum value. Alkoxymagnesium production method,
(2) The second and subsequent additions in the multiple additions of metallic magnesium to the reaction system, the generation rate S (liter / min) of hydrogen generated by reacting with the alcohol by the addition of the immediately preceding metallic magnesium. The production of the alkoxymagnesium according to (1) above, wherein the number of additions performed after increasing to the maximum value and then reducing to 45% or less of the maximum value is 35% or more of the number of additions after the second time. Method,
(3) In the multiple additions of metallic magnesium to the reaction system, the amount of metallic magnesium added at one time is 33% by mass or less of the total amount of metallic magnesium added to the reaction system (1) or The method for producing alkoxymagnesium according to (2),
(4) In the second addition of metallic magnesium to the reaction system, the generation rate S (liter / min) of hydrogen produced by reacting with the alcohol by the addition of the immediately preceding metallic magnesium increases to the maximum value. After that, the addition is performed after the hydrogen generation rate S (liter / min) is reduced to 0% of the maximum value within 180 seconds after the hydrogen generation rate S (liter / min) is reduced to 45% or less of the maximum value (1). ) To the method for producing alkoxymagnesium according to any one of (3).
(5) The bulk density is 0.160 to 0.400 g / ml, the particle size distribution index SPAN is 1.00 or less, and the integrated particle size of the volume integrated particle size distribution obtained by using the laser diffraction type particle size distribution measuring device is the particle size of 50% of the particles is taken as _{D 50,} the following formulas _(a 1)
(D ₅₀ x total volume of particles having a particle size of 1.25 or more / total volume of all particles) x 100 (a ₁ )
Alkoxymagnesium, characterized in that the proportion represented by is 30.0% by volume or less.
(6) when the cumulative particle size of cumulative volume particle size distribution obtained with a laser diffraction type particle size distribution measuring apparatus has a particle size of 50% of the particles and D _50, the following formulas (a ₂₎
(Number of particles having a particle size of D ₅₀ × 0.75 or less / total number of particles) × 100 (a ₂ )
The alkoxymagnesium according to (5) above, wherein the proportion represented by is 20% or less is provided.

According to the present invention, it is possible to provide a method for producing alkoxymagnesium capable of effectively preparing alkoxymagnesium having a high bulk density and a narrow particle size distribution, and alkoxymagnesium having a high bulk density and a narrow particle size distribution.

It is a figure which compares the amount of hydrogen generation in an Example of this invention and a comparative example.

First, a method for producing alkoxymagnesium according to the present invention will be described.
The method for producing alkoxymagnesium according to the present invention is a method for producing alkoxymagnesium by intermittently adding metallic magnesium to alcohol a plurality of times in a reaction system, and the second and subsequent metallic magnesiums to the reaction system. In the addition of 5% by mass or more of the total metallic magnesium to be added to the reaction system, the generation rate S of hydrogen generated by reacting with the alcohol by the addition of the immediately preceding metallic magnesium at least once. It is characterized in that the liter / min) is increased to the maximum value and then reduced to 45% or less of the maximum value.

The alcohol that can be used in the method for producing alkoxymagnesium according to the present invention is not particularly limited, and for example, the following general formula (I)
R ¹ OH (I)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms.)
Among them, lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol and hexanol are preferable, and ethanol is more preferable.
When the alcohol is ethanol, ethoxymagnesium formed by reacting with metallic magnesium significantly improves the catalytic performance when used as a material for forming a catalyst for olefin polymerization.
The purity and water content of the alcohol are not particularly limited, but the smaller the water content, the more preferable. Specifically, anhydrous alcohol or dehydrated alcohol having a water content of 200 ppm or less is desirable.

In the method for producing alkoxymagnesium according to the present invention, only one type of alcohol may be used, or two or more types may be used.

The metallic magnesium that can be used in the method for producing alkoxymagnesium according to the present invention is not particularly limited, and metallic magnesium having any shape can be used.
As the metallic magnesium, for example, granules, ribbons, powders and the like can be preferably used, and powdered metallic magnesium is more preferable.
Further, the surface condition of the metallic magnesium is not particularly limited, but it is desirable that a film such as magnesium oxide is not formed on the surface.

In the method for producing alkoxymagnesium according to the present invention, the average particle size of metallic magnesium is preferably 1 to 1000 μm, more preferably 20 to 800 μm, and even more preferably 10 to 500 μm.
In this application document, the average particle size of metallic magnesium is automatically measured by using a laser light scattering diffraction method particle size counter in a state where 30 to 300 mg of metallic magnesium particles are dispersed in 200 to 500 ml of solvent per sample. It means a particle size (D ₅₀ ) of 50% in the integrated particle size distribution in the volume integrated particle size distribution.
The laser light scattering diffraction method particle size measuring machine used for measuring the average particle size of metallic magnesium includes "MICROTRAC HRA 9320-X100" (manufactured by Nikkiso Co., Ltd.) and "MT3300EXII" (Microtrac Bell Co., Ltd.). Made) and the like.

In the method for producing alkoxymagnesium according to the present invention, metallic magnesium is intermittently added to the reaction system a plurality of times with respect to alcohol.

The number of times of addition of metallic magnesium to the reaction system is preferably 3 times or more, more preferably 4 times or more, further preferably 5 times or more, and particularly preferably 6 times or more. The upper limit of the number of additions is not particularly limited, but is usually 20 or less.
The metallic magnesium is preferably added into the reaction system in a state of being dispersed in alcohol or the like.

By increasing the number of times metallic magnesium is added to the reaction system, it becomes easier to control the heat of reaction generated during the addition, and it is possible to easily prepare alkoxymagnesium having a small amount of fine powder and a narrow particle size distribution and a high bulk density. The particle size of alkoxymagnesium can be controlled within a desired range. At the same time, it is possible to suppress the temporary mass generation of hydrogen gas.

In the method for producing alkoxymagnesium according to the present invention, the alcohol is represented by the above general formula R ¹ OH (I) (in the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms). When the alcohol to be used is used and contacted with and reacted with metallic magnesium, the reaction represented by the following general formula (II) occurs.

Mg + 2R ¹ OH → Mg (OR ¹ ) ₂ + H ₂ (II)

In the method for producing alkoxymagnesium according to the present invention, of the second and subsequent additions of metallic magnesium to the reaction system, one or more additions of 5% by mass or more of the total metallic magnesium added to the reaction system are performed. The hydrogen generation rate S (liter / min) generated by reacting with the alcohol is increased to the maximum value by the addition of the metal magnesium immediately before, and then reduced to 45% or less of the maximum value.

In the method for producing alkoxymagnesium according to the present invention, among the second and subsequent additions of metallic magnesium to the reaction system, one or more additions of 5% by mass or more of the total metallic magnesium added to the reaction system are performed. By adding the metal magnesium immediately before, the generation rate S (liters / minute) of hydrogen generated by reacting with the alcohol is increased to the maximum value, and then reduced to 45% or less of the maximum value. Alkoxymagnesium having a high bulk density and a narrow particle size distribution can be easily prepared.

In the method for producing alkoxymagnesium according to the present invention, it is the second and subsequent additions in a plurality of additions of metallic magnesium to the reaction system, and is produced by reacting with the alcohol by the addition of the immediately preceding metallic magnesium for 1 minute. After the hydrogen generation rate S (liter / minute) per hit has increased to its maximum value, the number of additions to be performed after reducing it to 45% or less of the maximum value is 35% or more of the number of additions after the second time. It is preferably 50% or more, more preferably 50 to 100% of the total number of additions, and even more preferably 65 to 100% of the total number of additions.

In the method for producing alkoxymagnesium according to the present invention, it is the second and subsequent additions in a plurality of additions of metallic magnesium to the reaction system, and is produced by reacting with the alcohol by the addition of the immediately preceding metallic magnesium for 1 minute. By controlling the number of additions to be performed after the per-hydrogen generation rate S (liters / minute) has increased to the maximum value and then reduced to 45% or less of the maximum value so as to satisfy the above regulation. Alkoxymagnesium having a high bulk density and a narrow particle size distribution can be more easily prepared.

In the addition of metallic magnesium to the reaction system a plurality of times, the amount of metallic magnesium added at one time is preferably 33% by mass or less, preferably 25% by mass or less, of the total amount of metallic magnesium added to the reaction system. It is more preferably 20% by mass or less, and even more preferably 18% by mass or less.
In the multiple additions of metallic magnesium to the reaction system, the lower limit of the amount of metallic magnesium added at one time is not particularly limited, but is 5% by mass or more of the total amount of metallic magnesium added to the reaction system. Is preferable.
The amount of metallic magnesium added at one time may be the same each time, or may be different each time.
Further, in the method for producing alkoxymagnesium according to the present invention, the maximum value of the amount of hydrogen produced per minute by the reaction with alcohol is generated by the reaction between magnesium and alcohol added to the reaction system each time. It is preferable to control the amount to exceed 5% by volume with respect to the total amount of hydrogen, more preferably to control the amount to exceed 10% by volume, and to be 12% by volume or more and less than 40% by volume. It is more preferable to control.

In the method for producing alkoxymagnesium according to the present invention, by controlling the amount of magnesium added to the reaction system at one time so as to satisfy the above specifications, alkoxymagnesium having a high bulk density and a narrow particle size distribution can be easily prepared. be able to.

In the method for producing alkoxymagnesium according to the present invention, alcohol may be added intermittently to the reaction system, or the entire amount may be added first.

When alcohol is added intermittently to the reaction system, the number of times the reaction accelerator is added to the reaction system is preferably 2 times or more, more preferably 3 times or more, still more preferably 4 times or more.
The upper limit of the number of times the alcohol is added to the reaction system is not particularly limited, but is usually 30 times or less.

By increasing the number of times alcohol is added to the reaction system, it becomes easier to control the heat generated during the reaction, and it is possible to easily prepare high bulk density alkoxymagnesium with a small amount of fine powder generated and a narrow particle size distribution. The particle size of magnesium can be controlled within a desired range. At the same time, it is possible to suppress the temporary mass generation of hydrogen gas.

In the method for producing alkoxymagnesium according to the present invention, the amount of alcohol added to the reaction system is not particularly limited as long as it is equal to or greater than the theoretical amount that reacts with magnesium added to the reaction system, and the total amount of alcohol added to the reaction system. However, the molar ratio to the total amount of metallic magnesium added to the reaction system (total molar amount of alcohol added to the reaction system / total molar amount of metallic magnesium added to the reaction system) is preferably 2 or more, preferably 3 to 30. Is more preferable, and 4 to 20 is even more preferable.

In the method for producing alkoxymagnesium according to the present invention, by controlling the amount of metallic magnesium and alcohol added to the reaction system as described above, uniform nucleation of alkoxymagnesium is performed, and alkoxymagnesium having a narrow particle size distribution can be easily produced. Can be prepared in.

In the method for producing alkoxymagnesium according to the present invention, of the second and subsequent additions of metallic magnesium to the reaction system, one or more additions of 5% by mass or more of the total metallic magnesium added to the reaction system are performed. The hydrogen generation rate S (liter / min) generated by reacting with the alcohol is increased to the maximum value by the addition of the metal magnesium immediately before, and then reduced to 45% or less of the maximum value.

In the method for producing alkoxymagnesium according to the present invention, among the second and subsequent additions of metallic magnesium to the reaction system, one or more additions of 5% by mass or more of the total metallic magnesium added to the reaction system are performed. Within 30 minutes after the generation rate S (liter / min) of hydrogen generated by reacting with the alcohol by the addition of the metal magnesium immediately before is increased to the maximum value and then reduced to 45% or less of the maximum value. It is preferable to add the following metallic magnesium to, and the next metallic magnesium should be added within 0 to 15 minutes after the hydrogen generation rate S (liter / min) is reduced to 45% or less of the maximum value. Is preferable.

Further, in the method for producing alkoxymagnesium according to the present invention, in the second and subsequent additions of metallic magnesium to the reaction system, in addition of 5% by mass or more of the total metallic magnesium added to the reaction system, the first After increasing the generation rate S (liters / minute) of hydrogen generated by reacting with the alcohol to the maximum value by adding the metal magnesium immediately before, and then reducing it to 45% or less of the maximum value. Further, it is preferable to add the following metallic magnesium within a time of 180 seconds after the hydrogen generation rate S (liter / min) is reduced to 0% of the maximum value.

In particular, in the method for producing alkoxymagnesium according to the present invention, the rate S of hydrogen generated by reacting with the alcohol by the addition of the metal magnesium immediately before is the second addition of the metal magnesium to the reaction system. After (liter / min) has increased to the maximum value, the addition is performed after reducing it to 45% or less of the maximum value, and the hydrogen generation rate S (liter / min) is reduced to 0% of the maximum value. It is preferable to carry out within 180 seconds after the above-mentioned hydrogen generation, and more preferably within 150 seconds after the above-mentioned hydrogen generation rate S (liter / min) is reduced to 0% of the above-mentioned maximum value. It is more preferable to carry out the process within 120 seconds after the generation rate S (liter / min) is reduced to 0% of the maximum value.

In the method for producing alkoxymagnesium according to the present invention, the second and subsequent additions of metallic magnesium to the reaction system, particularly the second addition of metallic magnesium to the reaction system, reacts with the alcohol by the addition of the immediately preceding metallic magnesium. After the generation rate S (liters / minute) of the generated hydrogen increases to its maximum value, it is reduced to 45% or less of the maximum value, and then the reaction is carried out within a predetermined time to react the metallic magnesium with alcohol. While suppressing the deterioration of the properties, the formation of coarse particles due to the reaction between the produced alkoxymagnesium can be easily suppressed, and for this reason, the alkoxy having a narrower particle size distribution than the conventional method for producing alkoxymagnesium. Magnesium can be easily obtained.

In the method for producing alkoxymagnesium according to the present invention, the entire step time of the step of adding alcohol and metallic magnesium to the reaction system to carry out the reaction (alcohol and metallic magnesium were first added to the reaction system and then added last. The time required for the amount of hydrogen produced by the reaction of metallic magnesium with alcohol to reach 0% by volume), the maximum value of the hydrogen generation rate S (liters / minute) due to the reaction between the alcohol and metallic magnesium in the same step. Percentage of time that is 45% or less of the maximum value after increasing to, that is, {(in the step of adding alcohol and metallic magnesium to the reaction system and carrying out the reaction, hydrogen is generated by the reaction of alcohol and metallic magnesium. After the rate S (liters / minute) has increased to its maximum value, the time (minutes) when it is 45% or less of the maximum value) / (the step of adding alcohol and metallic magnesium to the reaction system to carry out the reaction. The ratio calculated by the total process time (minutes)} × 100 is preferably 33% or more, more preferably 33 to 80%, and further preferably 40 to 70%.

In the method for producing alkoxymagnesium according to the present invention, even when the above ratio is within a predetermined range, coarse particles are formed by the reaction between the produced alkoxymagnesium while suppressing the decrease in the reactivity between the metallic magnesium and the alcohol. For this reason, alkoxymagnesium having a narrower particle size distribution can be easily obtained as compared with the conventional method for producing alkoxymagnesium.

In the method for producing alkoxymagnesium according to the present invention, the reaction between alcohol and metallic magnesium is preferably carried out in the presence of a reaction accelerator.

As the reaction accelerator, one or more selected from halogens and halogen compounds are preferable.

Examples of the halogen include one or more selected from fluorine, chlorine, bromine and iodine, and among these, one or more selected from chlorine, bromine and iodine are preferable, and iodine is more preferable.

Further, the halogen compound is preferably a compound containing at least one selected from the above halogen atoms in the molecule, and specifically, acid halides such as phthalic acid dichloride and phthalic acid dibromide, magnesium dichloride and trichloride. Metal halides such as aluminum, titanium trichloride, titanium tetrachloride, silicon halide compounds such as tetrachlorosilane, tetrabromosilane, tetraiodosilane, ethoxymagnesium monochloride, triethoxytitanium monochloride, diethoxytitanium dichloride, tri. One or more selected from halide alkoxy metals such as ethoxytitanium chloride can be mentioned. Among these halogen compounds, titanium halides such as titanium trichloride and titanium tetrachloride, silicon halide compounds such as tetrachlorosilane and tetraiodosilane, triethoxytitanium monochloride, diethoxytitanium dichloride, and ethoxytitanium trichloride. It is preferable that one or more selected from halogenated alkoxytitanium such as.

In the method for producing alkoxymagnesium according to the present invention, the shape and particle size of the halogen or halogen compound are not particularly limited, and one or more selected from the halogens and halogen compounds may be appropriately selected.

In the method for producing alkoxymagnesium according to the present invention, the amount of the reaction accelerator added to the reaction system is not particularly limited, and the molar ratio to the total amount of metallic magnesium added to the reaction system (total molar amount of the reaction accelerator added to the reaction system). The amount / total molar amount of metallic magnesium added to the reaction system) is preferably in the range of 0.001 to 1.0, more preferably 0.005 to 0.8, and 0.01 to 0. It is more preferably 5.
When the amount of the reaction accelerator added to the reaction system is within the above range, it becomes easy to control the particle size distribution of the obtained alkoxymagnesium.

In the method for producing alkoxymagnesium according to the present invention, the reaction accelerator may be added continuously or intermittently to the reaction system, or the whole amount may be added first.

When the reaction accelerator is added intermittently to the reaction system, the number of times the reaction accelerator is added to the reaction system is preferably 2 times or more, more preferably 3 times or more, still more preferably 4 times or more.
The upper limit of the number of times the reaction accelerator is added to the reaction system is not particularly limited, but is usually 15 times or less.
The reaction accelerator is preferably added to the reaction system in a state of being dispersed in alcohol or the like.

By increasing the number of times the reaction accelerator is added to the reaction system, it becomes easier to control the heat generated during the reaction between the metallic magnesium and the alcohol, and the rapid reaction between the metallic magnesium and the alcohol can be suppressed, so that the amount of fine powder generated is small. Alkoxymagnesium having a narrow particle size distribution and high bulk density can be easily prepared, and the particle size of the alkoxymagnesium can be controlled within a desired range. At the same time, it is possible to suppress the temporary mass generation of hydrogen gas.

In the method for producing alkoxymagnesium according to the present invention, when the reaction accelerator is intermittently added to the reaction system, metallic magnesium and the reaction accelerator may be added to the reaction system at the same time, but to the reaction system, The reaction accelerator may be added after adding the metallic magnesium.

In the method for producing alkoxymagnesium according to the present invention, the addition and contact of metallic magnesium, alcohol and a reaction accelerator in the reaction system are carried out under the atmosphere of an inert gas such as nitrogen and argon, and under the condition that water, oxygen and the like are removed. In the above, it is preferable to carry out the process while stirring in a container equipped with a stirrer.

The temperature at the time of addition and contact (reaction temperature) is preferably a temperature equal to or lower than the reflux temperature of the alcohol used in the reaction, more preferably room temperature to the reflux temperature of the alcohol used in the reaction, and 30 ° C. to the reaction. It is more preferably the reflux temperature of the alcohol to be served.
By setting the temperature at the time of addition and contact (reaction temperature) within the above temperature range, the reaction efficiency and the controllability of the reaction can be easily improved.
The total step time of the step of adding alcohol and metallic magnesium to the reaction system to carry out the reaction is preferably 30 minutes or more, more preferably 60 minutes or more, and further preferably 90 minutes or more. preferable.

The alkoxymagnesium obtained as described above is appropriately dried by a method such as heat drying, air flow drying or vacuum drying, or the alcohol is removed by a method such as washing with an inert hydrocarbon compound. Is desirable.

The contents of the alkoxymagnesium obtained by the production method according to the present invention are as described in detail in the following description of the alkoxymagnesium according to the present invention.

According to the present invention, it is possible to provide a method for producing alkoxymagnesium capable of effectively preparing alkoxymagnesium having a high bulk density and a narrow particle size distribution as compared with a conventional production method.

Next, the alkoxymagnesium according to the present invention will be described.
The alkoxymagnesium according to the present invention has a bulk density of 0.160 to 0.400 g / ml, a particle size distribution index SPAN of 1.00 or less, and a volume integrated particle size obtained by using a laser diffraction type particle size distribution measuring device. When the particle size of particles with an integrated particle size of 50% is D ₅₀ , the following formula (a ₁ )
(D ₅₀ x total volume of particles having a particle size of 1.25 or more / total volume of all particles) x 100 (a ₁ )
It is characterized in that the ratio represented by is 30.0% by volume or less.
The alkoxymagnesium according to the present invention has a sharp particle size distribution in which the variation in sphericity of each particle is small, the bulk density is high, and the number of fine particles and coarse particles is small.

The alkoxymagnesium according to the present invention has a bulk density (BD) of 0.160 to 0.400 g / ml, preferably 0.200 to 0.400 g / ml, and is preferably 0.200 to 0.350 g / ml. The one in ml is more preferable.
In this application document, the bulk density means a value measured in accordance with JIS K6721.

The average particle size of the alkoxymagnesium according to the present invention is preferably 1 to 200 μm, more preferably 5 to 100 μm.
The average particle size of the alkoxymagnesium is the integrated particle size in the volume integrated particle size distribution when automatically measured with a laser light scattering diffraction method particle size measuring machine in a state where 10 to 100 mg of particles are dispersed in 200 to 500 ml of a solvent. Means a particle size D of ₅₀ (μm) of 50%.
The laser light scattering diffraction method particle size measuring machine used for measuring the average particle size of the alkoxymagnesium includes "MICROTRAC HRA 9320-X100" (manufactured by Nikkiso Co., Ltd.) and "MT3300EXII" (Microtrack Bell). (Made by Co., Ltd.) and the like.

The alkoxymagnesium according to the present invention has the following formula particle size distribution index (SPAN) = (D _90- D ₁₀ ) / D _50.
(In the above formula, D ₉₀ , D ₅₀ and D ₁₀ are each automatically measured by using a laser diffraction type particle size distribution measuring device with 10 to 100 mg of particles per sample dispersed in 200 ml of solvent. , 90% particle size (μm), 50% particle size (μm), 10% particle size (μm), which means the integrated particle size in the volume integrated particle size distribution) is 1.00. It is less than or equal to, preferably 0.80 or less.
The laser light scattering diffraction method particle size measuring machine used when measuring D ₉₀ , D ₁₀ and D ₅₀ of alkoxymagnesium used for calculating the above SPAN is "MICROTRAC HRA 9320-X100" (Nikkiso Co., Ltd.). (Manufactured by) and "MT3300EXII" (manufactured by Microtrack Bell Co., Ltd.), etc.

The SPAN indicates the degree of spread of the particle size distribution, and the smaller this value is, the sharper the particle size distribution is and the more uniform the particle size is.

The alkoxymagnesium according to the present invention has the following formula (a ₁ ) when the particle size of particles having an integrated particle size of 50% in the volume integrated particle size distribution obtained by using a laser diffraction type particle size distribution measuring device is D _50.
(D ₅₀ x total volume of particles having a particle size of 1.25 or more / total volume of all particles) x 100 (a ₁ )
The ratio represented by is 30.0% by volume or less (0% by volume to 30.0% by volume), and preferably 25% by volume or less (0% by volume to 25% by volume).

In the alkoxymagnesium according to the present invention, the ratio of the total volume amount of the particles having a particle size of D ₅₀ × 1.25 or more represented by the formula (a ₁ ) is within the above range, so that the primary particles are excessive. The abundance ratio of the agglomerates formed by linking is reduced, the decrease in reactivity at the time of preparing the solid catalyst component for olefin polymerization is suppressed, and the agglomerates are disintegrated at the time of preparing the solid catalyst component for olefin polymerization. Poor sedimentation and clogging of the filter plate due to the generation of a large amount of fine particles are suppressed, and it becomes easy to suppress a decrease in the yield of the solid catalyst component.
Further, the alkoxymagnetim according to the present invention serves as a carrier when used as a constituent component of a solid catalyst component for olefin polymerization, and its particle size distribution affects the particle size distribution of the solid catalyst component for olefin polymerization. Furthermore, when olefins are polymerized using the solid catalyst component for olefin polymerization, it also affects the particle size distribution of the obtained polymer.
Therefore, in the alkoxymagnesium according to the present invention, the ratio of the total volume amount of the particles having a particle size of D ₅₀ × 1.25 or more represented by the formula (a ₁ ) is within the above range. When a solid catalyst component for olefin polymerization was prepared using the alkoxymagnesium according to the above and the olefins were polymerized, the decrease in fluidity due to the formation of a coarse polymer was suppressed, and the coarse particles collapsed in the polymerization step. It is possible to suitably suppress the generation of fine powder accompanying the above.

In the present application documents, the ratio of the total volume of particles having a particle size of D ₅₀ × 1.25 or more represented by the above formula (a ₁ ) is 10 to 100 mg using a laser light scattering diffraction method particle size counter. Particles having a particle size of D ₅₀ with an integrated particle size of 50% and a particle size of D ₅₀ × 1.25 or more, which is measured when the particles are automatically measured in a state of being dispersed in 200 ml of a solvent. It means a value calculated from the total volume of all particles and the total volume of all particles.
The laser light scattering diffraction method particle size measuring machine used when calculating the ratio of the total volume of particles having a particle size of D ₅₀ × 1.25 or more represented by the above formula (a ₁ ) is as follows. Examples thereof include "MICROTRAC HRA 9320-X100" (manufactured by Nikkiso Co., Ltd.) and "MT3300EXII" (manufactured by Microtrack Bell Co., Ltd.).

Further, alkoxy magnesium according to the present invention, when the cumulative particle size of cumulative volume particle size distribution obtained by a laser light scattering diffraction method particle size measuring instrument is a particle size of 50% of the particles was D _50, the following formula ( a ₂ )
(Number of particles having a particle size of D ₅₀ × 0.75 or less / total number of particles) × 100 (a ₂ )
The ratio represented by is preferably 20% or less (0% to 20%), more preferably 15% or less (0% to 15%), and more preferably 10% or less (0% to 10%). Is more preferable.

As described above, the alkoxymagnesim according to the present invention serves as a carrier when used as a constituent component of the solid catalyst component for olefin polymerization, and its particle size distribution is the particle size distribution of the solid catalyst component for olefin polymerization. It also affects the particle size distribution of the obtained polymer when olefins are polymerized using the solid catalyst component for olefin polymerization.
In the alkoxymagnesium according to the present invention, the alkoxymagnesium according to the present invention is used because the ratio of the number of particles having a particle size of D ₅₀ × 0.75 or less represented by the formula (a ₂ ) is within the above range. When a solid catalyst component for olefin polymerization is prepared and olefins are polymerized, it becomes easy to suppress the occurrence of fouling, filter clogging, etc. due to the formation of fine powdery polymers. Further, when a solid catalyst component for olefin polymerization is prepared using the alkoxymagnesium according to the present invention and the olefins are copolymerized, the formation of a fine powdery solid catalyst component for olefin polymerization having a small pore volume is suppressed. Since the proportion of the copolymer generated inside the catalyst particles can be increased (instead of the surface of the catalyst particles), it becomes easy to suppress stickiness of the obtained copolymer and clogging of pipes, filters, and the like.

In the present application documents, the number of particles having a particle size of D ₅₀ × 0.75 or less is measured at the same time when the volume integrated particle size distribution or D ₅₀ is measured using the laser diffraction type particle size distribution measuring device described above. It means a value calculated based on the number of particles.
As the laser light scattering diffraction method particle size measuring machine used when calculating the number of particles having a particle size of D ₅₀ × 0.75 or less, “MICROTRAC HRA 9320-X100” (manufactured by Nikkiso Co., Ltd.) and Examples thereof include "MT3300EXII" (manufactured by Microtrack Bell Co., Ltd.).

Since the alkoxymagnesium according to the present invention is spherical, has a sharp particle size distribution, has a small amount of fine powder and coarse powder, and has a high bulk density, an olefin is used using a solid catalyst component for olefin polymerization prepared using the alkoxymagnesium. By polymerizing the same type, it is possible to easily produce a polymer having a high bulk density, a reduced amount of fine powder and a reduced amount of coarse powder, and a sharp particle size distribution without deteriorating performance such as stereoregularity and polymerization activity. Can be done.

The alkoxymagnesium according to the present invention can be easily produced by the above-mentioned method for producing alkoxymagnesium according to the present invention.

According to the present invention, it is possible to provide alkoxymagnesium having a high bulk density and a narrow particle size distribution.

Next, the present invention will be described in more detail with reference to examples, but these are merely examples and do not limit the present invention.

(Example 1)
(1) A reflux condenser connected to an integrated gas meter, a thermometer, a dropping funnel for ethanol, and a nitrogen introduction pipe via a gas flow meter were installed in a 900 ml four-necked flask equipped with a stirrer. After sufficient nitrogen substitution in this reaction system, 1.1 g (46 mmol) of metallic magnesium powder (average particle diameter 118 μm) and 127.8 ml (2.2 mol) of ethanol were charged to form a suspension. .. Next, 0.54 g (4.3 mmol) of iodine is added, and the suspension is heated to the reflux temperature of ethanol while stirring at 500 rpm with a stirrer, and metallic magnesium reacts with alcohol to form per minute. After the amount of hydrogen generated reached the maximum amount produced (0.20 L / min), the reflux point was maintained for 25 minutes until it was reduced to 0 L / min (0% by volume of the maximum amount produced).
(2) Next, 1.1 g (46 mmol) of metallic magnesium powder (average particle size 118 μm), 9.6 ml (165 mmol) of ethanol and 0.11 g (0.83 mmol) of iodine are added to the flask and suspended. The reflux point is maintained while stirring the liquid at 500 rpm, and after the generation rate S (liter / min) of hydrogen generated by the reaction of the metallic magnesium powder and ethanol increases to the maximum value, 0 to 0 of the maximum value The operation of holding for 6 to 7 minutes until the reduction to 25% was repeated 12 times in total.
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S (liter / minute) was reduced to 45% or less of the maximum value was 12 times (100%) out of 12 times, which was the maximum value of 40. The number of times the metallic magnesium was added after the reduction to% or less and 35% or less was 12 times (100%) out of 12 times.
FIG. 1 shows fluctuations in the amount of hydrogen generated during the reactions of (1) and (2) above.
(3) Further, after the production of hydrogen is stopped, the suspension is stirred with a stirrer at 200 rpm to maintain the reflux point for 60 minutes to mature the slurry, cooled to room temperature, and dried under reduced pressure to remove ethanol. The aged product was obtained by sieving, and coarse particles having a particle size of 212 μm or more were removed to obtain 61 g of the desired diethoxymagnesium (yield 89% by mass).
The obtained dietoxymagnesium had an ethanol content of 1.3% by mass, a bulk density measured according to JIS K6721 of 0.347 g / ml, and a specific surface area measured by the BET method of 14.6 m ² / g.

<particle size, particle size distribution index, particle size distribution corresponding to D ₁₀ , D ₅₀ and D ₉₀ >
Laser diffraction type particle size distribution measuring device (MICROTRAC HRA 9320-X100 Nikki) (MICROTRAC HRA 9320-X100 day equipment) for the particle size (D ₁₀ , D ₅₀ and D ₉₀ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium. (Manufactured by Co., Ltd.) was used, and 10 to 100 mg of particles were automatically measured in a state of being dispersed in about 200 ml of a solvent.
The particle size distribution index SPAN was calculated from the particle sizes D ₁₀ , D ₅₀ , and D ₉₀ corresponding to the above integrated volume particle sizes of 10%, 50%, and 90% using the following formula.
Particle Size Distribution Index (SPAN) = (D _90- D ₁₀ ) / D ₅₀
(In the formula, D ₉₀ is the integrated particle size in the integrated volume particle size distribution and the particle size is 90% (μm), D ₅₀ is the integrated particle size in the integrated volume particle size distribution and the particle size is 50% (μm), and D ₁₀ is the integrated volume particle size. The integrated particle size in the distribution shows a particle size (μm) of 10%.)
In addition, the obtained diethoxymagnesium is automatically measured using a laser diffraction type particle size distribution measuring device (MICROTRAC HRA 9320-X100 manufactured by Nikkiso Co., Ltd.) in a state where 10 to 100 mg of particles are dispersed in 200 ml of a solvent. and, a cumulative particle size of 50% of the particle diameter D ₅₀ of the cumulative volume particle size distribution, the total volume of particles having a particle size of more than D ₅₀ × 1.25, the total volume of all the particles, the diethoxymagnesium The ratio (ratio (a ₁ )) of the total volume of particles having a particle size of D ₅₀ × 1.25 or more was calculated by the following formula (a ₁ ).
(D ₅₀ x total volume of particles having a particle size of 1.25 or more / total volume of all particles) x 100 (a ₁ )
Further, the obtained diethoxymagnesium is automatically measured using a laser light scattering diffraction method particle size counter (manufactured by MT3300EXII Microtrac Bell Co., Ltd.) in a state where 10 to 100 mg of particles are dispersed in about 200 ml of a solvent. Then, from the particle size D _{50 in} which the integrated particle size of the volume integrated particle size distribution is 50%, the number of particles having a particle size of D ₅₀ × 0.75 or more, and the total number of particles of all particles, D ₅₀ × of diethoxymagnesium The ratio (ratio (a ₂ )) of the number of particles having a particle size of 0.75 or less was calculated by the following formula (a ₂ ).
(Number of particles having a particle size of D ₅₀ × 0.75 or less / total number of particles) × 100 (a ₂ )
The results are shown in Table 1.

(Example 2)
(1) A reflux condenser connected to an integrated gas meter, a thermometer, a dropping funnel for ethanol, and a nitrogen introduction pipe via a gas flow meter were installed in a 900 ml four-necked flask equipped with a stirrer. After sufficient nitrogen substitution in this reaction system, 2.0 g (82 mmol) of metallic magnesium powder (average particle diameter 87 μm) and 95.0 ml (1.6 mol) of ethanol were charged to form a suspension. .. Next, 0.54 g (4.3 mmol) of iodine is added, and the suspension is heated to the reflux temperature of ethanol while stirring at 650 rpm with a stirrer, and metallic magnesium reacts with alcohol to form per minute. After the amount of hydrogen generated reached the maximum amount produced (0.33 L / min), it was maintained for 11 minutes until it was reduced to 0.04 L / min (12% by volume of the maximum amount produced).
(2) Next, 0.96 g (40 mmol) of metallic magnesium powder (average particle size 87 μm), 7.0 ml (121 mmol) of ethanol and 0.11 g (0.83 mmol) of iodine are added to the flask and suspended. The reflux point is maintained while stirring the liquid at 650 rpm, and after the generation rate S (liter / min) of hydrogen generated by the reaction of the metallic magnesium powder and ethanol increases to the maximum value, the maximum value of 4 to 4 to The operation of holding for 4 to 5 minutes until the value was reduced to 31% was repeated 6 times in total.
At this time, after the hydrogen generation rate S (liter / minute) was reduced to 45% or less of the maximum value, the number of times the metallic magnesium was added was 6 times (100%) out of 6 times, 40% of the maximum value. The number of times of addition of metallic magnesium after reducing the amount to 35% or less was 6 times (100%) out of 6 times.
(3) The obtained slurry is further aged at a reflux temperature at 650 rpm while maintaining the reflux point for 60 minutes, cooled to room temperature, and then dried under reduced pressure to remove ethanol to obtain a mature product. The obtained aged product was sieved to remove coarse particles having a particle size of 212 μm or more to obtain 29 g of the desired diethoxymagnesium (yield 79% by mass).
The obtained dietoxymagnesium had a bulk density of 0.169 g / ml measured according to JIS K6721 and a specific surface area of 19.8 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1. The results are shown in Table 1.

(Example 3)
In (1) of Example 1, the same molar amount of metal magnesium powder (average particle size 133 μm) is used instead of the metal magnesium powder (average particle size 118 μm), and the hydrogen produced by the reaction between the metal magnesium powder and ethanol is used. After the generation rate S reaches the maximum value (0.20 L / min), the hydrogen is generated instead of maintaining the reflux point for 25 minutes until it is reduced to 0 L / min (0 volume% of the maximum production amount). After the velocity S reached the maximum value (0.19 L / min), the reflux point was maintained for 10 minutes until it decreased to 0.08 L / min (43% of the maximum value), and in (2) of Example 1. Add 1.1 g (46 mmol) of metallic magnesium powder (average particle size 118 μm), 9.6 ml (165 mmol) of ethanol, and 0.11 g (0.83 mmol) of iodine, and the hydrogen generation rate S reaches the maximum value. Then, instead of repeating the operation of maintaining the recirculation point 12 times while stirring for 6 to 7 minutes until the value is reduced to 0 to 25% of the maximum value, 1.1 g (46 mmol) of metal magnesium powder (average particle size 133 μm) is used. ), 4.8 ml (83 mmol) of ethanol and 0.11 g (0.83 mmol) of iodine, and after the hydrogen generation rate S reaches the maximum value, until it is reduced to 4 to 25% of the maximum value 5 Aged products in the same manner as in Example 1 were obtained except that the operation of maintaining the reflux point while stirring for about 8 minutes was repeated 12 times to obtain 65 g of the target diethoxymagnesium (yield 95% by mass). ..
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value was 12 times (100%) out of 12 times, 40% or less of the maximum value, and 35% or less. The number of times the metallic magnesium was added after the reduction was 11 times (92%) out of 12 times.
The obtained dietoxymagnesium had a bulk density of 0.291 g / ml measured according to JIS K6721 and a specific surface area of 21.3 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 4)
In (1) of Example 2, the same molar amount of metal magnesium powder (average particle size 133 μm) is used instead of the metal magnesium powder (average particle size 87 μm), and the hydrogen produced by the reaction between the metal magnesium powder and ethanol is used. After the generation rate S (liter / min) reaches its maximum value (0.33 L / min), the reflux is maintained for 11 minutes until it is reduced to 0.04 L / min (12 vol% of the maximum production amount). Instead, after the hydrogen generation rate S reaches the maximum value (0.18 L / min), the reflux point is maintained for 9 minutes until it is reduced to 0.07 L / min (38% by volume of the maximum production amount). In (2) of Example 2, 0.96 g (40 mmol) of metallic magnesium powder (average particle size 87 μm), 7.0 ml (121 mmol) of ethanol and 0.11 g (0.83 mmol) of iodine were added, and the above hydrogen was added. After reaching the maximum value of the generation rate S, instead of repeating the operation of maintaining the recirculation point while stirring for 4 to 8 minutes until it is reduced to 4 to 31% of the maximum value, the metal magnesium powder (average). Particle size 133 μm) 0.96 g (40 mmol), ethanol 7.0 ml (121 mmol) and iodine 0.11 g (0.83 mmol) were added, and after the hydrogen generation rate S reached the maximum value, the maximum value The operation of maintaining the recirculation point while stirring for 6 to 7 minutes was repeated 6 times until it was reduced to 17 to 30% of the above, except that the rotation speed of the stirrer was changed from 650 rpm to 200 rpm in (3) of Example 2. Aged products were obtained in the same manner as in Example 2 to obtain 36 g of the target diethoxymagnesium (yield 98% by mass).
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value and 40% was 6 times (100%) out of 6 times, and 35% or less of the maximum value. The number of times metallic magnesium was added after the reduction was 5 out of 6 (83%).
The obtained dietoxymagnesium had a bulk density of 0.239 g / ml measured according to JIS K6721 and a specific surface area of 21.2 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN and ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 5)
In (1) of Example 4, 0.07 L after the generation rate S (liter / min) of hydrogen produced by the reaction of metallic magnesium powder and ethanol reaches its maximum value (0.18 L / min). Instead of maintaining reflux for 9 minutes until reduced to / min (38% of maximum production), after the hydrogen generation rate S reaches the maximum value (0.27 L / min), 0.11 L / min. The recirculation point was maintained for 12 minutes until it was reduced to minutes (39% of the maximum value), and in (2) of Example 4, after the hydrogen generation rate S reached the maximum value, 17 to 30% of the maximum value. Instead of maintaining the recirculation point while stirring for 6 to 7 minutes until the hydrogen generation rate is reduced to 25 to 38%, after the hydrogen generation rate S reaches the maximum value, the hydrogen generation rate is reduced to 25 to 38% of the maximum value for 5 to 7 minutes. Aged products were obtained in the same manner as in Example 4 except that the operation of maintaining the recirculation point was repeated the same number of times, and 68 g of the target diethoxymagnesium was obtained (yield 99.9% by mass).
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value and 40% or less was 6 times (100%) out of 6 times, and 35% or less of the maximum value. The number of times the metallic magnesium was added after the reduction was 3 times (50%) out of 6 times.
The obtained dietoxymagnesium had a bulk density of 0.216 g / ml measured according to JIS K6721 and a specific surface area of 13.9 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 6)
In (1) of Example 4, 0.07 L after the generation rate S (liter / min) of hydrogen produced by the reaction of metallic magnesium powder and ethanol reaches its maximum value (0.18 L / min). Instead of maintaining reflux for 9 minutes until reduced to / min (38% of maximum), after the hydrogen generation rate S reaches the maximum (0.27 L / min), 0.11 L / min. The recirculation point was maintained for 12 minutes until it decreased to (39% of the maximum value), and in (2) of Example 4, after the hydrogen generation rate S reached the maximum value, it reached 17 to 30% of the maximum value. Instead of maintaining the recirculation point while stirring for 6 to 7 minutes until it decreases, after the hydrogen generation rate S reaches the maximum value, stir for 5 to 7 minutes until it decreases to 16 to 43% of the maximum value. Aged products were obtained in the same manner as in Example 4 except that the operation of maintaining the recirculation point was carried out the same number of times, and 57 g of the desired diethoxymagnesium was obtained (yield 84% by mass).
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value was reduced to 6 times (100%) out of 6 times, and to 40% or less of the maximum value. The number of times metallic magnesium was added was 4 out of 6 (67%), and the number of times metallic magnesium was added after reducing to 35% or less of the maximum value was 3 out of 6 (50%). there were.
The obtained dietoxymagnesium had a bulk density of 0.221 g / ml measured according to JIS K6721 and a specific surface area of 23.3 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 7)
In (1) of Example 4, after the generation rate S of hydrogen generated by the reaction of the metallic magnesium powder and ethanol reaches the maximum value (0.18 L / min), 0.07 L / min (maximum value). Instead of maintaining reflux for 9 minutes until reduced to 38%), after the hydrogen generation rate S reaches the maximum value (0.27 L / min), 0.11 L / min (39% of the maximum value). ) Is maintained for 11 minutes, and in (2) of Example 4, after the hydrogen generation rate S reaches the maximum value, it is 6 to 7 until it is reduced to 17 to 30% of the maximum value. Instead of the operation of maintaining the recirculation point while stirring for minutes, after the hydrogen generation rate S reaches the maximum value, the recirculation point is maintained while stirring for 5 to 7 minutes until the hydrogen generation rate S is reduced to 30 to 39% of the maximum value. Aged products were obtained in the same manner as in Example 4 except that the operation was carried out the same number of times, and the desired diethoxymagnesium was obtained.
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less and 40% or less of the maximum value was 6 times (100%) out of 6 times, and 35% of the maximum production amount. The number of times the metallic magnesium was added after the reduction to the following was 2 out of 6 times (33%).
The obtained dietoxymagnesium had a bulk density of 0.227 g / ml measured according to JIS K6721 and a specific surface area of 19.0 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 8)
In (1) of Example 4, after the generation rate S of hydrogen generated by the reaction of the metallic magnesium powder and ethanol reaches the maximum value (0.18 L / min), 0.07 L / min (maximum value). Instead of maintaining reflux for 9 minutes until reduced to 38%), after the hydrogen generation rate S reaches the maximum value (0.30 L / min), 0.09 L / min (32% of the maximum value). ) Is maintained for 12 minutes, and in (2) of Example 4, after the hydrogen generation rate S reaches the maximum value, it is 6 to 7 until it is reduced to 17 to 30% of the maximum value. Instead of the operation of maintaining the recirculation point while stirring for minutes, after the hydrogen generation rate S reaches the maximum value, the recirculation point is maintained while stirring for 6 to 7 minutes until the hydrogen generation rate S is reduced to 26 to 35% of the maximum value. Aged products were obtained in the same manner as in Example 4 except that the operation was carried out the same number of times, and 54 g of the desired diethoxymagnesium was obtained (yield 79% by mass).
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value was 6 times (100%) out of 6 times, 40% or less of the maximum value, and 35% or less. The number of times metallic magnesium was added after the reduction was 5 out of 6 (83%).
The obtained dietoxymagnesium had a bulk density of 0.229 g / ml measured according to JIS K6721 and a specific surface area of 22.0 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 9)
(1) A reflux condenser to which an integrated gas meter was connected, a thermometer, a dropping funnel for ethanol, and a nitrogen introduction pipe via a gas flow meter were installed in an autoclave with a stirrer having a capacity of 32 L. After sufficient nitrogen substitution in this reaction system, 100 g (4.11 mol) of metallic magnesium powder (average particle size 133 μm) and 4750 ml (82.1 mol) of ethanol were charged to form a suspension. Next, 29.7 g (0.23 mol) of iodine is added, and the suspension is heated to the reflux temperature of ethanol while stirring at 330 rpm, and the generation rate S of hydrogen generated by the reaction of metallic magnesium with alcohol is maximum. After reaching the value (14.4 L / min), it was maintained for 20 minutes until it decreased to 2.75 L / min (19% of the maximum value).
(2) Next, 48.0 g (1.98 mol) of metallic magnesium powder (average particle size 133 μm), 5.8 g (0.05 mol) of iodine and 350 ml (6.05 mol) of ethanol were added to the flask. The operation of maintaining the reflux point while stirring the suspension at 330 rpm and holding the suspension for 7 to 8 minutes after the hydrogen generation rate S reaches the maximum value and then reducing it to 12 to 24% of the maximum value is performed in total. Repeated 6 times.
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value was 6 times (100%) out of 6 times.
The reaction of the alcohol and the metallic magnesium in the same step with respect to the total step time (seconds) of the step of adding the alcohol and the metallic magnesium to the reaction system to carry out the reaction (the total step time of the above (1) and (2)). The ratio of the time (minutes) in which the hydrogen generation rate S was 45% or less of the maximum value (24 L / min) was 75.1%.
(3) The obtained slurry is further aged at a reflux temperature at 650 rpm with a stirrer at a reflux point for 60 minutes, cooled to room temperature, and then dried under reduced pressure to remove ethanol. A product was obtained, and the obtained aged product was sieved to remove coarse particles having a particle size of 212 μm or more to obtain 1,384 g of the desired diethoxymagnesium (yield 76% by mass).
The obtained dietoxymagnesium had an ethanol content of 0.4% by mass, a bulk density measured according to JIS K6721 of 0.254 g / ml, and a specific surface area measured by the BET method of 26.0 m ² / g. there were.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Example 10)
(1) A reflux condenser connected to an integrated gas meter, a thermometer, a dropping funnel for ethanol, and a nitrogen introduction pipe via a gas flow meter were installed in a 900 ml four-necked flask equipped with a stirrer. After sufficient nitrogen substitution in this reaction system, 1.6 g (67 mmol) of metal magnesium powder (average particles 169 μm) and 36.0 ml (622 mmol) of ethanol were charged to form a suspension. Next, 0.30 g (2.4 mmol) of iodine is added, and the suspension is heated to the reflux temperature of ethanol while stirring at 500 rpm, and the generation rate S of hydrogen generated by the reaction of metallic magnesium with alcohol is maximum. After reaching the value (0.30 L / min), it was held for 13 minutes until it decreased to 0 L / min (0% of the maximum value).
(2) Next, 1.6 g (66 mmol) of metallic magnesium powder (average particles 169 μm), 17.5 ml (302 mmol) of ethanol, and 0.175 g (1.38 mmol) of iodine are added to the flask and suspended. A total of 4 operations are performed in which the reflux point is maintained while stirring the liquid at 500 rpm, and after the hydrogen generation rate S reaches the maximum value, it is held for 5 to 10 minutes until it is reduced to 0 to 47% of the maximum value. Repeated times.
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% or less of the maximum value was 3 times (75%) out of 4 times, 40% or less of the maximum value, and 35% or less. The number of times the metallic magnesium was added after the reduction was 3 times (75%) out of 4 times.
(3) Further, 35 ml of ethanol was added to the flask, and the slurry was aged by maintaining the reflux point for 120 minutes while stirring at 200 rpm, cooled to room temperature, and then dried under reduced pressure to remove ethanol. The obtained aged product was sieved to remove coarse particles having a particle size of 212 μm or more to obtain 26 g of the desired diethoxymagnesium (yield 68% by mass).
The obtained dietoxymagnesium had a bulk density of 0.270 g / ml measured according to JIS K6721 and a specific surface area of 15.6 m ² / g measured by the BET method.
In addition, the particle size (D ₁₀ , D ₅₀ and D ₉₀ ), SPAN, ratio (a ₁ ) and ratio (a ₂ ) corresponding to the integrated volume particle size of 10%, 50% and 90% of the obtained diethoxymagnesium are obtained. , Obtained by the same method as in Example 1.
The results are shown in Table 1.

(Comparative Example 1)
In (1) of Example 1, after the amount of hydrogen generated per minute reaches the maximum production amount (0.20 L / min), the reflux point is reduced to 0 L / min (0% by volume of the maximum production amount). After the hydrogen generation rate S reaches the maximum value (0.18 L / min), the recirculation point is reduced to 0.17 L / min (94% by volume of the maximum production amount). Was maintained for 6 minutes, and in (2) of Example 1, after the hydrogen generation rate S reached the maximum value by adding metallic magnesium or the like, it was 6 to 7 until it was reduced to 0 to 25% by volume of the maximum value. Instead of repeating the operation of maintaining the recirculation point 12 times while stirring for minutes, after adding metallic magnesium or the like and the hydrogen generation rate S reaches the maximum value, until it is reduced to the maximum value of 46 to 63% by volume. Aged products were obtained in the same manner as in Example 1 except that the operation of maintaining the recirculation point while stirring for 5 to 6 minutes was repeated 12 times, and the obtained aged products were sieved to a coarse size having a particle size of 212 μm or more. The particles were removed to obtain 61 g of the desired diethoxymagnesium (yield 80% by volume).
At this time, the number of times the metallic magnesium was added after the hydrogen generation rate S was reduced to 45% by volume or less of the maximum value was 0 times (0%) out of 12 times, 40% by volume or less of the maximum value, and 35. The number of times the metallic magnesium was added after the volume was reduced to 0% or less was 0 times (0%) out of 12 times.
In addition, in contrast to the total step time (seconds) of the step of adding the alcohol and metallic magnesium to the reaction system to carry out the reaction (total step times of (1) and (2) above), the alcohol and metallic magnesium in the same step. The ratio of the time (minutes) in which the amount of hydrogen generated by the reaction was 45% by volume or less of the average of the maximum values (0.28 L / min) was 0%.
FIG. 1 shows fluctuations in the amount of hydrogen generated during the reactions of (1) and (2) above.
The obtained dietoxymagnesium had an ethanol content of 2.8% by mass, a bulk density measured according to JIS K6721 of 0.297 g / ml, and a specific surface area measured by the BET method of 19.6 m ² / g.
In addition, the particle sizes (D10, D50 and D90), SPAN, ratios (a ₁ ) and ratios (a ₂ ) corresponding to the integrated volumetric particle sizes of 10%, 50% and 90% of the obtained diethoxymagnesium were set in Examples. It was obtained by the same method as in 1.
The results are shown in Table 1.

From Table 1 and FIG. 1, in Examples 1 to 10, in the production of alkoxymagnesium by intermittently adding metallic magnesium to the reaction system a plurality of times with respect to alcohol, the second and subsequent metals to the reaction system are produced. After the generation rate S (liter / min) of hydrogen produced by reacting at least a part of magnesium with alcohol by the addition of metallic magnesium immediately before increases to the maximum value, it reaches 45% or less of the maximum value. Since it is performed after reduction, the bulk density is high, the ratio (a ₁ ) is as small as 30.0% by volume or less, the ratio (a ₂ ) is as small as 20% or less, and the SPAN is 1.00 or less. It can be seen that alkoxymagnesium having a narrow particle size distribution can be effectively prepared by reducing the ratio of fine particles and coarse particles.
On the other hand, from Table 1 and FIG. 1, in Comparative Example 1, when metallic magnesium was intermittently added to the reaction system a plurality of times with respect to alcohol to produce alkoxymagnesium, the second and subsequent metallic magnesiums were added to the reaction system. The addition is performed after the generation rate S (liters / minute) of hydrogen generated by reacting with alcohol by the addition of the immediately preceding metallic magnesium increases to its maximum value and before it decreases to 45% or less of the maximum value. Therefore, the proportion (a ₁ ) is as large as more than 30.0% by volume, the proportion (a ₂ ) is as large as more than 20%, and the SPAN is as large as 1.65, so that the proportion of fine particles and coarse particles is high and the particle size distribution is wide. It turns out that only magnesium can be prepared.

(Example 11)
<Preparation of solid catalyst components for olefin polymerization>
A mixed solution was formed by charging 30 ml of titanium tetrachloride and 20 ml of toluene into a round-bottom flask having a capacity of 500 ml equipped with a stirrer, which was sufficiently replaced with nitrogen gas. Next, a suspension formed using 10 g of diethoxymagnesium, 50 ml of toluene and 3.3 ml (12.5 mmol) of di-n-butyl phthalate obtained in Example 1 above was subjected to a liquid temperature of −10 ° C. After the mixture was added in portions to the mixed solution held in, the liquid temperature was raised from −10 ° C. to 90 ° C., and the mixture was reacted at 90 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained solid product was washed 4 times with 100 ml of toluene at 90 ° C., 30 ml of titanium tetrachloride and 70 ml of toluene were newly added, the temperature was raised to 110 ° C., and the mixture was stirred at 110 ° C. for 2 hours. It was reacted. After completion of the reaction, the mixture was washed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A-1) for olefin polymerization.
The titanium content in the solid catalyst component (A-1) was measured and found to be 2.8% by mass.

<Formation of olefin polymerization catalyst and propylene polymerization>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and the above solid catalyst component (A-1) were converted into titanium atoms. A catalyst for olefin polymerization was formed by charging 0.0026 mmol in the above.
Next, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene are charged into an autoclave, prepolymerized at 20 ° C. for 5 minutes, heated to 70 ° C., and polymerized at 70 ° C. for 1 hour. To obtain a propylene polymer. The polymerization activity per 1 g of the solid catalyst component (propylene polymerization activity (g-pp / g-catalyst)) and the physical characteristics of the obtained polymer were determined by the following methods. The results are shown in Table 2.

<Polymerization activity per 1 g of solid catalyst component>
Propylene polymerization activity (g-pp / g-catalyst) = mass of polypropylene (g) / mass of solid catalyst component in catalyst for olefin polymerization (g)

<Percentage of p-xylene soluble component of polymer (XS)>
By charging 4.0 g of the polymer (polypropylene) and 200 ml of p-xylene into a flask equipped with a stirrer and setting the external temperature to the boiling point of xylene or higher (about 150 ° C.), the inside of the flask The polymer was dissolved over 2 hours while maintaining the temperature of p-xylene below the boiling point (137-138 ° C.). After that, the liquid temperature was cooled to 23 ° C. over 1 hour, and the insoluble component and the dissolved component were filtered and separated. A solution of the above dissolved components was collected, p-xylene was distilled off by heating under reduced pressure, the weight of the obtained residue was determined, and the relative ratio (mass%) to the produced polymer (polypropylene) was calculated. It was designated as a xylene-soluble component (C-XS).

<Polymer bulk density (BD)>
The bulk density (BD) of the obtained polymer was measured according to JIS K-6721: 1997.

<Average particle size of polymer, particle size distribution index and amount of fine powder with particle size less than 75 μm>
The average particle size of the obtained polymer is the particle size (D ₅₀ ) corresponding to 50% of the volume-based integrated particle size distribution, the particle size distribution index (SPAN), and the amount of fine powder less than 75 μm (-75 μm). Using a digital image analysis type particle size distribution measuring device (Camsizer, manufactured by Horiba Seisakusho Co., Ltd.), the volume-based integrated particle size distribution was automatically measured for the total amount of the obtained polymer under the following measurement conditions.
(Measurement condition)
Funnel position: 6mm
Camera coverage area: Basic camera less than 3%, Zoom camera less than 10% Target coverage area: 0.5%
Feeder width: 40 mm
Feeder control level: 57, 40 seconds Measurement start level: 47
Maximum control level: 80
Control criteria: 20
Image rate: 50% (1: 2)
Particle size definition: Minimum value of Martin diameter measured n times for each particle SPHT (spherical) fitting: 1
Class upper limit: Select 50 points in the range of 32 μm to 4000 μm on a logarithmic scale. The particle size distribution index (SPAN) corresponds to 10%, 50%, and 90% of the volume-based integrated particle size distribution of the obtained polymer. It was calculated using the following formula from the particle sizes D ₁₀ , D ₅₀ and D ₉₀ .
Particle Size Distribution Index (SPAN) = (D _90- D ₁₀ ) / D ₅₀
(In the formula, D ₉₀ is the integrated particle size in the integrated volume particle size distribution and the particle size is 90% (μm), D ₅₀ is the integrated particle size in the integrated volume particle size distribution and the particle size is 50% (μm), and D ₁₀ is the integrated volume particle size. The integrated particle size in the distribution shows a particle size (μm) of 10%.)

(Comparative Example 2)
A solid catalyst component for olefin polymerization (A-2) was used in the same manner as in Example 11 except that 10 g of diethoxymagnesium obtained in Comparative Example 1 was used instead of 10 g of diethoxymagnesium obtained in Example 1. ), Formation of an olefin polymerization catalyst and propylene polymerization were carried out, and the physical properties of the obtained polymer were evaluated. Table 2 shows the polymerization activity per 1 g of the solid catalyst component and the physical characteristics of the obtained polymer.

From Table 2, in Example 11, since the particle size distribution obtained in Example 1 is extremely narrow and dialkoxymagnesium having a good shape is used as a raw material for the solid catalyst component for olefin polymerization, the particle size distribution is distributed. It can be seen that polypropylene polymer particles having a narrow particle size and a small amount of fine powder polymer can be obtained.
On the other hand, from Table 2, in Comparative Example 2, it was obtained from the fact that the dialkenyl magnesium obtained in Comparative Example 1 having a wide particle size distribution and an irregular shape was used as a raw material for the solid catalyst component for olefin polymerization. It can be seen that the shape of the polypropylene particles is not uniform, the particle size distribution is wide, and the proportion of the fine powder polymer is large.

According to the present invention, it is possible to provide a method for producing alkoxymagnesium and an alkoxymagnesium capable of effectively preparing alkoxymagnesium having a high bulk density and a narrow particle size distribution.

Claims (6)

A method for producing alkoxymagnesium by intermittently adding metallic magnesium to alcohol multiple times in a reaction system.
Of the second and subsequent additions of metallic magnesium to the reaction system, in the addition of 5% by mass or more of the total metallic magnesium added to the reaction system, one or more of them are added.
The feature is that the hydrogen generation rate S (liters / minute) generated by reacting with the alcohol is increased to the maximum value by the addition of the metal magnesium immediately before, and then reduced to 45% or less of the maximum value. A method for producing alkoxymagnesium. It is the second and subsequent additions in the multiple additions of metallic magnesium to the reaction system, and the maximum hydrogen generation rate S (liters / minute) generated by reacting with the alcohol by the addition of the immediately preceding metallic magnesium. The method for producing alkoxymagnesium according to claim 1, wherein the number of additions performed after increasing to the value and then reducing to 45% or less of the maximum value is 35% or more of the number of additions after the second time. According to claim 1 or 2, the amount of metallic magnesium added to the reaction system a plurality of times is 33% by mass or less of the total amount of metallic magnesium added to the reaction system. The method for producing alkoxymagnesium according to the above. This is the second addition of metallic magnesium to the reaction system, and after the hydrogen generation rate S (liters / minute) generated by reacting with the alcohol by the addition of the metallic magnesium immediately before increases to the maximum value, Claim 1 or claim that the addition performed after reducing the maximum value to 45% or less is performed within 180 seconds after the hydrogen generation rate S (liter / minute) is reduced to 0% of the maximum value. Item 2. The method for producing alkoxymagnesium according to Item 2. The bulk density is 0.160 to 0.400 g / ml, the particle size distribution index SPAN is 1.00 or less, and the integrated particle size of the volume integrated particle size distribution obtained by using a laser diffraction type particle size distribution measuring device is 50%. When the particle size of the particles is D ₅₀ , the following formula (a ₁ )
(D ₅₀ x total volume of particles having a particle size of 1.25 or more / total volume of all particles) x 100 (a ₁ )
An alkoxymagnesium characterized in that the ratio represented by is 30.0% by volume or less. When the particle size of the particles having an integrated particle size of 50% in the volume integrated particle size distribution obtained by using the laser diffraction type particle size distribution measuring device is D ₅₀ , the following equation (a ₂ ) is used.
(Number of particles having a particle size of D ₅₀ × 0.75 or less / total number of particles) × 100 (a ₂ )
The alkoxymagnesium according to claim 5, wherein the proportion represented by is 20% or less.